JPH11130412A - Calcium phosphate composite material and its production - Google Patents
Calcium phosphate composite material and its productionInfo
- Publication number
- JPH11130412A JPH11130412A JP9309524A JP30952497A JPH11130412A JP H11130412 A JPH11130412 A JP H11130412A JP 9309524 A JP9309524 A JP 9309524A JP 30952497 A JP30952497 A JP 30952497A JP H11130412 A JPH11130412 A JP H11130412A
- Authority
- JP
- Japan
- Prior art keywords
- calcium phosphate
- acid
- titanium
- composite material
- mixture
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 239000001506 calcium phosphate Substances 0.000 title claims abstract description 43
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 title claims abstract description 43
- 229910000389 calcium phosphate Inorganic materials 0.000 title claims abstract description 41
- 235000011010 calcium phosphates Nutrition 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000010936 titanium Substances 0.000 claims abstract description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000011230 binding agent Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 16
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 28
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000843 powder Substances 0.000 abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 10
- 210000000988 bone and bone Anatomy 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 239000007858 starting material Substances 0.000 abstract description 7
- 238000001354 calcination Methods 0.000 abstract description 6
- 239000011575 calcium Substances 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 6
- 229910052588 hydroxylapatite Inorganic materials 0.000 abstract description 3
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 241000251468 Actinopterygii Species 0.000 abstract description 2
- 241001465754 Metazoa Species 0.000 abstract description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 abstract description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 abstract description 2
- 229940078499 tricalcium phosphate Drugs 0.000 abstract description 2
- 238000005342 ion exchange Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- -1 calcium phosphate compound Chemical class 0.000 description 3
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WEUCVIBPSSMHJG-UHFFFAOYSA-N calcium titanate Chemical compound [O-2].[O-2].[O-2].[Ca+2].[Ti+4] WEUCVIBPSSMHJG-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940036811 bone meal Drugs 0.000 description 1
- 239000002374 bone meal Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- XAAHAAMILDNBPS-UHFFFAOYSA-L calcium hydrogenphosphate dihydrate Chemical compound O.O.[Ca+2].OP([O-])([O-])=O XAAHAAMILDNBPS-UHFFFAOYSA-L 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ルチル型または、
アナターゼ型結晶構造を有した酸化チタンとCa/P比が1.
0から2.0であるリン酸カルシウムの混合物および当該物
質からなる成形体およびその製造方法に関するものであ
る。The present invention relates to a rutile type or
Titanium oxide with anatase crystal structure and Ca / P ratio 1.
The present invention relates to a mixture of calcium phosphate having a ratio of 0 to 2.0, a molded article comprising the substance, and a method for producing the same.
【０００２】[0002]
【従来の技術】近年、酸化チタンの光触媒反応を利用し
た様々な技術に関する研究開発がなされている。例え
ば、細菌感染防止(特開平7-462)、硫黄酸化物や窒素酸
化物等大気汚染物質の除去(特開平9-75748、特開平6-38
5、特開平6-496)、付着汚染物質の除去(特開平9-7143
7)、メタノールの合成装置(特開平7-33697)、水の浄化
装置(特開平8-47687)等が開示されている。これらの実
用形態としては酸化チタン単体でもしくは無機材料、金
属材料等に担持する方法が考えられている。一方、アパ
タイトをはじめとするリン酸カルシウムは有機分子、ウ
イルス等に対する吸着性が高いことから吸着剤や脱臭剤
として実用化がなされている（例えば特開平5-85665、
特開平5-115572）。以上の様な特性を有するリン酸カル
シウムと酸化チタンをそれぞれの特性を保ったまま複合
化することができれば、リン酸カルシウムの高い吸着性
により物質（においの元となる物質やウイルス等）を吸
着し、吸着した物質を酸化チタンの光触媒反応により分
解する機構による優れた有害物質除去システムが実現で
きる。2. Description of the Related Art In recent years, research and development on various technologies utilizing a photocatalytic reaction of titanium oxide have been made. For example, prevention of bacterial infection (JP-A-7-462), removal of air pollutants such as sulfur oxides and nitrogen oxides (JP-A-9-75748, JP-A-6-38)
5, JP-A-6-496), removal of attached contaminants (JP-A-9-7143)
7), an apparatus for synthesizing methanol (JP-A-7-33697), a water purification apparatus (JP-A-8-47687) and the like are disclosed. As a practical form of these, a method of supporting titanium oxide alone or on an inorganic material, a metal material, or the like has been considered. On the other hand, calcium phosphate such as apatite has been put to practical use as an adsorbent or a deodorant because of its high adsorptivity to organic molecules, viruses and the like (for example, JP-A-5-85665,
JP-A-5-115572). If calcium phosphate and titanium oxide having the above properties can be compounded while maintaining their respective properties, substances (such as substances and viruses that cause odor) are adsorbed and adsorbed due to the high adsorptivity of calcium phosphate. An excellent system for removing harmful substances can be realized by a mechanism for decomposing substances by the photocatalytic reaction of titanium oxide.
