WO2011115007A1 - 有機無機複合フィラー、及びその製造方法 - Google Patents
有機無機複合フィラー、及びその製造方法 Download PDFInfo
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- WO2011115007A1 WO2011115007A1 PCT/JP2011/055757 JP2011055757W WO2011115007A1 WO 2011115007 A1 WO2011115007 A1 WO 2011115007A1 JP 2011055757 W JP2011055757 W JP 2011055757W WO 2011115007 A1 WO2011115007 A1 WO 2011115007A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
- A61K6/836—Glass
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3072—Treatment with macro-molecular organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3676—Treatment with macro-molecular organic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
Definitions
- the present invention relates to an organic-inorganic composite filler, a method for producing the same, and a dental curable composition containing the organic-inorganic composite filler.
- Dental composite restorative materials are representative of dental curable compositions. For example, in a dental clinic, a dental composite restorative material is filled in a cavity of a tooth to be repaired and formed into a tooth shape, and then irradiated with active light using a special light irradiator and polymerized and cured. It is done. This restores the damaged tooth.
- a dental composite restorative material is built up in the form of a tooth to be repaired on a plaster model and then polymerized and cured by light irradiation. This is a dental clinic using a dental adhesive and a tooth. Bonded to quality. This restores the damaged tooth.
- the dental composite restorative material is superior in that it can provide the same color tone as natural teeth and has good operability.
- dental composite restorative materials have become rapidly popular in recent years and are now being applied in most anterior tooth treatments.
- dental composite restorative materials with considerably high mechanical strength have been developed.
- the dental composite restorative material has begun to be applied to the restoration of a molar portion to which a strong occlusal pressure is applied.
- Dental composite restorative materials are generally composed of a polymerizable monomer (monomer), a filler, and a polymerization initiator as main components.
- the dental composite restorative material is configured by selecting the type, shape, particle diameter, filling amount, and the like of the filler to be used. By appropriately selecting these, the operability of the paste-like dental composite restorative material, and various properties such as aesthetics and mechanical strength of the cured body are optimally adjusted.
- the resulting cured body of the composite restorative material has high mechanical strength.
- This in itself is advantageous as a dental composite restorative material.
- the surface smoothness and wear resistance of the cured body are reduced. As a result, it is difficult to obtain a finished surface of a hardened body similar to natural teeth.
- a fine inorganic filler having an average particle size of 1 ⁇ m or less gives a cured product having excellent surface lubricity and wear resistance.
- the fine inorganic filler has a large specific surface area, the paste-like composite restorative material is greatly thickened.
- the dentist needs to adjust the composite restorative material to a consistency suitable for use in the oral cavity. In order to reduce the consistency, it is necessary to reduce the blending amount of the fine inorganic filler. In this case, the operability at the time of treatment decreases, the shrinkage amount of the cured body increases due to the polymerization of the monomer when the composite restorative material is cured, and the mechanical strength of the obtained cured body decreases.
- This organic-inorganic composite filler is a composite filler containing a fine inorganic filler in an organic resin filler.
- This organic-inorganic composite filler has a smaller surface area than the fine inorganic filler. Therefore, a paste-like composite restorative material can be produced by blending a sufficient amount of the organic-inorganic composite filler without developing a thickening action.
- the organic-inorganic composite filler is generally produced by polymerizing a curable composition in which a fine inorganic filler and a polymerizable monomer are previously kneaded to obtain a cured product, and then pulverizing the cured product. (See paragraph [0012] of Patent Document 1).
- a method for producing an organic-inorganic composite filler having a narrow particle size distribution is also known (see the claims of Patent Document 2).
- inorganic agglomerated particles are produced by granulating the fine inorganic filler by a method such as spray drying.
- the produced inorganic agglomerated particles are decompressed in contact with the liquid polymerizable monomer under reduced pressure, so that the polymerizable monomer enters the agglomeration gap between the primary particles constituting the inorganic agglomerated particles.
- the infiltrated monomer is polymerized and cured to obtain an organic-inorganic composite filler.
- This organic-inorganic composite filler can be used even if not pulverized.
- the mechanical strength of the dental composite restorative material containing the organic-inorganic composite filler obtained by the conventional method is considerably high.
- the demand for improving the mechanical strength of the organic-inorganic composite filler is increasing. Therefore, further improvement in the mechanical strength of the organic-inorganic composite filler is desired.
- the object of the present invention is to develop an organic-inorganic composite filler that is blended in a dental curable composition and that further increases the mechanical strength of the cured product.
- the present inventors have intensively studied to solve the above problems. As a result, in the organic-inorganic composite filler, it was found that the above problem can be solved by leaving the gap having a specific pore volume instead of completely closing the aggregation gap of the inorganic primary particles with the organic resin phase, The present invention has been completed.
- the present invention Inorganic aggregated particles obtained by agglomerating inorganic primary particles having an average particle diameter of 10 to 1000 nm; An organic resin phase that covers the surface of each inorganic primary particle and binds each inorganic primary particle to each other;
- the pore volume formed between the organic resin phases covering the surface of each inorganic primary particle and measured by mercury porosimetry (herein, the pore means a pore having a pore diameter in the range of 1 to 500 nm) is 0.
- the present invention provides a production method suitable for obtaining an organic-inorganic composite filler in which agglomerated gaps of inorganic primary particles are formed with the above pore volume.
- the organic-inorganic composite filler of the present invention not only gives the dental curable composition containing the effect of reducing paste operability and polymerization shrinkage, but also the surface smoothness and wear resistance of the cured product. , Greatly improve the mechanical strength. These effects are due to the formation of pores composed of agglomeration gaps of inorganic primary particles having a specific pore volume in the organic-inorganic composite filler. That is, when the polymerizable monomer of the curable composition penetrates into the pores constituted by such agglomeration gap by a capillary phenomenon and cures, an anchor effect is generated, and the organic-inorganic composite filler has the curable property. It is presumed that the cured product of the composition is held with high fitting force and mechanical strength is improved.
- the organic-inorganic composite filler of the present invention having such an effect can be used without limitation as a filler in various applications such as dental materials and cosmetic materials.
- dental materials include dental filling restoration materials such as composite resins; dental indirect restoration materials for inlays, onlays, crowns and bridges; dental cements; and dental curability such as denture materials. Examples thereof include compositions.
- the organic-inorganic composite filler can be suitably used as a filler to be blended in a dental composite restorative material such as a dental filling restorative material and a dental indirect restorative material.
- FIG. 1 is a schematic cross-sectional view showing a typical embodiment of the organic-inorganic composite filler of the present invention.
- organic-inorganic composite filler 2 organic-inorganic composite filler 2; inorganic primary particles 3; organic resin phase 4;
- the organic-inorganic composite filler of the present invention is formed by agglomerating inorganic primary particles having an average particle diameter of 10 to 1000 nm, and each inorganic primary particle is bonded to each other by an organic resin phase covering the surface.
- the organic resin phase does not fill the entire space between the inorganic primary particles.
- pores composed of aggregation gaps are formed between the organic resin layers covering the surface of a large number of inorganic primary particles. That is, pores having a pore diameter in the range of 1 to 500 nm as measured by mercury porosimetry are formed at a volume of 0.01 to 0.30 cm 3 / g in the aggregation gaps of the inorganic primary particles covered with the organic resin phase.
- the polymerizable monomer blended in the curable composition penetrates into the agglomeration gap by capillary action and is cured.
- the cured resin produced by curing the polymerizable monomer is embedded in the pores and strongly bonded to the organic-inorganic composite filler. That is, by exhibiting a so-called anchor effect utilizing pores, a cured product of the curable composition containing the organic-inorganic composite filler of the present invention has high mechanical strength.
- the characteristic pore structure of the organic-inorganic composite filler of the present invention will be described with reference to the schematic diagram showing the particle cross section of FIG.
- the organic-inorganic composite filler 1 has an aggregate of a plurality of inorganic primary particles 2 having an average particle diameter of 10 to 1000 nm.
- Each of the plurality of inorganic primary particles 2 is covered with an organic resin phase 3, and these organic resin phases 3 are melted together and solidified in an integrated state, thereby being firmly bonded to each other. Yes.
