CN106540336A - A kind of hydrophilic modifying coating on medical introducing duct surface - Google Patents

Abstract

The invention discloses a kind of hydrophilic modifying coating on medical introducing duct surface, the hydrophilic modifying coating is made up of transition coating and lubrication coating, and the parts by weight of the composition and each component of transition coating are：5 10 parts of binding resin, I 0.1 0.2 parts of light trigger, 0.05 0.1 parts of levelling agent, I 85 95 parts of solvent；The composition and the parts by weight of each component of lubrication coating be：5 10 parts of hydrophilic resin, 15 parts of water cross-linking agent, II 0.2 0.5 parts of light trigger, II 80 95 parts of solvent.The present invention includes that transition zone and lubricating layer are light solidifying coating, and the curing of coatings time is short, and consumed energy is low, and convenient batch production.

Description

A kind of hydrophilic modification coating on the surface of medical intervention catheter

technical field

The invention relates to a hydrophilic modified coating on the surface of a medical interventional catheter, which belongs to the field of medical interventional catheters.

technical background

Interventional catheters are one of the most commonly used medical devices and consumables in the medical process. The commonly used base materials are polyurethane, polyvinyl chloride, polyester, etc. These materials are all hydrophobic materials, which are easy to bond with tissues during use. It causes pain to the patient and is prone to infection. The hydrophilic modification of the interventional catheter can improve its lubricity, reduce the discomfort of the patient when the interventional catheter is used, and improve the safety of the interventional catheter.

Regarding the design of hydrophilic modification and hydrophilic coating of interventional catheters, there are a large number of patent reports in China. For example, patent CN102993407A discloses a method for modifying polyurethane with a single-layer hydrophilic coating. The method first synthesizes a water-based polyurethane and then mixes it with N-vinylpyrrolidone and vinyl silicone have been copolymerized to prepare photocurable coatings. The hydrophilic coating prepared by this method may have NVP monomer residues after curing, and the friction coefficient after hydration is large; patent CN104448375A discloses a silicon A method for coating PVP on the surface of a PVC catheter after being modified by an oxane coupling agent, the hydrophilic coating prepared by this method has a low friction coefficient but poor adhesion after hydration; patent CN103933616A discloses a method for passing a catheter through plasma Grafting acrylic acid after treatment, and then coating the primer of water-based polyurethane and the modification method of the surface coating containing polymethyl vinyl ether-maleic anhydride, the hydrophilic coating obtained by this method has good adhesion, but due to containing acidic groups The dough needs to be neutralized with concentrated ammonia water, and there are too many preparation steps, and the processing process is cumbersome. Patent CN103289499A discloses a method for preparing a photocurable hydrophilic coating with a polymer chain containing a photoactive group-containing hydrophilic resin and a photoactive crosslinking agent. Active resin, the resin production and purification process is cumbersome, and the production cost is relatively high.

Therefore, it is very necessary to develop a hydrophilic lubricating coating with easy-to-obtain materials, simple and fast production and curing methods, good biocompatibility, excellent adhesion and lubricating properties, and low cost.

Contents of the invention

The purpose of the present invention is to provide a hydrophilic modified coating on the surface of a medical intervention catheter.

A hydrophilic modified coating on the surface of a medical interventional catheter is characterized in that the hydrophilic modified coating is composed of a transition layer coating and a lubricating layer coating, and the composition of the transition layer coating and the parts by weight of each component are: 5-10 parts of binder resin, 0.1-0.2 parts of photoinitiator I, 0.05-0.1 parts of leveling agent, 85-95 parts of solvent I; the composition of the lubricating layer coating and the parts by weight of each component are: hydrophilic 5-10 parts of permanent resin, 1-5 parts of water-based crosslinking agent, 0.2-0.5 parts of photoinitiator II, and 80-95 parts of solvent II.

The bonding resin is one or a mixture of unsaturated acrylic resin and unsaturated urethane acrylate.

