CN102146576A - Medical appliance and surface treatment method thereof - Google Patents
Medical appliance and surface treatment method thereof Download PDFInfo
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- CN102146576A CN102146576A CN2010101139850A CN201010113985A CN102146576A CN 102146576 A CN102146576 A CN 102146576A CN 2010101139850 A CN2010101139850 A CN 2010101139850A CN 201010113985 A CN201010113985 A CN 201010113985A CN 102146576 A CN102146576 A CN 102146576A
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Abstract
The invention provides a medical appliance and a surface treatment method thereof. The surface treatment method comprises the following steps of: first, providing a metal layer; then, forming an intermediate layer on the surface of the metal layer, wherein the thickness of the intermediate layer is greater than that of a natural oxide layer on the surface of the metal layer; and finally, grafting functional polymers on the intermediate layer by electrical deposition treatment. The medical appliance comprises the metal layer, the intermediate layer and the functional polymers with solubility, wherein the intermediate layer is formed on the metal layer; the thickness of the intermediate layer is greater than that of the natural oxide layer on the surface of the metal layer; and the functional polymers with the solubility are grafted on the intermediate layer. In the medical appliance, the intermediate layer is formed on the surface of the metal layer by a chemical soaking treatment or electrochemical anodic treatment or heat treatment method; and different colors and clusters appear according to different thicknesses of the intermediate layer. Therefore, the product has an obvious identification degree. In addition, the formation of the intermediate layer can improve the number of hydroxyls (-OH) on the surface of the metal surface.
Description
Technical field
The present invention relates to a kind of metallic surface treatment process and medical device, and relate in particular to a kind of in the high molecular treatment process of metallic surface grafting functional.
Background technology
Medical device (medical appliance) in the human implantable, as: nail (bone screw), hone lamella (bone plate), heart catheter support etc., these medical devices are used in fixing usually or support original bone or blood vessel in the human body.Or can temporarily invade the medical device of human body, and as: plain conductor (guidewire), instruments etc., these medical devices are used in the function of operation guiding or operation usually.And the manipulation in vitro medical device, as operation wrench, medical metals basin ware etc., be normally used in the surgical procedure.
In above-mentioned medical device product, have as the plain conductor product at present the specific functionality polymer is coated in surfaces of medical devices, as: " the MEDICALAPPLINCE AND PROCESS FOR PRODUCING THE APPLIANCE " that U.S. Patent Publication No. US 20090124984 is disclosed, in this patent, Hanawa proposes a kind of medical device with metallic surface, wherein there is a hydrophilic organic compound directly to be fixed on the metallic surface with electrochemical method, by hydrophilic organic compound, can reach the effect of surface lubrication.
But, in the content of above-mentioned patent, the percentage of grafting of its medical device institute grafted wetting ability organic compound is subject to the surface hydroxyl group (OH) quantity of medical device, therefore, the lubricated effect in metallic surface can be subjected to the percentage of grafting influence of this organic compound, limits its effectively anti-tissue and is stained with effect sticking and that anti-protein attaches.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of surface treatment method of medical device, and this metal surface treating method can improve the macromolecular grafted amount of specific functionality, and then the anti-tissue of lifting is stained with the sticking effects such as antibacterium, anti-protein attaching that reach.
The present invention proposes a kind of medical device in addition, and this medical device has can improve the macromolecular grafted amount of specific functionality, and then the anti-tissue of lifting is stained with the sticking effects such as antibacterium, anti-protein attaching that reach.
For achieving the above object, the present invention proposes a kind of surface treatment method of medical device, and the surface treatment method step comprises: at first, provide a metal level; Afterwards, form a media layer on the surface of metal level, the thickness of media layer is greater than the natural oxidation layer thickness of this metallic surface; At last, by an electrodeposition process one functional high-polymer is grafted on this media layer.
Wherein, this metal is alloy, a vitallium or the stainless steel that a titanium metal, contains titanium elements.
Wherein, this media layer is a titanium metal zone of oxidation, titanium alloy zone of oxidation, vitallium zone of oxidation, oxidizing layer of stainless steel.
Wherein, the color and luster that includes the medical device of this media layer is different from the color and luster of the medical device that includes natural oxidizing layer.
