JP3340992B2 - Lubricant hydrophilic coating resistant to wet wear - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION The present invention relates to hydrophilic lubricating coatings that lubricate biomedical devices when wet. The methods and coatings of the present invention are employed to reduce the coefficient of friction of catheters, condoms, contact lenses, peristaltic pump chambers, arteriovenous shunts, gastrointestinal feeding and endotracheal tubes, or other metal or polymer based implants. sell.

Known lubricating coatings that can be applied to biomedical devices include polyvinylpyrrolidone (PVP), polyurethane,
Coatings include acrylic polyesters, vinyl resins, fluorocarbons, silicones, rubbers, or combinations of these materials. For example, Micklus et al., U.S. Pat. Nos. 4,100,309 and 4,119,094, relate to hydrophilic coatings of PVD polyurethane copolymers made from polyisocyanates. Ratner et al., U.S. Pat. No. 3,939,049, relates to a method of using radiation to graft a hydrogel onto a polymer substrate. U.S. Pat. No. 3,975,350 to Hudgin et al. Relates to hydrophilic polyurethane polymers. Stoy et al.
No. 3,987,497 relates to an artificial tendon having a hydrogel coating.

[0003] These known hydrogel coatings have disadvantages: they may have an insufficient low coefficient of friction, they may lack durability (eg silicone or fluorocarbon), and May be difficult to handle due to the smoothness when dry and wet, or they may require the use of hazardous solvents to prepare (eg, Micklus et al. Coatings), It may require that separate and fresh solutions be prepared daily or more frequently to contain unstable and reactive materials.

[0004] Furthermore, in PVD-polyurethane coatings, only a small control can be exerted on the lubricity of the coating and on the degree of wet-wear resistance, and such coatings are therefore often unstable. To solve these problems, a hydrophilic lubricating coating that has sufficient lubricity to be useful for biomedical devices such as implants when wet, adheres and lubricates a wide variety of substrates What is needed is something that is not attacked by abrasion and can be made with chemically stable biocompatible solvents.

SUMMARY OF THE INVENTION One aspect of the present invention relates to a hydrophilic coating comprising a hydrophilic polymer and a stabilizing polymer in a layer adhered to the surface of the device. The hydrophilic polymer is a polyolefin, such as a vinyl polymer having polar pendant groups, a polyacrylate or methacrylate having a hydrophilic esterifying group, a polyether, polyethylene glycol, or other polyolefin having hydrophilic properties. The hydrophilic polymer is preferably PVP or PV
P is vinyl acetate. The stabilizing polymer is a water-insoluble polymer that does not significantly react with the hydrophilic polymer in solution, and is thus preferably a cellulose ester,
It is a copolymer of polymethyl vinyl ether and maleic anhydride, or nylon. Cellulose esters are most preferred. This includes ethyl cellulose, hydroxyethyl cellulose, cellulose nitrate, cellulose acetate, cellulose acetate butyrate and cellulose acetate propionate.

In one embodiment, the coating has an inner layer where the stabilizing polymer is concentrated and an outer layer where the hydrophilic polymer is concentrated. In another embodiment, the hydrophilic polymer and the stabilizing polymer are contained in a single coating and thus constitute a single coating.

The coating may include an adhesive polymer, such as polyurethane, polyester, styrene polybutadiene, acrylic resin, polyvinylidene chloride, polycarbonate and polyvinyl chloride, preferably in the inner layer to enhance adhesion to the surface of the device. . The most preferred outer layer composition is high molecular weight PVP (e.g.,
360,000).

The coatings of the present invention can be applied to polymer surfaces such as polyurethane, polyvinyl chloride, polyacrylate, polycarbonate, polystyrene, polyester resin, polybutadiene-styrene copolymer, nylon, polypropylene, polybutylene, Teflon, silicone and polyvinyl acetal. The coating of the present invention may be applied to glass or metal, such as stainless steel. The coating components can be selected to provide a coating with the desired properties on these surfaces.

