WO1999018029A1 - Boue d'apatite et procede de fabrication associe - Google Patents

Boue d'apatite et procede de fabrication associe Download PDF

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Publication number
WO1999018029A1
WO1999018029A1 PCT/JP1997/003619 JP9703619W WO9918029A1 WO 1999018029 A1 WO1999018029 A1 WO 1999018029A1 JP 9703619 W JP9703619 W JP 9703619W WO 9918029 A1 WO9918029 A1 WO 9918029A1
Authority
WO
WIPO (PCT)
Prior art keywords
apatite
hydroxyapatite
particles
slurry
water
Prior art date
Application number
PCT/JP1997/003619
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
Masatoshi Itoi
Michiro Kuwayama
Seikichi Tabei
Original Assignee
Nippon Chemical Industrial Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Chemical Industrial Co., Ltd. filed Critical Nippon Chemical Industrial Co., Ltd.
Priority to US09/319,382 priority Critical patent/US6159437A/en
Priority to PCT/JP1997/003619 priority patent/WO1999018029A1/ja
Priority to DE69723866T priority patent/DE69723866T2/de
Priority to EP97943158A priority patent/EP0949198B1/en
Publication of WO1999018029A1 publication Critical patent/WO1999018029A1/ja

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • C01B25/327—After-treatment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/15—Compositions characterised by their physical properties
    • A61K6/17—Particle size
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
    • A61K6/69—Medicaments
    • 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
    • A61K6/838—Phosphorus compounds, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/12—Phosphorus-containing materials, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
    • A61F2310/00005—The prosthesis being constructed from a particular material
    • A61F2310/00179—Ceramics or ceramic-like structures
    • A61F2310/00293—Ceramics or ceramic-like structures containing a phosphorus-containing compound, e.g. apatite

