WO2024022534A1 - 一种抛光组合物及其应用 - Google Patents

一种抛光组合物及其应用 Download PDF

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Publication number
WO2024022534A1
WO2024022534A1 PCT/CN2023/110247 CN2023110247W WO2024022534A1 WO 2024022534 A1 WO2024022534 A1 WO 2024022534A1 CN 2023110247 W CN2023110247 W CN 2023110247W WO 2024022534 A1 WO2024022534 A1 WO 2024022534A1
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Prior art keywords
acid
polishing
polishing composition
stent
salts
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PCT/CN2023/110247
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English (en)
French (fr)
Inventor
刘自强
张德元
张贵
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元心科技(深圳)有限公司
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Priority to CN202380009887.8A priority Critical patent/CN117795127A/zh
Publication of WO2024022534A1 publication Critical patent/WO2024022534A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F3/00—Brightening metals by chemical means

Definitions

  • the invention relates to the field of pure chemical polishing, and specifically to an efficient, stable and high-precision polishing composition.
  • polishing methods for metal surface treatment include electrochemical polishing, chemical polishing, mechanical polishing, and chemical mechanical polishing.
  • the polishing process is usually divided into several steps, that is, the polished parts are first Polishing, and then cleaning and passivation treatment on the newly polished surface of the polished parts, the process is relatively complicated.
  • patent CN102356184B discloses a method and solution for electropolishing stents made of high-strength medical alloys. This method requires attaching one or more conductive adapters to each stent. Distributors, current conductive components that connect the cathode and the anode, etc. are required at the same time. Not only do they have higher requirements for the equipment, but the embodiment also discloses that the entire polishing process needs to be repeated 4 times.
  • the present invention provides a chemical polishing composition and its application.
  • Each component in the chemical polishing composition is a relatively conventional compound with low cost.
  • the polishing composition can be used
  • the polishing process is simple and easy to operate, the polishing conditions are mild, the time is suitable and controllable, and the reproducibility is good, which is conducive to the precision control of the polished bracket.
  • the size of each position of the polished polished parts is uniform and the surface is smooth. , no burrs, rounded edges and corners, high precision, good stability, and the polished parts have good mechanical properties after polishing.
  • the technical solution of the present invention provides a polishing composition, which includes an acid, an oxidant and water, wherein the acid is selected from at least one of inorganic acids; the oxidant is selected from at least one of inorganic strong oxidants; the polishing combination
  • the pH of the material is ⁇ 1; further, the pH value of the polishing composition used in the present invention is not higher than 0.8, nor higher than 0.5. Furthermore, the pH value of the polishing composition used in the present invention is not higher than 0.2.
  • the speed of oxidation and corrosion on the surface of the pre-polished part can be fully controlled, and the amount of removal on the surface of the instrument can be increased to fully remove the internal factors of the pre-polished part. Cracks, etc. caused by the previous process can thereby improve the mechanical properties of the polished parts and meet the mechanical performance requirements of various types of instruments. On the other hand, it can fully improve the efficiency of polishing the polished parts and reduce the cost of polishing.
  • the inorganic acid in the polishing composition provided by the invention is selected from at least one of sulfuric acid, phosphoric acid, nitric acid, perchloric acid or hydrofluoric acid; in some embodiments of the invention, the inorganic acid in the polishing composition is sulfuric acid ; In other embodiments of the present invention, the inorganic acid in the polishing composition is a mixed acid of phosphoric acid and nitric acid. In still other embodiments of the present invention, the inorganic acid in the polishing composition is perchloric acid.
  • the inorganic strong oxidizing agent in the polishing composition provided by the invention is selected from the group consisting of persulfate, perchloric acid and its salts, perbromic acid and its salts, periodic acid and its salts, permanganic acid and its salts, and peroxyacid , iodic acid and its salts, chlorous acid and its salts, hypochlorous acid and its salts, hypoiodic acid and its salts, oxybromic acid and its salts, percarbonate, bromic acid and At least one of its salts, chloric acid and its salts, hydrogen peroxide, potassium nitrate or sodium nitrate.
  • the inorganic strong oxidant is one of the above-mentioned strong oxidants. In other embodiments, the inorganic strong oxidant is a mixture of two or more of the above-mentioned strong oxidants.
  • the mass percentage of inorganic acid in the polishing composition is 40%-70%; further, the mass percentage of inorganic acid in the polishing composition is 45%-70%, 48 %-70%, 50%-70%, 53%-70%, 55%-70%, 58%-70%, 40%-65%, 40%-68%, 40%-63%, 40%- 60%, 40%-58%, 40%-55%, 40%-53%, 40%-50%; further, the mass percentage of inorganic acid is 45%-65%, 45%-68% , 45%-63%, 45%-60%, 45%-58%, 45%-55%, 45%-53%, 45%-50%, 50%-65%, 55%-60% or 50 %-60%.
  • the mass percentage of the oxidant in the polishing composition is 5%-10%; further, the mass percentage of the oxidant in the polishing composition is 5%-8%, 5%- 9%, 5%-9.5%, 5%-8.5%, 5.5%-9.5%, 5.5%-10%, 6%-10%, 6.5%-10%, 7%-10%, 5%-7% , 6%-9% or 6%-8%; further, the mass percentage of the oxidant in the polishing composition is 6%-7% or 5%-6%.
  • the present invention controls the roundness of the instrument after polishing by regulating the viscosity of the polishing fluid.
  • the sharp edges of the instrument can be fully polished smooth. Roundness, no burrs, no edges and corners, etc., ensure that the medical device meets the corresponding safety requirements without polishing and removing too much of a certain part of the device, resulting in the formation of pits on its surface, which in turn affects the smoothness of its surface. and smoothness, and at the same time, the polishing fluid will not be too viscous and the polished parts will not be able to be polished in the polishing fluid.
  • the technical solution of the present invention puts forward higher requirements on the viscosity of the polishing liquid.
  • the viscosity of the polishing liquid cannot be too high. If it is too high, it will affect the rotation of the bracket, thereby affecting the polishing speed and polishing uniformity of the bracket.
  • Too viscous polishing fluid cannot flow smoothly on the inner wall of the stent, causing problems such as insufficient internal polishing of the stent, deep scratches on the inner wall, poor polished appearance, and poor mechanical properties of the polished stent; and if polished If the viscosity of the liquid is insufficient, the polished stent will be out of roundness, and the removal effect of burrs on the surface of the stent and scratches inside the stent matrix will be poor.
  • the viscosity of the polishing liquid is 1.1mPa s-4mPa s; further, the viscosity of the polishing liquid is 1.5mPa s-4mPa s, 1.2mPa s-4mPa s, 1.4mPa s-4mPa s, 1.6mPa s-4mPa s, 1.2mPa s-3.5mPa s, 1.4mPa s-3.5mPa s, 1.6mPa s-3.5 mPa s, 1mPa s-3.5mPa s, 1.8mPa s-3.5mPa s, 2.0mPa s-3.5mPa s, 1.2mPa s-3.4mPa s, 1.2mPa s-3.4mPa s, 1.2mPa s-3.4mPa s, 1.2mPa s-3.4mPa s, 1.2mPa s-3.2mPa
  • the viscosity of the polishing fluid is 1.9mPa s, 1.7mPa s, 2.1mPa s, 2.3mPa s, 2.5mPa s, 2.7mPa s, 2.9mPa s, 3.0mPa s, 3.1mPa s Or 3.3mPa s.
  • the viscosity of the polishing liquid is 3.5mPa s, 3.7mPa s or 3.9mPa s.
  • a viscous agent is used to further adjust the viscosity of the polishing liquid, and the mass percentage of the viscous agent is 1.5%-7%; further, the mass percentage of the viscous agent Content is 2%-7%, 2.5%-7%, 3%-7%, 3.5%-7%, 4.5%-7%, 4%-7%, 3.5%-6.5%, 2.5%-6.5%, 2.5%-7%, 2%-6.5%; further, the mass percentage of the thickener is 2%-6%, 2.5%-6%, 3%-6%, 4%-6% , 3.5%-6%, 1.5%-6%.
  • the viscous agent in the polishing composition is selected from alcohol, silicic acid, silicate, alginic acid, alginate, polyvinylpyrrolidone, modified organic matter of polyvinylpyrrolidone, ethanol Cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, polyacrylic acid, polysodium methacrylate, polycarboxylic acid sodium salt, carboxylic acid sodium salt copolymer substance, carboxylic acid sulfonic acid copolymer, guar gum, sodium starch phosphate, sodium polyacrylate, polyoxyethylene, carbomer, xanthic acid, gum arabic, carrageenan, agar, gelatin, gum arabic and its derivatives at least one of them.
  • the viscous agent of the polishing composition is silicic acid.
  • the viscous agent is hydroxypropyl methylcellulose.
  • the viscous agent is hydroxypropyl methylcellulose.
  • the thickener is a combination of a gum arabic derivative and alcohol.
  • the viscous agent in the polishing composition consists of at least one of the A components and at least one of the B components; wherein:
  • Component A is selected from alcohol, ethyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, polyvinylpyrrolidone, polyacrylic acid, polymethacrylate , at least one of polycarboxylic acid sodium salt, carboxylic acid sodium salt copolymer, carboxylic acid sulfonic acid copolymer and their derivatives;
  • Component B is selected from silicic acid, silicate, alginic acid, alginate, modified organic matter of polyvinylpyrrolidone, guar gum, sodium starch phosphate, sodium polyacrylate, polyoxyethylene, carbomer, xanthan A mixture of at least one of acid, gum arabic, carrageenan, agar, gelatin, gum arabic and derivatives thereof.
  • the thickener is ethyl cellulose and guar gum, and in other embodiments, the thickener is sodium silicate and sodium polymethacrylate.
  • the mass ratio of component A to component B of the viscous agent in the polishing composition is 0.5:1-15:1. Further, the mass ratio of component A and component B of the viscous agent is 0.5:1-10:1; further, the mass ratio of component A and component B of the viscous agent is 1.5. :1-10:1.
  • the molecular weight Mn of the alcohol in the viscous agent is ⁇ 800g/mol; further, the molecular weight of the viscous agent is ⁇ 720g/mol; further, in the present invention
  • Alcohols and their derivatives refer to alcohols that are liquid at room temperature. They can be straight-chain alcohols or branched-chain alcohols, and the position of the hydroxyl group is not fixed.
  • butanediol can be four methyl alcohols.
  • the radicals, methylene and/or methine are arranged in a straight chain, or the carbon chain can contain quaternary carbon atoms.
