JPH03219090A - Formation of calcium phosphate-chitin composite film - Google Patents
Formation of calcium phosphate-chitin composite filmInfo
- Publication number
- JPH03219090A JPH03219090A JP1449490A JP1449490A JPH03219090A JP H03219090 A JPH03219090 A JP H03219090A JP 1449490 A JP1449490 A JP 1449490A JP 1449490 A JP1449490 A JP 1449490A JP H03219090 A JPH03219090 A JP H03219090A
- Authority
- JP
- Japan
- Prior art keywords
- calcium phosphate
- film
- chitin
- slurry
- substrate
- 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
- 229920002101 Chitin Polymers 0.000 title claims abstract description 27
- 239000011575 calcium Substances 0.000 title claims abstract description 7
- 239000002131 composite material Substances 0.000 title claims abstract description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 title 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 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 claims abstract description 22
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 20
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- 230000001678 irradiating effect Effects 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 14
- 239000011521 glass Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 5
- 229910052586 apatite Inorganic materials 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000007943 implant Substances 0.000 description 4
- 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 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000007605 air drying Methods 0.000 description 2
- 238000005937 allylation reaction Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001962 electrophoresis Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 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 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 235000019731 tricalcium phosphate Nutrition 0.000 description 2
- 229940078499 tricalcium phosphate Drugs 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 241000238424 Crustacea Species 0.000 description 1
- 235000019739 Dicalciumphosphate Nutrition 0.000 description 1
- 229920002683 Glycosaminoglycan Polymers 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- GYSSRZJIHXQEHQ-UHFFFAOYSA-N carboxin Chemical compound S1CCOC(C)=C1C(=O)NC1=CC=CC=C1 GYSSRZJIHXQEHQ-UHFFFAOYSA-N 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 description 1
- 229910000390 dicalcium phosphate Inorganic materials 0.000 description 1
- 229940038472 dicalcium phosphate Drugs 0.000 description 1
- 235000019621 digestibility Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910000392 octacalcium phosphate Inorganic materials 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YIGWVOWKHUSYER-UHFFFAOYSA-F tetracalcium;hydrogen phosphate;diphosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[Ca+2].OP([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YIGWVOWKHUSYER-UHFFFAOYSA-F 0.000 description 1
- GBNXLQPMFAUCOI-UHFFFAOYSA-H tetracalcium;oxygen(2-);diphosphate Chemical compound [O-2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GBNXLQPMFAUCOI-UHFFFAOYSA-H 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、基体の表面にリン酸カルシウム−キチン複合
膜を形成する方法に関するものであり、その優れた生体
適合性によって特にインブラント材の分野に利用される
ものである。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for forming a calcium phosphate-chitin composite film on the surface of a substrate, and is particularly applicable to the field of implant materials due to its excellent biocompatibility. It is something that is used.
リン酸カルシウム、その中でもハイドロキシアパタイト
は生体適合性に優れ、吸着能も大きいことから種々の応
用が検討されてきた。特に生体硬組織の置換、あるいは
修復用のインブラント材としての利用に関し研究が活発
に進められている。Calcium phosphate, especially hydroxyapatite, has excellent biocompatibility and high adsorption capacity, so various applications have been investigated. In particular, research is being actively carried out regarding its use as an implant material for the replacement of biological hard tissue or for repair.
インブラント材としては、生体適合性のほかに生体力学
的強度が要求される。しかしながら、リン酸カルシウム
自体は、焼結体では強度の点で不十分である。従って金
属材料、セラミックス、ガラス等を基体あるいは芯材と
して、その表面にリン酸カルシウムの皮膜を形成するこ
とが実用的に最も有望視されている。Implant materials are required to have biomechanical strength in addition to biocompatibility. However, calcium phosphate itself is insufficient in strength when used as a sintered body. Therefore, forming a film of calcium phosphate on the surface of a substrate or core material made of a metal material, ceramics, glass, etc. is considered to be most promising in practice.