Definitions

  • the present invention relates to an apatite slurry and a method for producing the same.
  • the apatite particles have an average particle diameter of 1 m or less, and have a degree of dispersion in which particles of 3 ⁇ m or more are substantially absent, and the apatite particles are converted into an organic solvent compatible with water.
  • the present invention relates to a dispersed abatite slurry and a method for producing the same. Conventional technology
  • Apatites are well-known substances that are widely distributed in the form of phosphate rocks and animal bones, but have recently been used for artificial bone materials, tooth repair materials, ion exchange materials, and the like. It is a substance that is expected to enter into new fields in combination with its biocompatibility and environmentally friendly properties.
  • the primary particles generated during production are easily aggregated due to van der Waal scalar ion charge, etc.
  • aggregates of about 100 to 100 are formed.
  • JP-A-8631 dispersion by strong shearing treatment such as a homogenizer
  • JP-A-7-102005, JP-A-7-102006 dispersion by strong shearing treatment
  • the suspension polymerization stabilizer is prepared by a strong shearing treatment such as a homogenizer using water as a dispersion medium, even if the treatment is performed for a long time, it is extremely difficult to destroy the aggregated coarse particles.
  • the size cannot be reduced to 3 im or less, and particles of 4 m or more remain. That is, even if the aqueous slurry of the apatite slurry is dispersed as much as possible, the grinding equilibrium is reached, and there is a limit to the destruction of secondary particles in an aqueous system.
  • an object of the present invention is to provide an abatite slurry in which the secondary particles of the apatite are substantially completely redispersed, and a method for producing the same.
  • the apatite slurry according to the present invention is an apatite slurry in which apatite particles are dispersed in an organic solvent compatible with water, wherein the average particle diameter of the apatite particles is 1 / zm or less, And particles having a dispersity of substantially 3 / m or more.
  • the method for producing an apatite slurry according to the present invention is characterized in that an apatite slurry in which apatite particles are dispersed in an organic solvent compatible with water is supplied to a stirring type mill and a particle diameter of 3 m or more is supplied. Grinding and dispersing are performed until the particles have a degree of dispersion substantially free of particles.
  • FIG. 1 shows the particle size distribution of the apatite powder used in the examples.
  • FIG. 2 is a diagram showing the dispersion of the apatite slurry (product processed for 60 minutes) obtained in Example 2.
  • FIG. 3 is a diagram showing the dispersion of the apatite slurry (product treated for 60 minutes) obtained in Comparative Example 4.
  • FIG. 4 is a diagram showing the dispersion of the apatite slurry (30-minute processed product) obtained in Comparative Example 6.
  • FIG. 5 is a diagram showing the dispersion of the apatite slurry obtained in Comparative Example 8 (30-minute processed product).
  • FIG. 6 is a scanning electron micrograph showing the structure of the apatite particles in the apatite slurry obtained in Example 1.
  • FIG. 7 is a scanning electron micrograph of another field showing the structure of the apatite particles in the apatite slurry obtained in Example 1.
  • the apatite particles used in the apatite slurry of the present invention are hydroxyapatite and a derivative of Z or hydroxyapatite, but their production histories are not particularly limited, and can be obtained by any method. It can be used, but the following method can be mentioned as an example of the method for producing hydroxyapatite:
  • the hydroxyapatite derivative is obtained by partially exchanging or reacting a cation or anion with Ca 2 + or OH—, since the hydroxyapatite is an amphoteric ion exchanger.
  • a fluorine apatite in which a hydroxyl group is replaced by fluorine a chlorine apatite in which chlorine is replaced by chlorine, or a carbonate apatite
  • a Ba apatite in which Ca is replaced by another alkaline earth metal element Sr apatite
  • Mg apatite Cu-substituted abatite obtained by partially exchanging a part of Ca with a divalent metal ion, Zn-substituted abatite, Pb-substituted apatite, and others Represents an Ag-substituted aperture, a Ce-substituted aperture, and the like. Any of these It can also be obtained by treating the hydroxide a
  • the shape of the apatite particles used in the apatite slurry of the present invention is not particularly limited.
  • the apatite particles are aggregates having the shape of needle-like, columnar, rice-grain, or oval primary particles.
  • the size is usually divided into two types.
  • One is an apatite crystal having a short axis length of 100 to 100 nm and a long axis length of 30 to 300 nm obtained by a reaction in a temperature range from room temperature to 100 ° C.
  • the apatite particles are particles in which the primary particles are aggregated to a size of about 10 to 100 zm.
  • Solvents for dispersing the above-mentioned abatite particles are organic solvents which are compatible with water, but in many cases are alcohol compounds, preferably diol compounds.
  • Typical diol compounds include, for example, triethylene glycol, ethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, and butanediol, and other alcohols such as methanol, ethanol, propanol, and glycerin. Trihydric alcohols can be exemplified. If necessary, water or a desired dispersant may be directly added.
  • a polymerized phosphate dispersant such as sodium hexametaphosphate and sodium triribophosphate can be added to the organic solvent.
  • the amount of the dispersant added is not particularly limited, and the dispersant can be used within the usual range of addition.
  • the apatite slurry of the present invention is obtained by dispersing the apatite particles in an organic solvent compatible with water as described above.
  • the feature of the apatite slurry is that the degree of dispersion of the apatite slurry has an average particle diameter of 1 im. Less than 3 m In that the particles are substantially absent.
  • the apatite slurry according to the present invention is in a state where the secondary particles constituting the coarse particles of 3 m or more are completely removed by using the organic solvent as described above.
  • the main characteristic is that the average particle diameter of the apatite particles is 1 m or less, and as close to the primary particles as possible.
  • the degree of dispersion described in this specification refers to a value measured by a method described later.
