CN117357709A - Medical metal composite guide wire provided with super-hydrophilic friction-resistant coating and preparation method and application thereof - Google Patents

Abstract

The invention discloses a medical metal composite guide wire provided with a super-hydrophilic friction-resistant coating, and a preparation method and application thereof. The medical metal composite guide wire is sequentially subjected to low-temperature short-time preheating treatment and surface modification solution treatment; the low-temperature short-time preheating treatment is to mix the medical metal composite guide wire into a uniform solution in a silane coupling agent and a first solvent, and treat the medical metal composite guide wire for 30 to 90 minutes at the temperature of 100 to 200 ℃ under the ultrasonic cooperation; the surface modification solution treatment is to dip, pull and coat the medical metal composite guide wire subjected to the low-temperature short-time preheating treatment in a hydrophilic precursor solution for more than one time to cure. The coating prepared by the invention has excellent super-hydrophilic lubricity, the friction force reduction range can reach 93 percent, the binding force with the surface of the metal composite guide wire is strong, the metal composite guide wire is stable and not easy to fall off, the cyclic friction resistance is good, and the difference between the wire diameters of the coating before and after the preparation is not more than 10 mu m.

Description

Medical metal composite guide wire provided with super-hydrophilic friction-resistant coating and preparation method and application thereof

Technical Field

The invention relates to a medical metal composite guide wire in an interventional therapy process, in particular to a medical metal composite guide wire provided with a super-hydrophilic friction-resistant coating, and a preparation method and application thereof, and belongs to the technical fields of medical metal materials and chemical industry.

Background

In the interventional treatment process, the medical guide wire plays an irreplaceable role in guiding, positioning and transmitting, can assist the catheter to accurately enter various micro blood vessels of a human body, and guide the catheter to smoothly reach a lesion part in the human body for local diagnosis and treatment. The selection of the appropriate medical guide wire is the key to the success of the interventional therapy. At present, medical instruments used in interventional therapy mainly comprise a high molecular polymer (such as polyurethane) coated metal guide wire, a metal bare guide wire (mainly made of nickel-titanium alloy, stainless steel and the like), a metal microcoil (mainly made of stainless steel, platinum-tungsten alloy and the like) and the like. The interventional guide wire coated by the high polymer material has the characteristics of high softness, good compliance and the like, and the medical interventional metal guide wire inner core has the advantages of high strength, good toughness, good fatigue performance and excellent processability, thereby bringing good support, torsion control and protrusion. Most interventional operations require a composite metal spring head, and the good guiding function and pushing performance of the composite metal spring head can better ensure that the whole guide wire reaches the focus smoothly and protect vascular tissues from being damaged. The bare metal guide wire and the composite metal core micro spring guide wire have very large demand in the market.

The surface of the pure medical metal guide wire and the metal micro-spring has certain hydrophobicity, the surface friction coefficient is high, the phenomenon of astringency is easy to occur when the pure medical metal guide wire and the metal micro-spring are directly used, the actual guiding function is influenced, and the inner wall of a blood vessel is damaged by serious patients. The thin hydrophilic lubricating coating is introduced on the surface of the metal guide wire or the metal spring, so that coagulation reaction can be effectively avoided and vascular injury can be reduced when the guide wire moves, unnecessary pain and damage to a patient can be reduced, the surface of the guide wire can be ensured to have a lower friction coefficient, the tracking property and smoothness of the guide wire can be easily realized, and the operation difficulty of doctors can be effectively reduced. When in clinical use, an operator needs to drive the guide wire back and forth and repeatedly rub the guide wire, so that the falling of the hydrophilic coating with poor bonding effect can affect the guide wire to continue to smoothly penetrate and penetrate, and further secondary injury is caused to a patient, so that the metal composite guide wire is required to be durable in the treatment process, the hydrophilic coating cannot fall off easily, and the functionality of the metal guide wire and the metal spring head cannot be affected.

At present, most of the preparation methods of medical hydrophilic lubricating coatings are only aimed at medical devices coated by high polymer materials, namely, one or more layers of hydrophilic high polymer materials are coated on the basis of polyurethane coating, and then the medical devices are cured and molded in a heat curing mode, an ultraviolet curing mode and the like. For example, the chinese patent No. CN 102264403B and the US patent No. US 845094 B2 all adopt a single-layer coating scheme to prepare the coating, and although the preparation process is relatively simple, the connection between the single hydrophilic polymer chain and the substrate is often not strong, the adhesion of the coating is not enough and is easy to be rubbed off, so that the surface of the substrate is exposed, and the lubricity of the whole substrate is lost.