  • the positions of the two hydroxyl groups can also be freely changed on the four carbon atoms, and so on.
  • the alcohol and its derivatives are monoalcohol monomers and polyol monomers with a carbon number of no more than 6, and monoalcohols or polyols with a carbon number of no more than 6. At least one of the polymers formed.
  • the alcohol and its derivatives are ethylene glycol, propylene glycol, glycerin, butylene glycol, polyethylene glycol, butanol, cyclohexanol, polypropylene glycol, polybutylene glycol, etc. At least one of the glycols.
  • a complexing agent of a specific type and mass content can also be further added to the polishing composition containing inorganic acid and strong oxidant.
  • the complexing agent can be fully combined with the polished surface. Metal ions are combined to avoid excessive metal ion content and fully extend the service life of the polishing fluid.
  • the mass percentage of the complexing agent is 0.5%-2%, and further, the mass percentage of the complexing agent is 1%-2%.
  • the complexing agent has a monodentate or multidentate ligand; the complexing agent is selected from the group consisting of amino group, carboxyl group, cyanide, thiocyanate, isothiocyanate, nitrate radical, hydroxyl, sulfhydryl At least one of a group, an aromatic heterocyclic group, a nitroso group, a sulfo group, a phosphate group and an organic phosphine group.
  • the complexing agent is selected from at least one of hydroxycarboxylic acid, aminocarboxylic acid, hydroxylamine carboxylic acid, hydroxyphosphonic acid, dicarboxylic acid and their salts.
  • the complexing agent is selected from the group consisting of oxalic acid, aminotrimethylenephosphonic acid, hydroxyethylidenediphosphonic acid, ethylenediaminetetramethylenephosphonic acid, aminetrimethylenephosphonic acid, Ethylenetriaminepentacarboxylic acid, ethylenediaminetetramethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentamethylenephosphonic acid, aminotrimethylenephosphonic acid, hydroxyethylenediphosphonic acid, 2-hydroxyphosphine Acetoacetic acid, dihexenyl triamine pentamethylene phosphonic acid, 2-phosphono-1,2,4-butanetricarboxylic acid, heptose acid, 2-phosphonic acid butane-1,2,4-tri Carboxylic acid, itaconic acid, succinic acid, tartaric acid, maleic acid, glycolic acid, malonic acid, oxalic acid, malic
  • a certain component in the polishing composition of the present invention is selected from at least one of a, b, c, d and their derivatives, or a certain component in the polishing composition of the present invention is selected from the group consisting of a, b, c, d and their derivatives.
  • At least one of a, b, c, d and their salts refers to a component in the polishing composition selected from a, a derivative, b, b derivative, c, c derivative , at least one of the derivatives of d and d, or a certain component in the polishing composition selected from a, salts of a, salts of b, b, salts of c, c, salts of d, d At least one of the categories.
  • the complexing agent is selected from at least one of hydroxycarboxylic acid, aminocarboxylic acid, hydroxylamine carboxylic acid, hydroxyphosphonic acid, dicarboxylic acid and their salts
  • the complexing agent is selected from hydroxycarboxylic acid.
  • alginates include sodium alginate, potassium alginate, ammonium alginate, calcium alginate, and magnesium alginate;
  • silicates include aluminum silicate, iron silicate, calcium silicate, magnesium silicate, potassium silicate, and silicon. sodium acid, and so on.
  • polishing combinations containing inorganic acids and oxidants can also be used.
  • the surface protective agent is further added to the material to ensure that a thin protective film can be formed on the surface of the polished parts after polishing to prevent the polished parts from being oxidized in the air, thereby ensuring that the polished parts can remain bright and smooth for a long time. At the same time, it can also improve the chemical stability of polished parts and extend their shelf life or service life.
  • the polishing composition further includes a surface protective agent; the mass percentage of the surface protective agent is 0.02%-1%, and further, the mass percentage of the surface protective agent is 0.02%-1%.
  • the content is 0.05%-0.7%, 0.05%-0.8%, 0.05%-0.6%, 0.05%-0.5%, 0.05%-0.4%, 0.05%-0.3%, 0.05%-0.2%, 0.05%-0.1% , 0.1%-0.8%, 0.1%-0.7%, 0.1%-0.6%, 0.1%-0.5%, 0.1%-0.4% or 0.1%-0.3%, 0.1%-0.9%, 0.05%-1%.
  • the surface protective agent is selected from at least one of tannic acid, phytic acid, stearic acid, palmitic acid and their salts. That is, the surface protective agent can be at least one of tannic acid, phytic acid, stearic acid, palmitic acid, tanninate, phytate, stearate, and palmitate, or It can be a mixture of at least one of tannic acid, phytic acid, stearic acid, and palmitic acid and at least one of tannin, phytate, stearate, and palmitate, and the salt Including but not limited to sodium, potassium, ammonium, calcium or magnesium salts.
  • surfactants of a specific type and mass content can be further added to the polishing composition containing inorganic acid and strong oxidant, so that the surface tension of the liquid can be reduced through the surfactants, making the polishing liquid
  • the components in it are fully dispersed, which is conducive to the flow of polishing liquid on the inner and outer walls of the bracket, so that the composition of the polishing liquid near each part of the pre-polished part is basically the same, thereby ensuring that the effect of the polishing liquid on each part of the pre-polished part is basically the same. Maintain consistency and ultimately ensure the uniformity of the surface of the finished polished parts.
  • the surfactant also has a certain thickening effect on water.
  • polishing fluid on metal can also repair dents, damage and uneven parts on the surface of polished parts, thereby improving the flatness and brightness of the workpiece, making the surface of the polished parts bright and uniform.
  • the surfactant is at least one of anionic surfactant, cationic surfactant, nonionic surfactant and amphoteric surfactant.
  • the mass percentage of the surfactant is 0.05%-1%, and further, the mass percentage of the surfactant is 0.05%-0.7%, 0.05%- 0.8%, 0.05%-0.6%, 0.05%-0.5%, 0.05%-0.4%, 0.05%-0.3%, 0.05%-0.2%, 0.05%-0.1%, 0.1%-0.8%, 0.1%-0.7% , 0.1%-0.6%, 0.1%-0.5%, 0.1%-0.4% or 0.1%-0.3%, 0.1%-0.9%, 0.05%-1%.
  • the surfactant is selected from higher fatty acid salts, alkyl sulfonates, alkyl ether carboxylate surfactants, silicone surfactants, alkane sulfates, alkane sulfonates Acid, substituted amine salt, betaine, polyethylene oxide, polyvinyl alcohol, polyvinyl acetate, polyacrylic acid, polyvinylpyrrolidone, lecithin, amino acid derivatives, alkylphenol polyoxyethylene ether, fatty alcohol Polyoxyethylene ether sodium sulfate, isooctyl polyoxyethylene ether, alkyl glucoside, polyoxyethylene ether, polyethylene imine, alkyl trimethyl quaternary ammonium salt, alkyl dimethyl benzyl ammonium chloride salt Or at least one of pyridinium salts.
  • the surfactant is selected from sodium dodecyl sulfate, sodium dodecyl sulfonate, OP-10, linear alkyl benzene sodium sulfonate (LAS), fatty alcohol Sodium polyoxyethylene ether sulfate (AES), fatty alcohol ammonium polyoxyethylene ether sulfate (AESA), sodium lauryl sulfate (SDS), lauroyl glutamic acid, nonylphenol polyoxyethylene ether (TX-10), hard Fatty acid monoglyceride, lignin sulfonate, heavy alkyl benzene sulfonate, alkyl sulfonate, diffusing agent NNO, diffusing agent MF, alkyl polyether (PO-EO copolymer), fatty alcohol polyoxygen Vinyl ether (AEO-3), betaine, alkyl trimethyl quaternary ammonium salt, lecithin, amino acid derivatives, alkyl
  • the present invention also provides an application of a polishing composition in the polishing of medical devices.
  • the mass of the medical device is relatively small, and the mass of a single polished part of the medical device is generally less than 0.5Kg.
  • the single polished medical device here can be a certain part of a specific medical device, or it can be the entire medical device.
  • the medical device is a degradable medical device.
  • the medical devices include iron-containing medical devices; the iron-containing medical devices refer to devices that may be entirely composed of iron elements, or may be composed of iron elements and other elements.
  • the medical device composed of it can be made of pure iron material or iron-containing alloy; the iron-containing medical device can be that the entire device is made of iron-containing material, or a certain component or part of the device can be made of iron-containing material.
  • the medical device includes interventional materials/devices or implanted materials/devices used in the living body.
  • the medical device includes a degradable metal or a metal alloy; the medical device includes a vascular stent, a non-vascular intraluminal stent, an occluder, a gasket, an artificial Blood vessels, dental implants, vascular clips, artificial heart valves, orthopedic implants, dental implants, respiratory implants, gynecological implants, andrological implants, sutures or bolts.
  • the orthopedic implants include bone nails, bone plates, etc.
  • the polishing composition provided by the present invention is suitable for polishing metals, and is particularly suitable for polishing iron-based or iron-based alloys.
  • the iron-based alloys include low alloy steel or iron-based alloys with a carbon content of no more than 2.5 wt.%.
  • the polishing composition provided by the invention is suitable for polishing some products that are small in size and have complex structures.
  • the mass-to-volume ratio of the medical device polishing parts is 0.001g/cm 3 -0.4g/cm 3 ; further, the mass-to-volume ratio of the medical device polishing parts is 0.002g/ cm 3 -0.3g/cm 3 ; further, the mass-to-volume ratio of the polished medical device is 0.005g/cm 3 -0.25g/cm 3 .
  • the iron-containing medical device is pure iron or an iron-based alloy with a carbon content of no more than 2.11 wt%.
  • the mass percentage of each component described in the present invention refers to the mass percentage of the core component of each component as a solute in the entire polishing composition.
  • a certain component M itself is a solution, and its solute is J
  • the mass percentage of this component in the polishing composition refers to the mass percentage of J in the entire polishing composition K.
  • the mass percentage of M in the entire polishing composition Rather than the mass percentage of M in the entire polishing composition. That is, the mass of J as a percentage of the mass of composition K.
  • the mass percentage of each component plus water in the polishing composition of the present invention is 100%, that is, the composition is a mixed solution composed of each core component and water.
  • each component cooperates with each other and cooperates with each other, ultimately ensuring that the polished part has a smooth, round and bright surface, and ensures that the surface has no burrs or edges. , reduce the stimulation and damage of the device to the human body, and at the same time fully improve the mechanical performance of the device to ensure that it can meet the corresponding mechanical performance requirements in various application scenarios.