Wherein, the color and luster of this medical device is golden, dusty blue or grey bluish-green staggered.
Wherein, the thickness of this media layer is between between 10 nanometers to 20 micron.
Wherein, this electrodeposition process comprises: this metal level is inserted in the electrolytic solution that contains this functional high-polymer; And an electric current is provided, carry out this electrodeposition process reaction.
Wherein, this functional high-polymer is the polymer of a terminal tool amido.
Wherein, the polymer of this end tool amido is a polyvinyl alcohol.
Wherein, the mode that forms this media layer is an electrochemistry anodizing.
Wherein, this electrochemistry anodizing step comprises: this metal level is placed the anode place, and an electrode is placed the negative electrode place; And provide an electric current in this metal level.
Wherein, this electrochemistry anodizing range of reaction temperature can be between-20 to 60 ℃, and the impressed voltage when carrying out anodizing can be between 5 to 200 volts.
Wherein, preferably between-5 to 35 ℃, the impressed voltage when carrying out anodizing is preferably between 40 to 60 volts for this electrochemistry anodizing range of reaction temperature.
Wherein, the mode that forms this media layer is that a chemical immersion is handled.
Wherein, this chemical immersion treatment step comprises: this metal level is soaked in an acidic solution, and this acidic solution is the solution that contains hydrogen peroxide.
Wherein, the mode that forms this media layer is a thermal treatment.
Wherein, this heat treatment step comprises: this metal is placed a thermally equivalent space; And provide the reaction times of temperature of reaction and between 30 minutes to 8 hours between 100 to 1000 ℃.
And, for achieving the above object, the present invention proposes a kind of medical device in addition, this medical device comprises the functional high-polymer that a metal level, a media layer and have solubility, wherein, media layer is formed on the metal level, and the thickness of media layer is greater than the natural oxidation layer thickness of this layer on surface of metal, and the functional high-polymer with solubility is grafted on this media layer.
Wherein, this metal is alloy, a vitallium or the stainless steel that a titanium metal, contains titanium elements.
Wherein, this media layer is a titanium metal zone of oxidation, titanium alloy zone of oxidation, vitallium zone of oxidation, oxidizing layer of stainless steel.
Wherein, the color and luster that includes the medical device of this media layer is different from the color and luster of the medical device that includes natural oxidizing layer.
Wherein, the color and luster of this medical device is golden, dusty blue or grey bluish-green staggered.
Wherein, this media layer is the titanium metal zone of oxidation, and the thickness of this media layer is between between 10 nanometers to 20 micron.
Wherein, this medical device is for implanting the intravital object of body, and this object is nail, hone lamella or heart catheter support.
Wherein, this medical device is the temporary transient intravital object of body of invading.This object is plain conductor or instruments.
Wherein, this medical device is the object of the outer operation of health.This object is operation wrench or medical metals basin ware.
In sum, the present invention utilizes chemical immersion to handle or the electrochemistry anodizing forms a media layer on the surface of metal level, different and then present different color and lusters according to media layer thickness, therefore, product has tangible identification degree, in addition, the formation of media layer can improve the hydroxyl (OH) quantity of layer on surface of metal.
In addition, the present invention again by electrochemistry grafting specific functionality polymer in the hydroxyl groups on metal level zone of oxidation surface (OH), the method that produces media layer effectively increases surface hydroxyl group quantity, and then the high molecular quantity of lifting grafting specific functionality, therefore, can promote its anti-tissue of product and be stained with sticking effect.
Description of drawings
Fig. 1 is the schema of surfaces of medical devices treatment process of the present invention;
Fig. 2 to 4 is sectional views of surfaces of medical devices treatment process of the present invention;
Fig. 5 A to Fig. 5 G resists tissue to be stained with the bonding fruit in titanium metal implantation mouse next week of epidermis;
Fig. 6 A to Fig. 6 J resists tissue to be stained with the bonding fruit in titanium metal implantation mouse two weeks of epidermis; And
Fig. 7 A to Fig. 7 J is that anti-tissue of titanium metal implantation mouse epidermis four stars phase is stained with the bonding fruit.
