JPH1129311A - Production of coating film and production of calcium phosphate-based film - Google Patents
Production of coating film and production of calcium phosphate-based filmInfo
- Publication number
- JPH1129311A JPH1129311A JP9199402A JP19940297A JPH1129311A JP H1129311 A JPH1129311 A JP H1129311A JP 9199402 A JP9199402 A JP 9199402A JP 19940297 A JP19940297 A JP 19940297A JP H1129311 A JPH1129311 A JP H1129311A
- Authority
- JP
- Japan
- Prior art keywords
- coating
- solution
- film
- heat treatment
- calcium phosphate
- 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.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、金属化合物が溶解
された溶液を用い、特定の条件下、コーティング被膜を
製造する方法に関する。また、本発明は、特に、特定の
条件下、リン酸カルシウム系被膜を製造する方法に関す
る。The present invention relates to a method for producing a coating film under specific conditions using a solution in which a metal compound is dissolved. In addition, the present invention particularly relates to a method for producing a calcium phosphate-based coating under specific conditions.
【０００２】[0002]
【従来の技術】セラミックス粉末及びガラス粉末等を金
属などの基材の表面に塗布し、コーティング被膜を形成
する方法が従来より知られている。また、近年では、低
温で、良質な被膜を形成することができるゾル−ゲル法
等の各種の手法が研究されている。このゾル−ゲル法で
は、比較的低温で操作されるため加熱による基材の熱劣
化や酸化劣化が抑えられ、薄く、且つ緻密なコ−ティン
グ被膜を得ることができる。2. Description of the Related Art A method of applying a ceramic powder, a glass powder, or the like to a surface of a base material such as a metal to form a coating film is conventionally known. In recent years, various techniques such as a sol-gel method capable of forming a high-quality coating at a low temperature have been studied. In the sol-gel method, since the operation is performed at a relatively low temperature, thermal deterioration and oxidative deterioration of the substrate due to heating are suppressed, and a thin and dense coating film can be obtained.
【０００３】[0003]
【発明が解決しようとする課題】一般に、金属、セラミ
ックス等の基材の表面に形成されるコ−ティング被膜中
に残留有機物が含まれると、その被膜自身が本来有する
電気的、磁気的、光学的特性などが阻害されるため、残
留有機物は除去される。除去の方法としては、空気或い
は酸素を流通させつつ燃焼させる方法が一般的である。
この方法によって残留有機物を除去する際に特に問題と
なるのは、緻密、且つ微細なゲル構造を有するコ−ティ
ング被膜の場合である。このような緻密、且つ微細な被
膜では、残留有機物を除去するためには、空気或いは酸
素を流通させつつ高温において長時間の熱処理をする必
要がある。Generally, when a coating film formed on the surface of a base material such as a metal or ceramics contains residual organic substances, the coating film itself has its own electrical, magnetic and optical properties. The residual organic matter is removed because the chemical properties are impaired. As a removal method, a method of burning while flowing air or oxygen is general.
A particular problem in removing residual organic matter by this method is a coating film having a dense and fine gel structure. In such a dense and fine coating, it is necessary to perform a long-time heat treatment at a high temperature while flowing air or oxygen in order to remove residual organic substances.
【０００４】しかしながら、基材に酸化劣化され易い基
材を用いた場合には問題が生じる。高温で長時間の熱処
理により基材が酸化すると例えば、基材自身の強度が低
下したり、基材と被膜の密着強度が低下し、本来の目的
が達成されないため、基材の酸化劣化を抑える必要があ
る。この基材の酸化劣化の抑制と残留有機物の除去の両
立は非常に難しく、高温、長時間の熱処理では基材の劣
化を十分に抑えることができず、一方、窒素、アルゴン
等の不活性ガス雰囲気で熱処理した場合は、被膜中の残
留有機物を十分に除去することができない。本発明者ら
は、空気或いは酸素を流通させつつ、基材が劣化しない
程度の低温において熱処理を行った後、アルゴン雰囲気
下、高温で熱処理したみたが、残留有機物を十分に除去
することはできなかった。上記のように酸化し易い基材
の酸化劣化を抑え、且つ被膜中の残留有機物を十分に除
去することは非常に難しい。However, a problem arises when a substrate that is easily oxidized and deteriorated is used. When the base material is oxidized by a long-time heat treatment at a high temperature, for example, the strength of the base material itself is reduced, or the adhesion strength between the base material and the coating is reduced, and the original purpose is not achieved. There is a need. It is very difficult to achieve both the suppression of the oxidative deterioration of the substrate and the removal of residual organic substances, and it is not possible to sufficiently suppress the deterioration of the substrate by heat treatment at a high temperature for a long time. On the other hand, inert gases such as nitrogen and argon When heat treatment is performed in an atmosphere, the residual organic matter in the coating cannot be sufficiently removed. The present inventors conducted a heat treatment at a low temperature such that the base material did not deteriorate while flowing air or oxygen, and then performed a heat treatment at a high temperature under an argon atmosphere.However, the residual organic matter could not be sufficiently removed. Did not. As described above, it is very difficult to suppress the oxidative deterioration of the easily oxidizable base material and sufficiently remove the residual organic matter in the coating.
【０００５】一方、リン酸カルシウム系被膜の場合、通
常のアルコキシド法により得られる被膜は乾燥時、或い
は焼成時等の加熱による収縮によってクラックを生じ、
不均質な被膜となり易い。本発明者等は、エチレンジア
ミン四酢酸等のキレ−ト化剤を用いることによって、上
記の問題を解決することができ、低温において均質な水
酸アパタイト等の単相被膜が得られることを見いだし、
先に出願した（特開平８−９１８１４号公報）。しか
し、この方法においても、基材がアルミナ、ジルコニア
等の酸化物セラミックスである場合は残留有機物の問題
はないが、チタン、チタン合金、ステンレス鋼等、易酸
化性のものでは酸化劣化の問題があるため大気中或いは
酸素中での熱処理を高温で行うことができないため、被
膜中の残留カ−ボン等、残留有機物の除去が不十分とな
り、被膜が着色するなどの問題があった。[0005] On the other hand, in the case of a calcium phosphate coating, a coating obtained by a usual alkoxide method causes cracks due to shrinkage due to heating during drying or firing.