【０００３】[0003]
【発明が解決しようとする課題】上述のように優れた有
害物質除去システムの可能性を秘めたリン酸カルシウム
と酸化チタンの複合体であるが、リン酸カルシウムとチ
タンを乾式または湿式で攪拌混合し焼成をおこなうと、
チタンとリン酸カルシウム中のカルシウムが反応しチタ
ン酸カルシウムが生成し酸化チタンの光触媒活性が失わ
れてしまう。よって、複合体の成形焼結体は実現されて
おらず、現在考えられるリン酸カルシウムと酸化チタン
の複合材の製法は、個別に焼成したリン酸カルシウムと
酸化チタンを混合して得られた粉末をそのまま、もしく
は基材にコーティングする等の形態でのみ実現可能であ
る。しかし、粉末状では汎用性に問題があり、基材への
コーティングでは耐磨耗性に乏しい等実用化にはいたっ
ていない。As described above, the composite of calcium phosphate and titanium oxide has the potential for an excellent system for removing harmful substances as described above. Calcium phosphate and titanium are mixed by dry or wet stirring and firing. When,
Titanium reacts with calcium in calcium phosphate to form calcium titanate, and the photocatalytic activity of titanium oxide is lost. Therefore, a molded sintered body of the composite has not been realized, and the currently conceivable method for producing a composite material of calcium phosphate and titanium oxide is to use a powder obtained by mixing individually fired calcium phosphate and titanium oxide, or It can be realized only in a form such as coating on a substrate. However, the powder form has a problem in versatility, and the coating on a base material has not been put to practical use, such as poor abrasion resistance.
【０００４】[0004]
【課題を解決するための手段】上記の課題を解決するた
め本発明は、酸にチタン及びリン酸カルシウムをそれぞ
れ溶解したものを混合しさらにアルカリ溶液中に滴下す
ることにより溶解したチタン及びリン酸カルシウムを析
出させ得られた粉末を焼成することによりルチル型もし
くはアナターゼ型の結晶構造を有した酸化チタン、即ち
光触媒を含有したリン酸カルシウムが生成する。また、
焼成前に必要に応じてPVA等のバインダーを添加し例え
ば一軸加圧プレス等で成形後焼成することにより容易に
成形体とすることができる。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a method of mixing titanium and calcium phosphate dissolved in an acid and dropping the mixture in an alkaline solution to precipitate the dissolved titanium and calcium phosphate. By calcining the obtained powder, titanium oxide having a rutile-type or anatase-type crystal structure, that is, calcium phosphate containing a photocatalyst is produced. Also,
A molded body can be easily obtained by adding a binder such as PVA if necessary before firing, and forming and firing after molding with, for example, a uniaxial press.
【０００５】[0005]
【実施の形態】本発明の詳細を以下に示す。本発明は、
リン酸カルシウム出発原料を酸に溶解し、さらに別にチ
タンを酸に溶解し両酸液を混合後アルカリ液に滴下する
ことによりチタンとリン酸カルシウムの混合物を析出さ
せ、さらに焼成することにより得られるチタンとリン酸
カルシウムの複合材料および当該物質からなる成形体お
よびその製造方法である。DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below. The present invention
Dissolve the calcium phosphate starting material in the acid, further separately dissolve the titanium in the acid, mix the two acid solutions and then drop the mixture into an alkaline solution to precipitate a mixture of titanium and calcium phosphate, and further calcine to obtain the titanium and calcium phosphate. The present invention relates to a composite material, a molded article made of the substance, and a method for producing the same.
【０００６】本発明で示す出発原料としてのリン酸カル
シウムとしてはCa/Pが1.0〜2.0のリン酸カルシウム系化
合物、好ましくはハイドロキシアパタイト、リン酸三カ
ルシウムこれらの化合物を任意の割合に混合した粉末、
動物骨、魚骨、甲殻、及び天然骨を焼成したものを出発
原料として用いる。As the calcium phosphate as a starting material shown in the present invention, a calcium phosphate compound having a Ca / P of 1.0 to 2.0, preferably hydroxyapatite, tricalcium phosphate, a powder obtained by mixing these compounds in an arbitrary ratio,
Fired animal bones, fish bones, shells, and natural bones are used as starting materials.