Wherein, Reference numeral:
S100～S300 process step
10: medical device
12: metal level
14: media layer
16: functional high-polymer
Embodiment
Fig. 1 is the schema of surfaces of medical devices treatment process of the present invention; Fig. 2 to Fig. 4 is the sectional view of surfaces of medical devices treatment process of the present invention.See also Fig. 1 to Fig. 4, the surface-treated method comprises: at first, with reference to figure 2, provide a metal level 12 (or metal body) (step S100).The material of metal level 12 can be alloy, a vitallium or the stainless steel that a titanium metal, contains titanium elements.
Afterwards, with reference to figure 3, form a media layer 14 (step S200) on the surface of metal level 12, what need special instruction is that the thickness of media layer 14 described here is greater than the natural oxidation layer thickness of layer on surface of metal.The material of this media layer 14 can be a titanium metal zone of oxidation, titanium alloy zone of oxidation, vitallium zone of oxidation, oxidizing layer of stainless steel.In detail, be that titanium metal and media layer 14 are that the titanium metal zone of oxidation is an example with the material of metal level 12, about about 10 nanometers of the natural oxidation layer thickness on metal level 12 surfaces, and the thickness of media layer 14 described here is between between 10 nanometers to 20 micron.
The mode (step S200) that forms media layer 14 on metallic surface can be handled for a chemical immersion.The chemical immersion treatment step comprises: this metal level 12 is soaked in an acidic solution, and this acidic solution is hydrogen peroxide (H
2O
2) solution or can produce the solution of zone of oxidation in metal level 12 surface.In detail, after metal level 12 was soaked in an acidic solution, metal level 12 surfaces can form a metal oxide layer, and the thickness of this metal oxide layer is greater than the natural oxidation layer thickness of this metal level 12.
Perhaps, the mode (step S200) of formation media layer 14 is electrochemistry anodizing on the surface of metal level 12.The electrochemistry anodizing step comprises: this metal level 12 is placed the anode place, and an electrode is placed the negative electrode place; And provide an electric current in this metal level 12.After carrying out the electrochemistry anodizing, metal level 12 surfaces can form a metal oxide layer, and the thickness of this metal oxide layer is greater than the natural oxidation layer thickness of this metal level 12.
In addition, when carrying out the electrochemistry anodizing, can be by temperature of reaction and electric current that reaction provided, the thickness of control metal oxide layer, wherein the range of reaction temperature of anodizing can be between-20 to 60 ℃, preferably between-5 to 35 ℃, the voltage when carrying out anodizing can be 5 to 200 volts (V), preferably between 40 to 60 volts.
Perhaps, the mode (step S200) of formation media layer 14 is a heat treatment mode on the surface of metal level 12.Heat treatment mode comprises: this metal level 12 is placed a thermally equivalent space, and its proper temperature is provided.After heat-treating, metal level 12 surfaces can form a metal oxide layer, and the thickness of this metal oxide layer is greater than the natural oxidation layer thickness of this metal level 12.
In addition, when heat-treating, can be by temperature of reaction and time that reaction provided, the thickness of control metal oxide layer, its heat treated range of reaction temperature can be between 100 to 1000 ℃, preferably between 400 to 800 ℃, the reaction time range of heat-treating can be between 30 minutes to 8 hours, preferably between 30 minutes to 2 hours.
On the surface of metal level 12, form media layer 14 (step S200) afterwards, one functional high-polymer 16 is grafted on this media layer 14 (step S300) by an electrodeposition process.In detail, here the functional high-polymer 16 of indication is the polymer with tool terminal amido of solubility, as: (Poly Ethylene Glycol, PEG), and the solubility of indication is meant in these functional high-polymer 16 water solubles or the solvent polyvinyl alcohol here.Electrodeposition process comprises: after inserting this metal level 12 in the electrolytic solution that contains functional high-polymer 16, provide an electric current, so can carry out the electrodeposition process reaction.
After forming media layer 14 (step S200) on the surface of metal level 12, the different color and lusters (for example golden, dusty blue or grey bluish-green staggered) that the thickness of different media layers 14 can make medical device 10 present are different from the color and luster (also being the primary colors of metal level 12) of the medical device 10 that only has transparent natural oxidizing layer, therefore, the tangible identification of medical device 10 product tools; In addition, the formation of media layer 14 can impel the surface hydroxyl of metal level 12 (OH) quantity is effectively promoted.
