JPH09263958A - Pre-treatment of metallic base material surface - Google Patents
Pre-treatment of metallic base material surfaceInfo
- Publication number
- JPH09263958A JPH09263958A JP9595696A JP9595696A JPH09263958A JP H09263958 A JPH09263958 A JP H09263958A JP 9595696 A JP9595696 A JP 9595696A JP 9595696 A JP9595696 A JP 9595696A JP H09263958 A JPH09263958 A JP H09263958A
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- JP
- Japan
- Prior art keywords
- base material
- metallic base
- solution
- pretreatment
- treatment
- 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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- Chemical Treatment Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、液状原料を用い
て、金属基材の表面に被膜を形成する場合に、均質且つ
その表面が平滑であって、金属基材表面との密着性に優
れる被膜を得るための、金属基材表面の前処理方法に関
する。本発明の前処理方法は、金属基材表面に溶液、ス
ラリー、ゾルゲル法によって得られるゾル等を塗布し、
熱処理、焼成等することにより被膜を形成する場合など
に利用することができる。TECHNICAL FIELD The present invention relates to a method of forming a coating film on the surface of a metal base material using a liquid material, which is homogeneous and has a smooth surface and is excellent in adhesion to the surface of the metal base material. The present invention relates to a method for pretreating a surface of a metal substrate to obtain a coating. The pretreatment method of the present invention, a solution, a slurry, a sol obtained by a sol-gel method is applied to the surface of a metal substrate,
It can be used when forming a film by heat treatment, baking, or the like.
【０００２】[0002]
【従来の技術】セラミックスは耐食性、耐薬品性等に優
れており、種々の用途に用いられている。しかし、上記
の優れた特性を有する反面、靱性に欠け、割れ易いとい
う欠点がある。そこで、例えば、生体内硬組織代替部材
として、金属等の靱性の大きな、割れ難い材料が使用さ
れることも多いが、金属は生体不活性である。そのた
め、その表面に生体活性な素材をコーティングして改質
することが試みられている。このコーティングの方法と
しては、溶液、ゾル等を塗布した後、熱処理、焼成等を
行って被膜を形成する方法が一般的である。2. Description of the Related Art Ceramics are excellent in corrosion resistance, chemical resistance, etc. and are used for various purposes. However, although it has the above-mentioned excellent properties, it has the drawbacks of lacking toughness and being easily cracked. Therefore, for example, as a hard tissue substitute member in vivo, a material such as a metal having high toughness and which is difficult to break is often used, but the metal is inactive in the body. Therefore, it has been attempted to coat the surface with a bioactive material for modification. As a method of this coating, a method of applying a solution, sol or the like and then performing heat treatment, firing or the like to form a film is generally used.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、溶液、
ゾル等の塗布において、特にその溶液等が水系である場
合は、金属に対する濡れに劣り、はじかれてしまうた
め、均一なコーティングができないという問題がある。
そこで、この濡れを向上させるため、溶液、ゾル等の中
に界面活性剤などを添加する方法、或いは金属基材を予
め熱処理して、その表面に酸化被膜を形成する方法等が
試みられている。しかし、界面活性剤などを添加した場
合は、溶液等の変性又は残炭の問題を生ずることがあ
る。また、金属基材を熱処理した場合は、酸化による着
色、光沢の減少、及び表面の荒れ、劣化等、種々の問題
がある。However, the solution,
When applying a sol or the like, particularly when the solution or the like is water-based, there is a problem in that it is inferior in wettability with a metal and is repelled, and uniform coating cannot be performed.
Therefore, in order to improve this wetting, a method of adding a surfactant or the like to a solution, a sol or the like, or a method of preliminarily heat treating a metal base material to form an oxide film on the surface thereof has been attempted. . However, when a surfactant or the like is added, the problem of denaturation of the solution or residual carbon may occur. Further, when the metal base material is heat-treated, there are various problems such as coloring due to oxidation, reduction of gloss, and surface roughness and deterioration.