  • the polishing composition provided by the present invention not only has high polishing efficiency, but also keeps various parameters stable after polishing each two or more polishing parts, has high polishing accuracy and ensures controllable product weight.
  • the polishing composition provided in the present invention can polish polishing parts under certain conditions.
  • the removal amount of polishing parts after polishing can reach 20%-60%, and the polishing uniformity of each part of the instrument can reach 85% or 90%. , 95% or even above 98%.
  • all parts of the polished parts have a bright and smooth surface without scratches after being magnified 200 times by an optical microscope. There is no sign of breakage after the polished parts are bent hundreds of times, pulled up, and expanded several times. .
  • Each component in the polishing composition provided by the present invention is a relatively conventional compound with low cost.
  • Using this polishing composition for polishing not only has a simple polishing process and is easy to operate, but also has mild polishing conditions and suitable and controllable time. Good reproducibility is conducive to the precision control of polished brackets. Multiple identical brackets are polished under the same conditions. The RSD of the weight of multiple polished brackets is within 2%, or even within 0.8%.
  • the size of each position of the polished polishing part is uniform, the surface is smooth, burr-free, the edges and corners are rounded, the precision is high, the stability is good, and the polished polishing part has good mechanical properties.
  • the polishing process in the present invention is simple to operate. It only needs to put the pre-polished parts into the prepared polishing liquid and polish them under certain conditions for several minutes or tens of minutes. There is no need to perform subsequent passivation and other steps. High-quality polished parts can be obtained, and the polishing stability and repeatability of the polished parts are high.
  • the finished product after the polishing part is polished in the polishing composition is magnified 500 times under an SEM electron microscope and has slight scratches on the surface of the instrument polishing part, wherein the area occupied by the scratches is the same as the entire polishing
  • the ratio of the surface area of the polishing part is ⁇ 20%; further, when the polishing part provided by the invention is magnified 500 times under the SEM electron microscope, the scratch area on the surface of the polishing part only accounts for no more than 15% or 10% of the surface area of the entire polishing part. Not even more than 6%.
  • the scratch depth of the finished product after polishing the polishing part in the polishing composition is h ⁇ 2.5 ⁇ m. Furthermore, the scratch depth of the polishing part can be less than 1 ⁇ m; further, the scratch depth of the polishing part can be less than 1 ⁇ m. The depth of the mark may be less than 0.5 ⁇ m or less than 0.3 ⁇ m.
  • the roughness Sa of the finished product surface of the polished parts after being polished in the polishing composition is ⁇ 50 nm. Furthermore, the surface roughness Sa of the polished parts of medical devices is not greater than 30 nm. Furthermore, the surface roughness Sa of the polished parts of medical devices is not greater than 30 nm. The surface roughness Sa of the instrument polishing parts is not greater than 20nm.
  • a thin protective film is attached to the surface of the finished product after polishing the polishing part in the polishing composition, so that the surface of the polishing part has relatively good stability and is not easily oxygenated by the air. Chemicalization, etc., to ensure the stability of surface appearance and performance of polished instruments during transfer and storage.
  • the finished product after polishing the polishing parts in the polishing composition will have a smooth and bright surface after being magnified 100 times under an optical electron microscope; further, the polished parts will have a smooth and bright surface after being magnified 200 times under an optical electron microscope or It still has a smooth and bright surface after 250 times.
  • the polishing composition provided by the present invention can fully control the polishing removal amount of each part of the medical device polishing parts during the polishing process, ensuring that the polishing uniformity of the polishing parts can reach more than 85%. More preferably, the polishing uniformity of the polishing parts can be achieved in the polishing process. Control it at more than 90%, 95% or even 98%, thereby ensuring that the entire polished medical device has no weak points and has good mechanical properties as a whole.
  • the uniformity of polishing of the polishing part in the present invention refers to the relatively uniform size of the polishing part after polishing, that is, the polishing uniformity refers to the width/thickness R i of the polishing part after polishing at the same part of the polishing part and the same part of the polishing part
  • the ratio of the average width/thickness after polishing that is For example, if the size uniformity of polished parts of medical devices after polishing reaches more than 85% during the polishing process, it refers to
  • the polishing composition provided by the present invention has high stability during the polishing process of polishing parts. After polishing dozens of brackets at the same time, the brackets still have a good appearance, and the dimensions, weight and other parameters of the brackets still remain the same. Stablize.
  • the present invention describes the advantages of the technical solution of the present invention separately.
  • the solution provided by the present invention is an inseparable whole, and the various components in the solution need to cooperate and interact with each other to achieve the desired results.
  • a certain component cannot achieve very good results independently.
  • the viscous agent in the present invention can improve the smoothness of the surface of the polishing part
  • the viscosity of the solution is the result of the interaction of all components, not just the result of the action of the viscosity agent, that is, the final polished surface of the polishing part
  • the smoothness is inseparable from the joint action of each component.
  • the value of the interval range involved in the present invention is not limited to the provided interval range, but should be the value of a new interval composed of any two values in the interval or any one of the intervals. Any specific value can be taken.
  • the content of surfactant is 0.05%-0.1%
  • the content value of surfactant is not limited to the value range of 0.05-1%, and can be A new interval composed of any two values among the countless values between 0.05% and 1%, such as 0.05% and 0.5%, or 0.1% and 0.8%, etc.
  • each parameter can You can select any value within its value range, and the values of multiple parameters can be matched arbitrarily.
  • the viscosity of the polishing fluid is 1-4mPa s.
  • the pH value of the polishing fluid can be any value in the range of no more than 1, and the viscosity of the polishing fluid can be any value in the range of 1-4 mPa s. These two parameters can also be matched arbitrarily, for example, the pH value is 0.1, the viscosity of the polishing fluid is 3.5mPa s, and so on.
  • references to the terms “one embodiment,” “some embodiments,” “an example,” “specific examples,” or “some examples” or the like means that specific features are described in connection with the embodiment or example. , structures, materials or features are included in at least one embodiment or example of the present application. In this specification, the schematic expressions of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the specific features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, those skilled in the art may combine and combine different embodiments or examples and features of different embodiments or examples described in this specification unless they are inconsistent with each other.
  • Figure 1 is a characterization diagram of the stent in Example 1 magnified 500 times under a SEM scanning electron microscope;
  • Figure 2 is a characterization diagram of the stent in Example 1 magnified 200 times under an optical microscope
  • Figure 3 is a characterization diagram of the scaffold in Comparative Example 1 magnified 200 times under an optical microscope.
  • the Q-SIX cardiovascular stent detector produced by SENSOFAR Company is used to detect the roughness of the surface of the polished part under the condition of magnifying 400 times under the interference lens and setting the scanning height to 50 ⁇ m.
  • the stent was sealed and polished with a polishing machine until the cross-section of the stent was exposed. Finally, the polished cross-section was placed under a metallographic microscope to measure the scratch depth.
  • Radial strength In terms of performance testing of the lumen stent, the radial strength of the lumen stent can be used to apply radial pressure evenly on the stent through the compression module, causing the stent to compress and produce uniform deformation.
  • the radial strength of the stent is defined as the radial pressure exerted when the stent is deformed by 10% in the radial direction (outer diameter).
  • the depth is 1 ⁇ m
  • the depth of single-sided removal of the stent rod is 15 ⁇ m
  • the uniformity of the stent polishing is 90%
  • the mass loss rate of the stent is 45%
  • the roughness Sa of the stent surface measured under the sensofar3D optical profiler is 15nm
  • the stent surface roughness Sa is 15nm.
  • the radial strength is 120kPa; it is expanded to a diameter of 4.6mm with a balloon without cracks or breaks. Continuously repeat polishing of 5 stents, and the RSD of the polished stent quality is ⁇ 1%.
  • the surface scratch area accounted for 2%, and the scratches were the largest.
  • the depth is 0.5 ⁇ m, the depth of single-sided removal of the stent rod is 15 ⁇ m, and the uniformity of the stent polishing is 95%; the mass loss rate of the stent is 42%, and the roughness Sa of the stent surface measured under the sensofar3D optical profiler is 10nm;
  • the radial strength of the stent is 115kPa; it was expanded to a diameter of 4.6mm with a balloon without cracks or breaks. Continuously repeat polishing of 5 stents, and the RSD of the polished stent quality is ⁇ 1.5%. Continuously repeat polishing of 5 stents, and the RSD of the polished stent quality is ⁇ 1.5%.
  • the radial strength of the stent was 120kPa; it was expanded to a diameter of 4.6mm with a balloon, and there were no cracks or breaks. There was no obvious change after the stent was stored for 4 weeks. Continuously repeat polishing of 5 stents, and the RSD of the polished stent quality is ⁇ 2.5%.
  • the dried stent was observed under an optical microscope with a magnification of 200 times.
  • the surface was smooth and shiny. It was observed under a SEM with a magnification of 500 times.
  • the edges and corners of the stent were rounded.
  • the surface scratch area accounted for 2%, and the scratches were the largest.
  • the depth is 0.5 ⁇ m, the depth of single-sided removal of the stent rod is 15 ⁇ m, and the uniformity of the stent polishing is 92%; the mass loss rate of the stent is 46%, and the roughness Sa of the stent surface measured under the sensofar3D optical profiler is 20nm;
  • the radial strength of the stent is 115kPa; it was expanded to a diameter of 4.6mm with a balloon without cracks or breaks. Continuously repeat polishing of 5 stents, and the RSD of the polished stent quality is ⁇ 3%.
  • the dried stent was observed under an optical microscope with a magnification of 200 times.
  • the surface was smooth and shiny. It was observed under a SEM with a magnification of 500 times.
  • the edges and corners of the stent were rounded.
  • the surface scratch area accounted for 2%, and the scratches were the largest.
  • the depth is 0.3 ⁇ m, the depth of single-sided removal of the stent rod is 15 ⁇ m, and the uniformity of the stent polishing is 95%; the mass loss rate of the stent is 43%, and the roughness Sa of the stent surface measured under the sensofar3D optical profiler is 12nm;
  • the radial strength of the stent is 118kPa; it was expanded to a diameter of 4.6mm with a balloon without cracks or breaks. Continuously repeat polishing of 5 stents, and the RSD of the polished stent quality is ⁇ 3%.
  • the surface scratch area accounted for 2.5%, and the scratches were the largest.
  • the depth is 2 ⁇ m, the depth of single-sided removal of the stent rod is 15 ⁇ m, the uniformity of the stent polishing is 85%; the mass loss rate of the stent is 44%, and the roughness Sa of the stent surface measured under the sensofar3D optical profiler is 18nm; the stent surface roughness Sa is 18nm.