【０００７】これらの出発原料を任意にイオン交換水等
で薄めた酸、例えば、塩酸、硫酸、硝酸、クエン酸、リ
ンゴ酸、マレイン酸、ステアリン酸、その他の有機酸も
しくは無機酸、好ましくは塩酸であって例えばpH1〜3に
溶解する。溶解は、例えば攪拌機を用いてリン酸カルシ
ウムの場合10〜60分、好ましくは20〜30分間、チタンの
場合1時間〜48時間好ましくは24時間おこなう。この液
体を吸引濾過等で濾過することにより濾液として酸液を
得る。An acid obtained by optionally diluting these starting materials with ion-exchanged water, for example, hydrochloric acid, sulfuric acid, nitric acid, citric acid, malic acid, maleic acid, stearic acid, other organic or inorganic acids, preferably hydrochloric acid And dissolves, for example, at pH 1-3. The dissolution is carried out using, for example, a stirrer for 10 to 60 minutes, preferably 20 to 30 minutes for calcium phosphate, and 1 hour to 48 hours, preferably 24 hours for titanium. The acid solution is obtained as a filtrate by filtering this liquid by suction filtration or the like.
【０００８】以上のように調整されたリン酸カルシウム
/酸溶液、チタン/酸溶液を任意の割合で、具体的には、
リン酸カルシウム溶解量にたいしてチタン溶解量が0.1
〜99wt%となるように混合しリン酸カルシウム、チタン/
酸溶液を得る。このとき、チタンの溶解量が0.1から20w
t%程度では、後述焼成条件による焼成により光触媒活性
を発現しないチタン酸カルシウムの生成を完全に抑える
ことができる。また、20wt%以上では完全には抑えるこ
とができないが、チタンとリン酸カルシウムを物理的に
混合した場合に比べチタン酸カルシウムの生成を有為に
抑制することは可能である。[0008] Calcium phosphate adjusted as described above
/ Acid solution, titanium / acid solution at any ratio, specifically,
The amount of titanium dissolved is 0.1 compared to the amount of calcium phosphate dissolved.
~ 99wt% to mix calcium phosphate, titanium /
Obtain an acid solution. At this time, the dissolution amount of titanium is 0.1 to 20 w
At about t%, generation of calcium titanate that does not exhibit photocatalytic activity by firing under firing conditions described below can be completely suppressed. Although it cannot be completely suppressed at 20 wt% or more, it is possible to significantly suppress the formation of calcium titanate as compared with the case where titanium and calcium phosphate are physically mixed.
【０００９】中和液となるアルカリ液は任意のアルカリ
水溶液、例えば、水酸化ナトリウム、水酸化カリウム、
アンモニア、その他のアルカリ、好ましくは水酸化ナト
リウム水溶液であってpH11〜13を用いることが可能であ
る。The alkaline solution serving as the neutralizing solution may be any alkaline aqueous solution, for example, sodium hydroxide, potassium hydroxide,
Ammonia or other alkali, preferably aqueous sodium hydroxide, pH 11-13 can be used.
【００１０】上記の手順で調整したリン酸カルシウム、
チタン/酸溶液をビュレット等の器具、装置を用いてア
ルカリ液中に滴下する。滴下の際にアルカリ液は攪拌を
おこなうことが好ましい。さらに、滴下中アルカリ液の
pHを常時観測しあらかじめ決められたpH好ましくはpH３
からpH８となったら滴下を停止する。滴下停止後1時間
から20時間好ましくは15〜20時間攪拌後吸引濾過等の方
法により濾過をおこない生成物を得た。The calcium phosphate prepared according to the above procedure,
The titanium / acid solution is dropped into the alkaline solution using a device such as a burette. It is preferable that the alkaline liquid is stirred during the dropping. In addition, the alkaline solution
The pH is constantly monitored and a predetermined pH, preferably pH 3
When the pH reaches from 8, the dropping is stopped. After stirring for 1 to 20 hours, preferably 15 to 20 hours after stopping the dropping, filtration was performed by a method such as suction filtration to obtain a product.