  • the amount of abatite particles in the organic solvent which is the dispersion medium differs depending on the use, and is not particularly limited. However, if the slurry concentration is too low, If the effect is insufficient, and if the slurry concentration is too high, the viscosity of the slurry will increase, making it impossible to sufficiently pulverize the secondary particles of apatite and reagglomeration due to the interaction of the dispersed particles. In many cases, the content is in the range of from 0 to 80% by weight, preferably from 10 to 50% by weight, because it is likely to occur.
  • the application of the apatite slurry of the present invention is not particularly limited.
  • polyester fiber raw materials, polyurethane raw materials, adhesives, inks, brake oils, PET resin raw materials, antifreezes, pharmaceuticals, cosmetic raw materials, and electrolytic capacitor bases can be mentioned.
  • polyester raw materials and the like can be used as powders by directly removing the solvent, which is suitable for a slurry system, if necessary.
  • the apatite particles are suspended and dispersed in an organic solvent compatible with water, and the slurry is pulverized and dispersed in a stirring mill to the above-mentioned degree of dispersion. Is what you do.
  • the pulverizing medium used in the stirring mill is in a bead shape or a ball shape, and has a particle size of 5 mm ⁇ or less, preferably 1 mm ⁇ or less. If the particle size of the pulverizing medium exceeds 5 mm ⁇ , it takes a long processing time, which is not industrially preferable.
  • the material of the pulverizing medium is not particularly limited. For example, a pulverizing medium composed of metals such as stainless steel and iron, and ceramics such as glass, alumina, and zirconia.
  • the processing time of the stirring mill is usually from 10 to 240 minutes, preferably from about 10 to 120 minutes.
  • the apatite aggregate is subjected to dispersion treatment with a specific pulverizer using the above-mentioned special organic solvent as a dispersion medium, thereby pulverizing and dispersing the apatite particles to the above-mentioned degree of dispersion. be able to.
  • a commercially available aqueous slurry of hydroxyapatite [trade name: Superite: manufactured by Nippon Chemical Industry Co., Ltd.] was sprayed into an air stream at 150 ° C by using a spray dryer of a nozzle spray method to obtain a slurry.
  • the powder was collected with a cyclone-back filter to obtain an apatite powder.
  • the loss on drying of the obtained apatite powder (200 ° C., 3 hours) was 2.2%.
  • the average particle size of the abatite-order particles in the apatite powder was 30 nm in the short axis and 60 nm in the long axis.
  • the particle size distribution of the apatite powder [measured by icrotrac (FRA)] is as shown in Fig. 1, and the average particle size of the secondary particles is 23.64 m, and the maximum particle size is 80 m. there were.
  • the above abatite powder was dispersed under the conditions shown in Table 1 using a stirring mill of “Sand Grinder-14 TSG Type” manufactured by Ainux Corporation.
  • the vessel (crushing vessel) used was 400 ml and the filling amount of the media (crushing medium) was 250 m1.
  • Table 1 shows the dispersion conditions and the results obtained.
  • FIG. Figures 6 and 7 show scanning electron micrographs of the apatite slurry obtained in Example 1.
  • FIG. Figures 6 and 7 have different fields of view.
  • FIG. 2 shows the degree of dispersion of the apatite slurry (the product processed for 60 minutes) obtained in Example 2.
  • the apatite powder obtained in the above example was further heated at 110 ° C. for 3 hours.
  • the grains were grown by heating over a period to obtain an apatite powder having a primary particle diameter of 45 nm in the short axis and 90 nm in the long axis.
  • the obtained apatite powder was treated in the same manner as in Examples 1 to 7 under the dispersion treatment conditions shown in Table 1 to obtain an apatite slurry. The results obtained are shown in Table 1.
  • Example 9 An apatite slurry was obtained in the same manner as in Examples 1 to 7, except that 1,4-butanediol was used as the organic solvent. Table 1 also shows the dispersion conditions at this time and the results obtained.
  • Antibacterial apatite obtained by substituting a part of Ca ion of apatite with Ag ion and Zn ion [trade name "Avasider NBJ, manufactured by Sangi Co., Ltd., containing 2% by weight each of Ag and Zn" was used to obtain an apatite slurry in the same manner as in Examples 1 to 7.
  • the dispersion conditions at this time and the obtained results are also shown in Table 1.
  • the average particle size of the secondary particles of the used apasida-NB was 16.8 jm, and the maximum particle size was 65.0 m.
  • the degree of dispersion was measured using a laser diffraction scattering type particle size measuring device.
  • a medium for the measurement a 0.17% by weight sodium pyrophosphate solution was used, and the measurement was performed in a state where the particles were diluted to 0.01 to 0.02% by weight. No pretreatment was performed on the sample before measurement.
  • the measurement was performed using Microtrac (FRA) (made by Kisoso Co., Ltd.).
  • Circulating fluid volume 300 ml
  • Table 2 shows the results of pulverizing and dispersing the mixture of ethylene glycol: hydroxyapatite at a weight ratio of 9: 1 using a homogenizer [TK HOMO MIXER MARK IK550W manufactured by Tokushu Kika Kogyo Co., Ltd.].
  • Table 2 and FIG. 3 show the results of pulverizing and dispersing the mixture having a water: hydroxyapatite weight ratio of 9: 1 using a homogenizer.
  • a mixture of ethylene glycol (aqueous solution of 0.2% by weight of sodium hexametaphosphate) and hydroxyapatite in a weight ratio of 9: 1 is used as an ultrasonic disperser [UE-1200Z20S-7A (1.2 KW) manufactured by Ultrasonic Industry Co., Ltd.]
  • Table 2 and Fig. 4 show the results of pulverizing and dispersing treatments using.
  • Table 2 shows the results of pulverizing and dispersing the mixture of ethylene glycol and hydroxyapatite at a weight ratio of 7: 3 using an ultrasonic disperser.
  • the hydroxyapatite used in Examples 1 to 7 was repeatedly pulverized three times with a jet mill STJ-400 manufactured by SENSIN CORPORATION.
  • the obtained powder had an average particle diameter of 0.73 ⁇ m and a maximum diameter of 15.6 m and could not reach the target particle size.
  • Figure 5 shows the particle size distribution of the obtained powder. Table 2
  • an abatite slurry obtained by substantially completely redispersing secondary particles of an apatite obtained by substantially completely redispersing secondary particles of an apatite, and a method for producing the same.