  • the radial strength is 115kPa; it breaks when expanded with a balloon to a diameter of 4.5mm. Continuously repeat polishing of 5 stents, and the RSD of the polished stent quality is ⁇ 3%.
  • the surface scratch area accounted for 2%, and the scratches were the largest.
  • the depth is 1.2 ⁇ m, the depth of single-sided removal of the stent rod is 1.5 ⁇ m, the uniformity of the stent polishing is 88%; the mass loss rate of the stent is 48%, and the roughness Sa of the stent surface measured under the sensofar3D optical profiler is 25nm. ;
  • the radial strength of the stent is 120kPa; it was expanded to a diameter of 4.6mm with a balloon. There were no cracks or breaks. There were yellow spots on the surface of the stent after being stored for 7 days. Continuously repeat polishing of 5 stents, and the RSD of the polished stent quality is ⁇ 2%.
  • the surface scratch area accounted for 3%, and the scratches were the largest.
  • the depth is 2.5 ⁇ m, the depth of single-sided removal of the stent rod is 15 ⁇ m, and the uniformity of the stent polishing is 82%; the mass loss rate of the stent is 48%, and the roughness Sa of the stent surface measured under the sensofar3D optical profiler is 30nm;
  • the radial strength of the stent is 128kPa; it is expanded with a balloon to The stent broke when the diameter was 4.0mm. Continuously repeat polishing of 5 stents, and the RSD of the polished stent quality is ⁇ 1.5%.
  • the surface scratch area accounts for 5%, the maximum depth of the scratch is 6 ⁇ m, the depth of single-sided removal of the inner wall of the stent rod is 5 ⁇ m, the uniformity of the stent polishing is 50%; the mass loss rate of the stent is 50%, in sensofar3D
  • the roughness Sa of the stent surface measured by an optical profilometer was 200nm; the radial strength of the stent was 95kPa; the stent broke when expanded with a balloon to a diameter of 3.5mm. Continue to polish 5 stents repeatedly, and the RSD of the polished stent quality is ⁇ 3%.
  • the maximum depth of the scratch is 0.5 ⁇ m, the depth of single-sided removal of the inner wall of the stent rod is 16 ⁇ m, the uniformity of the stent polishing is 90%; the mass loss rate of the stent is 65%, and the roughness of the stent surface was measured under the sensofar3D optical profiler
  • the degree Sa is 250nm; the radial strength of the stent is 70kPa; the stent breaks when expanded with a balloon to a diameter of 4.0mm. Continue to polish 5 stents repeatedly, and the RSD of the quality of the polished stents is >10%.

Abstract

一种抛光组合物及其应用，具体涉及一种高效、稳定、高精度的抛光组合物。该抛光组合物包括酸、氧化剂和水，其中酸选自无机酸，氧化剂选自无机氧化剂，且抛光组合物的pH值≤1。所述抛光组合物适用于医疗器械的抛光，尤其适用于去除量比较大的医疗器械的抛光，该组合物应用于抛光具有抛光精度高、操作简单、方便、成本低等优点，同时抛光后的产品具有较好的机械性能、表面性能和生物安全性。

Description

一种抛光组合物及其应用 技术领域
本发明涉及纯化学抛光领域，具体涉及一种高效、稳定、高精度的抛光组合物。
背景技术
近几年来，随着医疗器械行业的高速发展，各类医疗器械大量的投入研发中，但由于绝大多数医疗器械在使用过程中对其棱角的光滑度，器械各部分的尺寸、强度等的均匀度等提出了较高的要求，而抛光工艺是影响上述性能的关键因素，因此对医疗器械的抛光工艺及抛光用组合物也提出了较高的要求。
目前，金属表面处理常用的抛光方法包括电化学抛光、化学抛光、机械抛光，以及化学机械抛光。在上述常用的抛光方法中，为了防止抛光之后所形成的新抛光表面在空气中很快被氧化，确保器械表面稳定性，通常都会将抛光工艺分为几步进行，也即先对抛光件进行抛光，再对抛光件新抛光后的表面进行清洗和钝化处理，工艺相对较为复杂。而电化学抛光由于电解槽中不同位置的电流密度等存在较大的差别，在抛光件整体去除量较大的情况下容易导致预抛光件不同位置的抛光去除量存在较大的差异，从而容易导致预抛光件抛光后的各处尺寸的均匀度不高；而机械抛光或化学机械抛光，通常会在抛光组合物中添加磨料，通过机械研磨的方法去除预抛光件的部分材料，从而达到相应的效果，但磨料的存在，一方面会容易粘附并残留在抛光件上，另一方面也容易在抛光件表面留下划痕，导致抛光件表面不够光滑，因此带有机械方式抛光的方法不太适合医疗器械等对产品有严格要求的技术领域，同时带有机械方式抛光的方法对抛光件的尺寸等也有一些限定，不太适合小尺寸且结构复杂的抛光件的抛光；而化学抛光虽然具有成本低、操作简单等优点，但是化抛常用的无机酸、强碱等组分，限制了其使用。
目前，在医疗器械领域，由于现有的医疗器械在抛光过程中的去除量小，使得电化学抛光也能满足现有器械对均匀性等方面的要求，因此，常用的仍为电化学抛光方法。如专利CN102356184B中公开了一种对高强度医疗合金制成的支架进行电抛光方法和溶液，该方法需要对每个支架附接一个或多个导电适 配器，同时需要连接阴极和阳极的电流传导构件等，不仅对设备有较高的要求，同时在其实施例中还公开需要将整个抛光工序重复4次，此外，在抛光之后还需将冲洗后的支架侵入钝化溶液中进行钝化处理抛光后形成的新抛光表面，进而防止新抛光表面在空气中快速被氧化，该专利中所公开的抛光工艺存在工序复杂、操作麻烦等问题。
发明内容
为了克服上述现有技术中存在的缺陷，本发明提供了一种化学抛光组合物及其应用，该化学抛光组合物中的各组分均为比较常规的化合物，成本低，同时用该抛光组合物进行抛光，不仅抛光工艺流程简单、易操作，抛光条件温和，时间适宜可控，重现性好，有利于抛光后支架的精度控制，同时抛光后的抛光件各个位置的尺寸均匀，表面光滑，无毛刺，棱角圆润，精度高，稳定性好，且抛光后的抛光件具有较好的机械性能。
本发明的技术方案提供了一种抛光组合物，该组合物包括酸、氧化剂和水，其中酸选自无机酸中的至少一种；氧化剂选自无机强氧化剂中至少一种；该抛光用组合物的pH≤1；进一步的，本发明中所用抛光组合物的pH值不高于0.8，也不高于0.5，更进一步的，本发明中所用抛光组合物的pH值不高于0.2。
本发明中通过采用特定种类的无机酸和强氧化剂，并调控其含量，可充分控制预抛光件表面的氧化和腐蚀的速度，同时可以增加器械表面的去除量，以便充分去除预抛光件内部因前序工艺所产生的裂痕等，进而提升抛光件的机械性能，满足各类器械对抛光件机械性能的要求，另一方面，可充分的提升抛光件抛光的效率，降低抛光的成本。