The photoinitiator I is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxyl-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxyl-2-methyl-1 - a combination of one or two of phenyl-1-propanones.

The leveling agent is one or a mixture of BKY 333 produced by BYK and DC57 produced by Dow Corning.

The solvent I is one or a mixture of ethanol, isopropanol and ethyl acetate.

The hydrophilic resin is polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), hyaluronic acid, N-vinylpyrrolidone-hydroxyethyl methacrylate copolymer (PVP- PHEMA) or a combination of two or more.

The water-based crosslinking agent is polyethylene glycol diacrylate (PEG600DA or PEG400DA).

The photoinitiator II is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxyl-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxyl-2-methyl-1 - One or a mixture of two or more of phenyl-1-propanone and benzophenone.

The solvent II is a mixture of two or more of methanol, ethanol, isopropanol and water.

As mentioned above, the method of using the hydrophilic modified coating on the surface of the medical interventional catheter is: soak the catheter cleaned by ethanol in the transition layer coating for 10-30 seconds, and then pull it at a speed of 1.0-1.5 cm/s to complete the coating. irradiate for 30-60 seconds under a 1000 W UV lamp to obtain the transition layer; soak the catheter that has completed the transition layer coating in the lubricating layer coating for 10-30 seconds, and then lift it at a speed of 0.5-1.0 cm/s After pulling, irradiate for 150-210 seconds under a 400 W UV lamp to cure completely.

The catheter is made of polyurethane, polyvinyl chloride or polyester.

The double bonds contained in the transition layer are not fully reacted after being irradiated by ultraviolet light, and can only be completely reacted after the lubricating layer is cured. the interaction force between them.

The interpenetrating network structure is formed between the hydrophilic resin in the lubricating layer and the water-based cross-linking agent, so it maintains the good hydrophilic lubricating performance of the resin itself, and at the same time, it has a very good performance due to being bound by the cross-linking agent good adhesion.

The method for detecting the lubricity and stability of the hydrophilic lubricating layer on the surface of the interventional catheter is as follows: a steel column with the same diameter as the inner diameter of the catheter is inserted inside the catheter so that the shape of the catheter remains unchanged, and the catheter is horizontally fixed on a water-filled After soaking in the water tank for 30 seconds, the reciprocating friction test was carried out on a dynamic and static friction tester (14WF, Shimadzu, Japan) with a silica gel sheet as a pair under different loads at a speed of 0.5 cm/s.

The beneficial effect that the present invention has compared with prior art is:

1. The present invention includes that both the transition layer and the lubricating layer are light-cured coatings, the coating has a short curing time, low energy consumption, and is convenient for mass production.

2. The present invention does not contain small molecular monomers and acidic groups, and there is no need to set steps for removing unreacted monomers and neutralization reaction steps during production, which simplifies the production method, reduces production costs, and improves the safety of product use at the same time .

3. There is a chemical bond between the transition layer and the lubricating layer in the present invention, an interpenetrating network structure is formed inside the lubricating layer, the biocompatibility is good, the adhesion of the lubricating layer is improved, and the good hydrophilic lubricating performance of the hydrophilic resin is maintained .

4. The coating of the present invention still has a low coefficient of friction under relatively large loads after wetting, and has good stability, and still maintains excellent stability and an ultra-low coefficient of friction after multiple frictions.

detailed description

A kind of hydrophilic modified coating on the surface of medical intervention catheter, the hydrophilic modified coating is composed of transition layer coating and lubricating layer coating, the preparation method of transition layer coating and lubricating layer coating is as follows:

Preparation of transition layer coating: add 5-10 parts of bonding resin to 50 parts of solvent I, stir well and add 0.1-0.2 parts of photoinitiator I under the condition of avoiding light, and add 35-45 parts after the initiator is completely dissolved. One part of solvent I, adjust the viscosity to 4.0-5.0mPa·s, add 0.05-0.1 part of leveling agent, continue to stir for 30 minutes, and pack it for later use;

Preparation of lubricating layer coating: add 0.2-0.5 parts of photoinitiator Ⅱ to 70-80 parts of solvent Ⅱ, add 5-10 parts of hydrophilic resin and 1-5 parts of water-based crosslinking agent under constant stirring after fully dissolved Stir for 5-8 hours, measure the viscosity after forming a uniform solution, and adjust the viscosity to 90-120 mPa·s with 10-25 parts of solvent II.