In addition,, one functional high-polymer 16 is grafted on this media layer 14 (step S300), so to form medical device 10 of the present invention by an electrodeposition process with reference to figure 4.Because the surface hydroxyl of metal level 12 (OH) is effectively promoted, and surface hydroxyl group (OH) can increase polyvinyl alcohol graft copolymerized place, therefore, polyvinyl alcohol graft copolymerized rate promoted, behind the surface grafting functional high-polymer 16 of metal level 12, can promote the anti-attaching rate of organizing.
With reference to figure 4, medical device 10 of the present invention comprises a metal level 12, media layer 14 and the functional high-polymer 16 with solubility again.This media layer 14 is formed on this metal level 12, and wherein the thickness of this media layer 14 is greater than the natural oxidation layer thickness on these metal level 12 surfaces.This functional high-polymer 16 is grafted on this media layer 14.This medical device 10 can be implants the intravital object of body, for example nail, hone lamella or heart catheter support.Perhaps, this medical device 10 can be the intravital object of temporary transient intrusion body, for example plain conductor or instruments.Perhaps, this medical device 10 is the object of the outer operation of health, for example perform the operation wrench or medical metals basin ware.
Below enumerate experimental example 1 to experimental example 3 the present invention is described, but the present invention is not limited in following experimental example.
Experimental example 1
The metal implant of experimental example 1 (being medical device) is an example with a titanium metal (be that medical device 10 comprises a metal level 12, this metal level 12 is a titanium metal), analyzes about 10 nanometers of surperficial natural oxidation layer thickness (nm) of this titanium metal; This titanium metal is soaked in one contains hydrogen peroxide (H
2O
2) acidic solution after, this acidic solution is 15%H
2O
2, soak time 6 hours, 40 ℃ of soaking temperatures, and analyze the titanium metal be soaked in behind the acidic solution, its result shows that the surface of metal titanium that is soaked in behind the acidic solution is a dusty blue, the thickness of its titanium metal zone of oxidation (that is: media layer 14) is greater than 300 nanometers (nm); At last, the titanium metal that is soaked in behind the acidic solution is carried out an electrodeposition process, with functional high-polymer 16: polyvinyl alcohol (PEG) is grafted on the media layer 14.Functional high-polymer 16 is transparent, and therefore, the color and luster of medical device 10 also is a dusty blue.
Whether afterwards, carry out animal experimental observation surface treatment method of the present invention can improve anti-tissue and be stained with sticking effect.Experimentation on animals is respectively with the titanium metal (PEG_Ti_H of experimental example 1 grafting functional polymer 16 after soaking acidic solution
2O
2), directly the titanium metal (PEG_Ti) of grafting functional polymer 16 and titanium metal (CP_Ti) are implanted the mouse epidermis and are observed it down and implant anti-tissue of a week, fortnight and implantation four stars phase and be stained with sticking effect, its result such as Fig. 5 are extremely shown in Figure 7.
Fig. 5 A to Fig. 5 G is that the tissue that resists in titanium metal implantation mouse next week of epidermis is stained with the bonding fruit, Fig. 6 A to Fig. 6 J resists tissue to be stained with the bonding fruit in titanium metal implantation mouse two weeks of epidermis, Fig. 7 A to Fig. 7 J is that anti-tissue of titanium metal implantation mouse epidermis four stars phase is stained with the bonding fruit, wherein the A group is stained with the bonding fruit for the subepidermal anti-tissue of titanium metal (CP_Ti) implantation mouse of tool natural oxidizing layer, the B group is implanted the subepidermal anti-tissue of mouse for the direct grafting functional polymer 16 of titanium metal (PEG_Ti) of tool natural oxidizing layer and is stained with the bonding fruit, and the C group is the titanium metal (PEG_Ti_H of grafting functional polymer 16 after soaking acidic solution
2O
2) implant the subepidermal anti-tissue of mouse and be stained with the bonding fruit.