In order to improve the binding force of the hydrophilic coating on the polymer substrate as a whole, a double-layer coating strategy is mostly adopted in the prior art. For example, in US patent 4119094, polyisocyanate and polyurethane are selected as main components of the bottom coating, polyvinylpyrrolidone is selected as main component of the top coating, and each layer is crosslinked and cured by long-term heat drying; the Chinese patent No. 110819183B selects a process route of initiating polymerization, dip coating and heating curing, and can obtain a relatively firm hydrophilic coating on the surface of a medical device. The hydrophilic coating prepared by the method not only has certain binding force, but also can resist friction and lubrication. However, the hydrophilic coating obtained by the method has larger thickness and can influence the overall functionality of the guide wire and the spring head, and is only suitable for medical guide wires coated by high polymers, and the whole coating preparation period is longer.

The preparation technology of the hydrophilic coating which can be applied to the surfaces of the metal bare guide wire and the metal spring head has less research, and the main problem is that the metal surface is difficult to establish stable connection with the high polymer hydrophilic coating. Some current solutions are single silylation of metal substrates to establish a robust bridge of metal and polymeric coatings. For example, according to the invention patent CN 107899092B, the intervention metal guide wire is pretreated by a silane coupling agent, soaked in a coupling agent hydrolysis solution and then cured, the silanization treatment condition is 100-150 ℃ for curing for 1-2 hours, and then the hydrophilic coating is coated and cured. However, the treatment purpose is to obtain a layer of polymeric silane film on the surface of the intervening metal guide wire, the silane film and the metal material are connected only by tightening force, the silane film and the hydrophilic coating are not crosslinked with each other, and the lubricity is improved by only 88-92.8%. Direct silylation may not be effective in bonding the metal surface to silanol, and thus, some have proposed hydroxylation of the metal substrate prior to silylation to better bond the metal surface to subsequent silane films. The method is characterized in that acid-alkali solution is adopted for treatment, but the use of the acid-alkali solution has great influence on the biocompatibility of the medical guide wire, is not friendly to the environment, and is difficult to adopt in actual production. The metal micro-spring head is connected with the metal guide wire base material through soldering, so that the high temperature of the treatment can cause failure conditions such as desoldering and even falling of the micro-spring head, the heat treatment needs a high temperature environment (more than 400 ℃) or long-time treatment (more than 2 hours), the treatment condition is not suitable for the metal composite guide wire of the metal core and the micro-spring head, and the technological parameters are only effective for silanization treatment of a single metal material.

In general, the current most hydrophilic coating preparation technology cannot ensure a long-term stable lubrication effect in the use process of the medical metal composite guide wire, and cannot simultaneously meet the requirements of simple operation, low cost, mild condition and environmental friendliness in the production of medical instruments. Current cardiovascular interventions require higher friction resistance (stronger adhesion) and better hydrophilicity (lower friction, super hydrophilicity) of the metallic guidewire, and therefore, a new super hydrophilic friction-resistant coating and its preparation technology are needed to meet the actual production and application requirements of metallic composite guidewires.

Disclosure of Invention

In view of the above, the invention provides a medical metal composite guide wire provided with a super-hydrophilic friction-resistant coating and a preparation method thereof, wherein the metal composite guide wire is subjected to low-temperature short-time preheating treatment and surface modification, and then adopts a single-solution dipping, lifting and coating scheme and an ultraviolet curing process to construct a structure which can be intertwined from a substrate network to the super-hydrophilic friction-resistant coating network, and the diameter difference of the metal composite guide wire before and after the preparation of the coating is not more than 10 mu m. The coating prepared according to the formula has excellent super-hydrophilicity and lubricity, and has strong binding force with various metal substrates, is stable and not easy to fall off, and is resistant to cyclic friction. The preparation process is simple and feasible, mild in condition and environment-friendly.

The invention aims at realizing the following technical scheme:

a medical metal composite guide wire provided with a super-hydrophilic friction-resistant coating is formed by connecting a metal inner core wire and a spring; the medical metal composite guide wire is obtained by sequentially carrying out low-temperature short-time preheating treatment and surface modification solution treatment; the low-temperature short-time preheating treatment is to mix the medical metal composite guide wire into a uniform solution in a silane coupling agent and a first solvent, and treat the medical metal composite guide wire for 30 to 90 minutes at the temperature of 100 to 200 ℃ under ultrasonic cooperation; the surface modification solution treatment is that medical metal composite guide wires subjected to low-temperature short-time preheating treatment are immersed, lifted and coated in a hydrophilic precursor solution for more than one time to be cured, and the hydrophilic precursor solution is prepared by dissolving a hydrophilic polymer, a hydrophilic monomer, a cross-linking agent and a photoinitiator in a second solvent, and stirring and mixing under a light-shielding condition; the hydrophilic polymer is one or more selected from hyaluronic acid, cellulose, polyethylene glycol, polyvinyl alcohol and polyvinylpyrrolidone.