【０００４】本発明は、上記問題点を解決するものであ
り、チタン等からなる金属基材の表面に被膜を形成する
場合に、予め、その表面を、アルカリ性化合物等を含む
水溶液、又は熱水若しくは水蒸気と接触させて処理する
方法を提供するものである。この前処理によって、均質
且つ平滑で、金属基材との密着性に優れた被膜を形成す
ることができる。The present invention is intended to solve the above-mentioned problems, and when a coating film is formed on the surface of a metal substrate made of titanium or the like, the surface thereof is previously treated with an aqueous solution containing an alkaline compound or hot water. Alternatively, it provides a method of treating by contacting with steam. By this pretreatment, it is possible to form a film which is homogeneous and smooth and has excellent adhesion to the metal substrate.
【０００５】[0005]
【課題を解決するための手段】第１発明の金属基材表面
の前処理方法は、液状原料を用いて、金属基材の表面に
被膜を形成する場合に、該表面を、予め、(1) アルカリ
性化合物及び過酸化水素のうちのいずれか一方を含む水
溶液、又は(2) 熱水若しくは水蒸気と接触させることを
特徴とする。A method for pretreating a surface of a metal substrate according to a first aspect of the present invention is such that when a film is formed on the surface of the metal substrate using a liquid raw material, the surface is preliminarily treated in accordance with (1 ) A contact with an aqueous solution containing one of an alkaline compound and hydrogen peroxide, or (2) hot water or steam.
【０００６】上記「液状原料」としては、溶媒に、上記
「被膜」を形成するための化合物等を溶解、分散、懸濁
等させたものを使用することができる。その性状は、溶
液、スラリー、ゾル、エマルジョン等いずれであっても
よい。上記の溶媒としては、水、又はアルコール、ケト
ン等の有機溶媒など、特に限定されず、いずれも使用す
ることができる。また、溶媒が水である場合、通常、金
属表面への濡れに劣り、塗布が容易ではないが、本発明
では、第２発明のように、「液状原料が水系」であって
も、何ら問題なく塗布することができる。As the above-mentioned "liquid raw material", it is possible to use a solvent in which a compound for forming the above "coating" is dissolved, dispersed or suspended. The property may be any of solution, slurry, sol, emulsion and the like. The above-mentioned solvent is not particularly limited, such as water or an organic solvent such as alcohol or ketone, and any of them can be used. Further, when the solvent is water, it is usually inferior in wettability to the metal surface and coating is not easy. However, in the present invention, even if the "liquid raw material is aqueous" as in the second invention, there is no problem. Can be applied without.
【０００７】尚、上記の「水系」とは、主たる溶媒又は
分散媒として水を使用している系を意味する。例えば、
水のみ、或いは水と水溶性の溶媒（メタノール、エタノ
ール、アセトン等）との混合溶媒を用いた溶液、スラリ
ーなどが挙げられる。水系では、主として有機溶媒を用
いる系に比べて、取り扱い易く、引火性、毒性等がな
く、且つ蒸気を吸い込んで中毒を起こすというようなこ
ともない。The above "aqueous system" means a system using water as a main solvent or dispersion medium. For example,
Examples thereof include a solution and a slurry using only water or a mixed solvent of water and a water-soluble solvent (methanol, ethanol, acetone, etc.). Compared to a system mainly using an organic solvent, an aqueous system is easy to handle, has no flammability and toxicity, and does not cause intoxication by inhaling vapor.
【０００８】本発明において、金属基材の表面と接触し
て、その表面を処理する処理液としては、水に「アルカ
リ性化合物」又は「過酸化水素」を溶解した水溶液を使
用することができる。また、「熱水若しくは水蒸気」を
用いることもできる。この熱水若しくは水蒸気は、特別
の処理をしていない上水をそのまま用いて加熱し、気化
させて生成させてもよいし、蒸留水等を使用してもよ
い。尚、本発明において、熱水の温度は５０℃以上、特
に６０℃以上とすることが好ましく、さらには７０℃以
上とすることが、より好ましい。In the present invention, as the treatment liquid for contacting the surface of the metal base material and treating the surface, an aqueous solution in which "alkaline compound" or "hydrogen peroxide" is dissolved in water can be used. Also, "hot water or steam" can be used. This hot water or steam may be produced by heating and vaporizing the tap water that has not been subjected to any special treatment as it is, or using distilled water or the like. In the present invention, the temperature of hot water is preferably 50 ° C. or higher, particularly 60 ° C. or higher, and more preferably 70 ° C. or higher.