It tends to be an inhomogeneous film. The present inventors have found that by using a chelating agent such as ethylenediaminetetraacetic acid, the above problem can be solved, and that a single-phase coating such as hydroxyapatite that is homogeneous at low temperatures can be obtained.
It was previously filed (Japanese Patent Laid-Open No. Hei 8-91814). However, even in this method, when the base material is an oxide ceramic such as alumina or zirconia, there is no problem of residual organic matter, but in the case of easily oxidizable materials such as titanium, titanium alloy, and stainless steel, there is a problem of oxidation deterioration. For this reason, heat treatment in air or oxygen cannot be performed at a high temperature, so that residual organic substances such as residual carbon in the coating are insufficiently removed, and there is a problem that the coating is colored.
【０００６】[0006]
【課題を解決するための手段】第１発明のコーティング
被膜の製造方法は、金属化合物が溶解された溶液を基材
に塗布し、コ−ティング被膜を製造する方法において、
オゾンの存在下、５０〜５００℃で熱処理する工程を備
えることを特徴とする。According to a first aspect of the present invention, there is provided a method for producing a coating film, which comprises applying a solution in which a metal compound is dissolved to a substrate and producing a coating film.
The method is characterized by comprising a step of performing a heat treatment at 50 to 500 ° C. in the presence of ozone.
【０００７】また、第４発明のリン酸カルシウム系被膜
の製造方法は、カルシウムを含む塩と、リンを含む塩
と、カルシウムイオン及びリンイオンのうちの少なくと
も一方に配位可能なキレ−ト化剤とが溶解された溶液を
基材に塗布し、リン酸カルシウム系被膜を製造する方法
において、オゾンの存在下、５０〜５００℃で熱処理す
る工程を備えることを特徴とする。In a fourth aspect of the present invention, there is provided a method for producing a calcium phosphate coating, comprising: a salt containing calcium; a salt containing phosphorus; and a chelating agent capable of coordinating to at least one of calcium ion and phosphorus ion. A method for applying a dissolved solution to a substrate to produce a calcium phosphate-based coating, comprising a step of performing a heat treatment at 50 to 500 ° C. in the presence of ozone.
【０００８】更に、第６発明のリン酸カルシウム系被膜
の製造方法は、カルシウムを含むキレート化合物とリン
を含むキレート化合物、又はカルシウムを含むキレート
化合物とリンを含む塩、又はリンを含むキレート化合物
とカルシウムを含む塩、が溶解された溶液を基材に塗布
し、リン酸カルシウム系被膜を製造する方法において、
オゾンの存在下、５０〜５００℃で熱処理する工程を備
えることを特徴とする。これら第１、第４及び第６発明
の製造方法によれば、基材の酸化劣化が抑えられ、且つ
被膜中の残留有機物、特に残留カーボン等が除去された
コーティング被膜及びリン酸カルシウム系被膜を得るこ
とができる。Further, the method for producing a calcium phosphate-based coating according to the sixth invention is characterized in that a chelate compound containing calcium and a chelate compound containing phosphorus, a chelate compound containing calcium and a salt containing phosphorus, or a chelate compound containing phosphorus and calcium are used. In a method for producing a calcium phosphate-based coating, a solution containing a dissolved salt is applied to a substrate,
The method is characterized by comprising a step of performing a heat treatment at 50 to 500 ° C. in the presence of ozone. According to the production methods of the first, fourth and sixth aspects of the present invention, it is possible to obtain a coating film and a calcium phosphate-based film in which the oxidative deterioration of the base material is suppressed and the residual organic substances, particularly the residual carbon, etc. in the film are removed. Can be.
【０００９】上記「金属化合物」は特に限定されず、金
属アルコキシド、金属アセチルアセテート等の有機金属
化合物及び各種の金属の無機塩を使用することができ
る。また、上記「溶液」は、この金属化合物が溶解され
た溶液であり、有機溶剤を溶媒とする溶液であってもよ
いし、水溶液であってもよい。この溶液としては、金属
イオンをキレート化剤で安定化させた溶液等、種々のも
のを用いることができる。The above "metal compound" is not particularly limited, and organic metal compounds such as metal alkoxides and metal acetyl acetates and inorganic salts of various metals can be used. The “solution” is a solution in which the metal compound is dissolved, and may be a solution using an organic solvent as a solvent or an aqueous solution. Various solutions such as a solution in which metal ions are stabilized with a chelating agent can be used as the solution.
【００１０】第４発明における上記「カルシウムを含む
塩」及び上記「リンを含む塩」としては、下記の各種の
無機塩及び有機塩を使用することができる。無機塩とし
ては、硝酸塩、塩化物、臭化物、ヨウ化物、塩素酸塩、
亜塩素酸塩、亜硝酸塩、亜硫酸塩等が挙げられる。ま
た、有機塩としては、酢酸塩、蓚酸塩、乳酸塩、酒石酸
塩、クエン酸塩、安息香酸塩、イソ酪酸塩、マレイン酸
塩等を用いることができる。As the "salt containing calcium" and the "salt containing phosphorus" in the fourth invention, the following various inorganic salts and organic salts can be used. Inorganic salts include nitrates, chlorides, bromides, iodides, chlorates,
Examples include chlorite, nitrite, sulfite and the like. As the organic salt, acetate, oxalate, lactate, tartrate, citrate, benzoate, isobutyrate, maleate and the like can be used.