To further achieve the object of the present invention, preferably, the hydrophilic precursor solution comprises the following components in percentage by mass: 3 to 10 percent of hydrophilic polymer, 1 to 10 percent of hydrophilic monomer, 2 to 10 percent of cross-linking agent, 0.05 to 0.5 percent of photoinitiator and the balance of second solvent.

Preferably, the raw material formula of the surface modification solution comprises the following components in percentage by mass: 1-10% of silane coupling agent and the balance of first solvent.

Preferably, the hydrophilic monomer is selected from one or more of vinyl pyrrolidone, ethyl acrylate, ethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, propyl acrylate, propyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate; the cross-linking agent is one or more selected from tripropylene glycol diacrylate, hexanediol diacrylate, polyethylene glycol diacrylate and pentaerythritol triacrylate;

the photoinitiator is one or more selected from Irgacure 184, irgacure 369, irgacure 1173, irgacure2959, TPO and benzophenone;

preferably, the first solvent and the second solvent are selected from one or both of deionized water and absolute ethanol.

Preferably, the brand of the silane coupling agent is one or more selected from KH-550, KH-560, KH-570 and KH-580; the molecular weight of the hyaluronic acid is 10000 ～ 2000000, and the molecular weight of the cellulose is 50000 ～ 2500000; the molecular weight of the polyethylene glycol is 200-2000000; the molecular weight of the polyvinyl alcohol is 20000-200000; the molecular weight of polyvinylpyrrolidone was 40000 ～ 2000000.

Preferably, the metal inner core wire is connected with the spring through welding; sharpening the front end of the metal inner core wire; the metal inner core wire and the spring are made of one of nickel-titanium alloy, stainless steel and platinum-tungsten alloy; the diameter of the metal inner core wire is 0.20-0.90 mm, and the diameter of the spring coil metal wire is 0.02-0.08 mm; the frequency of the ultrasonic wave is 20-120 kHz; the ultrasonic treatment time is 10-40 min; drying at 30-60 ℃ for 5-60 min after the low-temperature short-time preheating treatment; the mixing into the uniform solution is realized by stirring, wherein the stirring is mechanical stirring or magnetic stirring, and the stirring time is 0.5-2 h.

Preferably, the stirring and mixing under the light-shielding condition is that the stirring and mixing under the light-shielding condition is carried out mechanically or magnetically for 0.5 to 2 hours to obtain a uniform solution; the curing modes are all guide wire rotary curing processes, the distance between the guide wire and the ultraviolet lamp is 3-10 cm, and the rotating speed of the guide wire is 1-10 r/min; the ultraviolet irradiation time is 0.5-30 min, and the power of an ultraviolet lamp is 5-200W; the coating times are 2-5 times, the pulling speed is 0.5-12 mm/s each time, the standing time is 0.1-5 min after each time of coating is completed, and the next coating is performed after ultraviolet irradiation.

The preparation method of the medical metal composite guide wire provided with the super-hydrophilic friction-resistant coating comprises the following steps:

(1) Pretreatment of the surface of a metal composite guide wire: carrying out low-temperature short-time preheating treatment on the medical metal composite guide wire in the surface modification solution under the assistance of ultrasound, wherein the treatment temperature is 100-200 ℃ and the treatment time is 30-90 min;

(2) Preparing a hydrophilic precursor solution: dissolving a hydrophilic polymer, a hydrophilic monomer, a cross-linking agent and a photoinitiator in a solvent, stirring and mixing the mixture into a uniform solution under a light-shielding condition to obtain a hydrophilic precursor solution, and sealing the solution in a light-shielding condition;

(3) Coating and curing the metal composite guide wire: immersing the medical metal composite guide wire subjected to surface pretreatment in a hydrophilic precursor solution for lifting and coating, standing after coating, and curing by ultraviolet irradiation to form the super-hydrophilic friction-resistant coating on the surface of the metal composite guide wire.

The medical metal composite guide wire provided with the super-hydrophilic friction-resistant coating is applied to the preparation of cardiovascular internal guiding interventional therapy equipment.