- the organic resin phase 3 does not fill the entire space formed by aggregation of a plurality of inorganic primary particles, and the aggregation gap 4 remains.
- the total volume of pores in the pore diameter range of 1 to 500 nm by the mercury intrusion method described below is preferably 0.01 to 0.30 cm 3 / g, preferably 0.03 to 0.20 cm 3 / g.
- the pore volume of the organic-inorganic composite filler is a value measured by a mercury intrusion method.
- the measurement of the pore volume by the mercury intrusion method is as described below.
- a predetermined amount of the organic-inorganic composite filler is put in a measurement cell.
- the amount of mercury injected at a pressure corresponding to the diameter of each pore formed in the aggregation gap of the organic-inorganic composite filler is measured.
- the pore volume is obtained by integrating the amount of mercury injected into each pore. Note that the pore diameter of the pores to be measured when measuring the pore volume is in the range of 1 to 500 nm as described above.
- the organic-inorganic composite filler produced using these aggregates may have large pores having a pore diameter exceeding 500 nm.
- the capillary phenomenon is not sufficiently effective for such a large pore.
- the polymerizable monomer contained in the curable composition cannot sufficiently penetrate into the pores, and as a result, the anchor effect may not sufficiently act.
- the anchor effect may not be sufficiently effective.
- the presence of such large pores in the organic-inorganic composite filler is allowed.
- the giant pores are not included in the pores to be measured when determining the pore volume.
- pores with pore diameters smaller than 1 nm are difficult to measure the pore volume by mercury porosimetry.
- pores with small pore diameters are blocked, so that they do not exist as pores, and even if they exist, the anchor effect is not sufficiently exhibited. Therefore, in the present invention, pores having pore diameters other than the pore diameter range are not included in the pores whose pore volume is to be measured.
- the organic-inorganic composite filler having a pore volume of less than 0.01 cm 3 / g When the organic-inorganic composite filler having a pore volume of less than 0.01 cm 3 / g is added to the curable composition, the amount of the polymerizable monomer entering the pores is small. As a result, a sufficient anchor effect is not exhibited, and the mechanical strength of the obtained cured body is reduced.
- the pore volume of the organic-inorganic composite filler is particularly preferably 0.03 to 0.20 cm 3 / g from the viewpoint of exhibiting these effects to a higher degree.
- the average pore diameter of the pores composed of the aggregation gaps of the organic-inorganic composite filler is not particularly limited, but is preferably 3 to 300 nm, more preferably 10 to 200 nm. In the case of this average pore diameter range, the agglomeration gap having the pore volume can be easily formed. Note that the average pore diameter of pores composed of agglomerated gaps is the median pore diameter determined based on the pore volume distribution of pores in the pore diameter range of 1 to 500 nm measured by mercury porosimetry.
- the average particle size (particle size) of the organic-inorganic composite filler is preferably 3 to 100 ⁇ m, particularly preferably 5 to 70 ⁇ m.
- the average particle diameter is less than 3 ⁇ m, the filling rate of the filler that can be filled in the dental curable composition is lowered. As a result, the mechanical strength of the cured product is reduced, and the adhesiveness of the dental curable composition is increased, resulting in poor operability during tooth treatment.
- the average particle diameter exceeds 100 ⁇ m the fluidity of the dental curable composition decreases. As a result, operability at the time of tooth treatment is deteriorated.
- the average particle size of the organic-inorganic composite filler indicates the median size determined based on the particle size distribution by the laser diffraction-scattering method.
- a sample to be used for measurement is prepared by uniformly dispersing 0.1 g of an organic-inorganic composite filler in 10 ml of ethanol.
- the average particle diameter of the inorganic primary particles is 10 to 1000 nm, preferably 40 to 800 nm, and more preferably 50 to 600 nm.
- the average particle diameter of the inorganic primary particles is less than 10 nm, it becomes difficult to form the pores having the pore volume characterized by the present invention.
- the opening of the pore is easily closed by the organic resin phase. As a result, air bubbles are easily included in the obtained filler.
- air bubbles are encapsulated in the organic-inorganic composite filler, the transparency of the cured product of the curable composition containing the organic-inorganic composite filler decreases.
- the average particle diameter of the inorganic primary particles exceeds 1000 nm, if this is used for a dental composite restorative material, etc., the resulting hardened body will be less abrasive and it will be difficult to obtain a smooth surface hardened body.
- the shape of the inorganic primary particles is not particularly limited, and spherical, substantially spherical, or amorphous particles can be used.
- Inorganic primary because it has excellent wear resistance and surface smoothness, and the organic / inorganic composite filler has uniform pores, and the pore openings are closed by the organic resin phase, making it difficult to enclose air bubbles.
- the shape of the particles is preferably spherical or substantially spherical.
- a substantially spherical shape means that whose average uniformity is 0.6 or more. The average uniformity is more preferably 0.7 or more, and particularly preferably 0.8 or more.
- the primary particle diameter of the inorganic particles is measured using a scanning or transmission electron microscope. Specifically, by analyzing the image of the organic-inorganic composite filler, the equivalent circle diameter of the inorganic primary particles (the diameter of a circle having the same area as the area of the target particle) is obtained. As an image taken with an electron microscope, an image that is clear in brightness and capable of discriminating the particle outline is used.
- Image analysis is performed using image analysis software that can measure at least the particle area, maximum particle length, and minimum width.
- the primary particle diameter equivalent circle diameter
- the maximum length and minimum width of the particles are obtained by the above method
- the average particle diameter and average uniformity of the inorganic primary particles are calculated by the following formulas. calculate.
- the number of particles is defined as (n)
- the maximum length of the i-th particle is defined as the major axis (Li)
- the diameter perpendicular to the major axis is defined as the minimum width (Bi).
- the material of the inorganic primary particles is not particularly limited, and any material used as a filler in a conventional dental curable composition can be used. Specifically, simple metals selected from Group I, II, III, IV, and transition metals; oxides and composite oxides of these metals; fluorides, carbonates, sulfates, and silicic acids of these metals Metal salts composed of salts, hydroxides, chlorides, sulfites, phosphates and the like; and composites of these metal salts.
- metal oxides such as amorphous silica, quartz, alumina, titania, zirconia, barium oxide, yttrium oxide, lanthanum oxide, ytterbium oxide; silica-zirconia, silica-titania, silica-titania-barium oxide, silica -Silica-based composite oxides such as titania-zirconia, borosilicate glass, aluminosilicate glass, fluoroaluminosilicate glass, etc .; metals such as barium fluoride, strontium fluoride, yttrium fluoride, lanthanum fluoride, ytterbium fluoride Fluorides; inorganic carbonates such as calcium carbonate, magnesium carbonate, strontium carbonate and barium carbonate; metal sulfates such as magnesium sulfate and barium sulfate are employed.
- metal oxides and silica-based composite oxides are preferably those fired at a high temperature in order to make them dense materials.
- the metal oxide and the silica-based composite oxide preferably contain a small amount of Group I metal oxide such as sodium.
- the silica-based composite oxide particles can be easily adjusted in refractive index. Furthermore, since it has a large amount of silanol groups on the particle surface, it is particularly preferable because it can be easily modified with a silane coupling agent or the like.
- silica-zirconia, silica-titania, silica-titania-barium oxide, silica-titania-zirconia, etc. are suitable because they have strong X-ray contrast properties. Further, silica-zirconia particles are most preferable because a cured product having more excellent wear resistance can be obtained.
- These inorganic primary particles may be inorganic primary particles produced by any known method.
- it may be produced by any method of a wet method, a dry method, and a sol-gel method.
- a sol-gel method Considering that it is advantageous to industrially produce fine particles having a spherical shape and excellent monodispersibility, and that it is easy to adjust refractive index and impart X-ray contrast properties,
- the inorganic primary particles are preferably produced by a sol-gel method.
- the method for producing spherical silica-based composite oxide particles by the sol-gel method is disclosed in, for example, JP-A Nos. 58-110414, 58-151321, 58-156524, 58-156. It is described in Japanese Patent No. 156526 and so on.
- a hydrolyzable organosilicon compound or a mixed solution in which another hydrolyzable organometallic compound is added is prepared.