リン酸カルシウムの皮膜を形成する方法としてこれまで
種々の方法が提案されている。Various methods have been proposed so far for forming calcium phosphate films.
たとえば、特開昭５２−８２８９３号公報にはプラズマ
溶射法、特開昭５８−１０９０４９号公報にはスパッタ
リング法、特開昭５９−１１１７５３号公報にはＰＶＤ
法およびＣＶＤ法、特開昭５３−１２８１９０号公報に
は電気泳動法、特開昭５３−１１８４１１号公報には塗
布法がそれぞれ開示されている。For example, JP-A-52-82893 discloses the plasma spraying method, JP-A-58-109049 discloses the sputtering method, and JP-A-59-111753 discloses the PV method.
JP-A-53-128190 discloses an electrophoresis method, and JP-A-53-118411 discloses a coating method.
ところがプラズマ溶射法、スパッタリング法、ＰＶＤ法
、ＣＶＤ法においては、多孔体の内部のような複雑な形
状をした基体表面には皮膜の形成か困難であり、電気泳
動法においては、基体か非導電性のものには皮膜か形成
されないという問題を有している。However, in the plasma spraying method, sputtering method, PVD method, and CVD method, it is difficult to form a film on the surface of a substrate with a complex shape such as the inside of a porous body, and in the electrophoresis method, it is difficult to form a film on the surface of a substrate with a complex shape such as the inside of a porous body. The problem is that a film is not formed on the non-containing materials.
塗布法は操作か簡便であり、前記特開昭５３−１１８４
１１号公報ではアパタイトの微粉末を水に懸濁させ、こ
の懸濁液を基体の表面に塗布し、焼成する方法が開示さ
れているが、微粉末をより細かい粒子にすることか一般
には難しく、凝集粒が存在し易いこと、ならびに分散し
ている粒子が一般に０．５μｍより大きいことなとのた
めに、基体表面へのアパタイトの付着強度が弱く、剥離
し易いという問題を有している。The coating method is simple and easy to operate, and is described in Japanese Patent Application Laid-Open No. 53-1184.
Publication No. 11 discloses a method of suspending fine apatite powder in water, applying this suspension to the surface of a substrate, and firing it, but it is generally difficult to make the fine powder into finer particles. , because aggregated particles tend to exist and the dispersed particles are generally larger than 0.5 μm, the adhesion strength of apatite to the substrate surface is weak and it is easy to peel off. .
また塗布法において、アパタイトの微粉末の懸濁液に水
溶性高分子を共存させ、基体の表面に塗布し、焼成して
水溶性高分子を焼失せしめる方法かある。これは付着を
改善するが、チタンなど焼成温度にて変質する材料には
適用することができない。Further, as a coating method, there is a method in which a suspension of fine apatite powder is made to coexist with a water-soluble polymer, and the suspension is coated on the surface of a substrate, followed by firing to burn off the water-soluble polymer. Although this improves adhesion, it cannot be applied to materials that deteriorate at firing temperatures, such as titanium.
かかる実情に鑑み、本発明者らは焼成工程を経ずに基体
に付着強度の高い皮膜を形成する方法につき鋭意検討を
重ねた結果、メタノール可溶のカルボキシメチル化キチ
ン−アリル誘導体（以下ＡＣＭＣキーンと略記する）の
共存下に皮膜を形成し、しかるのちにこれを不溶化せし
めることにより良好なリン酸カルシウムを含有する皮膜
を形成することを見い出し、本発明を完成させるに至っ
た。In view of these circumstances, the present inventors have conducted intensive studies on a method of forming a film with high adhesion strength on a substrate without going through a firing process. They have discovered that a film containing good calcium phosphate can be formed by forming a film in the coexistence of calcium phosphate (hereinafter referred to as "calcium phosphate") and then insolubilizing the film, thereby completing the present invention.