【００１１】生成物を乾燥後、焼成温度が600℃〜1400
℃で焼成時間が1時間から20時間好ましくは5〜10時間焼
成し目的生成物を得る。After drying the product, the calcination temperature is from 600 ° C. to 1400
Calcination time is 1 to 20 hours, preferably 5 to 10 hours at ℃ to obtain the desired product.
【００１２】本発明の目的生成物であるリン酸カルシウ
ムと酸化チタンとの複合材におけるリン酸カルシウムと
しては、生体親和性、各種吸着性を必要とする場合は、
ハイドロキシアパタイト、α乃至β−ＴＣＰが例示され
るが、光触媒作用の目的が大きくしかも大量に必要とす
る場合は、特にpHの調整も要する事がなく、簡単に製造
可能で特に自然に対し害とならない物質、例えばブルッ
シャイト（ＣａＨＰＯ4・２Ｈ2Ｏ）、ピロリン酸カルシ
ウム（Ｃａ2Ｐ2Ｏ7）が好適である。The calcium phosphate in the composite material of calcium phosphate and titanium oxide, which is the object product of the present invention, may be selected from those which require biocompatibility and various adsorptivity.
Hydroxyapatite and α to β-TCP are exemplified, but when the purpose of the photocatalysis is large and a large amount is required, there is no need to adjust pH in particular, and it can be easily produced and is particularly harmful to nature. become not material, e.g. brushite (CaHPO 4 · 2H 2 O) , calcium pyrophosphate (Ca 2 P 2 O 7) is preferred.
【００１３】焼結成形体は、焼成前に、多孔質体、その
他成形性改善の為等、目的または必要に応じ、PVA等の
バインダーを添加しさらに一軸加圧プレス等で成形後焼
成することにより得られる。Before sintering, the sintered compact is prepared by adding a binder such as PVA or the like, if necessary or necessary, for the purpose of improving the formability, etc., before sintering, and further sintering after shaping with a uniaxial press. can get.
【００１４】その他の製造方法について以下に詳述す
る。上述した出発原料として、天然骨を使用する。この
天然骨を上述した酸液であって、pH1〜3好ましくはpH1
の塩酸からなる酸液で溶解濾過する。得られたろ液とチ
タンを酸で溶解したチタン溶液を混合し、これをアルカ
リ溶液に滴下することで、廃物利用を促進すると共に、
製造工程を簡素化し、より安価な光触媒物質を得る事を
可能とするものである。自然界に容易に受け入れられる
光触媒物質を安価に且つ大量に製造できる事は、水質汚
染、大気汚染等の公害に対処するための素材として、非
常に有益なものと成り得る。更に、溶解する際、pHを調
整し、攪拌を時間（例えば）をかけて充分に行う等の処
理を行うことにより、または、このろ液をアルカリ溶液
に滴下して得られる沈澱物を更に酸液で溶解するという
繰り返しの工程を採ることにより、所望のリン酸カルシ
ウムを得る事ができる。Other manufacturing methods will be described in detail below. Natural bone is used as the starting material described above. This natural bone is an acid solution as described above, and has a pH of 1 to 3, preferably pH 1.
The solution is filtered with an acid solution consisting of hydrochloric acid. The obtained filtrate and a titanium solution obtained by dissolving titanium with an acid are mixed, and this is dropped into an alkali solution, thereby promoting waste utilization,
This simplifies the manufacturing process and makes it possible to obtain a cheaper photocatalytic substance. The ability to produce inexpensively and in large quantities a photocatalytic substance that is easily accepted in nature can be very useful as a material for dealing with pollution such as water pollution and air pollution. Further, at the time of dissolution, the pH is adjusted, and a treatment such as sufficient stirring over time (for example) is performed, or the precipitate obtained by dropping the filtrate into an alkaline solution is further acidified. By taking a repeated step of dissolving with a liquid, a desired calcium phosphate can be obtained.
【００１５】また、複合材中の光触媒作用を発現する酸
化チタンの結晶構造はアナターゼ型とルチル型が知られ
ている。本発明によれば、例えば焼成温度500℃〜900℃
ではアナターゼ型が、900℃〜1400℃ではルチル型が焼
成温度以外の工程は変えることなく容易に生成すること
が可能である。特に、アナターゼ型は、ルチル型に比べ
酸化力が強く、より優れた光電気化学反応を生起させる
ことができる。ただし、ルチル型であっても、その用途
により十分な光電気化学反応を発現させることができる
場合もあり、結晶構造はその用途、使用態様等により適
宜選択されるものである。[0015] In addition, the crystal structure of titanium oxide exhibiting photocatalysis in the composite material is known to be an anatase type and a rutile type. According to the present invention, for example, a firing temperature of 500 ° C to 900 ° C
Then, the anatase type can be easily formed at 900 ° C. to 1400 ° C. without changing the rutile type at steps other than the calcination temperature. In particular, the anatase type has a stronger oxidizing power than the rutile type and can generate a more excellent photoelectrochemical reaction. However, even in the case of the rutile type, a sufficient photoelectrochemical reaction may be able to be developed depending on the application, and the crystal structure is appropriately selected depending on the application, usage mode, and the like.