The process for preparing the coatings of the present invention employs a stable, non-toxic solution that can be stored and handled with minimal precautions. The method of applying the coatings of the present invention can be from about 0.01 to about 30% by weight to volume, preferably from about 0.2% to
A first organic solution of about 10% of the stabilizing polymer is prepared, the solution is applied to the surface of the substrate, and the solvent is then evaporated, preferably at elevated temperature, after which about 0.01 to about 30% weight to volume, Comprising preparing a second solution of the hydrophilic polymer, preferably about 0.5% to about 20%, applied to the treated surface substrate described above and then evaporating the solvent at room or elevated temperature. Become.

[0010] The stabilizing polymer solution is about 0.01% to about 10%.
%, Preferably from about 0.1% to about 5%, of a hydrophilic polymer. The hydrophilic polymer solution has a concentration of about 0.01% to about 20%.
%, Preferably from about 0.1% to about 10%, of a stabilizing polymer. On the other hand, the stabilizing polymer and the hydrophilic polymer can be prepared in a single solution and applied in a single step.

The surface of the device may be pre-treated to increase the adhesion of the coating. The solution may include from about 0.1% to about 15%, preferably from about 1.0% to about 8.0% by weight of the adhesive polymer to enhance the adhesion between the substrate and the coating.

[0012] About 0.01% of plasticizer together with stabilizing polymer
It may be included at a concentration of about 10%, preferably about 0.1% to about 5.0% weight to volume. The plasticizer can be camphor, castor oil, dioctyl phthalate, acetyl tributyl citrate, dibutyl sebacate, sebacic acid, an alkyl resin, dibutyl phthalate, polyvinyl butyral or other commonly known plasticizers alone or in combination. The plasticizer is preferably contained in a solution of the stabilizing polymer. The coating of the present invention may include a plasticizer to increase the flexibility of the coating, which may be preferred when the object to be coated is prone to bending during use. In addition, the inclusion of a plasticizer is preferred when the stabilizing polymer is nitrocellulose, because the plasticizer may rapidly oxidize the nitrocellulose or even burn when it is dry in its pure state. This is because it lowers a certain tendency.

Solvents for stabilizing and adhesive polymers include organic solvents such as ketones, esters, toluene, lactone, dimethylformamide, halogenated solvents, tetrahydrofuran, dioxane, amine, glycol butyl ether, alkyl acetate, acetonitrile and other generally. Contains known organic solvents. Less toxic solvents are preferred. The presence of traces of hydroxyl groups, such as alcohols and moisture, in this solvent has no significant adverse effect on the coatings and methods of the present invention.

Solvents for the hydrophilic polymer include most of the above and solvents such as alcohols and acetic acid.
The solvent system allows for the dissolution of all components of the coating in a homogeneous solution, acts as a co-solvent in the layer, and may be chosen to be non-toxic. If desired, one that interacts with a particular substrate surface to enhance adhesion may be selected.

In another embodiment of the invention, the article to which the coating is to be applied has a polymer surface and is "active"
A solvent is used, which eliminates the need for an inner layer or basecoat by allowing the lubricating hydrophilic layer (or topcoat) to be applied directly on the polymer surface of the product. In this embodiment, the term "active solvent"
It is defined as a co-solvent for both the polymer or the polymer mixture which constitutes the polymer surface or, in the case of a mixed polymer substrate, at least one or more polymers, and for both the coating polymer (s).

The solution may be applied by dipping the object to be coated into a container containing the solution, or by pouring, pumping, brushing or spraying the solution onto the object.

DETAILED DESCRIPTION OF THE INVENTION The hydrophilic coating of the present invention is highly lubricious when wet with an aqueous solution, such as a bodily fluid, or an alcohol, such as ethanol or methanol, but substantially when dry. Not smooth. Thus, an implant coated in accordance with the present invention remains non-smooth due to ease of handling and manufacture, but becomes lubricious when implanted, thus protecting the patient. The lubricity of the coating can be adjusted within a desired range.

The coating according to the present invention can be applied to biomedical or other devices with sufficient thickness and durability to maintain the desired quality of the coating over the useful life of the coated device. The coating of the present invention is non-reactive with living tissue and is non-thrombotic in blood.

The coating of the present invention has advantageous features for use on surfaces of devices such as biomedical implants. The coating is hydrophilic, water-absorbing, and swells in an aqueous environment to form a hydrogel. This coating has lubricating properties and is smoother when wet than when dry. This coating is thin, 1/1000
It is an inch digit. The coating is tacky and durable to wet wear and adheres to a wide variety of substrates. The coating employs a biocompatible material that is neither toxic nor irritating. The functional properties of the coating can be varied to suit many different applications.