- the mixed solution is added to an alkaline solvent in which these organic compounds are dissolved but the product inorganic oxide is not substantially dissolved, and hydrolysis is performed. Since the inorganic oxide is precipitated by hydrolysis, the precipitate is filtered and then dried.
- the inorganic primary particles obtained by such a method may be baked at a temperature of 500 to 1000 ° C. after drying in order to impart surface stability. During firing, some of the inorganic primary particles may agglomerate. In this case, it is preferable to use after agglomerated particles are broken up into primary particles using a jet mill, a vibrating ball mill or the like, and the particle size is adjusted to a predetermined range. By treating in this way, the abrasiveness when used as a dental composite restorative material is improved.
- the inorganic primary particles may be a mixture of a plurality of inorganic primary particles having different average particle sizes, materials, and shapes.
- the organic resin phase covering the surface of the inorganic primary particles may be formed by using any known organic resin.
- the organic resin is preferably a polymer of a polymerizable monomer. This polymerizable monomer is preferably compatible with an organic solvent.
- Examples of the polymerizable monomer that forms the organic resin include the monomers shown in A to D below.
- a Monofunctional vinyl monomer Methacrylate such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, and acrylates corresponding to these methacrylates; or acrylic acid, methacrylic acid, p-methacryloyloxy Benzoic acid, N-2-hydroxy-3-methacryloyloxypropyl-N-phenylglycine, 4-methacryloyloxyethyl trimellitic acid and its anhydride, 6-methacryloyloxyhexamethylenemalonic acid, 10-methacryloyloxydecamemethylenemalon Acid, 2-methacryloyloxyethyl dihydrogen phosphate, 10-methacryloyloxydecamethylene Hydrogen phosphate, 2-hydroxyethyl hydrogen phenyl phosphonate or the like.
- B Bifunctional vinyl monomer B-1 Aromatic compound monomer 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxyphenyl] propane, 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane), 2,2 -Bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2 (4-methacryloyl) Oxydiethoxyphenyl) -2 (4-Methacryloyloxydiethoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-me
- B-2 Aliphatic monomer monomers Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1 , 4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and acrylates corresponding to these methacrylates; methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, or Vinyl monomers having —OH groups such as acrylates corresponding to these methacrylates and hex Diadducts obtained by addition reaction with diisocyanate compounds such as methylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcycl
- Trifunctional vinyl monomers Trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, methacrylates such as pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate, and acrylates corresponding to these methacrylates.
- diisocyanate compounds such as diisocyanate and tolylene-2,4-diisocyanate and glycidol dimethacrylate.
- a (meth) acrylic polymerizable monomer is preferred because the resulting polymer has good mechanical strength and biosafety.
- a bifunctional or more, more preferably a bifunctional to tetrafunctional polymerizable monomer is preferred because of high polymerizability and particularly high mechanical properties of the cured product.
- polymerizable monomers may be used alone or in a mixture of different types.
- the polymerizable monomer has a difference between the refractive index of the polymer and the refractive index of the inorganic primary particles of 0. It is preferable to select so as to be 1 or less. Thus, by selecting a monomer, sufficient transparency can be provided to the obtained organic-inorganic composite filler. Further, when the obtained organic-inorganic composite filler is used in a dental curable composition, the difference in refractive index between the organic-inorganic composite filler and a polymer of a polymerizable monomer constituting the dental curable composition is determined. It is preferable to select it to be 0.1 or less. By selecting the monomer in this way, a cured body of a transparent dental curable composition can be obtained.
- the content of the organic resin phase is usually 1 to 40 parts by mass, preferably 5 to 25 parts by mass with respect to 100 parts by mass of the inorganic primary particles.
- the content of the organic resin phase can be determined from the mass reduction amount when simultaneous differential thermal-thermogravimetric measurement is performed.
- Method for producing organic-inorganic composite filler Hereinafter, a method for producing the organic-inorganic composite filler of the present invention having an aggregation gap will be described.
- the method for producing the organic-inorganic composite filler of the present invention is not limited to a specific method. However, it is usually difficult to produce the organic-inorganic composite filler of the present invention using a conventional method for producing an organic-inorganic composite filler.
- the organic-inorganic composite filler of the present invention is preferably produced by the method described below.
- inorganic agglomerated particles in which inorganic primary particles having an average particle diameter of 10 to 1000 nm are agglomerated are used as starting materials, and the following steps are essential.
- inorganic aggregated particles obtained by aggregating a plurality of inorganic primary particles having an average particle diameter of 10 to 1000 nm as a starting material are prepared.
- the inorganic primary particles are obtained, for example, as agglomerated particles that are intensively aggregated when produced by a wet method, and are obtained as agglomerated particles that are gradually agglomerated even when produced by a dry method.
- the inorganic primary particles are usually agglomerated in the drying step or the firing step.
- the inorganic agglomerated particles obtained in this way may be used after being pulverized if necessary.
- an organic-inorganic composite filler using inorganic aggregated particles obtained by granulation by a spray drying method as a starting material.
- a spray drying method a slurry in which inorganic primary particles are dispersed in a volatile liquid medium such as water is prepared into fine mist droplets using, for example, a high-speed air flow, and the mist droplets are prepared.
- a method of making inorganic aggregated particles by volatilizing a liquid medium by contacting with a high-temperature gas and collecting a large number of inorganic primary particles dispersed in droplets into substantially one aggregated particle.
- the particle size and particle size distribution of the agglomerated particles are controlled depending on the spray format and spray conditions.
- the granulation method by the spray drying method is an advantageous method because inorganic agglomerated particles having an average particle size of 3 to 100 ⁇ m desired as the particle size of the organic-inorganic composite filler can be obtained with a narrow particle size distribution. . Further, the inorganic agglomerated particles naturally have an agglomerated gap having a pore volume measured by the mercury intrusion method of 0.015 to 0.35 cm 3 / g, more preferably 0.15 to 0.30 cm 3 / g. It is formed. When an organic-inorganic composite filler is produced using the inorganic aggregated particles in the aggregated state, usually 0.01 to 0.30 cm 3 / g, more preferably 0.03 is contained inside the obtained organic-inorganic composite filler.
- the pore volume of the inorganic aggregated particles is generally large when the size of the inorganic primary particles constituting the inorganic aggregated particles is narrow, while it is small when the size of the inorganic primary particles is wide. Furthermore, the pore volume of the inorganic aggregated particles can be further reduced by combining a plurality of types of inorganic primary particles having different average particle sizes. Furthermore, the pore volume of the inorganic agglomerated particles can be further reduced by combining a plurality of types of inorganic primary particles in such a ratio that the closest packing state is achieved.
- the spray drying method used suitably will be specifically described.
- this method there is a method in which a slurry in which inorganic particles are dispersed in an appropriate solvent such as water is prepared, and the slurry is finely sprayed by a high-speed air stream and dried. Furthermore, there is a method in which the slurry is dropped onto a disk-shaped rotating body, and the slurry is blown off in a mist shape by centrifugal force and dried.
- the solvent include water, ethanol, isopropyl alcohol, chloroform, dimethylformamide and the like.
- the concentration of the inorganic particles in the slurry is not limited as long as it can be atomized by a high-speed air current or a disk-shaped rotating body, but is generally 5 to 50% by mass, preferably 10 to 45% by mass.
- the rotational speed of the disk-shaped rotating body is generally 1000 to 50000 rpm.
- the diameter of the droplets is adjusted so that inorganic aggregate particles having the desired average particle diameter can be obtained in consideration of the inorganic primary particle diameter.
- inorganic agglomerated particles of uniform particle size can be obtained.
- the temperature of the gas used for drying is generally 60 to 300 ° C, preferably 80 to 250 ° C.
- the solvent used for preparing a slurry may remain in the inorganic aggregated particles obtained by the spray drying. For this reason, it is preferable to vacuum dry the resulting inorganic aggregated particles after spray drying.
- the time for vacuum drying is generally 1 to 48 hours, the temperature is 20 to 150 ° C., and the degree of vacuum is generally 0.01 to 100 hectopascals or less.
- the shape of the inorganic agglomerated particles obtained by spray drying is usually spherical, substantially spherical, donut-shaped, or dimple-shaped with a dent formed on the surface of the particles.