An application of a hydrophilic modified coating on the surface of a medical intervention catheter, comprising the steps of:

Coating of transitional layer: Clean the interventional catheter in medical ethanol and dry it, dip the catheter into the transitional layer coating at a speed of 3 cm/s through a lifting machine, soak for 10-30 seconds, and then immerse the catheter in 1.0-1.5 cm Pull at a speed of 1/second to complete the coating, quickly transfer to a 1000 W UV lamp, irradiate for 30-60 seconds, take it out and hang it in a clean place to avoid contact between the catheters;

Lubricating layer coating: dip the catheter that has completed the transition layer coating into the lubricating layer coating at a speed of 3 cm/s for 10-30 seconds, and then pull it at a speed of 0.5-1.0 cm/s Finally, quickly transfer to a curing box equipped with a 400 W UV lamp and irradiate for 150-210 seconds to cure completely.

A method for testing the lubricity and stability of the hydrophilic lubricating layer on the surface of a medical interventional catheter is as follows: a steel column with the same size as the inner diameter of the catheter is inserted inside the catheter to keep the shape of the catheter unchanged, and the catheter is horizontally fixed on a surface filled with water. After soaking for 30 seconds in a water tank, the silica gel sheet was used as a pair on a dynamic and static friction tester (14WF, Shimadzu, Japan), and the reciprocating friction test was carried out at a speed of 0.5 cm/s under different loads.

The present invention is further described below with specific embodiment:

Example 1

Paint preparation:

Add 10 parts of unsaturated acrylic resin to 50 parts of ethyl acetate, and add 0.2 parts of 2-hydroxyl-4'-(2-hydroxyethoxy)-2-methyl propiophenone under the condition of avoiding light after fully stirring. After the initiator is completely dissolved, add 43 parts of isopropanol, measure the viscosity of the solution to 4.5 mPa·s, add 0.1 parts of leveling agent BYK333 and continue stirring for 30 minutes to obtain a transition layer coating; add 0.3 parts to 50 parts of ethanol and 25 parts of methanol Benzophenone, after being fully dissolved, add 3.5 parts of PVP, 1.5 parts of PEG and 1.0 parts of water-based cross-linking agent PEG400DA under uniform stirring for 7-8 hours, and measure the viscosity after forming a uniform solution, adjust with 10-20 parts of ethanol When the viscosity reaches 90-95 mPa·s, a lubricating layer coating is obtained.

Coating method:

Clean and dry the interventional catheter in medical ethanol, dip the catheter into the transition layer coating prepared above at a speed of 3 cm/s through a pulling machine, pull it at a speed of 1.0 cm/s after soaking for 10 seconds to complete the coating quickly transfer it to a 1000W UV lamp, irradiate for 30 seconds, take it out and hang it in a clean place to avoid the catheters from touching each other; Immerse in the lubricating layer coating prepared above for 30 seconds, then pull it at a speed of 1.0 cm/s, and quickly transfer it to a curing box equipped with a 400W ultraviolet lamp for 180 seconds to cure completely.

Performance Testing:

A steel column with the same size as the inner diameter of the catheter is inserted inside the catheter to keep the shape of the catheter unchanged, and the catheter is horizontally fixed in a sink filled with water, soaked for 30 seconds and then tested on a dynamic and static friction test machine (14WF, Shimadzu, Japan) Taking the silica gel sheet as a pair, the reciprocating friction experiment was carried out for 20 cycles at a speed of 0.5 cm/s under 100 g, 300 g, and 500 g loads respectively, and the average friction coefficients obtained were 0.020, 0.023, and 0.028, respectively.