【０００９】上記のアルカリ性化合物としては、水酸化
ナトリウム、水酸化カリウム、水酸化カルシウム及び水
酸化マグネシウム等の、アルカリ金属或いはアルカリ土
類金属の水酸化物などを使用することができる。この
他、過酸化水素のナトリウム塩、カリウム塩等の、過酸
化水素のアルカリ金属塩などを用いることもできる。こ
れらの中では、第３発明のように、特に表面処理効果の
大きい「ナトリウム、カリウム及びマグネシウム」の水
酸化物及び過酸化水素塩などの化合物がより好ましい。As the above alkaline compound, hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide can be used. In addition, alkali metal salts of hydrogen peroxide such as sodium salt and potassium salt of hydrogen peroxide can also be used. Among these, as in the third invention, compounds such as "sodium, potassium and magnesium" hydroxides and hydrogen peroxides, which have particularly large surface treatment effects, are more preferable.
【００１０】上記「水溶液」中の、アルカリ性化合物及
び過酸化水素の濃度は、特に限定はされない。通常、そ
の濃度は１〜２０モル／リットル、特に３〜１７モル／
リットル、さらには７〜１４モル／リットル程度とする
ことができる。この水溶液の濃度が１モル／リットル未
満では、十分な処理効果を得るためには長時間を要し、
実用的ではない。また、２０モル／リットルを越えて高
濃度としても、それ以上あまり時間を短縮することはで
きない。また、特にアルカリ性化合物では、過度に高濃
度とした場合は、前処理後、金属基材表面から除去する
のに面倒な手間を要する。The concentrations of the alkaline compound and hydrogen peroxide in the above "aqueous solution" are not particularly limited. Usually, the concentration is 1 to 20 mol / liter, especially 3 to 17 mol / liter.
It may be liter, more preferably about 7 to 14 mol / liter. If the concentration of this aqueous solution is less than 1 mol / liter, it takes a long time to obtain a sufficient treatment effect,
Not practical. Further, even if the concentration is higher than 20 mol / liter, the time cannot be further shortened. Further, particularly in the case of an alkaline compound, if the concentration is excessively high, it is troublesome to remove it from the surface of the metal substrate after the pretreatment.
【００１１】金属基材の表面と水溶液又は熱水とは、通
常、水溶液又は熱水中へ金属基材を浸漬することにより
「接触」させる。接触の方法としては、この浸漬方法
が、装置が簡易であり、且つ操作が容易であって好まし
い。しかも、金属基材の処理を要する全表面を確実に、
且つ均等に処理することができる。尚、水蒸気の場合
は、水蒸気を充満させた密閉容器中に金属基材を静置し
てもよいし、基材の表面に連続的に水蒸気を吹き付ける
方法等であってもよい。The surface of the metal substrate and the aqueous solution or hot water are usually brought into "contact" by immersing the metal substrate in the aqueous solution or hot water. As the contact method, this dipping method is preferable because the apparatus is simple and the operation is easy. Moreover, it ensures that all surfaces that require treatment of the metal substrate are
And it can be processed evenly. In the case of water vapor, the metal base material may be left standing in a closed container filled with water vapor, or a method of continuously spraying water vapor on the surface of the base material may be used.