- the inorganic aggregated particles are generally obtained in a state where a plurality of inorganic aggregated particles having these shapes are mixed. Therefore, the organic-inorganic composite filler produced using the mixed inorganic aggregated particles is generally an organic-inorganic composite filler having a corresponding shape.
- spherical and substantially spherical inorganic agglomerated particles are likely to form hollow structures.
- a cured product of a curable composition containing a hollow-structure organic-inorganic composite filler tends to have a somewhat low mechanical strength.
- a large amount of the polymerizable monomer can selectively enter and fill the hollow portion, so that the light diffusibility can be changed. This effect can be advantageously used in dental applications.
- inorganic primary particles having an average particle diameter of 10 to 1000 nm by a spray drying method By granulating inorganic primary particles having an average particle diameter of 10 to 1000 nm by a spray drying method, 0.015 to 0.35 cm 3 / g, more preferably 0.15 to 0.30 cm 3 / g. It is possible to produce inorganic aggregated particles having a pore volume and having an aggregation gap formed therein. In these inorganic agglomerated particles, the inorganic primary particles agglomerated in the vicinity of the surface are usually arranged close to a hexagonal close-packed structure.
- Inorganic primary particles having an average particle diameter of 10 to 1000 nm are arranged along the surface of the inorganic agglomerated particles in a state close to a hexagonal close-packed structure, thereby comprising an agglomerated gap formed between adjacent inorganic primary particles.
- a pore is formed.
- the average pore diameter of these pores is usually 5 to 330 nm, more generally 20 to 300 nm.
- the pore volume and average pore diameter formed in the inorganic aggregated particles are determined by the same measurement method as that for the organic-inorganic composite filler described above.
- the inorganic agglomerated particles used for the production of the organic-inorganic composite filler are preferably surface-treated with a hydrophobizing agent in order to improve the wettability with respect to the polymerizable monomer.
- a hydrophobizing agent A conventionally well-known thing is used without a restriction
- hydrophobizing agents examples include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris ( ⁇ -methoxyethoxy) silane, ⁇ -methacryloyloxypropyltrimethoxysilane, ⁇ -methacryloyloxidedecyltrimethoxysilane, ⁇ - ( 3,4-epoxycyclohexyl) -ethyltrimethoxysilane, ⁇ -glycidoxypropyl-trimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyl-trimethoxysilane, ⁇ -ureidopropyl-triethoxysilane
- silane coupling agents such as ⁇ -chloropropyltrimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, and methyltriethoxysilane, and titanate coupling agents.
- the amount of the hydrophobizing agent used for hydrophobizing the inorganic agglomerated particles is not particularly limited, and the optimal value may be determined after confirming in advance experiments the mechanical properties of the obtained organic-inorganic composite filler.
- a suitable amount of the hydrophobizing agent is 1 to 30 parts by mass with respect to 100 parts by mass of the inorganic primary particles.
- the surface treatment method is not particularly limited, and a known method is adopted without limitation.
- inorganic particles and a hydrophobizing agent are dispersed and mixed in a suitable solvent using a ball mill or the like, and the solvent is dried by an evaporator or air drying, and then heated to 50 to 150 ° C. There is a way.
- the inorganic particles and the hydrophobizing agent are heated and distilled for several hours in a solvent such as alcohol.
- graft polymerization of a hydrophobizing agent on the particle surface is graft polymerization of a hydrophobizing agent on the particle surface.
- the surface treatment may be performed on the inorganic primary particles or the inorganic aggregated particles.
- inorganic agglomerated particles by spray drying, it is efficient to perform a surface treatment simultaneously with this treatment.
- the inorganic agglomerated particles produced as described above are then a polymerizable monomer solution containing 3 to 70 parts by weight of a polymerizable monomer and an effective amount of a polymerization initiator with respect to 100 parts by weight of an organic solvent. Soaked in.
- the polymerizable monomer solution enters the inside of the inorganic aggregated particles through the aggregation gap of the inorganic aggregated particles due to capillary action.
- the polymerizable monomer is diluted with an organic solvent, the liquid infiltration due to capillary action is high.
- the polymerizable monomer solution is filled to the deep part of the aggregation gap.
- the content of the polymerizable monomer with respect to the organic solvent needs to be controlled within the above range.
- the pore volume formed by the aggregation gap of the obtained organic-inorganic composite filler can be controlled within the specific range. That is, the organic solvent contained in the polymerizable monomer solution that has entered the aggregation gap of the inorganic aggregated particles is removed before the polymerization and curing of the polymerizable monomer. Volume pores corresponding to the volume reduction caused by the removal of the solvent are formed in the aggregation gaps of the inorganic primary particles.
- the polymerizable monomer contained in the polymerizable monomer solution The concentration needs to be the above content.
- the content of the polymerizable monomer is outside the above range, the amount of the polymerizable monomer filled in the pores is excessive or insufficient. Moreover, when there is too much content of a polymerizable monomer, an air bubble may be formed in a filler. Furthermore, the excess polymerizable monomer adheres to the outer periphery of the inorganic agglomerated particles, which tends to cause a disadvantage that the inorganic agglomerated particles are bonded together to form a lump. Considering these disadvantages, the content of the polymerizable monomer in the polymerizable monomer solution is more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the organic solvent.
- organic solvent contained in the polymerizable monomer solution a known solvent can be used without limitation.
- halogen-type organic solvents such as perchloroethylene, trichloroethylene, dichloromethane, chloroform, are mentioned.
- hydrocarbon compounds such as hexane, heptane and pentane
- aromatic compounds such as benzene, toluene and xylene
- alcohol compounds such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and 2-butanol
- diethyl Ether compounds such as ether, tetrahydrofuran and t-butyl methyl ether
- ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone
- non-halogen compounds such as ester compounds such as ethyl formate, methyl acetate, ethyl acetate, propyl acetate and isopropyl acetate
- Organic solvents are examples.
- solvents from the viewpoints of having high volatility that enables the solvent removal process to be shortened, easy to obtain and inexpensive, and highly safe to the human body during production. More preferred are methanol, ethanol, acetone, dichloromethane and the like.
- the polymerization initiator contained in the polymerizable monomer solution may be any of a photopolymerization initiator, a chemical polymerization initiator, and a thermal polymerization initiator.
- a photopolymerization initiator or a thermal polymerization initiator is preferable from the viewpoint that the timing of polymerization can be arbitrarily selected by energy applied from the outside such as light and heat, and the production operation is simple.
- a thermal polymerization initiator is more preferable in that it can be used without restriction of a working environment such as light shielding or red light.
- thermal polymerization initiator examples include peroxidation such as benzoyl peroxide, p-chlorobenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydicarbonate, diisopropyl peroxydicarbonate, etc.
- Azo compounds such as azobisisobutyronitrile, tributylborane, tributylborane partial oxide, sodium tetraphenylborate, sodium tetrakis (p-fluorophenyl) borate, tetraphenylborate triethanolamine salt, etc.
- Examples thereof include boron compounds, barbituric acids such as 5-butyl barbituric acid and 1-benzyl-5-phenylbarbituric acid, and sulfinates such as sodium benzenesulfinate and sodium p-toluenesulfinate.
- azo compounds such as azobisisobutyronitrile, which have high operational safety and are less affected by coloring on the organic-inorganic composite filler, are preferably used.
- the blending amount of the polymerization initiator may be an effective amount sufficient to cause the polymerization to proceed. Generally, the amount is 0.01 to 30 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
- additives such as an ultraviolet absorber, a pigment, a dye, a polymerization inhibitor, and a fluorescent agent may be added to the polymerizable monomer solution.
- Examples of the method of infiltrating the polymerizable monomer solution into the inorganic aggregated particles include a method of immersing the inorganic aggregated particles in the polymerizable monomer solution.
- the dipping is usually preferably carried out at normal temperature and pressure.
- the mixing ratio of the inorganic aggregated particles and the polymerizable monomer solution is preferably 30 to 500 parts by mass, more preferably 50 to 200 parts by mass with respect to 100 parts by mass of the inorganic aggregated particles.
- After mixing in the case of standing still, it is preferably left for 30 minutes or more, and more preferably left for 1 hour or more.
- the mixture may be shaken, stirred, pressurized, decompressed, or heated.