Example 2

Paint preparation:

Add 8 parts of unsaturated polyurethane acrylate resin to 25 parts of isopropanol and 25 parts of ethanol mixture, stir well and add 0.2 parts of 2-hydroxy-2-methyl-1-phenyl-1-acetone under dark conditions After the initiator is completely dissolved, add 40 parts of ethanol, measure the viscosity of the solution to be 5 mPa·s, add 0.05 parts of leveling agent DC57, and continue to stir for 30 minutes to obtain a transition layer coating; in 40 parts of water and 30 parts of ethanol mixed solution Add 0.5 parts of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, after fully dissolved, add 0.5 parts of PVA, 5.0 parts of PVP-PHEMA copolymer and 1.0 parts of water under constant stirring The joint agent PEG600DA is fully stirred for 7-8 hours, and the viscosity is measured after forming a uniform solution, and the viscosity is adjusted to 110-120 mPa·s with 15-25 parts of ethanol to obtain a lubricating layer coating.

Coating method:

Clean the interventional catheter in medical ethanol, dip the catheter into the transition layer coating prepared above at a speed of 3 cm/s through a pulling machine, soak for 20 seconds, and then pull at a speed of 1.5 cm/s to complete the coating , quickly transfer to a 1000W UV lamp, irradiate for 30 seconds, take it out and hang it in a clean place to avoid the catheters from touching each other; Immerse in the lubricating layer coating prepared above for 30 seconds, then pull it at a speed of 0.5 cm/s, and quickly transfer it to a curing box equipped with a 400W ultraviolet lamp for 210 seconds to cure completely.

Performance Testing:

With the method shown in Example 1, under the load of 100 g, 300 g, and 500 g, respectively, the reciprocating friction experiment was carried out at a speed of 0.5 cm/s for 20 cycles, and the average friction coefficients obtained were 0.018, 0.022, and 0.029, respectively.

Example 3

Paint preparation:

Add 10 parts of unsaturated polyurethane acrylate resin to 30 parts of isopropanol and 20 parts of ethyl acetate mixture, stir well and add 0.1 part of 2-hydroxy-2-methyl-1-phenyl-1 -Acetone and 0.1 part of 1-hydroxycyclohexyl phenyl ketone, after the initiator is completely dissolved, add 38 parts of isopropanol, measure the viscosity of the solution to 4.3 mPa s, add 0.05 part of leveling agent BYK333, continue to stir for 30 minutes, To obtain a transition layer coating; add 0.3 parts of 1-hydroxycyclohexyl phenyl ketone and 0.2 parts of 2-hydroxy-2-methyl-1-phenyl-1 to a mixture of 30 parts of ethanol, 20 parts of methanol and 20 parts of water - Acetone, after being fully dissolved, add 2.0 parts of polyethylene glycol (PEG), 5.5 parts of polyvinylpyrrolidone (PVP), 0.5 parts of hyaluronic acid and 2.0 parts of water-based crosslinking agent PEG600DA under constant stirring for 7-8 hours, Measure the viscosity after forming a uniform solution, and adjust the viscosity to 100-110 mPa·s with 10-25 parts of ethanol to obtain a lubricating layer coating.

Coating method:

Clean the interventional catheter in medical ethanol, dip the catheter into the transition layer coating prepared above at a speed of 3 cm/s through a pulling machine, soak for 30 seconds, and then pull at a speed of 1.0 cm/s to complete the coating , quickly transfer to a 1000 W UV lamp, irradiate for 30 seconds, take it out and hang it in a clean place to avoid the catheters from touching each other; Immerse it in the lubricating layer coating prepared above for 30 seconds, then pull it at a speed of 1.0 cm/s, and quickly transfer it to a curing box equipped with a 400 W UV lamp for 150 seconds to cure completely.