【００１２】また、前処理の温度及び時間は、処理効果
を確認しながら適宜設定すればよい。この処理温度、処
理時間は、水溶液と熱水若しくは水蒸気とでは異なる
し、水溶液の場合、その濃度によっても変える必要があ
る。この接触は、第４発明のように、水溶液又は熱水を
「沸騰」させて実施することが好ましく、これによって
処理時間を大幅に短縮することができる。例えば、アル
カリ性化合物又は過酸化水素の濃度が１０モル／リット
ルの水溶液の場合、３時間の処理で十分な効果が得られ
る。しかし、熱水の場合は、７０℃であっても５時間程
度と比較的長時間を要するため、この点を考慮して使用
する必要がある。Further, the temperature and time of the pretreatment may be set appropriately while checking the treatment effect. The treatment temperature and the treatment time are different between the aqueous solution and hot water or steam, and in the case of an aqueous solution, it needs to be changed depending on the concentration. This contact is preferably carried out by "boiling" an aqueous solution or hot water as in the fourth aspect of the invention, which can significantly reduce the processing time. For example, in the case of an aqueous solution having an alkaline compound or hydrogen peroxide concentration of 10 mol / liter, a sufficient effect can be obtained by treating for 3 hours. However, in the case of hot water, even at 70 ° C., it takes a relatively long time of about 5 hours, so it is necessary to consider this point before using.
【００１３】本発明の金属基材表面の前処理方法は、金
属基材或いは被膜の種類、得られる被覆品の用途等、何
ら特定はされない。そして、水溶液又は熱水若しくは水
蒸気によって前処理を実施するため、被膜を形成するた
めの液状原料も水系である場合に、特に大きな効果が奏
され、均質、且つ金属基材との密着性に優れた被膜を形
成することができる。そのような液状原料としては、例
えば、第５発明のように、「少なくともリンとカルシウ
ムとを含んでいるもの」などが挙げられる。The method of pretreatment of the surface of the metal substrate of the present invention is not specified at all in terms of the type of the metal substrate or the coating, the use of the resulting coated article and the like. Since the pretreatment is carried out with an aqueous solution or hot water or steam, a particularly large effect is exhibited when the liquid raw material for forming the coating is also an aqueous system, and it is homogeneous and has excellent adhesion to a metal substrate. A coated film can be formed. Examples of such a liquid raw material include "a material containing at least phosphorus and calcium" as in the fifth invention.
【００１４】上記の液状原料を金属基材に塗布した後、
３００〜５５０℃程度の温度で熱処理し、溶媒及び有機
物を除去し、その後、焼成することにより被膜を形成す
ることができる。金属基材に対する液状原料の塗布は、
流延、噴霧、ディッピング、スピニング等の種々の方法
によって実施することができる。そして、熱処理後、不
活性雰囲気下、６００〜１３００℃、特に８００℃程度
で焼成することにより、金属基材表面にリン酸カルシウ
ム系焼結体からなる被膜が形成された被覆品とすること
ができる。このような被覆品は、金属基材が、予め、人
口骨、人口歯根、人口関節等の生体内硬組織代替部材の
形状に成形されたものである場合に、特に有用である。After applying the above liquid raw material to the metal substrate,
A film can be formed by performing heat treatment at a temperature of about 300 to 550 ° C. to remove the solvent and organic substances, and then firing. Applying the liquid raw material to the metal substrate,
It can be carried out by various methods such as casting, spraying, dipping and spinning. Then, after the heat treatment, it is fired at 600 to 1300 ° C., especially at about 800 ° C. in an inert atmosphere to obtain a coated article in which a coating film made of a calcium phosphate-based sintered body is formed on the surface of the metal base material. Such a coated article is particularly useful when the metal base material is previously formed into the shape of an in-vivo hard tissue replacement member such as an artificial bone, an artificial tooth root, or an artificial joint.
【００１５】上記の生体内硬組織代替部材の場合、金属
基材としては、第６発明のように、「チタン、チタン合
金又はステンレス鋼からなる基材」が好ましい。特に、
強度が大きく、生体に対する毒性が低く、且つ耐食性に
優れるチタン及びチタン合金は、生体内硬組織代替部材
として好適である。また、金属基材としては、ステンレ
ス鋼からなるものも使用し得るが、Ｎａ+ 、Ｋ+ などの
イオンの多い生体内ではステンレス鋼は耐食性が不十分
な場合も考えられるため、チタン及びその合金がより好
ましい。In the case of the above-mentioned in-vivo hard tissue substitute member, the metal base material is preferably a "base material made of titanium, titanium alloy or stainless steel" as in the sixth invention. Especially,
Titanium and titanium alloys, which have high strength, low toxicity to the living body, and excellent corrosion resistance, are suitable as an in-vivo hard tissue substitute member. Further, as the metal base material, one made of stainless steel may be used, but titanium and its alloys may be insufficient in corrosion resistance in the living body where a lot of ions such as Na + and K + are present. Is more preferable.