Compared with the prior art, the invention has the following advantages and beneficial effects:

1) The invention aims at medical metal composite guide wires, and the hydroxylation scheme is low-temperature short-time heating treatment. The metal surface energy after the low-temperature short-time heating treatment and the surface modification layer form a stable covalent bond, the adhesion effect of the metal surface energy to the subsequent super-hydrophilic friction-resistant coating is obviously improved, and various metal substrates can form chemical bond connection with the super-hydrophilic friction-resistant coating at the same time, namely the wire guide coating is not easy to fall off in the operation process.

2) The super-hydrophilic friction-resistant coating can form a hydrogel crosslinked network structure, the silane film on the upper surface of the metal surface ensures that the hydrophilic layer can be firmly combined, the hydrophilic layer stably plays a role in reducing friction force, and the hydrophilic monomer is polymerized to supplement ultraviolet light curing to strengthen the bonding effect.

3) According to the invention, the medical metal composite guide wire provided with the super-hydrophilic friction-resistant coating is prepared by the pretreatment of low-temperature short-time heating and the cross-linked network structure, the difference of wire diameters of the prepared medical metal composite guide wire is not more than 10 mu m, the coating obtained on the surface of the guide wire is very thin, and the defect of the excessive thickness of the coating in the prior art is effectively overcome.

4) The super-hydrophilic friction-resistant coating provided by the invention greatly reduces the friction force of the metal composite guide wire during running, the reduction range can reach more than 93%, and the metal composite guide wire with the super-hydrophilic friction-resistant coating can not fall off after 25 times of circulation, namely the metal composite guide wire with the super-hydrophilic friction-resistant coating prepared by adopting the formula can meet the hydrophilic lubricity and the circulation friction resistance required by practical use.

5) The raw materials used for preparing the super-hydrophilic friction-resistant coating are friendly to personnel and environment, low in cost and easy to obtain.

6) The invention adopts the physical treatment under mild conditions, the dipping and pulling coating technology and the ultraviolet curing technology are simple and reliable, the environmental protection problem is avoided, the related equipment is simple to operate, and the invention is suitable for large-scale production.

Drawings

FIG. 1 is a graph of water contact angle measurements for stainless steel microcoils without any coating applied in example 1;

FIG. 2 is a graph of water contact angle measurements of stainless steel microcoils coated with a superhydrophilic friction-resistant coating in example 1;

FIG. 3 is a graph of friction versus displacement for a stainless steel microcoil without any coating applied in example 1;

FIG. 4 is a graph of friction versus displacement for a stainless steel microcoil coated with a superhydrophilic friction-resistant coating of example 1;

FIG. 5 is a metallographic micrograph of a stainless steel microcoil of example 1 without any coating applied thereto;

FIG. 6 is a metallographic micrograph of a stainless steel microcoil coated with a superhydrophilic friction-resistant coating of example 1.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail below with reference to specific embodiments thereof with reference to the accompanying drawings, but this does not mean that the embodiments limit the scope of the present invention. In the present invention, unless otherwise specified, the ratio or percentage refers to a mass ratio or a mass percentage.

The invention provides a medical metal composite guide wire provided with a super-hydrophilic friction-resistant coating, which is formed by connecting a metal inner core wire and a spring; the medical metal composite guide wire is obtained by sequentially carrying out low-temperature short-time preheating treatment and surface modification solution treatment; the low-temperature short-time preheating treatment is to mix the medical metal composite guide wire into a uniform solution in a silane coupling agent and a first solvent, and treat the medical metal composite guide wire for 30 to 90 minutes at the temperature of 100 to 200 ℃ under ultrasonic cooperation; the surface modification solution treatment is that medical metal composite guide wires subjected to low-temperature short-time preheating treatment are immersed, lifted and coated in a hydrophilic precursor solution for more than one time to be cured, and the hydrophilic precursor solution is prepared by dissolving a hydrophilic polymer, a hydrophilic monomer, a cross-linking agent and a photoinitiator in a second solvent, and stirring and mixing under a light-shielding condition; the hydrophilic polymer is one or more selected from hyaluronic acid, cellulose, polyethylene glycol, polyvinyl alcohol and polyvinylpyrrolidone.