Titanium metal is implanted mouse epidermis four stars after date, by Fig. 7 E, 7F and observe as can be known through OM to the experimentation on animals result of Fig. 7 G, white portion is organized the zone of seeking connections with, again by Fig. 7 H, 7I reaches to the sem analysis of Fig. 7 J and shows that its unfairness zone is tissue and is stained with sticking place, the result obtain A group and the titanium metal of B group implant the mouse epidermis down after, all there is clear and definite tissue to be stained with sticking phenomenon, sticking soft tissue is obviously organized than A or the B group is few and the surface of metal titanium of C group is stained with, in other words, surface treatment method of the present invention can promote anti-soft tissue attaching rate, promotes its anti-tissue of product whereby and is stained with sticking effect.
Experimental example 2
The metal implant of experimental example 2 (being medical device) is an example with a titanium metal, its about 10 nanometers of surperficial natural oxidation layer thickness (nm); This titanium metal is carried out an electrochemistry anodizing, the condition of electrochemistry anodizing is voltage 55V, 3 minutes treatment times, its result shows that the surface of metal titanium color and luster after the electrochemistry anodizing presents gold, its thickness of oxide layer then can be greater than 80 nanometers (nm) with the thickness of electro-deposition method grafting functional polymer 16 greater than 100 nanometers (nm).Therefore, can improve its surface oxidation layer thickness of titanium metal equally, effectively increase the surface hydroxyl amount, and then promote the quantity of grafting specific functionality polymer 16 by the electrochemistry anodizing.Functional high-polymer 16 is transparent, and therefore, the color and luster of medical device also is golden.
Experimental example 3
The metal implant of experimental example 3 (being medical device) is an example with a titanium metal, its about 10 nanometers of surperficial natural oxidation layer thickness (nm); This titanium metal is carried out a thermal treatment, its heat treated condition is, provide 600 ℃ of temperature to keep 1 hour in a thermally equivalent space, and the surface of metal titanium of analyzing after heat-treating is the bluish-green staggered color and luster of ash, its thickness of oxide layer then can be greater than 150 nanometers (nm) with the thickness of electro-deposition method grafting functional polymer 16 greater than 1 micron (μ m).Therefore, can improve its surface oxidation layer thickness of titanium metal equally, effectively increase the surface hydroxyl amount, and then promote the quantity of grafting specific functionality polymer 16 by thermal treatment.Functional high-polymer 16 is transparent, and therefore, the color and luster of medical device also is that ash is bluish-green staggered.
In sum, utilization of the present invention forms media layer by different modes, and is different and then present different color and lusters according to media layer thickness, therefore, the tangible identification degree of product tool, in addition, because the formation of media layer, and then the surface hydroxyl (OH) quantity of raising metal level.
In addition, the present invention again by electrochemistry grafting specific functionality polymer in the hydroxyl groups of layer on surface of metal (OH), effectively increase surface hydroxyl group quantity owing to produce the method for media layer, and then the high molecular quantity of lifting grafting specific functionality, therefore, can promote its anti-tissue of product and be stained with sticking effect.
Certainly; the present invention also can have other various embodiments; under the situation that does not deviate from spirit of the present invention and essence thereof; those of ordinary skill in the art work as can make various corresponding changes and distortion according to the present invention, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.
Claims (17)
1. the surface treatment method of a medical device is characterized in that, comprising:
One metal level is provided;
Form a media layer on the surface of this metal level, the thickness of this media layer is greater than the natural oxidation layer thickness of this layer on surface of metal; And
By an electrodeposition process one functional high-polymer with solubility is grafted on this media layer.
2. surface treatment method according to claim 1 is characterized in that, this electrodeposition process comprises:
This metal level is inserted in the electrolytic solution that contains this functional high-polymer; And
One electric current is provided, carries out this electrodeposition process reaction.
3. surface treatment method according to claim 1 is characterized in that, this functional high-polymer is the polymer of a terminal tool amido, and the polymer of this end tool amido is a polyvinyl alcohol.
4. surface treatment method according to claim 1 is characterized in that, the mode that forms this media layer is an electrochemistry anodizing, and this electrochemistry anodizing step comprises:
This metal level is placed the anode place, and an electrode is placed the negative electrode place; And
Provide an electric current in this metal level.