すなわち、本発明はリン酸カルシウム粉末とＡＣＭ−キ
チンのメタノール溶液とを混合したスラリーにより基体
表面に液膜を付与し、これを乾燥中または乾燥後に光照
射することからなるリン酸カルシウム−キチン複合膜の
形成方法を提供するものである。That is, the present invention provides a method for forming a calcium phosphate-chitin composite film, which comprises applying a liquid film to the surface of a substrate using a slurry of a mixture of calcium phosphate powder and a methanol solution of ACM-chitin, and irradiating this with light during or after drying. It provides:
本発明において用いられるリン酸カルシウムとしてはリ
ン酸二カルシウム、リン酸三カルシウム、リン酸テトラ
カルシウム、リン酸オクタカルシウム、ハイドロキシア
パタイトおよびこれらの混合物である。これらは乾式法
、湿式法なと周知の方法により製造される。粒径は皮膜
の性状に影響するために、粗大な凝集粒を含有しない方
が望ましく、粒径１０μｍ以下のものか好適である。Calcium phosphates used in the present invention include dicalcium phosphate, tricalcium phosphate, tetracalcium phosphate, octacalcium phosphate, hydroxyapatite, and mixtures thereof. These are manufactured by well-known methods such as dry and wet methods. Since the particle size affects the properties of the film, it is preferable that the particles do not contain coarse agglomerated particles, and particles with a particle size of 10 μm or less are preferable.
Ａ−ＣＭ−キチンは本発明者らの１人によって合成法か
見いだされたものであり、キチンの誘導体である。キチ
ンはムコ多糖類の１種で、天然には甲殻類、昆虫類、貝
類などの外骨格組織の成分として豊富に存在している。A-CM-chitin was synthesized by one of the inventors and is a derivative of chitin. Chitin is a type of mucopolysaccharide that exists in abundance in nature as a component of the exoskeletal tissues of crustaceans, insects, shellfish, etc.
しかし溶解性、反応性に乏しく、はとんどが廃棄されて
いるのが現状である。そこで化学修飾によって溶解性を
もたらすなど、機能化することを目的に種々の検討がな
されている。However, due to its poor solubility and reactivity, most of it is currently discarded. Therefore, various studies have been conducted with the aim of making it functional, such as by making it more soluble through chemical modification.
カルボキシメチル化キチンは本発明者らの１人によって
合成法が見いだされたものであって、Ｐｏｌｙｍｅｒ
Ｊｏｕｒｎａｌ誌、１５巻、４８５〜４８９頁（１９８
３）に記載されている。これは、Ｃ−６位の水酸基が部
分的にカルボキンメチル化された構造を有し、この置換
の程度によって水不溶性から水膨張性、水溶性へと変化
し、高置換度のものは高分子電解質的挙動を示し、低置
換度のものは陽イオン交換樹脂として作用することが明
らかとなっている。また、Ｃａ’＋イオンに対して特に
高い吸着能を有すること（Ｐｏｌｙｍｅｒ Ｊｏｕｒｎ
ａｌ誌、１５巻、５９７〜６０２頁（１９８３）） 、
アミノ酸の吸着特性を有すること（Ｊｏｕｒｎａｌ Ｍ
ａｃｒｏｍｏｌｅｃｕｌａｒ ５ｃｉｅｎｃｅ、 Ｃｈ
ｅｍｉｓｔｒｙＡ２５１０巻、１１巻、１４２７〜１４
４１頁（１９８６）） 、が明らかとなっている。The synthesis method for carboxymethylated chitin was discovered by one of the present inventors, and Polymer
Journal, vol. 15, pp. 485-489 (198
3). It has a structure in which the hydroxyl group at the C-6 position is partially carboxine methylated, and depending on the degree of this substitution, it changes from water-insoluble to water-swellable to water-soluble. It has been shown that they exhibit molecular electrolyte behavior and those with a low degree of substitution act as cation exchange resins. In addition, it has a particularly high adsorption capacity for Ca'+ ions (Polymer Jour
al magazine, vol. 15, pp. 597-602 (1983)),
Having adsorption properties for amino acids (Journal M
acromolecular 5science, Ch.
emistryA vol. 2510, vol. 11, 1427-14
41 (1986)).