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  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Public Health (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Transplantation (AREA)
  • Dermatology (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Colloid Chemistry (AREA)
PCT/JP1997/003619 1996-05-08 1997-10-08 Boue d'apatite et procede de fabrication associe WO1999018029A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US09/319,382 US6159437A (en) 1996-05-08 1997-10-08 Method for manufacturing an aptatite slurry
PCT/JP1997/003619 WO1999018029A1 (fr) 1997-10-08 1997-10-08 Boue d'apatite et procede de fabrication associe
DE69723866T DE69723866T2 (de) 1997-10-08 1997-10-08 Apatitaufschlämmung und verfahren zu deren herstellung
EP97943158A EP0949198B1 (en) 1997-10-08 1997-10-08 Apatite slurry and process for the preparation thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP1997/003619 WO1999018029A1 (fr) 1997-10-08 1997-10-08 Boue d'apatite et procede de fabrication associe

Publications (1)

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WO1999018029A1 true WO1999018029A1 (fr) 1999-04-15

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PCT/JP1997/003619 WO1999018029A1 (fr) 1996-05-08 1997-10-08 Boue d'apatite et procede de fabrication associe

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EP (1) EP0949198B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE69723866T2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
WO (1) WO1999018029A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62265108A (ja) * 1986-05-10 1987-11-18 Chichibu Cement Co Ltd 易焼結性水酸アパタイト粉末の製造方法
JPH01230413A (ja) * 1988-03-11 1989-09-13 Kanto Chem Co Inc 球形ヒドロキシアパタイト焼結体の製造方法、並びに該球形とヒドロキシアパタイト焼結体から成るクロマトグラフイ用充填剤
JPH02149408A (ja) * 1988-12-01 1990-06-08 Kobe Steel Ltd ヒドロキシアパタイト微粒子凝集体の製造方法
JPH0383805A (ja) * 1989-08-25 1991-04-09 Sumitomo Chem Co Ltd 球状ハイドロキシアパタイトの製造方法
JPH04175213A (ja) * 1990-11-09 1992-06-23 Sekisui Plastics Co Ltd 多孔質球状アパタイト粒子の製造方法

Family Cites Families (7)

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Publication number Priority date Publication date Assignee Title
JPS53126094A (en) * 1977-04-12 1978-11-02 Kureha Chem Ind Co Ltd Suspension copolymerization of acrylonitrile with styrene
US4659617A (en) * 1984-09-11 1987-04-21 Toa Nenryo Kogyo Kabushiki Kaisha Fibrous apatite and method for producing the same
US4689351A (en) * 1985-10-08 1987-08-25 Mitsubishi Yuka Badische Co., Ltd. Process for producing foamed particles of propylene copolymer resin
DE69207198C5 (de) * 1991-08-12 2007-12-06 Dytech Corp. Ltd., Stannington Poröse gegenstände
JP2783352B2 (ja) * 1993-08-13 1998-08-06 日本化学工業株式会社 懸濁重合用安定剤の製造方法
JP2984901B2 (ja) * 1994-12-16 1999-11-29 花王株式会社 熱圧力定着用カプセルトナー
JP3845464B2 (ja) * 1995-11-24 2006-11-15 宇部マテリアルズ株式会社 微粒子水酸アパタイト水性スラリーの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62265108A (ja) * 1986-05-10 1987-11-18 Chichibu Cement Co Ltd 易焼結性水酸アパタイト粉末の製造方法
JPH01230413A (ja) * 1988-03-11 1989-09-13 Kanto Chem Co Inc 球形ヒドロキシアパタイト焼結体の製造方法、並びに該球形とヒドロキシアパタイト焼結体から成るクロマトグラフイ用充填剤
JPH02149408A (ja) * 1988-12-01 1990-06-08 Kobe Steel Ltd ヒドロキシアパタイト微粒子凝集体の製造方法
JPH0383805A (ja) * 1989-08-25 1991-04-09 Sumitomo Chem Co Ltd 球状ハイドロキシアパタイトの製造方法
JPH04175213A (ja) * 1990-11-09 1992-06-23 Sekisui Plastics Co Ltd 多孔質球状アパタイト粒子の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0949198A4 *

Also Published As

Publication number Publication date
EP0949198A1 (en) 1999-10-13
EP0949198A4 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1999-11-17
DE69723866T2 (de) 2004-07-15
DE69723866D1 (de) 2003-10-09
EP0949198B1 (en) 2003-07-30

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