本发明所提供抛光组合物中的无机酸选自硫酸、磷酸、硝酸、高氯酸或氢氟酸中的至少一种；在本发明的一些实施例中，抛光组合物中的无机酸为硫酸；在本发明的另外一些实施例中，抛光组合物中的无机酸为磷酸和硝酸的混合酸，在本发明的还有一些实施例中，抛光组合物中的无机酸为高氯酸。
本发明所提供抛光组合物中的无机强氧化剂选自过硫酸盐、高氯酸及其盐、高溴酸及其盐、高碘酸及其盐、高锰酸及其盐、过氧酸盐、碘酸及其盐、亚氯酸及其盐、次氯酸及其盐、次碘酸及其盐、氧溴酸及其盐、过碳酸盐、溴酸及 其盐、氯酸及其盐、双氧水、硝酸钾或硝酸钠中的至少一种。在本发明的一些实施例中，所述无机强氧化剂为上述氧化剂中的一种，在其他一些实施例中，所述无机强氧化剂为上述强氧化剂中的两种或多种的混合物。
本发明所提供的上述技术方案中，抛光组合物中无机酸的质量百分含量为40％-70％；进一步的，抛光组合物中无机酸的质量百分含量为45％-70％、48％-70％、50％-70％、53％-70％、55％-70％、58％-70％、40％-65％、40％-68％、40％-63％、40％-60％、40％-58％、40％-55％、40％-53％、40％-50％；更进一步的，无机酸的质量百分含量为45％-65％、45％-68％、45％-63％、45％-60％、45％-58％、45％-55％、45％-53％、45％-50％、50％-65％、55％-60％或50％-60％。
本发明所提供的上述技术方案中，抛光组合物中氧化剂的质量百分含量为5％-10％；进一步的，抛光组合物中氧化剂的质量百分含量为5％-8％、5％-9％、5％-9.5％、5％-8.5％、5.5％-9.5％、5.5％-10％、6％-10％、6.5％-10％、7％-10％、5％-7％、6％-9％或6％-8％；更进一步的，抛光组合物中氧化剂的质量百分含量为6％-7％或5％-6％。
本发明通过调控抛光液的粘稠度，来控制器械抛光后的圆润度，本发明中通过将抛光液的粘稠度控制在一定的范围内，既可以充分的将器械的尖锐边缘抛得光滑圆润、无毛刺、边缘无棱角等，确保医疗器械达到相应安全性的要求，又不至于将器械某一位置抛光去除太多，从而导致在其表面形成凹坑等，进而影响其表面的光滑度和平整度，同时也不至于因为抛光液太过粘稠，抛光件在抛光液中无法。
本发明的技术方案对抛光液的粘稠度提出了较高的要求，抛光液的粘稠度不能太高，太高之后会影响支架的转动，进而影响支架的抛光速度和抛光均匀度，同时太粘稠的抛光液不能在支架内壁顺畅的流动，从而使得支架存在内部抛光不足、内壁存在较深的划痕、抛光的外观较差、抛光后支架的机械性能不好等问题；而如果抛光液的粘稠度不足，抛光后的支架会出现不圆润、支架表面的毛刺和支架基体内部的划痕的去除效果也不佳等。
本发明所提供的上述技术方案中，所述抛光液的粘稠度为1.1mPa s-4mPa s；进一步的，抛光液的粘稠度为1.5mPa s-4mPa s、1.2mPa s-4mPa s、1.4mPa s-4mPa s、1.6mPa s-4mPa s、1.2mPa s-3.5mPa s、1.4mPa s-3.5mPa s、1.6mPa s-3.5 mPa s、1mPa s-3.5mPa s、1.8mPa s-3.5mPa s、2.0mPa s-3.5mPa s、1.2mPa s-3.4mPa s、1.2mPa s-3.4mPa s、1.2mPa s-3.2mPa s、1.2mPa s-3.6mPa s、1.2mPa s-3.0mPa s、1.4mPa s-3.3mPa s；更进一步的，抛光液的粘稠度为1.4mPa s-3.0mPa s、1.4mPa s-3.2mPa s、1.6mPa s-3.0mPa s、1.6mPa s-2.9mPa s。在本发明的一些实施例中抛光液的粘稠度为1.9mPa s、1.7mPa s、2.1mPa s、2.3mPa s、2.5mPa s、2.7mPa s、2.9mPa s、3.0mPa s、3.1mPa s或3.3mPa s，在另外一些实施例中，抛光液的粘稠度为3.5mPa s、3.7mPa s或3.9mPa s。
本发明的上述技术方案中，采用粘稠剂来进一步的调整抛光液的粘稠度，粘稠剂的质量百分含量为1.5％-7％；进一步的，所述粘稠剂的质量百分含量为2％-7％、2.5％-7％、3％-7％、3.5％-7％、4.5％-7％、4％-7％、3.5％-6.5％、2.5％-6.5％、2.5％-7％、2％-6.5％；更进一步的，所述粘稠剂的质量百分含量为2％-6％、2.5％-6％、3％-6％、4％-6％、3.5％-6％、1.5％-6％。
在本发明所提供的上述技术方案中，抛光组合物中的粘稠剂选自醇、硅酸、硅酸盐、海藻酸、海藻酸盐、聚乙烯吡咯烷酮、聚乙烯吡咯烷酮的改性有机物、乙基纤维素、甲基纤维素、羟乙基纤维素、羟丙基甲基纤维素、羧甲基纤维素类、聚丙烯酸、聚甲基丙烯酸钠、聚羧酸钠盐、羧酸钠盐共聚物、羧酸磺酸共聚物、瓜尔胶、淀粉磷酸钠、聚丙烯酸钠、聚氧乙烯类、卡波姆、黄原酸、阿拉伯胶、卡拉胶、琼脂、明胶、阿拉伯树胶及其衍生物中的至少一种。如在本发明的一些实施方式中，所述抛光组合物的粘稠剂为硅酸，在另外一些实施例中，所述粘稠剂为羟丙基甲基纤维素，在还有一些实施例中，所述粘稠剂为阿拉伯树胶衍生物和醇的组合物。
在本发明的上述技术方案中，所述抛光组合物中的粘稠剂由A组分中的至少一种和B组分中的至少一种组成；其中：
A组分选自醇、乙基纤维素、甲基纤维素、羟乙基纤维素、羟丙基甲基纤维素、羧甲基纤维素类、聚乙烯吡咯烷酮、聚丙烯酸、聚甲基丙烯酸盐、聚羧酸钠盐、羧酸钠盐共聚物、羧酸磺酸共聚物及其衍生物中的至少一种；
B组分选自硅酸、硅酸盐、海藻酸、海藻酸盐、聚乙烯吡咯烷酮的改性有机物、瓜尔胶、淀粉磷酸钠、聚丙烯酸钠、聚氧乙烯类、卡波姆、黄原酸、阿拉伯胶、卡拉胶、琼脂、明胶、阿拉伯树胶及其衍生物中的至少一种的混合物。
在本发明的一些实施方式中，所述粘稠剂为乙基纤维素和瓜尔胶，在另外一些实施例中，粘稠剂为硅酸钠和聚甲基丙烯酸钠。
在本发明所提供的上述技术方案中，抛光组合物中的粘稠剂的A组分与B组分的质量比为0.5:1-15:1。进一步的，所述粘稠剂的A组分和B组分的质量比为0.5:1-10:1；更进一步的，所述粘稠剂的A组分和B组分的质量比为1.5:1-10:1。
在本发明所提供的上述技术方案中，所述粘稠剂中的醇的分子量Mn≤800g/mol；进一步的，所述粘稠剂的分子量≤720g/mol；更进一步的，本发明中的醇及其衍生物是指在常温下为液态的醇，可以是直链的醇，也可以是支链的醇，且其中羟基的位置也不固定，如丁二醇，既可以是四个甲基、亚甲基和/或次甲基成直链排列，也可以是碳链中含有季碳原子，此外，两个羟基的位置也可以在四个碳原子上随意变换，以此类推。
在本发明所提供的上述技术方案中，所述醇及其衍生物为碳原子数不大于6的单元醇单体、多元醇单体，以及碳原子数不大于6的单元醇或多元醇所形成的聚合物中的至少一种。
需要说明的是，本发明中的不大于、不高于均表示既可以小于也可以等于，如本发明中所述的“碳原子数不大于6的单元醇、多元醇”，是指碳原子数小于或等于6的单元醇或多元醇。
在本发明所提供的上述技术方案中，所述醇及其衍生物为乙二醇、丙二醇、丙三醇、丁二醇、聚乙二醇、丁醇、环己醇、聚丙二醇、聚丁二醇中的至少一种。
本发明所提供的上述技术方案中，还可以通过在含无机酸、强氧化剂的抛光组合物中进一步添加特定种类和质量含量的配位剂，一方面可以使配位剂充分的与抛光下来的金属离子结合，避免金属离子含量过高，充分延长抛光液的使用寿命。
在本发明所提供的上述技术方案中，所述配位剂的质量百分含量为0.5％-2％，进一步的，所述配位剂的质量百分含量为1％-2％。
在本发明所提供的上述技术方案中，所述配位剂具有单齿或多齿配体；所述配位剂选自含有氨基、羧基、氰根、硫氰根、异硫氰根、硝基、羟基、巯 基、芳杂环基团、亚硝基、磺基、磷酸基团及有机膦基团中的至少一种。
在本发明所提供的上述技术方案中，所述配位剂选自羟基羧酸、氨基羧酸、羟胺基羧酸、羟基膦酸、双羧酸及其盐类中的至少一种。
在本发明所提供的上述技术方案中，所述配位剂选自乙二酸、氨基三甲叉膦酸、羟基乙叉二膦酸、乙二胺四甲叉膦酸、胺三甲叉磷酸、二乙烯三胺五羧酸、乙二胺四甲叉磷酸、乙二胺四乙酸、二乙烯三胺五甲叉膦酸、氨基三亚甲基膦酸、羟基亚乙基二膦酸、2-羟基膦酰基乙酸、二己烯三胺五亚甲基膦酸、2-膦酰基-1,2,4-丁烷三羧酸、庚糖酸、2-膦酸丁烷-1，2，4-三羧酸、衣康酸、琥珀酸、酒石酸、马来酸、乙醇酸、丙二酸、草酸、苹果酸、葡萄糖酸、丙氨酸、甘氨酸、乳酸、二乙烯三胺五乙酸、三乙烯二胺、丙二胺四乙酸、羟乙基乙二胺、羟乙基乙二胺三乙酸、焦磷酸、2-氨基乙基膦酸、1-羟基乙叉1,1-二膦酸、氨基三亚甲基膦酸、乙二胺四亚甲基膦酸、二亚乙基三胺五亚甲基膦酸、乙烷-1,1-二膦酸、乙烷-1,1,2-三膦酸、甲烷羟基膦酸、1-膦酰基丁烷-2,3,4-三羧酸及其盐类、二羟基甘氨酸、EDTA二钠、丁二酸、聚乙烯醇、三乙醇胺及其盐中的至少一种。
需要说明的是，本发明中的抛光组合物中的某组分选自a、b、c、d及其衍生物中的至少一种，或本发明中的抛光组合物中的某组分选自a、b、c、d及其盐类中的至少一种，是指抛光组合物中的某组分选自a、a的衍生物、b、b的衍生物、c、c的衍生物、d、d的衍生物中的至少一种，或者抛光组合物中的某组分选自a、a的盐类、b、b的盐类、c、c的盐类、d、d的盐类中的至少一种。如“所述配位剂选自羟基羧酸、氨基羧酸、羟胺基羧酸、羟基膦酸、双羧酸及其盐类中的至少一种”是指所述配位剂选自羟基羧酸、氨基羧酸、羟胺基羧酸、羟基膦酸、双羧酸、羟基羧酸盐、氨基羧酸盐、羟胺基羧酸盐、羟基膦酸盐、双羧酸盐中的至少一种。
在本发明中所述的某某盐类，均指其对应的酸与相应的金属离子所形成的钠盐、钾盐、铵盐、钙盐、镁盐。如海藻酸盐包括海藻酸钠、海藻酸钾、海藻酸铵、海藻酸钙、海藻酸镁；硅酸盐包括硅酸铝、硅酸铁、硅酸钙、硅酸镁、硅酸钾、硅酸钠，以此类推。