カルボキシメチル化キチンに更にアリル基を導入する方
法が本発明者らの１人によって見いだされたものである
。このＡ−ＣＭ−キチンは、Ｃ−６位、Ｃ−３位の水酸
基にアリル基が置換されたもので、これによってメタノ
ールに可溶となる。また、カルボキシメチル化キチンの
有する生体内消化性はアリル化によって消失したが、毒
性は全く見いだされていない。構造式は次の通りである
。One of the present inventors has discovered a method for further introducing allyl groups into carboxymethylated chitin. This A-CM-chitin has allyl groups substituted for the hydroxyl groups at the C-6 and C-3 positions, which makes it soluble in methanol. Further, although the in vivo digestibility of carboxymethylated chitin was abolished by allylation, no toxicity was found at all. The structural formula is as follows.
アリル基が導入されたものも、２価金属イオン吸着能を
有することが明らかにされている。Ａ−ＣＭ−キチンの
メタノール溶液の濃度は、カルボキノメチル化の程度と
アリル化の程度によってメタノール溶解性か異なるため
に一部に示すことは難しいか、１−１５重量％程度が操
作し易いので好ましい。It has been revealed that those into which an allyl group has been introduced also have the ability to adsorb divalent metal ions. The concentration of A-CM-chitin in methanol solution is difficult to indicate because the solubility in methanol varies depending on the degree of carboquinomethylation and the degree of allylation, or it is easy to operate at around 1-15% by weight. Therefore, it is preferable.
リン酸カルシウム粉末とＡ、−ＣＭ−キチンのメタノー
ル溶液とを混合する割合は、用いられるリン酸カルシウ
ム粉末の粒径によって異なる。粒径数μｍのものを用い
る場合は、リン酸カルシウム粉末とＡ−ＣＭ−キチンの
比率は３：Ｉないし０．０１１の範囲が望ましい。粉末
か３：ｌより多くなるとスラリーの流動性が損なわれる
ために好ましくす＜ 、０．０１： １より少ないとリ
ン酸カルシウムの存在する効果が失われる。粒径が１μ
ｍ以下の微細なものを用いる場合は、リン酸カルシウム
粉末とＡ−ＣＭ−キチンノ比率は０．２：１ないし０．
０１：１の範囲か望ましい。粉末が０．２：ｌより多く
なるとキチンか粉末に吸着され、凝集粒となって沈降す
るのて好ましくない。０．０１・１より少ないとリン酸
カルシウムの存在する効果が失われる。The mixing ratio of the calcium phosphate powder and the methanol solution of A, -CM-chitin varies depending on the particle size of the calcium phosphate powder used. When using particles with a particle size of several μm, the ratio of calcium phosphate powder to A-CM-chitin is preferably in the range of 3:I to 0.011. If the powder ratio exceeds 3:1, the fluidity of the slurry will be impaired, so it is preferable.If the ratio is less than 0.01:1, the effect of the presence of calcium phosphate will be lost. Particle size is 1μ
When using fine particles of less than m, the ratio of calcium phosphate powder to A-CM-chitin is between 0.2:1 and 0.2:1.
A range of 01:1 is desirable. If the amount of powder exceeds 0.2:l, chitin will be adsorbed to the powder, forming aggregates and settling, which is not preferable. If it is less than 0.01.1, the effect of the presence of calcium phosphate will be lost.
本発明に用いられる基体としては、金属、セラミックス
、ガラスなどいずれも可能であるが、油脂などの汚れを
溶剤で除去しておく方が好ましい。The substrate used in the present invention may be made of metal, ceramics, glass, etc., but it is preferable to remove dirt such as oil and fat with a solvent.