【００１１】更に、カルシウムイオン及びリンイオンの
うちの少なくとも一方に配位可能な上記「キレ−ト化
剤」としては、カルシウムイオン、リンイオンに配位可
能なものであればいずれも使用することができる。例え
ば、ジメチルグリオキシム、ジチゾン、オキシン、アセ
チルアセトン、グリシン、アチレンジアミン四酢酸（以
下、「ＥＤＴＡ」という。）及びニトリロ三酢酸等が挙
げられる。このキレート化剤としては、溶解度が高く、
反応性に優れるＥＤＴＡが特に好ましい。Further, as the above-mentioned "chelating agent" capable of coordinating at least one of calcium ion and phosphorus ion, any one capable of coordinating calcium ion and phosphorus ion can be used. . For example, dimethylglyoxime, dithizone, oxine, acetylacetone, glycine, acetylenediaminetetraacetic acid (hereinafter, referred to as “EDTA”), nitrilotriacetic acid and the like can be mentioned. This chelating agent has high solubility,
EDTA having excellent reactivity is particularly preferred.
【００１２】また、リン酸カルシウム化合物を生成させ
るための出発原料として、第４発明では、上記の各塩と
キレート化剤とを用いているが、第６発明に記載の出発
原料を使用することもできる。即ち、「カルシウムを含
むキレート化合物」と「リンを含むキレート化合物」、
又はカルシウムを含むキレート化合物とリンを含む塩、
又はリンを含むキレート化合物とカルシウムを含む塩、
を組み合わせた場合も、第４発明とまったく同様に均
質、透明な溶液が得られ、同様に緻密で、且つ良質なリ
ン酸カルシウム系被膜を形成することができる。尚、こ
れら第４及び第６発明においても、溶液は、有機溶剤を
溶媒とする溶液であってもよいし、水溶液であってもよ
い。In the fourth invention, each of the above salts and a chelating agent is used as a starting material for producing a calcium phosphate compound. However, the starting material described in the sixth invention can also be used. . That is, "chelate containing calcium" and "chelate containing phosphorus",
Or a salt containing calcium and a chelate compound containing phosphorus,
Or a chelate compound containing phosphorus and a salt containing calcium,
Also in the case of combining the same, a homogeneous and transparent solution can be obtained exactly as in the fourth invention, and a dense and high-quality calcium phosphate-based coating can be similarly formed. In the fourth and sixth inventions, the solution may be a solution using an organic solvent as a solvent or an aqueous solution.
【００１３】有機溶剤としては、各成分が容易に溶解す
るものであれば用いることができる。例えば、メタノー
ル、エタノール等のアルコール類、アセトン、メチルエ
チルケトン等のケトン類などが挙げられ、特にアルコー
ル類が好ましい。これら有機溶剤は表面張力が小さく、
金属、セラミックス等の基材に濡れ易い。そのため、基
材に塗布した場合に、特に、表面の凹凸が激しい基材で
あっても、均一な厚さの被膜が得られる。また、一般に
沸点が低く、基材に塗布した後、加熱、乾燥することに
より、容易に気化させて除去することができる。As the organic solvent, any solvent can be used as long as each component can be easily dissolved. Examples thereof include alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, and alcohols are particularly preferable. These organic solvents have low surface tension,
Easily wets substrates such as metals and ceramics. For this reason, when applied to a substrate, a film having a uniform thickness can be obtained, even on a substrate having particularly severe surface irregularities. Further, it generally has a low boiling point, and can be easily vaporized and removed by heating and drying after coating on a substrate.
【００１４】更に、溶媒として水を使用した場合も、有
機溶剤の場合と同様に、有機金属化合物は容易に溶解
し、キレート化も容易になされ、安定なキレート化合物
が生成する。また、出発原料として使用するキレート化
合物も有機溶剤の場合と同様に速やかに溶解する。Furthermore, when water is used as the solvent, the organic metal compound is easily dissolved and chelated easily, as in the case of the organic solvent, and a stable chelate compound is produced. Also, the chelate compound used as a starting material dissolves quickly as in the case of an organic solvent.
【００１５】第４及び第６発明において、溶液中のカル
シウムとリンとの原子比（Ｃａ／Ｐ）は、１．４０〜
１．７５とすることが好ましい。原子比をこの範囲とし
て、所定の熱処理をし、焼成をすれば水酸アパタイト
（ＨＡｐ；Ｃａ／Ｐ＝１．６７）が得られ、リンの量比
が高い場合は第三リン酸カルシウム（ＴＣＰ；Ｃａ／Ｐ
＝１．５０）が生成する。このカルシウムとリンとの原
子比は、出発原料のＣａ／Ｐ比によって容易に制御する
ことができ、ＨＡｐとＴＣＰとの混合相とすることもで
きる。In the fourth and sixth aspects, the atomic ratio (Ca / P) of calcium to phosphorus in the solution is from 1.40 to 1.40.
It is preferably 1.75. When a predetermined heat treatment and baking are performed with the atomic ratio in this range, hydroxyapatite (HAp; Ca / P = 1.67) is obtained. When the amount ratio of phosphorus is high, tricalcium phosphate (TCP; Ca) is used. / P
= 1.50). The atomic ratio of calcium to phosphorus can be easily controlled by the Ca / P ratio of the starting material, and can be a mixed phase of HAp and TCP.