【００１６】チタン、チタン合金、ステンレス鋼等の金
属からなる生体硬組織代替部材は、強度が大きく、毒性
もないが、生体活性はない。一方、リン酸カルシウム系
焼結体からなる生体硬組織代替部材は、強度は小さい
が、生体活性に優れる。従って、上記のような被膜を形
成すれば、強度、生体活性ともに優れた生体硬組織代替
部材が得られる。本発明の前処理方法によって、生体内
硬組織代替部材の形状に成形されたチタン等からなる金
属基材の表面を処理した後、その表面に、リン酸カルシ
ウム系焼結体からなる被膜を形成した場合、均質であっ
て、且つ密着性に優れた被膜とすることができる。A biohard tissue substitute member made of a metal such as titanium, titanium alloy, or stainless steel has high strength and is not toxic, but is not bioactive. On the other hand, the biohard tissue replacement member made of a calcium phosphate-based sintered body has low strength but excellent bioactivity. Therefore, by forming the coating film as described above, it is possible to obtain a bio-hard tissue replacement member having excellent strength and bioactivity. When the surface of a metal base material made of titanium or the like formed into the shape of an in-vivo hard tissue substitute member is treated by the pretreatment method of the present invention, and then a coating film made of a calcium phosphate-based sintered body is formed on the surface It is possible to obtain a film that is homogeneous and has excellent adhesion.
【００１７】[0017]
【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。各実施例及び比較例においては、前処理
後の金属基材表面に対する水の接触角によって、前処理
の効果の確認を行った。即ち、接触角が小さいほど、液
状原料の金属基材表面に対する濡れが良好であり、均一
な厚さの塗膜とすることができ、焼成後は均質、且つ密
着性に優れた被膜が形成される。尚、以下の各実施例に
おいて、○はその処理を実施した場合、×は処理しなか
った場合を表す。また、接触角の測定は、協和科学株式
会社製の接触角測定機を使用した。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below with reference to Examples. In each of the examples and comparative examples, the effect of the pretreatment was confirmed by the contact angle of water with respect to the surface of the metal substrate after the pretreatment. That is, the smaller the contact angle, the better the wettability of the liquid raw material with respect to the surface of the metal base material, and the coating film having a uniform thickness can be formed. After firing, a coating film that is homogeneous and has excellent adhesiveness is formed. It In each of the following examples, ◯ means that the treatment was performed, and x means that the treatment was not performed. The contact angle was measured using a contact angle measuring device manufactured by Kyowa Kagaku Co., Ltd.
【００１８】実施例１ チタンからなる板状体を濃度１０モル／リットルの水酸
化ナトリウム（ＮａＯＨ）水溶液に浸漬し、加熱して昇
温させ、３時間、沸騰状態で接触させて前処理を行っ
た。 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 試験片番号 １ ２ ３ ４ ５ ６ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 前処理 ○ ○ ○ × × × −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 接触角（°） 32.2 29.0 28.8 74.4 73.8 72.2 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−Example 1 A plate made of titanium was immersed in an aqueous sodium hydroxide (NaOH) solution having a concentration of 10 mol / liter, heated to raise the temperature, and contacted in a boiling state for 3 hours for pretreatment. It was −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Test piece number 1 2 3 4 5 6 −−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−− Pretreatment ○ ○ ○ × × × −−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−− Contact angle (°) 32.2 29.0 28.8 74.4 73.8 72.2 −−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−
【００１９】実施例２ チタンをＴｉ−６Ａｌ−４Ｖのチタン合金に代えた他
は、実施例１と同様にして前処理した。 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 試験片番号 １ ２ ３ ４ ５ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 前処理 ○ ○ × × × −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 接触角（°） 45.4 41.3 72.3 55.8 67.4 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−Example 2 Pretreatment was performed in the same manner as in Example 1 except that titanium was replaced with a titanium alloy of Ti-6Al-4V. −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Test piece number 1 2 3 4 5 −−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−− Pretreatment ○ ○ × × × −−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−− Contact angle (°) 45.4 41.3 72.3 55.8 67.4 −−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−
【００２０】実施例３ ＮａＯＨを水酸化カリウムに代えた他は、実施例１と同