本发明所提供的技术方案中，还可以通过在含无机酸、氧化剂的抛光组合 物中进一步的添加表面保护剂，确保抛光件在抛光后可在抛光件表面形成一层薄薄的保护膜，防止抛光件在空气中被氧化，进而确保抛光件可以长期的保持光亮、平滑，同时也可以提升抛光件的化学稳定性，延长其保质期或使用期。
在本发明所提供的上述技术方案中，所述抛光组合物还包括表面保护剂；所述表面保护剂的质量百分含量为0.02％-1％，进一步的，所述表面保护剂的质量百分含量为0.05％-0.7％、0.05％-0.8％、0.05％-0.6％、0.05％-0.5％、0.05％-0.4％、0.05％-0.3％、0.05％-0.2％、0.05％-0.1％、0.1％-0.8％、0.1％-0.7％、0.1％-0.6％、0.1％-0.5％、0.1％-0.4％或0.1％-0.3％、0.1％-0.9％、0.05％-1％。
本发明所提供的上述技术方案中，所述表面保护剂选自单宁酸、植酸、硬脂酸、软脂酸及其盐中的至少一种。也即所述表面保护剂既可以是单宁酸、植酸、硬脂酸、软脂酸、单宁酸盐、植酸盐、硬脂酸盐、软脂酸盐中的至少一种，也可以是单宁酸、植酸、硬脂酸、软脂酸中的至少一种与单宁酸盐、植酸盐、硬脂酸盐、软脂酸盐中的至少一种的混合物，而盐包括但不限于钠盐、钾盐、铵盐、钙盐或镁盐。
本发明所提供的技术方案中，还可以通过在含无机酸、强氧化剂的抛光组合物中进一步添加特定种类和质量含量的表面活性剂，既可以通过表面活性剂降低液体表面张力，使抛光液中的各组分充分的分散开，有利于抛光液在支架内壁和外壁流动，从而使得预抛光件各个部位附近的抛光液成分基本相同，进而确保预抛光件各个部位所受到抛光液的作用基本保持一致，最终确保抛光件成品表面的均匀度，此外表面活性剂对水也有一定的增稠的效果，同时对抛光件表面也具有较大的亲和力及润湿性能，既可以渗入金属表面，增加抛光液对金属的抛光效果，又可以修复抛光件表面的凹痕，损伤及不平整部分，从而提高工件的平整度和光亮度，使得抛光件表面光亮均匀。
本发明所提供的上述技术方案中，所述表面活性剂为阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂和两性表面活性剂的至少一种。
本发明所提供的上述技术方案中，所述表面活性剂的质量百分含量为0.05％-1％，进一步的，所述表面活性剂的质量百分含量为0.05％-0.7％、0.05％-0.8％、0.05％-0.6％、0.05％-0.5％、0.05％-0.4％、0.05％-0.3％、0.05％-0.2％、0.05％-0.1％、0.1％-0.8％、0.1％-0.7％、0.1％-0.6％、0.1％-0.5％、0.1％-0.4％或 0.1％-0.3％、0.1％-0.9％、0.05％-1％。
本发明所提供的上述技术方案中，所述表面活性剂选自高级脂肪酸盐、烷基磺酸盐、烷基醚羧酸盐表面活性剂、有机硅表面活性剂、烷烃硫酸盐、烷烃磺酸盐、取代的胺盐、甜菜碱、聚环氧乙烷、聚乙烯醇、聚乙酸乙烯酯、聚丙烯酸、聚乙烯吡咯烷酮、卵磷脂、氨基酸衍生物、烷基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚硫酸钠、异辛醇聚氧乙烯醚、烷基葡糖苷、聚氧乙烯醚、聚乙烯亚胺、烷基三甲基季铵盐、烷基二甲基苄基氯化铵盐或吡啶盐中的至少一种。
本发明所提供的上述技术方案中，所述表面活性剂选自十二烷基硫酸钠、十二烷基磺酸钠、OP-10、直链烷基苯磺酸钠(LAS)、脂肪醇聚氧乙烯醚硫酸钠(AES)、脂肪醇聚氧乙烯醚硫酸铵(AESA)、月桂醇硫酸钠(SDS)、月桂酰谷氨酸、壬基酚聚氧乙烯醚(TX-10)、硬脂酸甘油单酯、木质素磺酸盐、重烷基苯磺酸盐、烷基磺酸盐、扩散剂NNO、扩散剂MF、烷基聚醚(PO-EO共聚物)、脂肪醇聚氧乙烯醚(AEO-3)、甜菜碱、烷基三甲基季铵盐、卵磷脂、氨基酸衍生物、烷基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚硫酸钠、异辛醇聚氧乙烯醚、烷基葡糖苷、聚氧乙烯醚、烷基二甲基苄基氯化铵盐或吡啶盐中的至少一种。
本发明所提供的上述技术方案中，本发明还提供一种抛光组合物在医疗器械抛光中的应用。
本发明所提供的上述技术方案中，医疗器械的质量相对较小，单个医疗器械抛光件的质量一般在0.5Kg以下。此处的单个医疗器械抛光件可以是某一特定医疗器械的某一部分，也可以是某一医疗器械的整体。
本发明所提供的上述技术方案中，所述的医疗器械为可降解的医疗器械。
本发明所提供的上述技术方案中，所述的医疗器械包括含铁的医疗器械；所述含铁的医疗器械是指可以全部由铁元素组成的器械，也可以是由铁元素和其他元素所组成的器械，也即可以是纯铁材料也可以是含铁合金；所述含铁的医疗器械可以是整个器械均为含铁材料，也可以为器械的某一个部件或某一部分为含铁材料。
本发明所提供的上述技术方案中，所述的医疗器械包括用于生物体内的介入材料/器械或植入材料/器械。
本发明所提供的上述技术方案中，所述的医疗器械包括所述医疗器械为可降解金属或金属合金；所述医疗器械包括血管支架、非血管腔内支架、封堵器、垫片、人工血管、牙科植入器械、血管夹、人工心脏瓣膜、骨科植入物、齿科植入物、呼吸科植入物、妇科植入物、男科植入物、缝合线或者螺栓。所述骨科植入物包括骨钉、骨板等。
本发明所提供的抛光组合物适合金属的抛光，尤其适合铁基或铁基合金的抛光，所述铁基合金包括低合金钢或碳含量不高于2.5wt.％的铁基合金。进一步的，发明所提供的抛光组合物适合一些体型较小，结构复杂的产品的抛光。
本发明所提供的上述技术方案中，所述医疗器械抛光件的质量体积比为0.001g/cm3-0.4g/cm3；进一步的，所述医疗器械抛光件的质量体积比为0.002g/cm3-0.3g/cm3；更进一步的，所述医疗器械抛光件的质量体积比为0.005g/cm3-0.25g/cm3。
本发明所提供的上述技术方案中，所述含铁的医疗器械为纯铁或含碳量不高于2.11wt％的铁基合金。
本发明中的“/”表示“或”的意思，如“介入材料/器械”表示“介入材料或介入器械”。
需要说明的是，本发明中所述的各组分的质量百分含量是指各组分的核心成分作为溶质占整个抛光组合物的质量百分比，如某一组分M本身是溶液，其溶质为J，那么抛光组合物中该组分的质量百分含量是指J在整个抛光组合物K中所占的质量百分比。而非M在整个抛光组合物中所占的质量百分比。也即J的质量与组合物K的质量的百分比。
需要说明的是，本发明的抛光组合物中各组分的质量百分比加水的质量百分比为100％，也即组合物是由各核心组分与水所组成的混合溶液。
本发明中通过各个组分的合理搭配及控制各组分的相对含量，使得各个组分相互配合，相互协同，最终确保抛光件既具有光滑、圆润、光亮的表面，确保表面无毛刺、无棱角，减少器械对人体的刺激和损伤，同时又可充分的提升器械的机械性能，确保其能在各个应用场景下，满足相应的机械性能要求。
本发明中所提供的抛光组合物，既具有较高的抛光效率，同时又使得每两个或多个抛光件抛光后的各项参数保持稳定，抛光精度高，确保产品重量可控。
本发明中所提供的抛光组合物，在一定条件下对抛光件进行抛光，抛光后抛光件的去除量可以达到20％-60％，同时器械各个部位的抛光均匀度可以达到85％、90％、95％甚至98％以上。抛光后的抛光件的各个部位在光学显微镜放大200倍后均具有光亮度和光滑的表面、无刮痕，在抛光件被折弯几百次、拉升、扩张几倍之后均无断裂的迹象。
本发明所提供的抛光组合物中的各组分均为比较常规的化合物，成本低，用该抛光组合物进行抛光，不仅抛光工艺流程简单、易操作，且抛光条件温和，时间适宜可控，重现性好，有利于抛光后支架的精度控制，多个相同的支架在相同条件下进行抛光，抛光后的多个支架的重量的RSD在2％以内，甚至在0.8％以内。
本发明所提供的抛光组合物，抛光后的抛光件各个位置的尺寸均匀，表面光滑，无毛刺，棱角圆润，精度高，稳定性好，且抛光后的抛光件具有较好的机械性能。
本发明中的抛光工艺的操作简单，仅需要将预抛光件放入配置好的抛光液中在一定条件下抛光数分钟或数十分钟之后既可，不需要再进行后续的钝化等步骤，即可获得高质量的抛光件，且抛光件抛光的稳定性和可重复性较高。
本发明所提供的抛光组合物，抛光件在抛光组合物中抛光后的成品在SEM电镜下放大500倍后器械抛光件表面具有轻微的划痕，其中，所述划痕所占面积与整个抛光件表面积之比≤20％；进一步的，本发明所提供的抛光件在SEM电镜下放大500倍条件下，抛光件表面的划痕面积仅占整个抛光件表面积的不大于15％或10％，甚至不大于6％。
本发明所提供的抛光组合物，抛光件在抛光组合物中抛光后的成品的划痕深度h≤2.5μm，进一步的，抛光件的划痕深度可以小于1μm；更进一步的，抛光件的划痕深度可以小于0.5μm或小于0.3μm。
本发明所提供的抛光组合物，抛光件在抛光组合物中抛光后的成品表面的粗糙度Sa≤50nm，进一步的，医疗器械抛光件的表面的粗糙度Sa不大于30nm；更进一步的，医疗器械抛光件的表面的粗糙度Sa不大于20nm。
本发明所提供的抛光组合物，抛光件在抛光组合物中抛光后的成品表面附有一层薄薄的保护膜，使得抛光件表面具有比较好的稳定性，不容易被空气氧 化等，确保器械抛光件在中转及保存期间表面外观及性能的稳定性。
本发明所提供的抛光组合物，抛光件在抛光组合物中抛光后的成品在光学电子显微镜下放大100倍后呈光滑的光亮表面；更进一步的，抛光件在光学电子显微镜下放大200倍或250倍后仍呈光滑的光亮表面。
本发明所提供的抛光组合物，可以充分控制医疗器械抛光件在抛光过程中各个部位抛光的去除量，确保抛光件抛光的均匀度可达到85％以上，更优的，抛光件在抛光均匀度控制在90％、95％甚至98％以上，从而确保医疗器械抛光件整体都没有薄弱部位，整体具有较好的机械性能。本发明中所述抛光件抛光的均匀度是指抛光后的抛光件的尺寸比较均匀，也即抛光均匀度是指抛光件在抛光后相同部位抛光后的宽度/厚度Ri与抛光件相同部位抛光后宽度/厚度的平均值的比值，也即如医疗器械抛光件在抛光过程中各个部位抛光后尺寸的均匀度达到85％以上，是指