The method of the present invention is advantageous because its components can be varied to adjust lubricity, swellability, flexibility and resistance to peeling due to wet wear. These properties of the coating can thus be adjusted for various substrates and applications. This method is further advantageous because the solutions of the present invention have good shelf stability and remain substantially free of sediment over a period of up to months or years, and thus various solutions Can be prepared at one time and subsequently coated on a substrate. On the other hand, the hydrophilic and stabilizing polymer, and if desired, the plasticizer and adhesive polymer could even be prepared in a single solution. Furthermore, the present invention does not require the use of chlorinated solvents or other acute toxicants, so that less precautionary measures are needed to protect workers from health risks.

While not intending to limit the invention to its mode of operation, it is clear that the stabilizing polymers of the invention, especially the modified cellulose polymers, are hydrophilic polymers such as PVP
And PVP-vinyl acetate copolymers can be stable and insoluble in water and lower alcohols. The resulting combination, when applied to a substrate, becomes a stable layer (or layers) adhered to the substrate surface, is not smooth when dry but has the desired lubricity when wet, And wet wear conditions result in a coating that is durable to peel. This coating layer adheres to an impermeable surface, such as stainless steel or glass. It also adheres to the polymer surface such that the surface interacts with the components of the coating.

By varying the weight-to-volume percentage of the components in the coating solution, it is possible to adjust the degree of stability, wet lubricity, insolubility, flexibility and adhesion of the coating. Substantially all of the polymer and plasticizer which has been deposited on the surface of the object to be coated from the solution remains in this coating layer after the solvent has evaporated. Furthermore, the time and temperature of the evaporation step are selected to obtain the stability of the coating layer;
An adhesion between the coated surface and this coating layer can be obtained.

Preferably, the outer layer solution has a certain amount of "active"
Solvents, or co-solvents, are included for the outer and inner layer components. It is believed that the active solvent thereby causes the outer layer solution to penetrate into the inner layer and results in a molecular level complexation of both components.

It is believed that such molecular complexes can result in chemical reactions, such as cross-linking between components, or consist only of physical complexes without the chemical reaction (s). In any case, in certain preferred embodiments, a high degree of cross-linking or molecular bonding between the hydrophilic polymer and the stabilizing polymer at the interface between the inner and outer layers of the coating relative to the outer surface of the outer layer. There is a complex between them. Thus, copolymers between these two layers can result from cross-linking or intermolecular conjugation between the polymers contained in each layer. The slope or lack of cross-linking at the outer surface of the coating helps to provide lubricity to the coating of the present invention.

In practice, the activity of the solvent mixture is adjusted so that the extent of penetration of the outer layer into the inner layer is in a useful range.
For example, if the outer layer solvent mixture is too active for the inner layer, too much penetration into the inner layer will occur and the outer layer will not be sufficiently lubricious when wet. Conversely, if this outer layer solvent is too inert to the inner layer, too little penetration of the outer layer into the inner layer occurs,
The coating will therefore be too easily detached from the inner layer by wet wear.

In another embodiment of the present invention, the lubricating hydrophilic layer is applied directly on the polymer surface as a topcoat, and an active solvent is used, which may be a plastic-based polymer or, in the case of a mixed polymer substrate, For a polymer mixture or one or more polymers,
And a co-solvent for both the coating polymer (s) in the hydrophilic layer.

After drying, which is typically performed at a temperature of 50 ° C. to 100 ° C., but may be performed at higher or lower temperatures, the topcoat polymer layer (s) is It remains partially buried inside. In the case of a two-layer system, the topcoat penetrates into the polymer surface to the extent that the solvent used during application of the coating is too active and the coating acts as if it were highly crosslinked. Sometimes. This results in the topcoat not fully swelling and becoming lubricious when wet with an aqueous fluid. The solvent mixture can also be too inert, so that the coating is not sufficiently resistant to abrasion when wet and is too easily stripped off.

In the case of a two-layer system, other polymers or crosslinkers may be included in the lubricating layer with the plurality of hydrophilic polymers to increase the adhesion of the layer to the polymer surface and make the lubricating layer more resistant to wet wear. can do.