【００１６】また、溶液中のカルシウムとリンとの合計
モル濃度は０．２５モル／リットル以下とすることが好
ましい。このモル濃度が０．２５モル／リットルを越え
ると、調製時には透明な溶液となるものの、濃縮した場
合に結晶が析出したり、表面が白濁したりすることがあ
る。これは熱処理工程及び焼成工程における不純物生成
の原因となるため好ましくない。このような現象は上記
のモル濃度が０．２５モル／リットル以下であれば生ず
ることはない。第４及び第６発明では、このカルシウム
とリンとの合計モル濃度はさらに低濃度であってもよ
く、例えば、０．０５モル／リットル程度でも実用上は
特に問題ない。The total molar concentration of calcium and phosphorus in the solution is preferably not more than 0.25 mol / liter. If the molar concentration exceeds 0.25 mol / liter, the solution becomes transparent at the time of preparation, but when concentrated, crystals may precipitate or the surface may become cloudy. This is not preferable because it causes generation of impurities in the heat treatment step and the firing step. Such a phenomenon does not occur if the molar concentration is 0.25 mol / liter or less. In the fourth and sixth inventions, the total molar concentration of calcium and phosphorus may be even lower, and for example, there is no practical problem even if it is about 0.05 mol / liter.
【００１７】尚、上記の溶液のｐＨを４以上に保持する
ことが好ましい。ｐＨが４以上であれば安定な溶液状態
が維持される。しかし、ｐＨが４未満になると溶液から
結晶が析出することがある。この析出する結晶はＥＤＴ
Ａであるが、ｐＨが低い場合は錯体の安定度が低下する
ため析出するものと考えられる。溶液のｐＨはアルカリ
性側へはアンモニア水、酸性側へは塩酸を加えることに
より容易に調整することができる。It is preferable that the pH of the above solution is maintained at 4 or more. If the pH is 4 or more, a stable solution state is maintained. However, if the pH is less than 4, crystals may precipitate from the solution. This precipitated crystal is EDT
As for A, it is considered that if the pH is low, the stability of the complex is reduced, and thus the complex is precipitated. The pH of the solution can be easily adjusted by adding aqueous ammonia to the alkaline side and hydrochloric acid to the acidic side.
【００１８】第１発明において２種以上の有機金属化合
物を使用する場合、及び第４及び第６発明において、各
成分を有機溶剤或いは水に添加する順序は特に限定され
ない。どのような添加順序であっても、有機金属化合物
は容易に溶解し、キレート化は容易になされ、また、キ
レート化合物は速やかに溶解する。そして、カルシウム
分等の沈殿のまったくない、均質、透明な溶液となる。
この溶液を金属、セラミックス等の基材に塗布し、熱処
理することにより、コーティング被膜又はリン酸カルシ
ウム系被膜を形成することができる。When two or more kinds of organometallic compounds are used in the first invention, and in the fourth and sixth inventions, the order of adding each component to the organic solvent or water is not particularly limited. Regardless of the order of addition, the organometallic compound is easily dissolved, chelation is easily performed, and the chelated compound is rapidly dissolved. And it becomes a homogeneous and transparent solution without any precipitation such as calcium content.
This solution is applied to a base material such as a metal or ceramic and heat-treated to form a coating film or a calcium phosphate-based film.
【００１９】基材に対する溶液の「塗布」は、流延、噴
霧、ディッピング、スピニング、刷毛塗り等、公知の方
法によって実施することができる。尚、得られる溶液を
そのまま塗布してもよいが、数倍、例えば５〜１５倍程
度に濃縮した液を塗布することもできる。このような濃
縮液を用いれば、被膜は厚くなり、また、緻密になる。
この濃縮は、１００〜１５０℃で加熱し、又は４０〜９
０℃の比較的低温において減圧下に加熱し、溶剤を徐々
に除去することにより行うことができる。このようにし
て濃縮すれば、溶液に沈殿を生ずることはなく、粘度が
上昇して、やや粘稠な透明な溶液が得られる。The "application" of the solution to the substrate can be carried out by a known method such as casting, spraying, dipping, spinning, or brushing. The obtained solution may be applied as it is, but a solution concentrated several times, for example, about 5 to 15 times may be applied. If such a concentrated solution is used, the film becomes thicker and denser.
This concentration is heated at 100-150 ° C. or 40-9
It can be carried out by heating under reduced pressure at a relatively low temperature of 0 ° C. and gradually removing the solvent. When the solution is concentrated in this manner, the solution does not precipitate, the viscosity increases, and a slightly viscous transparent solution is obtained.
【００２０】本発明は、溶液を基材に塗布した後、「オ
ゾンの存在下」、「５０〜５００℃」で「熱処理」する
ことを最も大きな特徴とする。この熱処理の温度が５０
℃未満では残留有機物が十分に分解、除去されず、５０
０℃を越える場合も、残留有機物が十分に除去されな
い。この熱処理の温度は更に好ましくは１００〜３５０
℃、特に１５０〜３５０℃の範囲が好ましく、熱処理の
時間は特に限定されないが、例えば３０秒〜３０分、特
に３０秒〜１５分、とすることが好ましい。また、この
オゾンの存在下でのオゾン濃度は１０００ｐｐｍ以上、
特に５０００ｐｐｍ以上が好ましい。The most characteristic feature of the present invention is that after the solution is applied to the substrate, it is "heat treated" at "50-500 ° C." in the presence of ozone. The temperature of this heat treatment is 50
If the temperature is lower than 50 ° C., residual organic matter is not sufficiently decomposed and removed, and
Even when the temperature exceeds 0 ° C., residual organic substances are not sufficiently removed. The temperature of this heat treatment is more preferably 100 to 350.
C., preferably 150-350 ° C., and the heat treatment time is not particularly limited, but is preferably, for example, 30 seconds to 30 minutes, particularly 30 seconds to 15 minutes. The ozone concentration in the presence of this ozone is 1000 ppm or more,
Especially 5000 ppm or more is preferable.