Performance Testing:

With the method shown in Example 1, under the load of 100 g, 300 g, and 500 g, respectively, the reciprocating friction experiment was carried out at a speed of 0.5 cm/s for 20 cycles, and the friction coefficients were respectively 0.014, 0.020, and 0.025.

Claims (10)

1. a kind of hydrophilic modifying coating on medical introducing duct surface, it is characterised in that the hydrophilic modifying coating is by transition coating Constitute with lubrication coating, the composition of transition coating and the parts by weight of each component are：Binding resin 5-10 parts, light I 0.1-0.2 parts of initiator, levelling agent 0.05-0.1 parts, I 85-95 parts of solvent；The composition and each component of the lubrication coating Parts by weight be：Hydrophilic resin 5-10 parts, water cross-linking agent 1-5 parts, II 0.2-0.5 parts of light trigger, II 80-95 of solvent Part.

2. hydrophilic modifying coating as claimed in claim 1, it is characterised in that the binding resin is unsaturated acrylic resin, One or two mixture in unsaturated polyurethanes acrylate.

3. hydrophilic modifying coating as claimed in claim 1, it is characterised in that the light trigger I is 1- hydroxycyclohexylphenyls One kind in ketone, 2- hydroxyl -4'- (2- hydroxy ethoxies) -2- methyl phenyl ketones, 2- hydroxy-2-methyl -1- phenyl -1- acetone Or two kinds of compositionss；The light trigger II is 1- hydroxycyclohexyl phenyl ketones, 2- hydroxyl -4'- (2- hydroxy ethoxies) -2- One or more mixture in methyl phenyl ketone, 2- hydroxy-2-methyl -1- phenyl -1- acetone, benzophenone.

4. hydrophilic modifying coating as claimed in claim 1, it is characterised in that the levelling agent is the BKY of Bi Ke companies production 333rd, one or two the mixture in the DC57 of Dow Corning Corporation's production.

5. hydrophilic modifying coating as claimed in claim 1, it is characterised in that the solvent I is ethanol, isopropanol, ethyl acetate In one or two mixture；The solvent II is methanol, ethanol, the two or more mixture in isopropyl alcohol and water.

6. hydrophilic modifying coating as claimed in claim 1, it is characterised in that the hydrophilic resin is Polyethylene Glycol, polyethylene One kind in alcohol, polyvinylpyrrolidone, hyaluronic acid, NVP-hydroxyethyl methylacrylate copolymer or Two or more compositionss.

7. hydrophilic modifying coating as claimed in claim 1, it is characterised in that the water cross-linking agent is two propylene of Polyethylene Glycol Acid esters.

8. as any one of claim 1 to 7 medical introducing duct surface hydrophilic modifying coating, it is characterised in that the painting The using method of material is：Jing ethanol purges clean conduit is soaked the 10-30 seconds in transition coating, then with 1.0-1.5 The speed lifting of cel completes application, and under the uviol lamp of 1000 W, the irradiation 30-60 seconds obtain final product transition zone；Completed The conduit for crossing layer application soaks the 10-30 seconds in lubrication coating, after then being lifted with the speed of 0.5-1.0 cels, The 150-210 seconds are irradiated under the uviol lamp of 400 W can completion of cure.

9. hydrophilic modifying coating as claimed in claim 8, it is characterised in that the material of the conduit is polyurethane, polrvinyl chloride Or polyester.

10. hydrophilic modifying coating as claimed in claim 8, it is characterised in that it is described catheter surface formed by transition zone and Lubricating layer formed the lubricity of hydrophilic lubrication layer and the detection method of stability be：Insert a diameter and lead in catheter interior The steel column of bore formed objects, makes catheter shape keep constant, conduit is horizontally fixed in the tank for filling water, immersion 30 Carried out respectively back and forth with the speed of 0.5 cel with silica gel piece as antithesis in different loads on sound tester for friction between after second Frictional experiment.