様にして前処理した。 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 試験片番号 １ ２ ３ ４ ５ ６ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 前処理 ○ ○ ○ × × × −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 接触角（°） 27.8 29.5 30.1 75.5 71.3 72.6 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−Example 3 Pretreatment was carried out in the same manner as in Example 1 except that potassium hydroxide was used instead of NaOH. −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Test piece number 1 2 3 4 5 6 −−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−− Pretreatment ○ ○ ○ × × × −−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−− Contact angle (°) 27.8 29.5 30.1 75.5 71.3 72.6 −−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−
【００２１】実施例４ ＮａＯＨを過酸化水素に代えた他は、実施例１と同様に
して前処理した。 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 試験片番号 １ ２ ３ ４ ５ ６ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 前処理 ○ ○ ○ × × × −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 接触角（°） 26.2 27.9 28.1 75.8 73.7 70.2 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−Example 4 Pretreatment was carried out in the same manner as in Example 1 except that hydrogen peroxide was used instead of NaOH. −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Test piece number 1 2 3 4 5 6 −−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−− Pretreatment ○ ○ ○ × × × −−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−− Contact angle (°) 26.2 27.9 28.1 75.8 73.7 70.2 −−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−
【００２２】実施例５ チタンをステンレス鋼に代えた他は、実施例１と同様に
して前処理した。 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 試験片番号 １ ２ ３ ４ ５ ６ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 前処理 ○ ○ ○ × × × −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 接触角（°） 29.3 27.1 25.9 78.6 73.1 79.6 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−Example 5 Pretreatment was carried out in the same manner as in Example 1 except that titanium was replaced with stainless steel. −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Test piece number 1 2 3 4 5 6 −−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−− Pretreatment ○ ○ ○ × × × −−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−− Contact angle (°) 29.3 27.1 25.9 78.6 73.1 79.6 −−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−
【００２３】実施例６ ＮａＯＨ水溶液を７０℃の熱水に代え、処理時間を５時
間とした他は、実施例１と同様にして前処理した。 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 試験片番号 １ ２ ３ ４ ５ ６ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 前処理 ○ ○ ○ × × × −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− 接触角（°） 31.2 30.9 29.3 74.2 75.1 73.0 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−Example 6 Pretreatment was carried out in the same manner as in Example 1 except that the NaOH aqueous solution was replaced with hot water at 70 ° C. and the treatment time was 5 hours. −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Test piece number 1 2 3 4 5 6 −−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−− Pretreatment ○ ○ ○ × × × −−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−− Contact angle (°) 31.2 30.9 29.3 74.2 75.1 73.0 −−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−
【００２４】実施例１、３及び４の結果によれば、接触
角は同様に大きく低下し、前処理の効果が明らかであ
る。このように、アルカリ性化合物の種類、又は過酸化
水素による前処理の効果の差はほとんどないことが分か
る。また、実施例５のステンレス鋼の場合も、同様の優
れた効果が奏されているが、実施例２のチタン合金の場
合は、これら各実施例に比べて接触角の低下が小さい。
しかし、それでも前処理によって接触角は相当に低下し
ている。尚、熱水を使用した実施例６では、５時間と長
時間の処理を実施すれば、接触角は十分に低下すること
が分かる。According to the results of Examples 1, 3 and 4, the contact angle was similarly greatly reduced, and the effect of the pretreatment is clear. Thus, it can be seen that there is almost no difference in the effect of the type of alkaline compound or the pretreatment with hydrogen peroxide. In addition, the same excellent effect is exhibited also in the case of the stainless steel of Example 5, but in the case of the titanium alloy of Example 2, the decrease in contact angle is smaller than that in each of these examples.
However, the contact angle is still considerably reduced by the pretreatment. In addition, in Example 6 using hot water, it can be seen that the contact angle is sufficiently reduced by performing the treatment for a long time of 5 hours.