The active solvents useful in the present invention can be individual solvents or solvent mixtures containing two or more solvents. In the case of a solvent mixture, one or more solvents in the mixture are active while the other (s) in the mixture are active.
The solvent can be inert. In any case, the solvent or solvent mixture will dissolve or at least disperse the topcoat polymer (s).

If the topcoat polymer is dispersed rather than dissolved, the time is reached for the topcoat polymer (s) to be in solution before all of the solvent leaves the coating. During the period of drying when the topcoat polymer (s) is in solution, the solvent also penetrates the base polymer (s) on the polymer surface. Thus, intermolecular conjugation between the base polymer (s) and the topcoat polymer (s) can occur.

Examples of active solvents useful in the present invention include butyrolactone, alcohols, dimethylacetamide and n-methyl-2-pyrrolidone. These solvents and others may result in varying degrees of swelling of the plastic substrate or inner layer. The hydrophilic polymer of this coating is typically a high molecular weight PVP of 120,000-360,000. Low molecular weight PVP's as low as 15,000 can be used on the substrate or base next to the substrate without compromising performance. Some or all of the PVP may be replaced with a PVP-vinyl acetate copolymer either in a single coat embodiment or in either layer of a two-layer coat embodiment.

The most preferred stabilizing polymer has been found to be a water-insoluble cellulose polymer.
As an alternative to modified cellulose polymers, for example, polymethyl vinyl ether maleic anhydride and nylon can be used instead of or in addition to this modified cellulose polymer, however, they are more difficult to work with and use Tend to result in a coating that has less abrasion resistance than a coating prepared without. When the stabilizing polymer is nitrocellulose, it is preferable to include a plasticizer.

When tested by a subjective method, the coatings of the present invention are smoother than wet grease glass when wet and not as smooth as dry glass when dry. The coating of the present invention is resistant to delamination by wet abrasion, which was determined by running water over the coating and then rubbing between fingers that were squeezed while wet. The coating of the present invention has a high adhesion when dry, which means that an adhesive tape is applied, the tape is peeled off with a vigorous operation, and a lubricating coating remains on the taped part. It was determined by wetting the coated substrate to see if it was. The coating of the present invention remained adherent and tacky for a long time without peeling, dissolving or disintegrating when stored in water.

The coating systems described herein provide abrasion resistant surfaces on surfaces such as polyethylene, polypropylene, silicon, glass, stainless steel, and other substrates that are generally considered to exhibit adhesion problems. It will provide a hydrophilic lubricating coating that is resistant to it. Such surfaces may need to be subjected to a gas plasma or other ionization treatment to enhance adhesion to the substrate. The following examples show how the invention can be used.

Example 1 Polyurethane tubing was prepared using 36.0 ml toluene 13.1 ml butyl acetate 5.9 ml isopropanol 25.4 ml ethyl acetate 18.1 ml ethanol 1.5 ml acetone in a solvent mixture of 5.4 gm low viscosity (1/1) 2 seconds) Nitrocellulose 2.0 gm dibutyl phthalate 1.5 gm camphor 1.9 gm polyvinyl butyral was dipped and coated in a polymer solution for stabilization. The coated tube was dried at 65 ° C. for 5 minutes. It was then dip coated with a hydrophilic polymer solution containing 6.6 gm of polyvinylpyrrolidone, 63.8 ml of denatured ethanol, 23.6 ml of ethyl acetate, 12.6 ml of dimethylformamide, and then dried at 65 ° C. for 5 minutes. A hydrophilic coating was obtained, which was smooth when wet.

Example 2: Styrene butadiene tube was charged with 1.9 gm of 1/2 second nitrocellulose in 60 ml of ethyl acetate, 34.4 ml of denatured ethanol, 4.6 ml of acetic acid, 1 ml of isopropanol, hydrophilic polymer, 1.5 gm of polyvinyl Dip coated in a stabilizing polymer solution with pyrrolidone then dried at 80 ° C. for 5 minutes. The sample is then immersed in a hydrophilic polymer solution containing 7.5 gm of polyvinylpyrrolidone, together with 0.3 g of nitrocellulose, with 7.5 gm of polyvinylpyrrolidone in 73 ml of denatured ethanol 26.8 ml of ethyl acetate 0.2 ml of isopropanol Coated and then dried at 80 ° C. for 5 minutes. A hydrophilic coating was obtained, which was smooth when wet.