基体に液膜を付与する方法としては、塗布法、浸漬法、
噴霧法など周知の方法を利用することができる。Methods for applying a liquid film to the substrate include coating method, dipping method,
Well-known methods such as spraying methods can be used.
液膜を乾燥する方法としては自然乾燥、通風乾燥、加熱
乾燥など周知の方法を利用することが出来るが、キチン
質の熱による変質を避けるために通常は１００°Ｃ以下
、好ましくは４０℃以下の温度が適している。Well-known methods such as natural drying, ventilation drying, and heat drying can be used to dry the liquid film, but in order to avoid deterioration of chitin due to heat, the temperature is usually below 100°C, preferably below 40°C. temperature is suitable.
乾燥中または乾燥後の光照射は可視光または紫外光を照
射すればよく、照射光の照度は室内灯の明るさ以上であ
れば十分であり、好ましくは紫外線ランプ照射が好適で
ある。この光照射によってキチン質の不溶化がもたらさ
れる。Visible light or ultraviolet light may be used for light irradiation during or after drying, and it is sufficient that the illuminance of the irradiation light is equal to or higher than the brightness of an indoor light, and preferably ultraviolet lamp irradiation is suitable. This light irradiation brings about insolubilization of chitin.
以下、本発明を実施例により説明するが、本発明はこれ
らに限定されるものではない。EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.
なお、実施例において用いる「％」は「重量％」を意味
する。Note that "%" used in Examples means "% by weight".
実施例１
直径ＩＯ闘のガラス管にＡ−ＣＭ−キチン０．０４９ｇ
メタノール１．１５６６ｇを入れ、よく振盪して溶解さ
せた。Ａ−ＣＭ−キチンの濃度は４．０％に相当する。Example 1 0.049 g of A-CM-chitin in a glass tube with a diameter of IO
1.1566 g of methanol was added and shaken well to dissolve it. The concentration of A-CM-chitin corresponds to 4.0%.
これにα型リン酸三カルシウム粉末（平均粒径５μｍ）
０．０９５ｇを入れ、さらによく振盪し、スラリーを
調製した。Add to this α-type tricalcium phosphate powder (average particle size 5 μm)
0.095 g was added and further shaken to prepare a slurry.
ガラスプレートの上にこのスラリーの一部を滴下し、３
日間自然乾燥したのち、紫外線ランプで２時間光照射し
た。生成した皮膜の重量は０．０００８ｇ、厚みは２１
μｍであった。Drop some of this slurry onto a glass plate and
After air drying for a day, it was irradiated with an ultraviolet lamp for 2 hours. The weight of the produced film is 0.0008g and the thickness is 21
It was μm.
塩化カルシウム３．３ＸＩＯ−’モル水溶液４０ｍ１中
に上記の皮膜付きガラスプレートを浸漬し、２日後の観
察では皮膜に全く変化はなかった。The glass plate with the film was immersed in 40 ml of a 3.3XIO-' molar calcium chloride aqueous solution, and observation two days later showed no change in the film.
実施例２
直径１０ｍｍのガラス管にＡ−ＣＭ−キチン０．１０６
６ｇ、メタノール１．３１２３ｇを入れ、よく振盪して
溶解させた。Ａ −ＣＭ−キチンの濃度は７．５１％に
相当する。これにハイドロキンアパタイト粉末（平均粒
径０．３μｍ） ０．００４４ｇを入れ、さらによく振
盪し、スラリーを調製した。Example 2 A-CM-chitin 0.106 in a glass tube with a diameter of 10 mm
6g of methanol and 1.3123g of methanol were added thereto, and the mixture was thoroughly shaken to dissolve. The concentration of A-CM-chitin corresponds to 7.51%. 0.0044 g of hydroquine apatite powder (average particle size: 0.3 μm) was added to this, and the mixture was further shaken to prepare a slurry.