Preferably, the metal inner core wire head end of the invention is sharpened and then connected with a spring; the connection is preferably a weld; the springs can be one or more, and a plurality of springs are welded at one time. Preferably, the metal inner core wire and the spring ring are made of one of nickel-titanium alloy, stainless steel and platinum-tungsten alloy; the diameter of the metal inner core wire is 0.20-0.90 mm, and the diameter of the metal wire of the spring is 0.02-0.08 mm;

the super-hydrophilic friction-resistant coating is based on a metal composite guide wire subjected to surface pretreatment, and is obtained by directly carrying out dip-coating and ultraviolet curing on the outer surface of the whole metal composite guide wire by hydrophilic precursor solution, so that a structure which can be intertwined from a substrate network to a super-hydrophilic friction-resistant coating network is constructed.

The low-temperature short-time preheating treatment provides abundant surface hydroxyl groups for the metal substrate; the surface modification solution consists of a silane coupling agent and a solvent, and is prepared by soaking the surface modification solution, then drying at a low temperature for a short time, and retaining part of silane which is not dehydrated and condensed on the surface so as to increase entanglement of a subsequent coating crosslinked network and a substrate network; the hydrophilic precursor solution consists of a hydrophilic polymer, a hydrophilic monomer, a cross-linking agent, a photoinitiator and a solvent, wherein the super-hydrophilic friction-resistant coating takes a hydrophilic monomer polymerized long chain as a main supporting mode, the hydrophilic monomer and the cross-linking agent form a hydrogel three-dimensional network structure through a photopolymerization process to construct a cross-linked network, and the hydrophilic polymer long chain is embedded in the cross-linked network. Firstly, the difference of the wire diameters of the metal composite guide wires before and after the coating preparation is not more than 10 mu m; secondly, the super-hydrophilic performance is good; and the third characteristic is that the friction-resistant coating of the coating is good.

Example 1

(1) Pretreatment of the surface of a metal composite guide wire: the metal composite guide wire of the embodiment 1 adopts a nickel-titanium alloy inner core wire with phi 0.34mm (the head end of the inner core wire is sharpened to phi 0.24 mm) and a microcoil which is formed by winding a stainless steel wire with phi 0.05mm, and the microcoil is subjected to heating treatment at 110 ℃ for 85min;

preparing a surface modification solution 1, taking 4.5% KH-560 and 95.5% absolute ethyl alcohol according to mass percent, and mixing the materials into a uniform solution through magnetic stirring for 1.5 hours. Immersing the metal composite guide wire subjected to the heating treatment in the surface modification solution 1 for 45kHz ultrasonic treatment for 28min, and drying at 60 ℃ for 10min after the completion;

(2) Preparing a hydrophilic precursor solution 1: according to mass percentage, 8% polyvinyl alcohol (molecular weight is 150000), 7% hydroxyethyl methacrylate, 6% polyethylene glycol diacrylate 1000, 0.1% TPO and 78.9% absolute ethyl alcohol are taken, mechanically stirred for 1h under the condition of light shielding, mixed into a uniform solution, and then the hydrophilic precursor solution 1 is obtained and sealed in the dark;

(3) Coating and curing the metal composite guide wire: immersing the metal composite guide wire subjected to surface pretreatment in a hydrophilic precursor solution 1, carrying out lifting coating for 4 times at the speed of 1mm/s, standing for 0.5min after each coating, and irradiating for 20min by using 6W ultraviolet light, so that a super-hydrophilic friction-resistant coating is formed on the surface of the metal composite guide wire.

Surface wettability test, friction force test and wire diameter difference measurement were performed on the stainless steel microcoil provided in this example 1:

surface wettability test: and (3) placing the metal composite guide wire sample in an air environment at room temperature by adopting a contact angle measuring instrument, dripping 0.5 mu L of distilled water drop on a certain area of the surface of the metal composite guide wire sample, and identifying the water contact angle by using software of the system after the water drop spreads stably. The water contact angle value can represent the wettability of the surface of the sample, and the smaller the measured contact angle, the better the hydrophilicity of the sample.

Friction test: using a guide wire friction force testing machine, adopting 300gf clamping force, soaking a metal composite guide wire sample in distilled water at room temperature, lifting the metal composite guide wire sample upwards at a speed of 10mm/s, testing the length of 100mm, testing for 25 times of cycles, carrying out reciprocating friction on the contact part of the metal composite guide wire and a chuck, and recording a friction force-displacement curve graph. The graph intuitively reflects the friction force level and friction resistance cycle of the metal composite guide wire sample, and the lower the measured friction force level is, the better the lubricity of the sample is; with the increase of the number of friction tests, the denser the test curve is, the more the friction force level can be kept at a certain level, and the better the cyclic friction resistance of the test sample is, so that the coating can not fall off in the test. In the figure, the black line represents a 20gf friction force horizontal line, under the test condition, the friction force value of the middle section is less than 20gf and the friction force value of the front section is less than 50gf in at least 25 times of tests, and the lubricating property and the cyclic friction resistance required by the actual use of the metal composite guide wire can be met.