本发明所提供的抛光组合物，在抛光件的抛光过程中具有较高的稳定性，在同时抛光数十个支架后，支架仍然具有较好的外观，支架的各项尺寸、重量等参数仍然稳定。
需要说明的是，本发明为了便于表述，将本发明技术方案的优势分开进行描述，但本发明所提供的方案为一个不可割裂的整体，需要方案中各个组分相互协同、相互作用才可以达到最终的效果，在缺少其他组分的助力下，某一组分也不能独立的达到非常好的效果。如本发明中的粘稠剂虽可以提高抛光件表面的光滑度，但溶液的粘稠度是所有组分相互作用的结果，并非只有粘稠剂作用的结果，也即抛光件最终抛光后表面的光滑度是离不开各个组分的共同作用的。
本发明中所涉及的区间范围的取值，并不仅仅局限于所提供的区间范围，而应该是所述区间中任意两个取值所组成的新区间的值或者所述区间中的任意一个具体的取值均可以，如本发明中“表面活性剂的含量为0.05％-0.1％”，其中表面活性剂的含量值并不仅仅局限于0.05-1％这一个取值范围区间，可以是0.05％-1％之间的无数个取值中任意两个取值所组成的新的区间，如可以是0.05％-0.5％，也可以是0.1％-0.8％等等。另外，当有多个数值组合时，每一项参数可 以在其取值范围内任意取值，且多个参数的值可以任意搭配。如抛光液的pH值≤1，抛光液的粘稠度为1-4mPa s。抛光液的pH值可以为不大于1的取值范围中的任意一取值，抛光液的粘稠度可以为1-4mPa s范围内的任意一取值。此两个参数也可以任意搭配，如pH值为0.1，抛光液的粘稠度为3.5mPa s，等等以此类推。
应理解的是，文中使用的术语仅出于描述特定示例实施方式的目的，而无意于进行限制。除非上下文另外明确地指出，否则如文中使用的单数形式“一”、“一个”以及“所述”也可以表示包括复数形式。术语“包括”、“包含”、“含有”以及“具有”是包含性的，并且因此指明所陈述的特征、步骤、操作、元件和/或部件的存在，但并不排除存在或者添加一个或多个其它特征、步骤、操作、元件、部件、和/或它们的组合。文中描述的方法步骤、过程、以及操作不解释为必须要求它们以所描述或说明的特定顺序执行，除非明确指出执行顺序。还应当理解，可以使用另外或者替代的步骤。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本申请的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。
附图说明
通过阅读下文优选实施方式的详细描述，各种其它的优点和益处对于本领域普通技术人员将变得清楚明了。附图仅用于示出优选实施方式的目的，而并不认为是对本发明的限制。而且在整个附图中，用相同的附图标记表示相同的部件。其中：
图1为实施例1中支架的在SEM扫描电镜下放大500倍后的表征图；
图2为实施例1中支架的在光学显微镜下放大200倍后的表征图；
图3为对比例1中支架的在光学显微镜下放大200倍后的表征图。
具体实施方式
以下所述的仅为本发明的优选实施方式，本发明所保护的不限于以下优选实施方式，如实施例中均以支架或某一个型号的支架为示例进行说明，但并不代表本发明的技术方案仅适用于支架或某一个型号的支架。应当指出，对于本领域的技术人员来说在此发明创造构思的基础上，做出的若干变形和改进，都属于本发明的保护范围。所用试剂或仪器未注明生产商者，均为可以通过市购获得的常规产品。
测试方法
1.粗糙度
本发明中采用SENSOFAR公司生产的Q-SIX心血管支架检测仪在干涉镜头下放大400倍，扫描高度设置为50μm的条件下对抛光件表面的粗糙度进行检测。
2.粘度
将抛光液倒入蔡氏杯CUP1#中，记录流出的时间t，根据公式动力粘度＝1.1(t-29)*ρ(ρ指溶液密度)算出溶液的粘度。
3.支架宽度及厚度的测量
将支架置于光学显微镜下，在光学显微镜放大100-200倍下观察并测量其尺寸。
4.划痕深度
将支架封样，并用抛磨机抛磨至支架露出支架横截面，最后将抛磨后的横截面置于金相显微镜下测量其划痕深度。
5.径向强度
径向强度：在管腔支架的性能测试方面，管腔支架的径向强度可通过压缩模块均匀地对支架施加径向压力，使支架压缩，产生均匀变形。定义支架径向(外径)发生10％变形时所施加的径向压强大小为支架的径向强度。
6.过扩塑性
将支架选择相应长度和适当外径的球囊导管。从6-8atm开始充压扩开，保 压30s后在200倍三维测量显微镜下遍历整个支架，记录是否有裂纹/断杆。如无裂纹/断杆。重复加压2atm后保压30s进行观察记录的操作直至发现裂纹/断杆或者加压到支架扩张外径达到接收准则以上为止。
7.外观
三维测量显微镜在适宜放大倍数下(如50-200倍)下全检整个支架的外壁和内壁的光亮度和粗糙度。
实施例1
切割30018支架，将切割后的支架放入超声波中清洗2min，再放入粘稠度为4.0mPa s的由100ml硫酸、3gEDTA、10ml丙三醇、5g硝酸钠、5g硅酸钠、0.1ml植酸、0.05g十二烷基硫酸钠和50ml水混合后制成的抛光液中，控制抛光液的流动速度为1.0m/s，在20℃下抛光3min。取出支架，清洗后烘干。将烘干后的支架置于放大200倍的光学显微镜下观察，表面光滑发亮；置于放大500倍的SEM下观察，支架棱角圆润，表面划痕面积占比为2％，划痕的最大深度为1μm，支架杆单面去除的深度为15μm，支架抛光的均匀度为90％；支架的质量损失率为45％，在sensofar3D光学轮廓仪下测得支架表面的粗糙度Sa为15nm；支架的径向强度为120kPa；用球囊扩张到直径4.6mm，无裂纹及断裂。连续重复抛光5个支架，抛光后支架质量的RSD<1％。
实施例2
切割30018支架，将切割后的支架放入超声波中清洗2min，再放入粘稠度为2.0mPa s的由100ml盐酸、5g酒石酸、10ml乙二醇、10ml高氯酸、5g海藻酸钠、0.1g植酸钠、0.05gOP-10和50ml水混合后制成的抛光液中，控制抛光液的流动速度为0.8m/s，在25℃下抛光3min。取出支架，清洗后烘干。将烘干后的支架置于放大200倍的光学显微镜下观察，表面光滑发亮；置于放大500倍的SEM下观察，支架棱角圆润，表面划痕面积占比为2％，划痕的最大深度为0.5μm，支架杆单面去除的深度为15μm，支架抛光的均匀度为95％；支架的质量损失率为42％，在sensofar3D光学轮廓仪下测得支架表面的粗糙度Sa为10nm；支架的径向强度为115kPa；用球囊扩张到直径4.6mm，无裂纹及断裂。 连续重复抛光5个支架，抛光后支架质量的RSD<1.5％。连续重复抛光5个支架，抛光后支架质量的RSD<1.5％。
实施例3
切割30018支架，将切割后的支架放入超声波中清洗5min，再放入粘稠度为3.0mPa s的由100ml磷酸、5gEDTA二钠、10ml丁二醇、10ml硝酸、5g硅酸钠、0.1ml单宁酸、0.05g聚乙二醇和50ml水混合后制成的抛光液中，控制抛光液的流动速度为0.5m/s，在30℃下抛光3min。取出支架，清洗后烘干。将烘干后的支架置于放大200倍的光学显微镜下观察，表面光滑发亮；置于放大500倍的SEM下观察，支架棱角圆润，表面划痕面积占比为2％，划痕的最大深度为1.5μm，支架杆单面去除的深度为15μm，支架抛光的均匀度为92％；支架的质量损失率为45％，在sensofar3D光学轮廓仪下测得支架表面的粗糙度Sa为20nm；支架的径向强度为125kPa；用球囊扩张到直径4.6mm，无裂纹及断裂。连续重复抛光5个支架，抛光后的支架质量的RSD<2％。
实施例4
切割30018支架，将切割后的支架放入超声波中清洗2min，再放入粘稠度为1.5mPa s的由100ml盐酸、3g丁二酸、10ml丙二醇、10ml双氧水、5g硅酸钠、0.1g硬脂酸、0.05g十二烷基磺酸钠和50ml水混合后制成的抛光液中，控制抛光液的流动速度为0.5m/s，在30℃下抛光3min。取出支架，清洗后烘干。将烘干后的支架置于放大200倍的光学显微镜下观察，表面光滑发亮；置于放大500倍的SEM下观察，支架棱角圆润，表面划痕面积占比为2％，划痕的最大深度为2μm，支架杆单面去除的深度为15μm，支架抛光的均匀度为92％；支架的质量损失率为44％，在sensofar3D光学轮廓仪下测得支架表面的粗糙度Sa为20nm；支架的径向强度为120kPa；用球囊扩张到直径4.6mm，无裂纹及断裂，支架保存4周后无明显变化。连续重复抛光5个支架，抛光后的支架质量的RSD<2.5％。
实施例5
切割30018支架，经12.5％盐酸超声波清洗支架2min，再放入粘稠度为1.0mPa s由100ml氢氟酸、3g二乙烯三胺五甲叉膦酸、10ml环己醇、10ml高锰酸钾、5g海藻酸钠、0.1g软脂酸和50ml纯水溶液中，将溶液置于低温磁力槽，温度30度，抛光液以0.8.0m/s的速度流动，支架置于其中抛光3min，取出支架，清洗后烘干。将烘干后的支架置于放大200倍的光学显微镜下观察，表面光滑发亮；置于放大500倍的SEM下观察，支架棱角圆润，表面划痕面积占比为2％，划痕的最大深度为0.5μm，支架杆单面去除的深度为15μm，支架抛光的均匀度为92％；支架的质量损失率为46％，在sensofar3D光学轮廓仪下测得支架表面的粗糙度Sa为20nm；支架的径向强度为115kPa；用球囊扩张到直径4.6mm，无裂纹及断裂。连续重复抛光5个支架，抛光后的支架质量的RSD<3％。
实施例6