【００２５】実施例７ 蒸留水１リットル中に、硝酸カルシウム３．１２５×１
０-2モルを溶解した。この溶液に、エチレンジアミン四
酢酸アンモニウム塩を等モル量添加し、３０分間攪拌し
て反応させた。その後、この反応溶液に、リン酸アンモ
ニウムを１．８７５×１０-2モル加えて（リンとカルシ
ウムとの合計モル濃度；０．０５モル／リットル）、透
明な溶液となるまで更に攪拌を続けた。次いで、加熱し
て１２０℃に昇温させ、蒸留水を徐々に除去して１０倍
に濃縮した後、ｐＨを４．０に調整した。Example 7 3.125 × 1 calcium nitrate in 1 liter of distilled water
0 -2 mol was dissolved. An equimolar amount of ethylenediaminetetraacetic acid ammonium salt was added to this solution, and the mixture was reacted by stirring for 30 minutes. Then, 1.875 × 10 -2 mol of ammonium phosphate was added to this reaction solution (total molar concentration of phosphorus and calcium; 0.05 mol / liter), and stirring was continued until a transparent solution was obtained. . Then, the temperature was raised to 120 ° C. by heating, the distilled water was gradually removed and the solution was concentrated 10 times, and then the pH was adjusted to 4.0.
【００２６】その後、上記の実施例１において前処理し
たチタンからなる板状体を基材として、この基材を上記
の濃縮溶液中に浸漬して製膜し、５℃／分の速度で昇温
して、５２５℃の温度で熱処理を行った。この浸漬、製
膜と熱処理とを繰り返し実施した後、アルゴン雰囲気
下、８００℃で焼成してリン酸カルシウム系焼結体から
なる被膜を形成した。得られた被膜に亀裂等はなく、そ
の表面は平滑であった。また、ビッカース圧子埋入試験
を行ったが、被膜の剥離は認められず、密着性も良好で
あった。Then, using the plate-shaped body made of titanium pretreated in Example 1 as a base material, the base material was immersed in the concentrated solution to form a film, and the film was heated at a rate of 5 ° C./min. It was heated and heat-treated at a temperature of 525 ° C. After repeating the immersion, film formation and heat treatment, the film was baked at 800 ° C. in an argon atmosphere to form a film made of a calcium phosphate-based sintered body. The obtained coating had no cracks and the surface was smooth. Further, a Vickers indenter embedding test was conducted, but no peeling of the coating film was observed and the adhesion was good.
【００２７】比較例１ 実施例７において、前処理していない板状体を使用した
他は、同様にして濃縮溶液を調製し、同様にして浸漬、
製膜と熱処理及び焼成を行って、被膜の形成を試みた。
しかし、前処理をしていない板状体は濡れ難く、濃縮溶
液がはじかれてしまって、均質、平滑な被膜を形成する
ことはできなかった。Comparative Example 1 A concentrated solution was prepared in the same manner as in Example 7 except that the plate-like body which was not pretreated was used.
An attempt was made to form a film by performing film formation, heat treatment and firing.
However, the plate-shaped body not subjected to the pretreatment was difficult to get wet, and the concentrated solution was repelled, so that a uniform and smooth film could not be formed.
【００２８】実施例７と比較例１とを比べれば、本発明
の前処理の効果が実用上も十分であることが分かる。ま
た、この実施例７の結果は、チタンからなる生体内硬組
織代替部材を基材とすれば、強度と生体活性とを併せ有
する優れた性能の生体内硬組織代替部材が得られること
を十分に裏付けるものである。Comparing Example 7 with Comparative Example 1, it can be seen that the effect of the pretreatment of the present invention is practically sufficient. In addition, the result of this Example 7 is that it is sufficient to obtain an in-vivo hard tissue substitute member having excellent performance having both strength and bioactivity when the in-vivo hard tissue substitute member made of titanium is used as the base material. It is something to support.