【００２１】上記の熱処理によって所定のコーティング
被膜又はリン酸カルシウム系被膜を形成することができ
る。しかし、より緻密な被膜を得るためには、熱処理の
後、第２及び第７発明のように、「不活性雰囲気中」、
「６００〜９００℃」で「焼成」することが好ましい。
この焼成の温度はコーティング被膜の性状により決定さ
れるが、前記リン酸カルシウム系被膜の場合には７００
〜９００℃の範囲が好ましく、焼成の時間は特に限定さ
れないが、２〜３０分、特に１０〜２０分が好ましい。
この焼成温度及び焼成時間とすれば、緻密で良質な被膜
を得ることができる。尚、不活性雰囲気とは、窒素、ヘ
リウム、ネオン、アルゴン、クリプトン、キセノン、ラ
ドン等、不活性ガスからなる雰囲気をいうが、入手のし
易さ、コストなどの点から窒素又はアルゴンが好まし
い。但し、チタンを基材とする場合は、窒素雰囲気中で
は窒化チタンが生成するため、アルゴン雰囲気中で焼成
することがより好ましい。A predetermined coating film or a calcium phosphate film can be formed by the above heat treatment. However, in order to obtain a denser film, after heat treatment, as in the second and seventh inventions, "in an inert atmosphere"
It is preferable to perform "firing" at "600 to 900C".
The firing temperature is determined by the properties of the coating film.
The temperature is preferably in the range of -900 ° C, and the firing time is not particularly limited, but is preferably 2-30 minutes, particularly preferably 10-20 minutes.
With this firing temperature and firing time, a dense and good quality coating can be obtained. The inert atmosphere refers to an atmosphere composed of an inert gas such as nitrogen, helium, neon, argon, krypton, xenon, and radon, and is preferably nitrogen or argon in terms of availability, cost, and the like. However, when titanium is used as the base material, titanium nitride is generated in a nitrogen atmosphere, and thus it is more preferable to perform firing in an argon atmosphere.
【００２２】第１、第４及び第６発明において、上記
「基材」としては、金属、セラミックス等、熱処理或い
は焼成時の加熱に耐えられるものであれば使用すること
ができる。本発明では、特に、第３及び第８発明のよう
に、易酸化性基材であっても、これを酸化劣化させるこ
となく被膜を形成することができる。この易酸化性基材
であっても、何ら問題なく適用することができるとの利
点は、特に、リン酸カルシウム系被膜の場合において有
用である。In the first, fourth and sixth aspects of the present invention, as the above-mentioned "substrate", any metal, ceramic or the like can be used as long as it can withstand heat treatment or heating during firing. In the present invention, in particular, as in the third and eighth inventions, it is possible to form a film without oxidatively deteriorating even an easily oxidizable substrate. The advantage that even this easily oxidizable substrate can be applied without any problem is particularly useful in the case of a calcium phosphate coating.
【００２３】アルミナ、ジルコニア等のセラミックスを
基材とする場合、ＥＤＴＡ等のキレート化剤を用いて
も、基材の劣化や着色等の問題のないリン酸カルシウム
系被膜が得られる。しかし、チタン、チタン合金、ステ
ンレス鋼等の酸化劣化し易い基材を用いた場合において
は、この劣化を抑えるために熱処理温度を低くすれば、
残留有機物が十分に除去されず、被膜が着色し、本来の
高純度のリン酸カルシウム系被膜が得られないとの問題
を生ずることは前記の通りである。本発明では、この熱
処理をオゾンの存在下に行うことにより、被膜中の残留
有機物を低温でも十分に除去することができ、且つ基材
の酸化劣化を生ずることもなく、緻密、且つ良質なリン
酸カルシウム系被膜を形成することができる。When a ceramic such as alumina or zirconia is used as a base material, a calcium phosphate-based coating free from problems such as deterioration or coloring of the base material can be obtained even when a chelating agent such as EDTA is used. However, in the case of using a substrate which is easily oxidized and deteriorated, such as titanium, a titanium alloy, and stainless steel, if the heat treatment temperature is lowered to suppress the deterioration,
As described above, the residual organic matter is not sufficiently removed, the coating is colored, and a problem that an original high-purity calcium phosphate coating cannot be obtained. In the present invention, by performing this heat treatment in the presence of ozone, the residual organic matter in the coating film can be sufficiently removed even at a low temperature, and dense and high-quality calcium phosphate can be obtained without causing oxidative deterioration of the substrate. A system coating can be formed.
【００２４】従って、アルミナ、ジルコニア、炭化珪
素、窒化珪素等のセラミックスばかりでなく、第８発明
のように、基材が、チタン、チタン合金、ステンレス鋼
等の鉄、銅などの易酸化性基材であっても、何ら問題な
くリン酸カルシウム系被膜を形成することができる。特
に、チタン、チタン合金等からなる、生体に対する毒性
がなく、耐腐食性に優れ、且つ強度の大きい基材に、生
体活性に優れるリン酸カルシウム系被膜を形成すること
により、生体活性に優れ、強度の大きい生体硬組織代替
部材を得ることができる。Therefore, in addition to ceramics such as alumina, zirconia, silicon carbide and silicon nitride, the base material is made of an easily oxidizable base such as iron, copper such as titanium, titanium alloy, stainless steel, etc. as in the eighth invention. Even with a material, a calcium phosphate-based coating can be formed without any problem. In particular, by forming a calcium phosphate-based coating having excellent bioactivity on a substrate having excellent corrosion resistance and high strength, which is not toxic to living organisms made of titanium, titanium alloy, etc., it is excellent in bioactivity and strength. A large living hard tissue replacement member can be obtained.
【００２５】厚い被膜を得るためには、溶液の塗布及び
熱処理の操作を数回繰り返し、その後、焼成を実施する
ことにより、所定厚さの被膜とすることができる。In order to obtain a thick film, the operations of applying the solution and heat-treating are repeated several times, and then firing is performed to obtain a film having a predetermined thickness.
【００２６】[0026]
【作用】酸素存在下での熱処理による燃焼除去では効果
が不十分であることから、オゾンと有機膜の単なる熱的
効果ではなく、化学的、熱的な反応によるものと推察さ
れる。[Action] Since the effect of heat removal by heat treatment in the presence of oxygen is insufficient, it is presumed that the effect is not a mere thermal effect of ozone and the organic film but a chemical or thermal reaction.