【００１６】[0016]
【実施例】実施例１ 1N HCl 100mlにCa/Pが1.67であるリン酸カルシウムを10
g溶解したもの（HAp/HCl）、及び、12N HClに純チタン
粉末2.00gを入れ1日間静置したものを（Ti/HCl）調整し
た。25mlのHAp/HCl に、Ti/HClをリン酸カルシウム溶
解量に対してチタンの溶解量が0.8wt%、、2.5wt%、5.0w
t%、10wt%、15wt%となるように混合したものを酸液と
し、アルカリ液として1N NaOHを適量用いた。アルカリ
液に酸液をpH8となるまで滴下した。1日攪拌後濾過、乾
燥し粉末を得た。 Example 1 Calcium phosphate having a Ca / P ratio of 1.67 was added to 100 ml of 1N HCl.
g (HAp / HCl) and 2.00 g of pure titanium powder in 12N HCl and allowed to stand for 1 day to prepare (Ti / HCl). In 25 ml of HAp / HCl, the dissolved amount of titanium is 0.8 wt%, 2.5 wt%, 5.0 w
What was mixed so that it might become t%, 10 wt%, and 15 wt% was made into the acid solution, and an appropriate amount of 1N NaOH was used as the alkali solution. The acid solution was added dropwise to the alkaline solution until the pH reached 8. After stirring for one day, the mixture was filtered and dried to obtain a powder.
【００１７】実施例２ 実施例1で得た粉末を1000℃で焼成後XRD測定をおこなっ
た。得られた粉末はXRD測定の結果リン酸カルシウムと
酸化チタン（ルチル型）の複合体であり、チタン酸カル
シウム（ＣａＴｉＯ3）は検出されなかった。生成物を
表1に示す。チタン溶解量15wt%のXRDチャートを図１に
示す。 Example 2 The powder obtained in Example 1 was fired at 1000 ° C. and subjected to XRD measurement. As a result of XRD measurement, the obtained powder was a composite of calcium phosphate and titanium oxide (rutile type), and calcium titanate (CaTiO 3 ) was not detected. The products are shown in Table 1. FIG. 1 shows an XRD chart when the amount of titanium dissolved is 15 wt%.
【表１】 [Table 1]
【００１８】実施例３ 実施例1で得たチタン溶解量10wt%の粉末を700℃で1時間
焼成後、XRD測定をおこなった。得られた粉末はXRD測定
の結果リン酸カルシウムと酸化チタン（アナターゼ型）
の複合体であり、チタン酸カルシウム（ＣａＴｉＯ3）
は検出されなかった（図２）。 Example 3 The powder having a titanium dissolution amount of 10 wt% obtained in Example 1 was calcined at 700 ° C. for 1 hour, and then subjected to XRD measurement. The powder obtained was analyzed by XRD to find calcium phosphate and titanium oxide (anatase type).
Is a complex of calcium titanate (CaTiO 3 )
Was not detected (FIG. 2).
【００１９】実施例４ リン酸カルシウム源を牛骨粉として実施例1の製造方法
で製造をおこなった。Ti/HClはリン酸カルシウム溶解量
に対して10wt%となるよう調整した。得られた粉末を100
0℃、1時間焼成した。XRD測定によりその組成はリン酸
カルシウムと酸化チタン（ルチル型）であった（図
３）。 Example 4 Production was performed by the production method of Example 1 using bovine bone meal as a calcium phosphate source. Ti / HCl was adjusted to be 10 wt% with respect to the dissolved amount of calcium phosphate. 100 powder obtained
It was baked at 0 ° C. for 1 hour. According to XRD measurement, the composition was calcium phosphate and titanium oxide (rutile type) (FIG. 3).