5. surface treatment method according to claim 4 is characterized in that, this electrochemistry anodizing range of reaction temperature can be between-20 to 60 ℃, and the voltage when carrying out anodizing can be between 5 to 200 volts.
6. surface treatment method according to claim 5 is characterized in that, preferably between-5 to 35 ℃, the voltage preferred range when carrying out anodizing is between 40 to 60 volts to this electrochemistry anodizing range of reaction temperature.
7. surface treatment method according to claim 1, it is characterized in that, the mode that forms this media layer is that a chemical immersion is handled, and this chemical immersion treatment step comprises: this metal level is soaked in an acidic solution, and this acidic solution is the solution that contains hydrogen peroxide.
8. surface treatment method according to claim 1 is characterized in that, the mode that forms this media layer is a thermal treatment, and this heat treatment step comprises: this metal is placed a thermally equivalent space; And provide the reaction times of temperature of reaction and between 30 minutes to 8 hours between 100 to 1000 ℃.
9. a medical device is characterized in that, comprising:
One metal level;
One media layer is formed on this metal level, and wherein, the thickness of this media layer is greater than the natural oxidation layer thickness of this layer on surface of metal; And
One has the functional high-polymer of solubility, is grafted on this media layer.
10. medical device according to claim 9 is characterized in that, this metal is alloy, a vitallium or the stainless steel that a titanium metal, contains titanium elements.
11. medical device according to claim 10 is characterized in that, this media layer is a titanium metal zone of oxidation, titanium alloy zone of oxidation, vitallium zone of oxidation or oxidizing layer of stainless steel.
12. medical device according to claim 11 is characterized in that, the color and luster that includes the medical device of this media layer is different from the color and luster of the medical device that includes natural oxidizing layer.
13. medical device according to claim 9 is characterized in that, this metal is a titanium metal, and this media layer is a titanium metal zone of oxidation, and the color and luster of this medical device is golden, dusty blue or grey bluish-green staggered.
14. medical device according to claim 9 is characterized in that, the thickness of this media layer is between between 10 nanometers to 20 micron.
15. medical device according to claim 9 is characterized in that, this medical device is for implanting the intravital object of body, and this object is nail, hone lamella or heart catheter support.
16. medical device according to claim 9 is characterized in that, this medical device is the temporary transient intravital object of body of invading, and this object is plain conductor or instruments.
17. medical device according to claim 9 is characterized in that, this medical device is the object of the outer operation of health, and this object is operation wrench or medical metals basin ware.
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|---|---|---|---|
| CN2010101139850A CN102146576A (en) | 2010-02-05 | 2010-02-05 | Medical appliance and surface treatment method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103170015A (en) * | 2011-12-21 | 2013-06-26 | 财团法人金属工业研究发展中心 | Electrostatic spinning device, implantation materials for guiding texture regeneration, and manufacturing method thereof |
| CN106662415A (en) * | 2014-08-07 | 2017-05-10 | 夏普株式会社 | Heat exchanger including fins with surface having bactericidal activity, metallic member with surface having bactericidal activity, method for inhibiting mold growth and sterilization method both using surface of fins of heat exchanger or surface of metallic member, and electrical water boiler, beverage supplier, and lunch box lid all including metallic member |
-
2010
- 2010-02-05 CN CN2010101139850A patent/CN102146576A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103170015A (en) * | 2011-12-21 | 2013-06-26 | 财团法人金属工业研究发展中心 | Electrostatic spinning device, implantation materials for guiding texture regeneration, and manufacturing method thereof |
| CN103170015B (en) * | 2011-12-21 | 2014-08-20 | 财团法人金属工业研究发展中心 | Electrostatic spinning device, implantation materials for guiding texture regeneration, and manufacturing method thereof |
| CN106662415A (en) * | 2014-08-07 | 2017-05-10 | 夏普株式会社 | Heat exchanger including fins with surface having bactericidal activity, metallic member with surface having bactericidal activity, method for inhibiting mold growth and sterilization method both using surface of fins of heat exchanger or surface of metallic member, and electrical water boiler, beverage supplier, and lunch box lid all including metallic member |
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Application publication date: 20110810 |