【００２７】[0027]
【発明の実施の形態】以下、実施例によって本発明を詳
しく説明する。 実施例１ 蒸留水１リットルに、硝酸カルシウムを３．１２５×１
０-2モル溶解した。この水溶液にＥＤＴＡを等モル量加
え、３０分攪拌した。この反応液にリン酸アンモニウム
を１．８７５×１０-2モル加え、透明な溶液となるまで
攪拌した。その後、１２０℃にまで昇温させて水を徐々
に除去し、１０倍に濃縮した後、ｐＨを４．４に調整し
た。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to examples. Example 1 3.125 × 1 of calcium nitrate in 1 liter of distilled water
0 -2 mol was dissolved. EDTA was added to this aqueous solution in an equimolar amount and stirred for 30 minutes. 1.875 × 10 -2 mol of ammonium phosphate was added to the reaction solution, and the mixture was stirred until a clear solution was obtained. Thereafter, the temperature was raised to 120 ° C. to gradually remove water, and after concentrating 10-fold, the pH was adjusted to 4.4.
【００２８】この濃縮液をチタンの平板からなる基材に
ディッピングにより塗布した。次いで、この基材を２０
０℃で加熱しながらオゾンを１万ｐｐｍの濃度下で流通
させ、１０分間熱処理した。その後、オゾンの流通を停
止し、恒温槽内を大気雰囲気とし、５℃／分の速度で５
５０℃まで昇温させ、再び１０分間熱処理した。形成さ
れた被膜は白色を呈していた。この塗布と熱処理とを繰
り返し所定の厚さの被膜とした後、アルゴン雰囲気下、
８００℃で１０分間焼成し、被膜の緻密度を高めた。焼
成後の被膜は厚さが約１μｍで透明な白色を呈してい
た。Ｘ線回折法によって構成結晶相の同定を行ったとこ
ろ、この被膜はＨＡｐ単相であることが確認された。This concentrated solution was applied to a titanium substrate by dipping. Then, the base material was
Ozone was flowed under a concentration of 10,000 ppm while heating at 0 ° C., and heat treatment was performed for 10 minutes. After that, the flow of ozone was stopped, the inside of the thermostat was set to the atmospheric air, and the temperature was reduced to 5 ° C./min.
The temperature was raised to 50 ° C., and heat treatment was performed again for 10 minutes. The formed film was white. After repeating this coating and heat treatment to form a film of a predetermined thickness, under an argon atmosphere,
It was baked at 800 ° C. for 10 minutes to increase the denseness of the film. The fired film had a thickness of about 1 μm and was transparent white. When the constituent crystal phases were identified by the X-ray diffraction method, it was confirmed that this coating was a single HAp phase.
【００２９】実施例２ 硝酸カルシウムを３．００×１０-2モルとし、リン酸ア
ンモニウムを２．００×１０-2モルとした他は、実施例
１と同様にして被膜を形成した。焼成後の被膜は厚さが
約１μｍで透明な白色を呈していた。また、Ｘ線回折法
によって構成結晶相の同定を行ったところ、この被膜は
ＴＣＰ単相であることが確認された。Example 2 A coating film was formed in the same manner as in Example 1 except that calcium nitrate was 3.00 × 10 -2 mol and ammonium phosphate was 2.00 × 10 -2 mol. The fired film had a thickness of about 1 μm and was transparent white. When the constituent crystal phases were identified by the X-ray diffraction method, it was confirmed that this film was a TCP single phase.
【００３０】実施例３ リン酸アンモニウム２．００×１０-2モルに代えて、硝
酸ジルコニウム３．００×１０-2モルとした他は、実施
例２と同様にして被膜を形成した。焼成後の被膜は厚さ
が約１μｍで透明な白色を呈していた。また、Ｘ線回折
法によって構成結晶相の同定を行ったところ、この被膜
はジルコン酸カルシウム単相であることが確認された。 実施例４ オゾンの存在下の熱処理温度を１００℃とした以外は実
施例１と同様にして被膜を形成した。焼成後の被膜は厚
さが約１μｍで透明な白色を呈していた。また、Ｘ線回
折法によって構成結晶相の同定を行ったところ、この被
膜はＨＡｐ単相であることが確認された。Example 3 A coating was formed in the same manner as in Example 2 except that zirconium nitrate was replaced with 3.00 × 10 -2 mol of 2.00 × 10 -2 mol of ammonium phosphate. The fired film had a thickness of about 1 μm and was transparent white. When the constituent crystal phases were identified by the X-ray diffraction method, it was confirmed that this coating was a single phase of calcium zirconate. Example 4 A coating was formed in the same manner as in Example 1 except that the heat treatment temperature in the presence of ozone was changed to 100 ° C. The fired film had a thickness of about 1 μm and was transparent white. When the constituent crystal phases were identified by the X-ray diffraction method, it was confirmed that this film was a single HAp phase.
【００３１】実施例５ オゾンの存在下の熱処理温度を４００℃とした以外は実
施例１と同様にして被膜を形成した。焼成後の被膜は厚
さが約１μｍで透明な白色を呈していた。また、Ｘ線回
折法によって構成結晶相の同定を行ったところ、この被
膜はＨＡｐ単相であることが確認された。 実施例６ 基材をＴｉ６Ａ１４Ｖとした以外は実施例１と同様にし
て被膜を形成した。焼成後の被膜は厚さが約１μｍで透
明な白色を呈していた。また、Ｘ線回折法によって構成
結晶相の同定を行ったところ、この被膜はＨＡｐ単相で
あることが確認された。Example 5 A coating was formed in the same manner as in Example 1 except that the heat treatment temperature in the presence of ozone was set at 400 ° C. The fired film had a thickness of about 1 μm and was transparent white. When the constituent crystal phases were identified by the X-ray diffraction method, it was confirmed that this film was a single HAp phase. Example 6 A coating was formed in the same manner as in Example 1 except that the substrate was changed to Ti6A14V. The fired film had a thickness of about 1 μm and was transparent white. When the constituent crystal phases were identified by the X-ray diffraction method, it was confirmed that this film was a single HAp phase.