- the organic solvent is removed from the polymerizable monomer solution filled in the aggregation gap.
- substantially the entire amount of the organic solvent (usually 95% by mass or more) that has entered the aggregation gaps of the inorganic aggregated particles is removed.
- the removal may be performed until there is no coagulum adhering to each other and a powder in a fluid state is obtained.
- the organic solvent removal operation may be performed by any known drying method.
- heating system drying such as convection heat transfer drying, radiant heat transfer drying, conduction heat transfer drying, internal heat generation drying, vacuum drying, vacuum freeze drying, centrifugal drying, absorbent drying, suction drying, pressure drying
- Non-heating system drying such as sonic drying is exemplified.
- heating system drying, vacuum drying, vacuum freeze drying and the like are preferable.
- the degree of reduced pressure may be appropriately selected in consideration of the boiling point and volatility of the organic solvent.
- the degree of vacuum is 100 hectopascals or less, preferably 0.01 to 50 hectopascals, and most preferably 0.1 to 10 hectopascals.
- the heating temperature may be appropriately selected according to the boiling point of the organic solvent.
- a thermal polymerization initiator is contained as a polymerization initiator in the organic solution, it is necessary to operate at or below the polymerization start temperature.
- the drying method may be a combination of the above methods.
- the removal operation of the organic solvent may be performed under stirring as long as the characteristics of the organic-inorganic composite filler are not impaired.
- the polymerizable monomer After removing the organic solvent, the polymerizable monomer is polymerized and cured.
- the polymerization curing method to be employed varies depending on the polymerizable monomer and polymerization initiator to be used, and therefore an optimal method may be selected as appropriate.
- a thermal polymerization initiator When a thermal polymerization initiator is used, the polymerization is performed by heating, and when a photopolymerization initiator is used, the polymerization is performed by irradiating light of a corresponding wavelength.
- the polymerization temperature varies depending on the polymerization initiator used, and therefore an optimal temperature may be selected as appropriate. In general, the polymerization temperature is 30 to 170 ° C., preferably 50 to 150 ° C.
- the light source to be used varies depending on the type of polymerization initiator, and therefore an optimal light source may be selected as appropriate.
- a light source generally, a halogen lamp, an LED, a xenon lamp, a high pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, a helium cadmium laser, an argon laser, a visible light source, a low pressure mercury lamp, a xenon arc lamp, Examples include an ultraviolet light source such as a deuterium arc lamp, a mercury xenon arc lamp, a tungsten halogen incandescent lamp, a UV-LED, and a xenon plasma discharge tube.
- an organic-inorganic composite filler having pores inside can be efficiently produced. These operations may be repeated a plurality of times depending on the concentration of the polymerizable monomer solution. By repeating these operations a plurality of times, the amount of organic resin covering the surface of the inorganic primary particles can be increased, and the amount of pore volume formed can be adjusted.
- the obtained organic-inorganic composite filler can be used as it is as long as it is produced using inorganic aggregated particles having an appropriate particle size.
- examples of the inorganic aggregated particles having an appropriate particle size include inorganic aggregated particles granulated by the spray drying method.
- the particle size of the obtained organic-inorganic composite filler is too large, it may be pulverized to an appropriate particle size as necessary.
- the pulverization can be performed using a vibration ball mill, a bead mill, a jet mill or the like. Further, if necessary, classification may be performed using a sieve, an air classifier, or a water classifier. Note that the pulverization process may be performed after impregnating the inorganic agglomerated particles with the polymerizable monomer solution and removing the organic solvent, and before the polymerizable monomer is polymerized. good.
- the organic-inorganic composite filler may be subjected to a surface treatment.
- a surface treatment By performing the surface treatment, higher mechanical strength is imparted to the cured body of the dental curable composition containing the organic-inorganic composite filler.
- the surface treatment agent and the surface treatment method are the same as the surface treatment of the inorganic primary particles described above.
- the organic-inorganic composite filler of the present invention is particularly useful as a dental filler to be blended in a dental curable composition.
- a polymerizable monomer and a polymerization initiator are blended in the dental curable composition.
- the polymerizable monomer known ones used for the purpose can be used without limitation. Usually, it may be selected from the same category as the polymerizable monomer exemplified for the production of the organic-inorganic composite filler.
- the compounding amount of the polymerizable monomer is 10 to 100 parts by mass, preferably 20 to 80 parts by mass with respect to 100 parts by mass of the organic-inorganic composite filler.
- any known polymerization initiator can be used without limitation.
- the thermal polymerization initiator etc. which were illustrated in order to carry out the polymerization hardening of the monomer infiltrated into the said inorganic aggregated particle can be used.
- a photopolymerization method is often employed as a means for curing (polymerizing) a dental curable composition because of its ease of operation during use. For the above reason, it is preferable to use a photopolymerization initiator as a polymerization initiator also in the dental curable composition of the present invention.
- Preferred photopolymerization initiators include, for example, benzoin alkyl ethers, benzyl ketals, benzophenones, ⁇ -diketones, thioxanthone compounds, bisacylphosphine oxides, and the like.
- a reducing agent is often added to the photopolymerization initiator.
- the reducing agent include aromatic amines, aliphatic amines, aldehydes, sulfur-containing compounds and the like.
- a trihalomethyltriazine compound, an aryl iodonium salt, etc. can also be added as needed.
- the polymerization initiator is generally blended in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
- inorganic fillers can be added to the dental curable composition as long as the effects of the present invention are not impaired.
- known fillers used for the application can be used without limitation.
- other inorganic fillers can include inorganic particles made of the same material as the inorganic primary particles.
- additives can be blended within a range that does not significantly impair the effect.
- additives include polymerization inhibitors, pigments, ultraviolet absorbers, and fluorescent agents.
- the dental curable composition of the present invention is obtained by sufficiently kneading a predetermined amount of each essential component and each optional component added as necessary to obtain a paste, and further defoaming the paste under reduced pressure. It can be manufactured by removing bubbles.
- the use of the dental curable composition is not particularly limited, but a particularly suitable use is a dental composite restorative material such as a dental filling restorative material and an indirect dental restorative material.
- Inorganic particles F-1 Spherical silica (average homogeneity 0.95) silica-zirconia produced by the sol-gel method with an average primary particle size of 200 nm
- F-2 Average primary particle size 400 nm Spherical (average homogeneity 0.95) silica-zirconia
- F-3 produced by the sol-gel method: Spherical silica (average homogeneity 0.95) silica-zirconia produced by the sol-gel method with an average primary particle size of 70 nm
- F-4 Spherical silica (average homogeneity 0.95) silica-titania manufactured by the sol-gel method with an average primary particle size of 80 nm
- F-5 manufactured by the sol-gel method with an average primary particle size of 700 nm Spherical (average homogeneity 0.95)
- silica-zirconia F-6 primary particles having an average particle diameter of 200 nm, amorphous silica-zirconia F-7 produced by the sol-
- n the number of primary particles observed in the unit visual field (n), the maximum length of the primary particles as the major axis (Li), and the diameter perpendicular to the major axis as the minimum width (Bi), n, Li, Bi Asked.
- the average uniformity of the inorganic primary particles was calculated by the following formula.
- Organic resin content in organic / inorganic composite filler Using the differential thermal-thermogravimetric simultaneous measurement device “TG / DTA6300” (manufactured by SII Nanotechnology Inc.), the organic resin content is measured by the following procedure. did. 0.03 g of organic-inorganic composite filler was put in an aluminum pan to prepare a sample. Heating was performed at a rate of temperature increase of 5 ° C./min, an upper limit temperature of 500 ° C., and an upper limit temperature mooring time of 30 minutes, and the mass loss was measured. Using the obtained mass reduction amount, the ratio of the inorganic particles to the organic resin was determined, and the organic resin amount (parts by mass) relative to 100 parts by mass of the inorganic particles was calculated. Further, 0.03 g of aluminum oxide was used as a reference for simultaneous differential thermal-thermogravimetric measurement.
- the paste of this dental curable composition was made of stainless steel.
- the mold was filled.
- a polypropylene sheet was pressed against the paste surface, and light was irradiated through the polypropylene sheet. Irradiation was performed using a visible light irradiator power light (manufactured by Tokuyama Corporation).