Wire diameter difference measurement: the thickness of the surface coating of the sample is expressed as the corresponding wire diameter difference. Taking metallographic pictures of any uncoated coating sample and the sample coated with the super-hydrophilic friction-resistant coating according to the invention by adopting a metallographic microscope, respectively taking length to measure the wire diameters of the outer surfaces of the samples, and finally subtracting to obtain the wire diameter difference before and after coating preparation.

As can be taken from fig. 1, the stainless steel microcoil without any coating layer has a water contact angle of 92.2 ° after the droplet spreading is stabilized, exhibiting a certain hydrophobicity; as can be seen from fig. 2, the water contact angle of the stainless steel microcoil coated with the superhydrophilic friction-resistant coating of this example 1 was 3.1 ° after the droplet spread was stabilized. From this, it is seen that the surface of the stainless steel microcoil coated with the superhydrophilic friction-resistant coating of example 1 has a significantly reduced water contact angle, and the coating of example 1 has excellent superhydrophilic properties, compared with the sample not coated with any coating. The contact angle test results for other embodiments of the present invention are similar.

As can be taken from fig. 3, the average level of the 25 test friction force of the stainless steel microcoil without any coating was 202.2gf; as can be seen from fig. 4, the average level of the 25 test friction force of the stainless steel microcoil coated with the superhydrophilic friction-resistant coating of this example 1 was stabilized at 7.9gf. As can be seen from comparison of fig. 3 and fig. 4, the friction resistance of the stainless steel microcoil without any coating is larger, the friction resistance of the stainless steel microcoil coated with the super-hydrophilic friction-resistant coating of this example 1 is greatly reduced to below 20gf, and the average drop width reaches 96.1%, which means that the coating friction force level does not significantly change and is stable and not dropped in 25 test cycles, indicating that the super-hydrophilic friction-resistant coating of this example 1 can satisfy the required lubricity and cyclic friction resistance of the stainless steel microcoil.

As can be taken from fig. 5, the outer surface wire diameter of the stainless steel microcoil region without any coating is 344.9 μm; as can be seen from FIG. 6, the outer surface wire diameter of the stainless steel microcoil portion, which had been coated with the superhydrophilic friction-resistant coating of this example 1, was 349.2. Mu.m. As a result, the difference in wire diameter between the preparation of this example 1 and the preparation thereof was 4.3. Mu.m, which indicates that the surface coating of the guide wire was thin.

The friction-displacement curves and metallographic micrographs of the other examples are substantially similar to those of FIGS. 3-6 of example 1, and are not provided one by one, and the test results are set forth in the examples.

Example 2

(1) Pretreatment of the surface of a metal composite guide wire: example 2 a metal composite guide wire was a microcoil formed by coiling a phi 0.60mm stainless steel core wire (the tip of which was sharpened to phi 0.48 mm) with a phi 0.06mm platinum tungsten alloy wire, and heat-treated at 155 ℃ for 60min;

preparing a surface modification solution 2, taking 9% KH-550 and 91% deionized water, and mixing the solution into a uniform solution by magnetic stirring for 1 h. Immersing the metal composite guide wire subjected to the heating treatment in the surface modification solution 2 for carrying out 28kHz ultrasonic treatment for 40min, and drying at 35 ℃ for 40min after the completion;

(2) Preparing a hydrophilic precursor solution 2: taking 5% polyvinylpyrrolidone K60 (molecular weight is 360000), 2% hydroxypropyl methacrylate, 2.5% hexanediol diacrylate, 0.2%Irgacure 2959, 90.3% deionized water and absolute ethyl alcohol, wherein the absolute ethyl alcohol is equal to 1:3, mechanically stirring for 2 hours under a light-proof condition to mix into a uniform solution, obtaining a hydrophilic precursor solution 2, and sealing in a light-proof state;

(3) Coating and curing the metal composite guide wire: immersing the metal composite guide wire subjected to surface pretreatment in a hydrophilic precursor solution 2, carrying out lifting coating for 3 times at the speed of 3mm/s, standing for 0.1min after each coating, and irradiating with 150W ultraviolet light for 1min to form a super-hydrophilic friction-resistant coating on the surface of the metal composite guide wire.