【００３２】実施例７ 基材をステンレス鋼とした以外は実施例１と同様にして
被膜を形成した。焼成後の被膜は厚さが約１μｍで透明
な白色を呈していた。また、Ｘ線回折法によって構成結
晶相の同定を行ったところ、この被膜はＨＡｐ単相であ
ることが確認された。 実施例８ チタンの平板からなる基材を、透明な石英ガラスの平板
からなる基材とした他は、実施例１と同様にして被膜を
形成した。焼成後の被膜は厚さが約１μｍで透明な白色
を呈していた。また、Ｘ線回折法によって構成結晶相の
同定を行ったところ、この被膜はＨＡｐ単相であること
が確認された。尚、この実施例８では、基材が透明であ
るため、チタンの平板からなる基材の影響が考えられる
実施例１に比べて、被膜が残留有機物による着色がない
ことを、より確実に確認することができた。Example 7 A coating was formed in the same manner as in Example 1 except that the substrate was stainless steel. The fired film had a thickness of about 1 μm and was transparent white. When the constituent crystal phases were identified by the X-ray diffraction method, it was confirmed that this film was a single HAp phase. Example 8 A coating was formed in the same manner as in Example 1 except that the base material made of a flat plate of titanium was used as the base material made of a flat plate of titanium. The fired film had a thickness of about 1 μm and was transparent white. When the constituent crystal phases were identified by the X-ray diffraction method, it was confirmed that this film was a single HAp phase. In this Example 8, since the substrate was transparent, it was more reliably confirmed that the coating was not colored by residual organic substances as compared with Example 1 in which the influence of the substrate composed of a flat plate of titanium was considered. We were able to.
【００３３】比較例１ オゾンの存在下の熱処理温度を６００℃とした以外は実
施例１と同様にして被膜を形成した。焼成後の被膜は厚
さが約１μｍであった。また、この比較例１では、被膜
中の残留有機物が十分に除去されないため、被膜は褐色
を呈していた。 比較例２ オゾンの存在下での熱処理を行わなかった以外は実施例
１と同様にして被膜を形成した。焼成後の被膜は厚さが
約１μｍであり、褐色を呈していた。その後、基材を２
００℃で加熱しながら、オゾンを１万ｐｐｍの濃度で流
通させ、３０分間熱処理したが、被膜は褐色のままであ
った。Comparative Example 1 A coating was formed in the same manner as in Example 1 except that the heat treatment temperature in the presence of ozone was changed to 600 ° C. The fired film had a thickness of about 1 μm. Further, in Comparative Example 1, the residual organic matter in the coating was not sufficiently removed, so that the coating exhibited a brown color. Comparative Example 2 A coating was formed in the same manner as in Example 1 except that the heat treatment in the presence of ozone was not performed. The fired film had a thickness of about 1 μm and exhibited a brown color. Then, 2
While heating at 00 ° C., ozone was passed at a concentration of 10,000 ppm, and heat treatment was performed for 30 minutes, but the film remained brown.
【００３４】比較例３ 基材を透明な石英ガラスの平板からなるものとし、オゾ
ンの存在下の熱処理温度を６００℃とした以外は実施例
２と同様にして被膜を形成した。焼成後の被膜は厚さが
約１μｍであった。また、この比較例３では、被膜中の
残留有機物が十分に除去されないため、被膜は褐色を呈
していた。 比較例４ オゾンの存在下での熱処理を行わず、また、恒温槽中に
純酸素を８ミリリットル／分の流速で流通させ、５℃／
分の速度で５５０℃まで昇温させ、１０分間熱処理した
他は実施例１と同様にして被膜を形成した。この被膜は
褐色を呈していた。また、焼成後の被膜は厚さが約１μ
ｍであり、焼成前の被膜と同様に褐色を呈していた。Comparative Example 3 A coating was formed in the same manner as in Example 2 except that the substrate was made of a transparent quartz glass flat plate, and the heat treatment temperature in the presence of ozone was 600 ° C. The fired film had a thickness of about 1 μm. In Comparative Example 3, the residual organic matter in the coating was not sufficiently removed, and the coating was brown. Comparative Example 4 No heat treatment was performed in the presence of ozone, and pure oxygen was passed through a thermostat at a flow rate of 8 ml / min.
A film was formed in the same manner as in Example 1 except that the temperature was raised to 550 ° C. at a speed of 10 minutes and heat treatment was performed for 10 minutes. This coating had a brown color. The thickness of the fired film is about 1μ.
m, which was brown in the same manner as the film before firing.
【００３５】比較例５ オゾンの存在下での熱処理を行わず、また、恒温槽中に
水にバブリングさせた空気を８ミリリットル／分の流速
で流通させ、５℃／分の速度で５５０℃まで昇温させ、
１０分間熱処理した他は実施例１と同様にして被膜を形
成した。この被膜は褐色を呈していた。また、焼成後の
被膜は厚さが約１μｍであり、焼成前の被膜と同様に褐
色を呈していた。Comparative Example 5 No heat treatment was performed in the presence of ozone, and air bubbled in water was passed through a thermostat at a flow rate of 8 ml / min to 550 ° C. at a rate of 5 ° C./min. Raise the temperature,
A film was formed in the same manner as in Example 1 except that the heat treatment was performed for 10 minutes. This coating had a brown color. Further, the film after firing had a thickness of about 1 μm, and exhibited a brown color like the film before firing.