切割30018支架，经12.5％盐酸超声波清洗支架2min，再放入粘稠度为2.5mPa s由100ml高氯酸、5g葡萄糖酸钠、10ml丁醇、5g硝酸钾、5g海藻酸钠、0.1g硬脂酸钠、0.05g甜菜碱、0.05g月桂醇硫酸钠和50ml纯水溶液中，将溶液置于低温磁力槽，温度25度，抛光液以0.6.0m/s的速度流动，支架置于其中抛光3min，取出支架，清洗后烘干。将烘干后的支架置于放大200倍的光学显微镜下观察，表面光滑发亮；置于放大500倍的SEM下观察，支架棱角圆润，表面划痕面积占比为2％，划痕的最大深度为0.3μm，支架杆单面去除的深度为15μm，支架抛光的均匀度为95％；支架的质量损失率为43％，在sensofar3D光学轮廓仪下测得支架表面的粗糙度Sa为12nm；支架的径向强度为118kPa；用球囊扩张到直径4.6mm，无裂纹及断裂。连续重复抛光5个支架，抛光后的支架质量的RSD<3％。
实施例7
切割30018支架，将切割后的支架放入超声波中清洗2min，再放入粘稠度为2.5mPa s的由100ml硫酸、5gEDTA二钠、10ml乙二醇、5g硝酸钠、0.1ml植酸和50ml水混合后制成的抛光液中，控制抛光液的流动速度为0.5m/s，在 25℃下抛光3min。取出支架，清洗后烘干。将烘干后的支架置于放大200倍的光学显微镜下观察，表面光滑发亮；置于放大500倍的SEM下观察，支架棱角圆润，表面划痕面积占比为2.5％，划痕的最大深度为2μm，支架杆单面去除的深度为15μm，支架抛光的均匀度为85％；支架的质量损失率为44％，在sensofar3D光学轮廓仪下测得支架表面的粗糙度Sa为18nm；支架的径向强度为115kPa；用球囊扩张到直径4.5mm时断裂。连续重复抛光5个支架，抛光后的支架质量的RSD<3％。
实施例8
切割30018支架，将切割后的支架放入超声波中清洗2min，再放入粘稠度为3.5mPa s的由100ml盐酸、3g丁二酸、10ml丙三醇、10ml硝酸、5g海藻酸钠和50ml水混合后制成的抛光液中，控制抛光液的流动速度为0.6m/s，在30℃下抛光3min。取出支架，清洗后烘干。将烘干后的支架置于放大200倍的光学显微镜下观察，表面光滑发亮；置于放大500倍的SEM下观察，支架棱角圆润，表面划痕面积占比为2％，划痕的最大深度为1.2μm，支架杆单面去除的深度为1.5μm，支架抛光的均匀度为88％；支架的质量损失率为48％，在sensofar3D光学轮廓仪下测得支架表面的粗糙度Sa为25nm；支架的径向强度为120kPa；用球囊扩张到直径4.6mm，无裂纹及断裂，支架保存7天后表面有黄斑。连续重复抛光5个支架，抛光后的支架质量的RSD<2％。
实施例9
切割30018支架，将切割后的支架放入超声波中清洗2min，再放入粘稠度为3.5mPa s的100ml磷酸、5g苹果酸、10ml丁二醇、10ml高氯酸和50ml水混合后制成的抛光液中，控制抛光液的流动速度为0.8m/s，在35℃下抛光3min。取出支架，清洗后烘干。将烘干后的支架置于放大200倍的光学显微镜下观察，表面光滑发亮；置于放大500倍的SEM下观察，支架棱角圆润，表面划痕面积占比为3％，划痕的最大深度为2.5μm，支架杆单面去除的深度为15μm，支架抛光的均匀度为82％；支架的质量损失率为48％，在sensofar3D光学轮廓仪下测得支架表面的粗糙度Sa为30nm；支架的径向强度为128kPa；用球囊扩张到 直径4.0mm时支架断裂。连续重复抛光5个支架，抛光后的支架质量的RSD<1.5％。
对比例1
切割30018支架，将切割后的支架放入超声波中清洗2min，再放入140ml冰醋酸、60ml高氯酸混合后制成的抛光液中，用直流电源恒流以0.1A电流抛光20秒。取出支架，清洗后烘干。将烘干后的支架置于放大200倍的光学显微镜下观察，表面光滑发亮，但支架局部发黄且两端尺寸小，中部尺寸大；置于放大500倍的SEM下观察，支架棱角圆润，表面划痕面积占比为5％，划痕的最大深度为6μm，支架杆内壁单面去除的深度为5μm，支架抛光的均匀度为50％；支架的质量损失率为50％，在sensofar3D光学轮廓仪下测得支架表面的粗糙度Sa为200nm；支架的径向强度为95kPa；用球囊扩张到直径3.5mm时支架断裂。续重复抛光5个支架，抛光后的支架质量的RSD<3％。
对比例2
切割30018支架，将切割后的支架放入超声波中清洗2min，以60ml磷酸、30ml硫酸、10ml硝酸混合制成的抛光液加热至沸腾，支架置于其中抛光10s，清洗后烘干。将烘干后的支架置于放大200倍的光学显微镜下观察，表面粗糙有凹坑并发黄，置于放大500倍的SEM下观察，支架棱角圆润，表面划痕面积占比为8％，划痕的最大深度为0.5μm，支架杆内壁单面去除的深度为16μm，支架抛光的均匀度为90％；支架的质量损失率为65％，在sensofar3D光学轮廓仪下测得支架表面的粗糙度Sa为250nm；支架的径向强度为70kPa；用球囊扩张到直径4.0mm时支架断裂。续重复抛光5个支架，抛光后的支架质量的RSD＞10％。
通过对比例可以看出，对比例1中电化学抛光之后的支架各个部位的尺寸不均匀，表面发黄且比较粗糙，表面划痕的面积占比较高，划痕具有较大深度，同时支架的径向支撑力和过扩能力都相对比较低；对比例2中的高温化学抛光后，支架表面发黄粗糙，抛光件表面划痕的面积占比也比较高，同时该方法抛 光时间非常短，仅有5s，产品的抛光精度不高，多次重复抛光后多个抛光产品之间的产品尺寸和质量的RSD相对比较大，抛光的稳定性不好。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，如本发明的实施例中均以支架为示例进行说明，并不代表本申请的方案仅适用于支架的抛光。也可以适用于其他的一些医疗器械甚至其他一些非医疗器械类质量较小的精密件的抛光。尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (16)

  1. 一种抛光组合物，包括酸、氧化剂和水，其特征在于，所述抛光组合物的pH值≤1，其中：
    所述酸选自无机酸中的至少一种；所述氧化剂选自无机强氧化剂中至少一种。
  2. 根据权利要求1所述的抛光组合物，其特征在于，所述无机酸的质量百分含量为40％-70％；所述无机强氧化剂的质量百分含量为5％-10％。
  3. 根据权利要求1所述的抛光组合物，其特征在于，所述抛光液的粘稠度为1mPa s-4mPa s。
  4. 根据权利要求1所述的抛光组合物，其特征在于，所述无机酸选自硫酸、磷酸、硝酸、高氯酸或氢氟酸中的至少一种；所述无机氧化剂选自过硫酸盐、高氯酸及其盐、高溴酸及其盐、高碘酸及其盐、高锰酸及其盐、过氧酸盐、碘酸及其盐、亚氯酸及其盐、次氯酸及其盐、次碘酸及其盐、氧溴酸及其盐、过碳酸盐、溴酸及其盐、氯酸及其盐、双氧水、硝酸钾或硝酸钠中的至少一种。
  5. 根据权利要求1所述的抛光组合物，其特征在于，所述抛光组合物还包括粘稠剂；所述粘稠剂的质量百分含量为1.5-7％。
  6. 根据权利要求5所述的抛光组合物，其特征在于，所述粘稠剂选自醇、硅酸、硅酸盐、海藻酸、海藻酸盐、聚乙烯吡咯烷酮、聚乙烯吡咯烷酮的改性有机物、乙基纤维素、甲基纤维素、羟乙基纤维素、羟丙基甲基纤维素、羧甲基纤维素类、聚丙烯酸、聚甲基丙烯酸钠、聚羧酸钠盐、羧酸钠盐共聚物、羧酸磺酸共聚物、瓜尔胶、淀粉磷酸钠、聚丙烯酸钠、聚氧乙烯类、卡波姆、黄原酸、阿拉伯胶、卡拉胶、琼脂、明胶、阿拉伯树胶及其衍生物中的至少一种。
  7. 根据权利要求5所述的抛光组合物，其特征在于，所述粘稠剂由A组分中的至少一种和B组分中的至少一种组成；其中：
    A组分选自醇、乙基纤维素、甲基纤维素、羟乙基纤维素、羟丙基甲基纤维素、羧甲基纤维素类、聚乙烯吡咯烷酮、聚丙烯酸、聚甲基丙烯酸钠、聚羧酸钠盐、羧酸钠盐共聚物、羧酸磺酸共聚物及其衍生物中的至少一种；
    B组分选自硅酸、硅酸盐、海藻酸、海藻酸盐、聚乙烯吡咯烷酮的改性有机物、瓜尔胶、淀粉磷酸钠、聚丙烯酸钠、聚氧乙烯类、卡波姆、黄原酸、阿 拉伯胶、卡拉胶、琼脂、明胶、阿拉伯树胶及其衍生物中的至少一种的混合物。
  8. 根据权利要求7所述的抛光组合物，所述A组分与B组分的质量比为0.5:1-15:1。
  9. 根据权利要求1所述的抛光组合物，其特征在于，所述抛光组合物还包括配位剂，所述配位剂为单齿或多齿配体；所述配位剂选自含有氨基、羧基、氰根、硫氰根、异硫氰根、硝基、羟基、巯基、芳杂环基团、亚硝基、磺基、磷酸基团及有机膦基团中的至少一种。
  10. 根据权利要求9所述的抛光组合物，其特征在于，所述配位剂的质量百分含量为0.5％-2％。
  11. 根据权利要求1所述的抛光组合物，其特征在于，所述抛光组合物还包括表面保护剂；所述表面保护剂的质量百分含量为0.02％-1％。
  12. 根据权利要11所述的抛光组合物，其特征在于，所述表面保护剂选自单宁酸、植酸、硬脂酸、软脂酸及其盐中的至少一种。
  13. 根据权利要求1所述的抛光组合物，其特征在于，所述抛光组合物还包括表面活性剂；所述表面活性剂的质量百分含量为0.05％-1％。
  14. 根据权利要求13所述的抛光组合物，其特征在于，所述表面活性剂为阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂或两性表面活性剂中的至少一种；所述表面活性剂选自高级脂肪酸盐、烷基磺酸盐、烷基醚羧酸盐表面活性剂、有机硅表面活性剂、烷烃硫酸盐、烷烃磺酸盐、取代的胺盐、甜菜碱、卵磷脂、氨基酸衍生物、烷基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚硫酸钠、异辛醇聚氧乙烯醚、烷基葡糖苷或聚氧乙烯醚中的至少一种。
  15. 一种权利要求1-14任一项所述抛光组合物在医疗器械抛光中的应用；所述的医疗器械包括生物体内的介入器械或植入器械。
  16. 根据权利要求15所述的抛光组合物在医疗器械抛光中的应用，所述医疗器械为可降解金属或金属合金；所述医疗器械包括血管支架、非血管腔内支架、封堵器、垫片、人工血管、牙科植入器械、血管夹、人工心脏瓣膜、骨科植入物、齿科植入物、呼吸科植入物、妇科植入物、男科植入物、缝合线或者螺栓。
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