- the irradiation window of the visible light irradiator was brought into close contact with the polypropylene sheet, and irradiation was performed three times for 30 seconds each from one side at different places so that the entire cured body was exposed to light. Next, light was irradiated from the opposite surface three times for 30 seconds in the same manner to obtain a cured product.
- the cured body was arranged into a 2 ⁇ 2 ⁇ 25 mm prismatic shape.
- This sample piece was mounted on a testing machine (manufactured by Shimadzu Corp., Autograph AG5000D), and the three-point bending fracture strength was measured under the test conditions of a distance between fulcrums of 20 mm and a crosshead speed of 1 mm / min. Five test pieces were evaluated, and the average value was defined as the bending strength.
- Example 1 100 g of the inorganic particles F-1 were added to 200 g of water, and a dispersion liquid in which the inorganic particles were dispersed was obtained using a circulation grinder SC mill (manufactured by Mitsui Mining Co., Ltd.).
- the spray dryer used was a spray dryer (spray dryer “TSR-2W” manufactured by Sakamoto Giken Co., Ltd.) equipped with a rotating disk and atomized by centrifugal force.
- the disk rotation speed was 10,000 rpm, and the temperature of the dry atmosphere air was 200 ° C.
- the spray-dried inorganic powder was vacuum-dried at 60 ° C. for 18 hours to obtain 71 g of inorganic agglomerated particles.
- the pore volume of the aggregation gap of the inorganic aggregated particles was 0.25 cm 3 / g, and the average pore diameter was 50 nm.
- the average particle size of the inorganic aggregated particles was 40.0 ⁇ m.
- the above mixture was dried using a rotary evaporator for 1 hour under stirring at a reduced pressure of 10 hectopascals and a heating condition of 40 ° C. (warm water bath temperature) to remove the organic solvent.
- a powder having no aggregation property and high fluidity was obtained.
- the powder While stirring the above powder with a rotary evaporator, the powder is heated for 1 hour under conditions of a degree of vacuum of 10 hectopascal and a heating condition of 100 ° C. (oil bath temperature) to polymerize and cure the polymerizable monomer in the powder.
- 8.5g of organic-inorganic composite filler was obtained.
- the pore volume of the aggregation gap of the organic-inorganic composite filler was 0.09 cm 3 / g, and the average pore diameter was 30 nm.
- the average particle diameter of the organic-inorganic composite filler was 40.4 ⁇ m, and it was also confirmed that the average particle diameter of the inorganic primary particles constituting it was 200 nm.
- the organic resin content in the organic-inorganic composite filler was measured, the organic resin content was 17.4 parts by mass with respect to 100 parts by mass of the inorganic particles F-1.
- Example 2 Inorganic by the same method as in Example 1 except that 70 g of inorganic particles F-2 and 30 g of inorganic particles F-3 were put into 200 g of water and a dispersion liquid was obtained using a SC grinder. 66 g of aggregated particles were obtained. The pore volume of the aggregation gap of the obtained inorganic aggregated particles was 0.20 cm 3 / g, and the average pore diameter was 35 nm. The average particle size of the inorganic aggregated particles was 33.7 ⁇ m.
- an organic-inorganic composite filler was produced by the same method as in Example 1 using the inorganic aggregated particles.
- the pore volume of the aggregation gap of the organic-inorganic composite filler was 0.04 cm 3 / g, and the average pore diameter was 14 nm.
- the average particle diameter of the inorganic aggregated particles was 34.2 ⁇ m, and it was also confirmed that the average particle diameter of the inorganic primary particles constituting the inorganic aggregated particles was 400 nm.
- the organic resin content in the organic-inorganic composite filler was measured, the organic resin content was 17.4 parts by mass with respect to 100 parts by mass of the inorganic particles F-2.
- Examples 3 to 16 Except for changing the types of inorganic particles used in producing the inorganic aggregated particles, the types and amounts of the polymerizable monomers and polymerization initiators contained in the polymerizable monomer solution, as shown in Table 1, respectively. Obtained the organic-inorganic composite filler in the same manner as in Example 1, and measured each physical property in the same manner as in Example 1. The results are also shown in Table 1.