【００３６】[0036]
【発明の効果】第１発明のコーティング被膜の製造方法
によれば、チタン、チタン合金等の酸化し易い基材であ
っても、その酸化が抑えられ、且つ電気的、磁気的及び
光学的特性等、被膜が本来有する特性を低下させる残留
有機物等が十分に除去されたコーティング被膜を容易に
製造することができる。また、被膜の美観も何ら損なわ
れることはない。これらは、電気的、磁気的、光学的特
性を要求される用途等において有用である。更に、第４
及び第６発明のリン酸カルシウム系被膜の製造方法によ
れば、特に、均質で緻密で白色の、且つ生体活性に優れ
る被膜を容易に製造することができる。According to the method for producing a coating film of the first invention, even if the substrate is easily oxidized such as titanium or a titanium alloy, the oxidation is suppressed and the electrical, magnetic and optical properties are improved. For example, it is possible to easily produce a coating film from which residual organic substances and the like, which deteriorate the inherent properties of the film, are sufficiently removed. Also, the appearance of the coating is not impaired at all. These are useful in applications requiring electrical, magnetic, and optical characteristics. Furthermore, the fourth
According to the method for producing a calcium phosphate-based coating of the sixth invention, it is particularly easy to produce a homogeneous, dense, white coating excellent in bioactivity.
Claims (8)
布し、コ−ティング被膜を製造する方法において、オゾ
ンの存在下、５０〜５００℃で熱処理する工程を備える
ことを特徴とするコ−ティング被膜の製造方法。A method for producing a coating film by applying a solution in which a metal compound is dissolved to a substrate, comprising a step of performing a heat treatment at 50 to 500 ° C. in the presence of ozone. -A method for producing a coating.
気中、６００〜９００℃で焼成する工程を備える請求項
１記載のコ−ティング被膜の製造方法。2. The method for producing a coating film according to claim 1, further comprising a step of firing at 600 to 900 ° C. in an inert atmosphere after the step of performing the heat treatment.
２記載のコ−ティング被膜の製造方法。3. The method according to claim 1, wherein the substrate is easily oxidizable.
と、カルシウムイオン及びリンイオンのうちの少なくと
も一方に配位可能なキレ−ト化剤とが溶解された溶液を
基材に塗布し、リン酸カルシウム系被膜を製造する方法
において、オゾンの存在下、５０〜５００℃で熱処理す
る工程を備えることを特徴とするリン酸カルシウム系被
膜の製造方法。4. A solution in which a salt containing calcium, a salt containing phosphorus, and a chelating agent capable of coordinating at least one of calcium ions and phosphorus ions are applied to a base material, and calcium phosphate is applied to the substrate. A method for producing a calcium phosphate-based coating, comprising a step of performing a heat treatment at 50 to 500 ° C. in the presence of ozone.
酢酸である請求項４記載のリン酸カルシウム系被膜の製
造方法。5. The method according to claim 4, wherein the chelating agent is ethylenediaminetetraacetic acid.
を含むキレート化合物、又はカルシウムを含むキレート
化合物とリンを含む塩、又はリンを含むキレート化合物
とカルシウムを含む塩、が溶解された溶液を基材に塗布
し、リン酸カルシウム系被膜を製造する方法において、
オゾンの存在下、５０〜５００℃で熱処理する工程を備
えることを特徴とするリン酸カルシウム系被膜の製造方
法。6. A solution in which a chelate compound containing calcium and a chelate compound containing phosphorus, a chelate compound containing calcium and a salt containing phosphorus, or a solution containing a chelate compound containing phosphorus and a salt containing calcium are used as a base material. In the method of applying and manufacturing a calcium phosphate-based coating,
A method for producing a calcium phosphate-based coating, comprising a step of performing a heat treatment at 50 to 500 ° C. in the presence of ozone.
気中、６００〜９００℃で焼成する工程を備える請求項
４乃至６のいずれか１項に記載のリン酸カルシウム系被
膜の製造方法。7. The method for producing a calcium phosphate-based coating according to claim 4, further comprising a step of firing at 600 to 900 ° C. in an inert atmosphere after the step of performing the heat treatment.
７のいずれか１項に記載のリン酸カルシウム系被膜の製
造方法。8. The method according to claim 4, wherein the substrate is easily oxidizable.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19940297A JP3846817B2 (en) | 1997-07-08 | 1997-07-08 | Method for producing calcium phosphate coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19940297A JP3846817B2 (en) | 1997-07-08 | 1997-07-08 | Method for producing calcium phosphate coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1129311A true JPH1129311A (en) | 1999-02-02 |
| JP3846817B2 JP3846817B2 (en) | 2006-11-15 |
Family
ID=16407203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19940297A Expired - Fee Related JP3846817B2 (en) | 1997-07-08 | 1997-07-08 | Method for producing calcium phosphate coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3846817B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010202475A (en) * | 2009-03-05 | 2010-09-16 | Tftech:Kk | Treatment method of covering structure have three dimensional void shape with calcium phosphate compound and method of producing the structure |
| JP2011504454A (en) * | 2007-11-26 | 2011-02-10 | プロミミック・アクチボラゲット | Production of nano-sized calcium phosphate particles in powder or coating form using bifunctional precursors |
| JP2015025209A (en) * | 2014-10-06 | 2015-02-05 | 株式会社イーエスティージャパン | Metal corrosion inhibition method |
-
1997
- 1997-07-08 JP JP19940297A patent/JP3846817B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011504454A (en) * | 2007-11-26 | 2011-02-10 | プロミミック・アクチボラゲット | Production of nano-sized calcium phosphate particles in powder or coating form using bifunctional precursors |
| JP2010202475A (en) * | 2009-03-05 | 2010-09-16 | Tftech:Kk | Treatment method of covering structure have three dimensional void shape with calcium phosphate compound and method of producing the structure |
| JP2015025209A (en) * | 2014-10-06 | 2015-02-05 | 株式会社イーエスティージャパン | Metal corrosion inhibition method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3846817B2 (en) | 2006-11-15 |
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