The test method for the surface wettability test, the friction force test and the wire diameter difference measurement of the metal composite guide wire provided by the embodiment 2 of the invention is the same as that of the embodiment 1 of the invention, and the test result shows that: compared with a sample without any coating, the surface water contact angle of the platinum tungsten alloy spring coil part coated with the super-hydrophilic friction-resistant coating of the embodiment 2 is 5.5 degrees, the average reduction amplitude of friction force after 25 times of testing is 93.0 percent, and the coating is stable and does not fall, namely the coating has excellent super-hydrophilic lubricity and cyclic friction resistance, and the wire diameter difference before and after coating of the part is 3.0 mu m.

Example 3

(1) Pretreatment of the surface of a metal composite guide wire: example 3 a metal composite wire was a microcoil formed by coiling phi 0.89mm nickel-titanium alloy core wire (the tip of which was sharpened to phi 0.73 mm), phi 0.08mm stainless steel wire and phi 0.06mm platinum-tungsten alloy wire, respectively, with a platinum-tungsten spring at the tip, and was heat treated at 200 ℃ for 30min;

preparing a surface modification solution 3, taking 2% KH-580 and 98% absolute ethyl alcohol, and mixing into a uniform solution through ultrasonic vibration for 0.5 h. Immersing the metal composite guide wire in the surface modification solution 3 for 110kHz ultrasonic treatment for 11min, and drying at 45 ℃ for 60min after the completion;

(2) Preparing a hydrophilic precursor solution 3: taking 4% polyethylene glycol (molecular weight is 210000), 4% vinyl pyrrolidone, 10% pentaerythritol triacrylate, 0.5% benzophenone and 81.5% deionized water, magnetically stirring for 1.5h under a light-proof condition, mixing to obtain a uniform solution, obtaining a hydrophilic precursor solution 3, and sealing in a light-proof state;

(3) Coating and curing the metal composite guide wire: immersing the metal composite guide wire subjected to surface pretreatment in a hydrophilic precursor solution 3, carrying out pulling coating for 2 times at 10mm/s, standing for 5min, and irradiating with 50W ultraviolet light for 9min to form a super-hydrophilic friction-resistant coating on the surface of the metal composite guide wire.

The test method for the surface wettability test, the friction force test and the wire diameter difference measurement of the metal composite guide wire sample provided by the embodiment 3 of the invention is the same as the test method provided by the embodiment 1 of the invention, and the test result shows that: compared with a sample without any coating, the surface water contact angle of the nickel-titanium alloy inner core wire part coated with the super-hydrophilic friction-resistant coating of the embodiment 3 is 1.6 degrees, the average reduction amplitude of friction force after 25 times of testing is 96.7 percent, and the coating is stable and does not fall, namely the coating has good super-hydrophilic lubricity and cyclic friction resistance, and the wire diameter difference before and after coating of the part is 8.1 mu m.

The embodiments of the present invention are not limited to the above examples. It should be noted that persons skilled in the art may make corresponding changes in form and details without departing from the scope of the invention as defined by the appended claims, and all such changes are intended to be encompassed by the present invention.

Claims (10)

1. A medical metal composite guide wire provided with a super-hydrophilic friction-resistant coating is formed by connecting a metal inner core wire and a spring; the medical metal composite guide wire is characterized by being obtained by sequentially carrying out low-temperature short-time preheating treatment and surface modification solution treatment; the low-temperature short-time preheating treatment is to mix the medical metal composite guide wire into a uniform solution in a silane coupling agent and a first solvent, and treat the medical metal composite guide wire for 30 to 90 minutes at the temperature of 100 to 200 ℃ under ultrasonic cooperation; the surface modification solution treatment is that medical metal composite guide wires subjected to low-temperature short-time preheating treatment are immersed, lifted and coated in a hydrophilic precursor solution for more than one time to be cured, and the hydrophilic precursor solution is prepared by dissolving a hydrophilic polymer, a hydrophilic monomer, a cross-linking agent and a photoinitiator in a second solvent, and stirring and mixing under a light-shielding condition; the hydrophilic polymer is one or more selected from hyaluronic acid, cellulose, polyethylene glycol, polyvinyl alcohol and polyvinylpyrrolidone.

2. The medical metal composite guide wire provided with the super-hydrophilic friction-resistant coating according to claim 1, wherein the hydrophilic precursor solution comprises the following components in percentage by mass: 3 to 10 percent of hydrophilic polymer, 1 to 10 percent of hydrophilic monomer, 2 to 10 percent of cross-linking agent, 0.05 to 0.5 percent of photoinitiator and the balance of second solvent.