- Comparative Example 1 The same inorganic agglomerated particles as in Example 1, 12 g of GMA as a polymerizable monomer, 8 g of 3G, 13.3 g of HD, and 0.10 g of AIBN as a polymerization initiator were put into a mortar, mixed and pasted A shaped mixture was prepared. This pasty mixture was defoamed under reduced pressure and then polymerized and cured at 100 ° C. for 30 minutes. The cured product was pulverized with a vibration ball mill (zirconia ball particle size: 5 mm), and the pulverized product was sieved to remove particles of 100 ⁇ m or more.
- a vibration ball mill zirconia ball particle size: 5 mm
- the average particle diameter of the obtained organic-inorganic composite filler was 20.3 ⁇ m, and pores could not be confirmed by measurement with a mercury porosimeter.
- the organic resin content in the organic-inorganic composite filler was measured, the organic resin was 33.0 parts by mass with respect to 100 parts by mass of the inorganic particles F-1.
- Comparative Examples 2-5 As shown in Table 2, the types of inorganic particles used in the production of the inorganic aggregated particles and the types and amounts of the polymerizable monomer and the polymerization initiator contained in the polymerizable monomer solution were changed. Except for the above, an organic-inorganic composite filler was obtained in the same manner as in Example 1.
- Example 17 to 32, Comparative Examples 6 to 10 A dental curable composition was prepared using each organic-inorganic composite filler shown in Table 3, and bending strength was measured and transparency was evaluated. The results are also shown in Table 3.
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Abstract
Description
平均粒子径10~1000nmの無機一次粒子が凝集されてなる無機凝集粒子と、
各無機一次粒子の表面を覆うと共に、各無機一次粒子を相互に結合する有機樹脂相と、
各無機一次粒子の表面を覆う有機樹脂相の間に形成され、水銀圧入法で測定した細孔容積(ここで、細孔とは細孔径が1~500nmの範囲の孔をいう)が0.01~0.30cm3/gの凝集間隙と、
を含む有機無機複合フィラーである。
平均粒子径10~1000nmの無機一次粒子が凝集してなる無機凝集粒子を、有機溶媒100質量部に対して重合性単量体3~70質量部と有効量の重合開始剤とを含有する重合性単量体溶液に浸漬する工程と、
浸漬した無機凝集粒子から有機溶媒を除去する工程と、
無機凝集粒子に含浸されている重合性単量体を重合硬化させる工程と、
を有する有機無機複合フィラーの製造方法を提供する。
2;無機一次粒子
3;有機樹脂相
4;凝集間隙
本発明の有機無機複合フィラーは、平均粒子径10~1000nmの無機一次粒子が凝集されてなり、各無機一次粒子は、その表面を覆う有機樹脂相により互いに結合されている。有機樹脂相は、上記各無機一次粒子間の全空間を埋めるものではない。多数存在する無機一次粒子の表面を覆う有機樹脂層の間には、凝集間隙からなる細孔が形成されている。すなわち、有機樹脂相に覆われる無機一次粒子の凝集間隙には、水銀圧入法で測定して孔径1~500nmの範囲の細孔が、0.01~0.30cm3/gの容積で、形成されている。前記のように、この凝集間隙に、硬化性組成物に配合される重合性単量体が毛細管現象により浸入して硬化する。その結果、重合性単量体が硬化して生成する硬化樹脂が前記細孔内に埋込まれ、有機無機複合フィラーと強く結合する。即ち、細孔を利用する、いわゆるアンカー効果を発揮することにより、本発明の有機無機複合フィラーを配合した硬化性組成物の硬化体は、高い機械的強度を有するものになる。
メチルメタクリレート、エチルメタクリレート、イソプロピルメタクリレート、ヒドロキシエチルメタクリレート、テトラヒドロフルフリルメタクリレート、グリシジルメタクリレート等のメタクリレート、およびこれらのメタクリレートに対応するアクリレート;あるいはアクリル酸、メタクリル酸、p-メタクリロイルオキシ安息香酸、N-2-ヒドロキシ-3-メタクリロイルオキシプロピル-N-フェニルグリシン、4-メタクリロイルオキシエチルトリメリット酸、及びその無水物、6-メタクリロイルオキシヘキサメチレンマロン酸、10-メタクリロイルオキシデカメチレンマロン酸、2-メタクリロイルオキシエチルジハイドロジェンフォスフェート、10-メタクリロイルオキシデカメチレンジハイドロジェンフォスフェート、2-ヒドロキシエチルハイドロジェンフェニルフォスフォネート等。
B-1 芳香族化合物系のモノマー
2,2-ビス(メタクリロイルオキシフェニル)プロパン、2,2-ビス〔4-(3-メタクリロイルオキシ)-2-ヒドロキシプロポキシフェニル〕プロパン、2,2-ビス(4-メタクリロイルオキシフェニル)プロパン、2,2-ビス(4-メタクリロイルオキシポリエトキシフェニル)プロパン、2,2-ビス(4-メタクリロイルオキシジエトキシフェニル)プロパン)、2,2-ビス(4-メタクリロイルオキシテトラエトキシフェニル)プロパン、2,2-ビス(4-メタクリロイルオキシペンタエトキシフェニル)プロパン、2,2-ビス(4-メタクリロイルオキシジプロポキシフェニル)プロパン、2(4-メタクリロイルオキシジエトキシフェニル)-2(4-メタクリロイルオキシジエトキシフェニル)プロパン、2(4-メタクリロイルオキシジエトキシフェニル)-2(4-メタクリロイルオキシジトリエトキシフェニル)プロパン、2(4-メタクリロイルオキシジプロポキシフェニル)-2-(4-メタクリロイルオキシトリエトキシフェニル)プロパン、2,2-ビス(4-メタクリロイルオキシプロポキシフェニル)プロパン、2,2-ビス(4-メタクリロイルオキシイソプロポキシフェニル)プロパン、およびこれらのメタクリレートに対応するアクリレート;2-ヒドロキシエチルメタクリレート、2-ヒドロキシプロピルメタクリレート、3-クロロ-2-ヒドロキシプロピルメタクリレート等のメタクリレート、あるいはこれらのメタクリレートに対応するアクリレート等の-OH基を有するビニルモノマーと、ジイソシアネートメチルベンゼン、4,4'-ジフェニルメタンジイソシアネート等の芳香族基を有するジイソシアネート化合物との付加から得られるジアダクト等。
エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ブチレングリコールジメタクリレート、ネオペンチルグリコールジメタクリレート、プロピレングリコールジメタクリレート、1,3-ブタンジオールジメタクリレート、1,4-ブタンジオールジメタクリレート、1,6-ヘキサンジオールジメタクリレートおよびこれらのメタクリレートに対応するアクリレート;2-ヒドロキシエチルメタクリレート、2-ヒドロキシプロピルメタクリレート、3-クロロ-2-ヒドロキシプロピルメタクリレート等のメタクリレートあるいはこれらのメタクリレートに対応するアクリレート等の-OH基を有するビニルモノマーと、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ジイソシアネートメチルシクロヘキサン、イソフォロンジイソシアネート、メチレンビス(4-シクロヘキシルイソシアネート)等のジイソシアネート化合物との付加反応によって得られるジアダクト;無水アクリル酸、無水メタクリル酸、1,2-ビス(3-メタクリロイルオキシ-2-ヒドロキシプロポキシ)エチル、ジ(2-メタクリロイルオキシプロピル)フォスフェート等。
トリメチロールプロパントリメタクリレート、トリメチロールエタントリメタクリレート、ペンタエリスリトールトリメタクリレート、トリメチロールメタントリメタクリレート等のメタクリレート、およびこれらのメタクリレートに対応するアクリレート等。
ペンタエリスリトールテトラメタクリレート、ペンタエリスリトールテトラアクリレート及びジイソシアネートメチルベンゼン、ジイソシアネートメチルシクロヘキサン、イソフォロンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、メチレンビス(4-シクロヘキシルイソシアネート)、4,4-ジフェニルメタンジイソシアネート、トリレン-2,4-ジイソシアネート等のジイソシアネート化合物と、グリシドールジメタクリレートとの付加反応によって得られるジアダクト等。
以下、凝集間隙を有する本発明の有機無機複合フィラーの製造方法について説明する。本発明の有機無機複合フィラーの製造方法は、特定の方法に限定されるものではない。しかし、従来の有機無機複合フィラーの製造方法を用いて本発明の有機無機複合フィラーを製造することは通常困難である。
既に説明した通り、本発明の有機無機複合フィラーは、歯科用硬化性組成物に配合される歯科用フィラーとして、特に有用である。歯科用硬化性組成物には、有機無機複合フィラーに加えて、重合性単量体と重合開始剤とが配合される。
・3G:トリエチレングリコールジメタクリレート
・HD:1,6-ヘキサンジオールジメタクリレート
・GMA:2,2-ビス[(3-メタクリロイルオキシ-2-ヒドロキシプロピルオキシ)フェニル]プロパン
・UDMA:1,6-ビス(メタクリルエチルオキシカルボニルアミノ)-2,2-4-トリメチルヘキサン
・D2.6E:下記式で示される化合物
以下、無機粒子の略称を以下に示す。
・F-1:一次粒子の平均粒子径200nmの、ゾルゲル法で製造した球状(平均均斉度0.95)のシリカ-ジルコニア
・F-2:一次粒子の平均粒子径400nmの、ゾルゲル法で製造した球状(平均均斉度0.95)のシリカ-ジルコニア