【００２０】実施例５ 実施例１で得た粉末1gをポリビニルアルコール5wt%水溶
液に加え混合、攪拌した。得られたスラリーをテルモシ
リンジ10mlに充填し、注射針24G（内径0.47mm)を用いて
液体窒素上に滴下した。得られた凍結物を真空乾燥機を
用いて乾燥させた後、1400℃で5時間焼成し球状セラミ
ックス0.9gを得た得られたセラミックスは直径0.8から
1.0mmであった。走査型電子顕微鏡で表面及び断面を観
察したところ得られた球体は、多孔質であった。当該球
体状の複合材を図４、図５に示す。また、濾過剤やフィ
ルター剤として利用可能な強度を有していた。 Example 5 1 g of the powder obtained in Example 1 was added to a 5 wt% aqueous solution of polyvinyl alcohol, and mixed and stirred. The obtained slurry was filled in 10 ml of a thermosyringe, and dropped on liquid nitrogen using an injection needle 24G (inner diameter 0.47 mm). The obtained frozen material was dried using a vacuum dryer, and then baked at 1400 ° C. for 5 hours to obtain 0.9 g of spherical ceramic.
1.0 mm. Observation of the surface and the cross section with a scanning electron microscope revealed that the obtained sphere was porous. The spherical composite material is shown in FIGS. Further, it had a strength that could be used as a filtering agent or a filtering agent.
【図１】 本発明を説明するための図。FIG. 1 is a diagram illustrating the present invention.
【図２】 本発明を説明するための図。FIG. 2 is a diagram illustrating the present invention.
【図３】 本発明を説明するための図。FIG. 3 is a diagram illustrating the present invention.
【図４】 本発明を説明するための写真図。FIG. 4 is a photograph for explaining the present invention.
【図５】 本発明を説明するための写真図。FIG. 5 is a photograph for explaining the present invention.
Claims (3)
酸に溶解し、混合したものをアルカリ中に滴下し析出さ
せることを特徴とするリン酸カルシウム複合材の製造方
法。1. A method for producing a calcium phosphate composite material, comprising dissolving calcium phosphate and a titanium member in an acid, respectively, and mixing and dropping the mixture in an alkali to precipitate.
うに酸液を滴下する請求項１に記載のリン酸カルシウム
系複合材の製造方法。2. The method for producing a calcium phosphate composite material according to claim 1, wherein the acid solution is dropped so that the pH of the alkaline solution is from pH 3 to pH 8.
形後焼成する請求項１に記載のリン酸カルシウム系複合
材の製造方法。3. The method for producing a calcium phosphate composite material according to claim 1, wherein a binder such as PVA is added as necessary, followed by molding and firing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30952497A JP3898309B2 (en) | 1997-10-24 | 1997-10-24 | Method for producing calcium phosphate composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30952497A JP3898309B2 (en) | 1997-10-24 | 1997-10-24 | Method for producing calcium phosphate composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11130412A true JPH11130412A (en) | 1999-05-18 |
| JP3898309B2 JP3898309B2 (en) | 2007-03-28 |
Family
ID=17994054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30952497A Expired - Fee Related JP3898309B2 (en) | 1997-10-24 | 1997-10-24 | Method for producing calcium phosphate composite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3898309B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| WO2004026470A1 (en) * | 2002-09-17 | 2004-04-01 | Fujitsu Limited | Photocatalyst apatite-containing film, method of forming the same, coating fluid, and electronic apparatus having member covered with photocatalyst apatite-containing film |
| KR100431159B1 (en) * | 2001-03-22 | 2004-05-12 | 김철생 | Method for producing Ti-based implant having bioactive surface as substitute for bone tissue |
| WO2005058754A1 (en) * | 2003-12-18 | 2005-06-30 | Imuno-Science Co., Inc. | Sintered body of titanium compound |
| JP2007014686A (en) * | 2005-07-11 | 2007-01-25 | Univ Kinki | Biomaterial, medical material using the same, and method for producing the material for organism |
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|---|---|---|---|---|
| KR100431159B1 (en) * | 2001-03-22 | 2004-05-12 | 김철생 | Method for producing Ti-based implant having bioactive surface as substitute for bone tissue |
| JP2003089587A (en) * | 2001-09-14 | 2003-03-28 | National Institute Of Advanced Industrial & Technology | Humidity-controlled ceramics material |
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| JPWO2005058754A1 (en) * | 2003-12-18 | 2007-07-12 | イムノサイエンス株式会社 | Sintered titanium compound |
| WO2005058754A1 (en) * | 2003-12-18 | 2005-06-30 | Imuno-Science Co., Inc. | Sintered body of titanium compound |
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