Example 3: A polyurethane tube was filled with 33 ml
5.9 gm in ethyl acetate and 67 ml of chloroform
1/2 sec cellulose acetate butyrate and 5.9 gm
Was applied by dip coating with a solution of a stabilizing and hydrophilic polymer containing polyvinylpyrrolidone, and then dried at 80 ° C. for 5 minutes. This was then dip coated in a hydrophilic polymer solution containing 5 gm of polyvinylpyrrolidone in 95 ml of denatured ethanol and then dried at 80 ° C. for 5 minutes. A hydrophilic coating was obtained, which was smooth when wet.

Example 4: A sample of polyurethane tubing was prepared using 1.9 gm of nitrocellulose 1.1 gm of polyester resin 1.0 gm of polymethyl vinyl ether / monobutyl ester of maleic anhydride copolymer 0.8 ml of isopropanol 57.8 ml of ethyl acetate 33.4 ml of Denatured ethanol was coated with a stabilizing and adhesive polymer solution containing 8 ml of dimethylformamide. The sample was dried at 80 ° C. for 5 minutes. The samples were then dip coated in a hydrophilic polymer solution containing 6.6 gm of polyvinylpyrrolidone, 63.8 ml of denatured ethanol, 23.6 ml of ethyl acetate, 12.6 ml of dimethylformamide. The sample was dried at 80 ° C. for 5 minutes to form an adhesive, lubricious layered film. Similar coatings were made on polyvinyl chloride tubes.

Example 5 This example shows what various "adhesive" resins can be added to enhance adhesion to a substrate. a. The following stabilizing polymer solution was dip-coated on a polyurethane tube and dried at 80 ° C. for 5 minutes. Nitrocellulose 56 gm Camphor 15 gm Dibutyl phthalate 20 gm Isopropanol 23 mL Toluene 225 mL Ethyl acetate 330 mL Butyl acetate 96 mL Acetone 7 mL Next, this was dip-coated with the following hydrophilic polymer solution. Polyvinylpyrrolidone (PVP) 3 gm Denatured alcohol 27 ml Ethyl acetate 10 ml Dimethylformamide 12 ml This coating separated from the tube when immersed in water. b. Example 5 (a) was repeated with the addition of 5.0 gm to 17 gm of polyurethane resin to the nitrocellulose solution to produce a sample that exhibited excellent adhesion when immersed in water. c. Example 5 (a) was repeated with the addition of 5.0 gm to 17 gm of polyester resin to the nitrocellulose solution to produce a sample that exhibited excellent adhesion when immersed in water. d. Example 5 (a) was repeated with 5.0 gm to 17 gm of styrene butadiene resin added to the nitrocellulose solution to produce a sample that exhibited excellent adhesion when immersed in water. e. Example 5 (a) was repeated by adding 5.0 gm to 17 gm of urea formaldehyde resin to the nitrocellulose solution,
A sample was produced that exhibited excellent adhesion when immersed in water.

Example 6: A polyurethane tube was coated with the following stabilizing polymer solution and dried at 65 ° C for 5 minutes. Nitrocellulose 65 gm Dibutyl phthalate 24 gm Camphor 18 gm Polyvinyl butyral 23 gm Acetone 28 ml Ethanol 306 ml Bralar acetate 257 ml Ethyl acetate 500 ml Toluene 550 ml Isopropanol 28 ml Dimethylformamide 200 ml This sample is overcoated with the following hydrophilic polymer solution.
Then, it was dried at 65 ° C. for 5 minutes. Polyvinylpyrrolidone 1 gm ethanol 9 ml dimethylformamide 3 ml water 0.5 ml This sample had excellent adhesion when immersed in water.

Example 7: An acrylic surface was coated with the following stabilizing polymer solution and dried at 70 ° C for 5 minutes. Cellulose acetate propionate 12.9 gm dibutyl phthalate 4.8 gm camphor 3.6 gm acetone 3.2 gm ethyl acetate 55.7 gm toluene 58.6 gm butyl acetate 28.5 gm isopropanol 5.6 gm This sample was then coated with the following hydrophilic polymer solution and at 70 ° C. Dry for 5 minutes. Acetonitrile 5 ml Ethanol 4.5 ml PVP (360,000 MW) 0.5 gm This coating was not soluble in water and was very smooth.