・F-3:一次粒子の平均粒子径70nmの、ゾルゲル法で製造した球状(平均均斉度0.95)のシリカ-ジルコニア
・F-4:一次粒子の平均粒子径80nmの、ゾルゲル法で製造した球状(平均均斉度0.95)のシリカ-チタニア
・F-5:一次粒子の平均粒子径700nmの、ゾルゲル法で製造した球状(平均均斉度0.95)のシリカ-ジルコニア
・F-6:一次粒子の平均粒子径200nmの、ゾルゲル法で製造した不定形のシリカ-ジルコニア
・F-7:一次粒子の平均粒子径200nmの、高温溶融法で製造した略球状(平均均斉度0.60)のアルミナ
・F-8:一次粒子の平均粒子径2000nmの、ゾルゲル法で製造した不定形のシリカ-ジルコニア
・F-9:一次粒子の平均粒子径50nmの、ゾルゲル法で製造した球状(平均均斉度0.95)のシリカ-ジルコニア
・F-10:一次粒子の平均粒子径50nmの、ゾルゲル法で製造した略球状(平均均斉度0.60)の3フッ化イッテルビウム
以下、重合開始剤の略称を以下に示す。
・AIBN:アゾビスイソブチロニトリル
・CQ:カンファーキノン
・DMBE:N,N-ジメチル-p-安息香酸エチル
無機一次粒子の平均粒子径及び平均均斉度、無機凝集粒子および有機無機複合フィラーの特性(平均粒子径、細孔容積、平均孔径)、有機無機複合フィラー中の有機樹脂含有量、曲げ強さの測定、透明性の評価は以下の方法に従って測定した。
走査型電子顕微鏡(XL-30S FEG,フィリップス(PHILIPS)社製)を用い、有機無機複合フィラーの写真を5000~100000倍で撮影した。画像解析ソフトウエア(IP-1000PC、旭化成エンジニアリング社製)を用いて、撮影した画像の処理を行い、単位視野内における一次粒子の円相当径(粒子径)、最大長、最小幅、粒子数を求めた。観察対象の粒子数は100個以上であった。下記式により一次粒子の平均体積径を求め、これを平均粒子径とした。
0.1gの無機凝集粒子をエタノール10mlに分散させ、手を用いて十分振とうした。レーザー回折-散乱法による粒度分布計(「LS230」、ベックマンコールター製)を用い、光学モデル「フラウンフォーファー」(Fraunhofer)を適用して、体積統計のメディアン径を求めた。
有機無機複合フィラーをエタノールに分散させる際、超音波を20分間照射した以外は(2)無機凝集粒子の場合と同様に操作して、粒度を求めた。
水銀ポロシメータ〔「ポアマスター」(PoreMaster)、クワンタクローマ(Quantachrome)社製〕を用い、細孔容積分布を測定した。0.2gの無機凝集粒子または有機無機複合フィラーを測定セルに入れて、測定した。細孔容積分布孔径1~500nmの範囲の細孔の容積を積算し、細孔容積とした。更に、この範囲の細孔を対象にして、細孔容積分布から求めたメディアン細孔直径を凝集間隙の平均孔径とした。
示差熱-熱重量同時測定装置「TG/DTA6300」(エスアイアイ・ナノテクノロジー社製)を用いて、以下の手順で、有機樹脂含有量を測定した。0.03gの有機無機複合フィラーをアルミパンに入れて試料とした。昇温速度を5℃/min、上限温度500℃、上限温度係留時間30分のスケジュールで加熱を行って、質量減少量を測定した。得られた質量減少量を用いて、無機粒子と有機樹脂の比率を求め、無機粒子100質量部に対する有機樹脂量(質量部)を算出した。また示差熱-熱重量同時測定のリファレンスには、0.03gの酸化アルミニウムを用いた。
下記に示す配合比の重合性単量体、及び光重合開始剤よりなる有機マトリックスに、各実施例及び比較例において調製した所定量の有機無機複合フィラーと無機充填材とを配合し、赤色光下にて乳鉢を用いて均一に攪拌、脱泡して、ペースト状の歯科用硬化性組成物を調製した。
GMA 60質量部
CQ 0.20質量部
DMBE 0.35質量部
有機無機複合フィラー240質量部
F-1 160質量部
充填器を用いて、この歯科用硬化性組成物のペーストをステンレス製型枠に充填した。ペースト表面にポリプロピレンシートを圧接し、ポリプロピレンシートを通して光照射を行なった。照射は、可視光線照射器パワーライト(トクヤマ社製)を用いた。可視光線照射器の照射窓をポリプロピレンシートに密着させ、硬化体の全体に光が当たるように、場所を変えて一方の面から各30秒間ずつ3回照射した。次いで、反対の面からも同様にして各30秒間ずつ3回光照射し、硬化体を得た。
前記(6)の方法で調製したペーストと同じ歯科用硬化性組成物のペーストを、7mmφ×1mmの孔を有する型に充填した。孔の両端のペースト表面にポリエステルフィルムを圧接した。ポリエステルフィルムを通して、可視光線照射器(トクヤマ製、パワーライト)でペーストの両表面を30秒間光照射した。ペーストが硬化した後、型から取り出した。色差計(東京電色製、TC-1800MKII)を用いて、硬化したペーストの三刺激値のY値(背景色黒及び白)を測定した。下記式、
コントラスト比=背景色黒の場合のY値/背景色白の場合のY値
に基づいてコントラスト比を計算し、透明性の指標とした。
無機粒子F-1の100gを200gの水に加え、循環型粉砕機SCミル(三井鉱山(株)製)を用いて、無機粒子を分散させた分散液を得た。
無機粒子F-2の70gと無機粒子F-3の30gを200gの水に投入し、循環型粉砕機SCミルを用いて、分散液を得た以外は、実施例1と同様の方法で無機凝集粒子を66g得た。得られた無機凝集粒子の凝集間隙の細孔容積は0.20cm3/g、平均細孔径は35nmであった。また、無機凝集粒子の平均粒子径は、33.7μmであった。
無機凝集粒子を製造する際に使用する無機粒子の種類、重合性単量体溶液に含まれる重合性単量体および重合開始剤の各種類と量について、それぞれ表1に示すように変更した以外は、実施例1と同様にして有機無機複合フィラーを得、それぞれについて実施例1と同様にして各物性を測定した。その結果を表1に併せて示した。
実施例1と同じ無機凝集粒子、重合性単量体としてGMAを12g、3Gを8g、HDを13.3g、重合開始剤としてAIBNを0.10gのそれぞれを乳鉢に投入し、混合してペースト状の混合物を調製した。このペースト状混合物を減圧下で脱泡した後、100℃で30分間重合硬化させた。硬化物を振動ボールミル(ジルコニアボール粒径:5mm)で粉砕し、粉砕物を篩にかけることで100μm以上の粒子を除去した。得られた有機無機複合フィラーの平均粒子径は20.3μmであり、水銀ポロシメータによる測定によれば、細孔は確認できなかった。なお、有機無機複合フィラー中の有機樹脂含有量を測定したところ、無機粒子F-1の100質量部に対して有機樹脂は33.0質量部であった。
比較例2~5
無機凝集粒子を製造する際に使用する無機粒子の種類、重合性単量体溶液に含まれる重合性単量体および重合開始剤の各種類と量とについて、それぞれ表2に示すように変更した以外は、実施例1と同様にして有機無機複合フィラーを得た。これら有機無機複合フィラーのそれぞれについて、実施例1と同様にして各物性を測定した。その結果を、表2に併せて示した。
実施例17~32、比較例6~10
表3に示した各有機無機複合フィラーを用いて歯科用硬化性組成物を調製し、曲げ強さの測定、透明性の評価を行った。その結果を表3に併せて示した。
Claims (8)
- 平均粒子径10~1000nmの無機一次粒子が凝集されてなる無機凝集粒子と、
各無機一次粒子の表面を覆うと共に、各無機一次粒子を相互に結合する有機樹脂相と、
各無機一次粒子の表面を覆う有機樹脂相の間に形成され、水銀圧入法で測定した細孔容積(ここで、細孔とは細孔径が1~500nmの範囲の孔をいう)が0.01~0.30cm3/gの凝集間隙と、
を含む有機無機複合フィラー。 - 無機一次粒子がシリカ系複合酸化物粒子である請求項1に記載の有機無機複合フィラー。
- 有機樹脂相が、(メタ)アクリル系重合性単量体の重合硬化物相からなる請求項1に記載の有機無機複合フィラー。
- 有機樹脂相の含有量が、無機一次粒子100質量部に対して1~40質量部である請求項1に記載の有機無機複合フィラー。
- 平均粒子径10~1000nmの無機一次粒子が凝集してなる無機凝集粒子を、有機溶媒100質量部に対して重合性単量体3~70質量部と有効量の重合開始剤とを含有する重合性単量体溶液に浸漬する工程と、
浸漬した無機凝集粒子から有機溶媒を除去する工程と、
無機凝集粒子に含浸されている重合性単量体を重合硬化させる工程と、
を有することを特徴とする請求項1記載の有機無機複合フィラーの製造方法。 - 無機凝集粒子が、水銀圧入法で測定した細孔容積(ここで、細孔とは細孔径1~500nmの範囲の孔をいう)が0.015~0.35cm3/gの無機凝集粒子である請求項5に記載の有機無機複合フィラーの製造方法。
- 無機凝集粒子が、噴霧乾燥により造粒して得られる無機凝集粒子である請求項5に記載の有機無機複合フィラーの製造方法。
- 請求項1~4のいずれか一項に記載の有機無機複合フィラーと、重合性単量体と、重合開始剤とを含んでなる歯科用硬化性組成物。
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WO2013039169A1 (ja) * | 2011-09-15 | 2013-03-21 | 株式会社トクヤマデンタル | 有機無機複合フィラー、及びその製造方法 |
JP2014177443A (ja) * | 2013-03-15 | 2014-09-25 | Tokuyama Dental Corp | 無機凝集粒子、有機無機複合フィラー、及びそれらの製造方法 |
JP2015105254A (ja) * | 2013-12-02 | 2015-06-08 | 株式会社トクヤマデンタル | 歯科用硬化性組成物 |
JP2016047922A (ja) * | 2014-08-27 | 2016-04-07 | 三洋化成工業株式会社 | インク用複合粒子、インク組成物及びその製造方法 |
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EP2548916B2 (en) | 2023-03-22 |
JP5079928B2 (ja) | 2012-11-21 |
CN102812078B (zh) | 2014-05-07 |
US10005910B2 (en) | 2018-06-26 |
US20130005846A1 (en) | 2013-01-03 |
EP2548916B1 (en) | 2016-12-28 |
JPWO2011115007A1 (ja) | 2013-06-27 |
US11001713B2 (en) | 2021-05-11 |
EP2548916A4 (en) | 2014-07-30 |
US20180273766A1 (en) | 2018-09-27 |
CN102812078A (zh) | 2012-12-05 |
EP2548916A1 (en) | 2013-01-23 |
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