【００２９】[0029]
【発明の効果】本発明によれば、金属基材と処理液とを
接触させるという、極めて簡便な操作によって、金属基
材表面の濡れを向上させることができる。それにより、
水系等の液状原料を使用して、金属基材表面に、均質、
且つ密着性に優れた被膜を容易に形成することができ
る。特に、第５発明のリンとカルシウムとを含む液状原
料を使用して、第６発明の、特にチタン又はチタン合金
からなる生体内硬組織代替部材の表面に、リン酸カルシ
ウム系焼結体からなる被膜を形成した場合は、大きな強
度と優れた生体活性とを併せ有する生体内硬組織代替部
材を得ることができる。According to the present invention, the wetting of the surface of the metal base material can be improved by a very simple operation of bringing the metal base material and the treatment liquid into contact with each other. Thereby,
Using liquid raw materials such as water, it is possible to
In addition, it is possible to easily form a film having excellent adhesion. In particular, a liquid raw material containing phosphorus and calcium of the fifth invention is used to form a coating film of a calcium phosphate-based sintered body on the surface of the in-vivo hard tissue substitute member of the sixth invention, particularly titanium or titanium alloy. When formed, an in-vivo hard tissue substitute member having both high strength and excellent bioactivity can be obtained.
Claims (6)
膜を形成する場合に、該表面を、予め、(1) アルカリ性
化合物及び過酸化水素のうちのいずれか一方を含む水溶
液、又は(2) 熱水若しくは水蒸気と接触させることを特
徴とする金属基材表面の前処理方法。1. When a liquid material is used to form a coating on the surface of a metal base material, the surface is previously formed with an aqueous solution containing one of (1) an alkaline compound and hydrogen peroxide, or (2) A method of pretreating the surface of a metal substrate, which comprises contacting with hot water or steam.
の金属基材表面の前処理方法。2. The pretreatment method for the surface of a metal substrate according to claim 1, wherein the liquid raw material is water-based.
合物、カリウム化合物及びマグネシウム化合物のうちの
少なくとも１種である請求項１又は２記載の金属基材表
面の前処理方法。3. The method for pretreatment of the surface of a metal substrate according to claim 1, wherein the alkaline compound is at least one selected from a sodium compound, a potassium compound and a magnesium compound.
る請求項１乃至３のいずれか１項に記載の金属基材表面
の前処理方法。4. The method for pretreating the surface of a metal substrate according to claim 1, wherein the aqueous solution or hot water is heated and boiled.
シウムとを含んでいる請求項１乃至４のいずれか１項に
記載の金属基材表面の前処理方法。5. The pretreatment method for a surface of a metal base material according to claim 1, wherein the liquid raw material contains at least phosphorus and calcium.
はステンレス鋼からなるものである請求項１乃至５のい
ずれか１項に記載の金属基材表面の前処理方法。6. The pretreatment method for the surface of a metal base material according to claim 1, wherein the metal base material is made of titanium, a titanium alloy or stainless steel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9595696A JPH09263958A (en) | 1996-03-25 | 1996-03-25 | Pre-treatment of metallic base material surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9595696A JPH09263958A (en) | 1996-03-25 | 1996-03-25 | Pre-treatment of metallic base material surface |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09263958A true JPH09263958A (en) | 1997-10-07 |
Family
ID=14151702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9595696A Pending JPH09263958A (en) | 1996-03-25 | 1996-03-25 | Pre-treatment of metallic base material surface |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09263958A (en) |
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|---|---|---|---|---|
| WO2002068715A1 (en) * | 2001-02-26 | 2002-09-06 | Sumitomo Metal Industries, Ltd. | Surface treated steel product, method for production thereof and chemical conversion treatment solution |
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-
1996
- 1996-03-25 JP JP9595696A patent/JPH09263958A/en active Pending
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|---|---|---|---|---|
| US6756092B2 (en) | 2001-02-26 | 2004-06-29 | Sumitomo Metal Industries, Ltd. | Surface treated steel material, a method for its manufacture, and a chemical conversion treatment liquid |
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| WO2002068715A1 (en) * | 2001-02-26 | 2002-09-06 | Sumitomo Metal Industries, Ltd. | Surface treated steel product, method for production thereof and chemical conversion treatment solution |
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| JP2011177804A (en) * | 2010-02-26 | 2011-09-15 | Showa Denko Kk | Cutting tool, method of manufacturing the same, and cutting method |
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