ガラスプレートの上にこのスラリーの一部を滴下し、３
日間自然乾燥したのち、紫外線ランプで２時間光照射し
た。生成した皮膜の重量は０．０００７ｇ１厚みは１８
μｍであった。Drop some of this slurry onto a glass plate and
After air drying for a day, it was irradiated with an ultraviolet lamp for 2 hours. The weight of the produced film is 0.0007g 1 thickness is 18
It was μm.
塩化カルシウム３．３ Ｘ １０−’モル水溶液４０ｍ
１中に上記の皮膜付きガラスプレートを浸漬し、２日後
の観察では皮膜に全く変化はなかった。Calcium chloride 3.3 x 10-' molar aqueous solution 40ml
The above-mentioned coated glass plate was immersed in No. 1, and observation after 2 days showed that there was no change in the coating at all.
比較例１
Ａ−ＣＭ−キチンを全く使用しなかったこと以外は実施
例１と全く同様に操作して、スラリーを調製し、ガラス
プレートの上にこのスラリーの一部を滴下した。乾燥後
には皮膜は形成されず、塩化カルシウム３．３Ｘ１０−
’モル水溶液４０ｍ１中に浸漬するとすべて剥離した。Comparative Example 1 A slurry was prepared in the same manner as in Example 1 except that A-CM-chitin was not used at all, and a portion of this slurry was dropped onto a glass plate. No film was formed after drying, and calcium chloride 3.3X10-
When immersed in 40 ml of a molar aqueous solution, all of the material peeled off.
本発明によれば皮膜の付着強度が強く、しかも焼成工程
を必要としないので高温における変質のある基体に対し
ても皮膜を形成することか可能となった。得られた皮膜
は種々の用途に使用でき、特にインブラント材、吸着分
離材なとに有用である。According to the present invention, the adhesion strength of the film is strong, and since a baking process is not required, it has become possible to form a film even on a substrate that undergoes deterioration at high temperatures. The obtained film can be used for various purposes, and is particularly useful as an implant material and an adsorption/separation material.
手
続
補
正
書
（自
発）
平成２年３月２２日
■、事件の表示
平成２年 特許願 第１４４９４号
２、発明の名称
リン酸カルシウム
キチン複合膜の形成方法
３゜
補正をする者
事件との関係 特許出願人
住 所 大阪市中央区北浜四丁目５番３３号名 称 （
２０９）住友化学工業株式会社代表者 森 英
雄
４゜Procedural amendment (spontaneous) March 22, 1990■, Indication of case 1990 Patent application No. 14494 2, Title of invention Method for forming calcium phosphate chitin composite membrane 3゜ Person making the amendment Relationship to the case Patent application Address 4-5-33 Kitahama, Chuo-ku, Osaka Name (
209) Sumitomo Chemical Co., Ltd. Representative Hideo Mori 4゜
Claims (1)
リル誘導体のメタノール溶液とを混合したスラリーによ
り基体表面に液膜を付与し、これを乾燥中または乾燥後
に光照射することからなるリン酸カルシウム−キチン複
合膜の形成方法。A method for forming a calcium phosphate-chitin composite film, which comprises applying a liquid film to the surface of a substrate using a slurry of a mixture of calcium phosphate powder and a methanol solution of a carboxymethylated chitin-allyl derivative, and irradiating the film with light during or after drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1449490A JP2847847B2 (en) | 1990-01-23 | 1990-01-23 | Method for forming calcium phosphate-chitin composite film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1449490A JP2847847B2 (en) | 1990-01-23 | 1990-01-23 | Method for forming calcium phosphate-chitin composite film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03219090A true JPH03219090A (en) | 1991-09-26 |
| JP2847847B2 JP2847847B2 (en) | 1999-01-20 |
Family
ID=11862612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1449490A Expired - Fee Related JP2847847B2 (en) | 1990-01-23 | 1990-01-23 | Method for forming calcium phosphate-chitin composite film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2847847B2 (en) |
-
1990
- 1990-01-23 JP JP1449490A patent/JP2847847B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2847847B2 (en) | 1999-01-20 |
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