3. The medical metal composite guide wire provided with the super-hydrophilic friction-resistant coating according to claim 1, wherein the raw material formula of the surface modification solution comprises the following components in percentage by mass: 1-10% of silane coupling agent and the balance of first solvent.

4. The medical metal composite guide wire provided with the super-hydrophilic friction-resistant coating according to claim 1 or 2, wherein the hydrophilic monomer is one or more selected from the group consisting of vinyl pyrrolidone, ethyl acrylate, ethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, propyl acrylate, propyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate; the cross-linking agent is one or more selected from tripropylene glycol diacrylate, hexanediol diacrylate, polyethylene glycol diacrylate and pentaerythritol triacrylate;

the photoinitiator is one or more selected from Irgacure 184, irgacure 369, irgacure 1173, irgacure2959, TPO and benzophenone.

5. The medical metal composite guide wire provided with the super-hydrophilic friction-resistant coating according to claim 1, 2 or 3, wherein the first solvent and the second solvent are selected from one or both of deionized water and absolute ethyl alcohol.

6. The medical metal composite guide wire provided with the super-hydrophilic friction-resistant coating according to claim 1, wherein the marks of the silane coupling agent are one or more selected from KH-550, KH-560, KH-570 and KH-580; the molecular weight of the hyaluronic acid is 10000 ～ 2000000, and the molecular weight of the cellulose is 50000 ～ 2500000; the molecular weight of the polyethylene glycol is 200-2000000; the molecular weight of the polyvinyl alcohol is 20000-200000; the molecular weight of polyvinylpyrrolidone was 40000 ～ 2000000.

7. The medical metal composite guide wire provided with the super-hydrophilic friction-resistant coating according to claim 1, wherein the metal inner core wire and the spring are connected through welding; sharpening the front end of the metal inner core wire; the metal inner core wire and the spring are made of one of nickel-titanium alloy, stainless steel and platinum-tungsten alloy; the diameter of the metal inner core wire is 0.20-0.90 mm, and the diameter of the spring coil metal wire is 0.02-0.08 mm; the frequency of the ultrasonic wave is 20-120 kHz; the ultrasonic treatment time is 10-40 min; drying at 30-60 ℃ for 5-60 min after the low-temperature short-time preheating treatment; the mixing into the uniform solution is realized by stirring, wherein the stirring is mechanical stirring or magnetic stirring, and the stirring time is 0.5-2 h.

8. The medical metal composite guide wire provided with the super-hydrophilic friction-resistant coating according to claim 1, wherein the stirring and mixing under the light-shielding condition is that the medical metal composite guide wire is mechanically or magnetically stirred under the light-shielding condition for 0.5-2 hours to be mixed into a uniform solution; the curing modes are all guide wire rotary curing processes, the distance between the guide wire and the ultraviolet lamp is 3-10 cm, and the rotating speed of the guide wire is 1-10 r/min; the ultraviolet irradiation time is 0.5-30 min, and the power of an ultraviolet lamp is 5-200W; the coating times are 2-5 times, the pulling speed is 0.5-12 mm/s each time, the standing time is 0.1-5 min after each time of coating is completed, and the next coating is performed after ultraviolet irradiation.

9. A method of preparing a medical metal composite guidewire provided with a super hydrophilic friction-resistant coating as defined in claim 1, comprising the steps of:

(1) Pretreatment of the surface of a metal composite guide wire: carrying out low-temperature short-time preheating treatment on the medical metal composite guide wire in the surface modification solution under the assistance of ultrasound, wherein the treatment temperature is 100-200 ℃ and the treatment time is 30-90 min;

(2) Preparing a hydrophilic precursor solution: dissolving a hydrophilic polymer, a hydrophilic monomer, a cross-linking agent and a photoinitiator in a solvent, stirring and mixing the mixture into a uniform solution under a light-shielding condition to obtain a hydrophilic precursor solution, and sealing the solution in a light-shielding condition;

(3) Coating and curing the metal composite guide wire: immersing the medical metal composite guide wire subjected to surface pretreatment in a hydrophilic precursor solution for lifting and coating, standing after coating, and curing by ultraviolet irradiation to form the super-hydrophilic friction-resistant coating on the surface of the metal composite guide wire.

10. The use of a medical metal composite guide wire provided with a super-hydrophilic friction-resistant coating as claimed in claim 1 for preparing a cardiovascular internal guiding interventional therapy device.