Example 8: An acrylic surface was coated with the following stabilizing polymer solution and dried at 70 ° C. for 5 minutes. Cellulose acetate 12.9 gm dibutyl phthalate 4.8 gm camphor 3.6 gm methyl ethyl ketone 148.3 ml dimethylformamide 20.0 ml This sample was then coated with the following hydrophilic polymer solution and dried at 70 ° C. for 5 minutes. PVP (360,000 mw) 0.5 gm cellulose acetate 0.1 gm acetone 6 ml ethanol 4.5 ml acetic acid 1.0 ml methyl ethyl ketone 0.9 gm This coating was not soluble in water and was very smooth.

Example 9: An acrylic surface was coated with the following stabilizing and adhesive polymer solution and dried at 70 ° C for 5 minutes. Cellulose acetate butyrate 6.5 gm polyester resin 6.0 gm dibutyl phthalate 2.4 gm camphor 1.8 gm acetone 2.5 ml ethyl acetate 43.6 ml toluene 43.6 ml butyl acetate 22.4 ml This sample was then coated with the following hydrophilic polymer solution and at 70 ° C. Dry for 5 minutes. Acetonitrile 5 ml Ethanol 4.5 ml PVP (360,000 mw) 0.5 gm This coating was insoluble in water and was smooth when wet.

Example 10: A nylon tube was coated with a stabilizing polymer with the following solution and dried at 75 ° C for 10 minutes. Nylon resin 2 gm trifluoroethanol 18 ml The sample was then overcoated with a hydrophilic polymer by the following solution and dried at 75 ° C for 10 minutes. PVP (360,000 mw) 1.0 gm Nylon resin 0.3 gm ethanol 9.0 ml dimethylformamide 3.0 ml trifluoroethanol 2.7 ml This coating was insoluble in water.

Example 11: A stainless steel wire guide was coated with a stabilizing polymer with the following solution and dried at 70 ° C for 10 minutes. Nitrocellulose 64.6gm Dibutyl phthalate 24.3gm Camphor 17.9gm Polyvinyl butyral 22.5gm Acetone 28.4ml Ethanol 306.1ml Butyl acetate 257.0ml Ethyl acetate 499.2ml Toluene 552.8ml Isopropanol 27.5ml Dimethylformamide 200.0ml The polymer was overcoated and dried at 70 ° C. for 10 minutes. PVP 1.0 gm ethanol 9.0 ml dimethylformamide 2.0 ml This coating was insoluble in water and was very smooth.

Example 12: The coating procedure of Example 11 was repeated on an acrylic surface, again producing a water-insoluble and very smooth coating.

Example 13: A nylon tube is coated with a stabilizing and adhesive polymer with the following solution and at 65 ° C
For 5 minutes. Nitrocellulose 32.3gm Polyurethane 11.2gm Dibutyl phthalate 12.2gm Camphor 9.0gm Polyvinyl butyral 11.2gm Acetone 25ml Ethanol 254ml Butyl acetate 225.3ml Ethyl acetate 439.2ml Toluene 467.8ml Isopropanol 13.8ml Dimethylformamide 100ml The polymer was coated and dried at 65 ° C for 5 minutes. PVP 1.0 gm nitrocellulose 0.12 gm ethanol 9.0 ml dimethylformamide 2.0 ml ethyl acetate 0.4 ml This coating was insoluble in water and very smooth.

Example 14: Polyurethane tubing is coated with a stabilizing polymer with the following solution and
Dried for minutes. Nitrocellulose 64.6gm Dibutyl phthalate 24.3gm Camphor 17.9gm Polyvinyl butyral 22.5gm Acetone 28.4ml Ethanol 306.1ml Butyl acetate 257.0ml Ethyl acetate 499.2ml Toluene 552.8ml Isopropanol 27.5ml Dimethylformamide 200.0ml The polymer was overcoated and dried at 65 ° C for 5 minutes. PVP 1.0 gm ethanol 9.0 ml dimethylformamide 2.0 ml This coating was insoluble in water and was very smooth when wet.

Example 15: The coating procedure of Example 13 was repeated on an acrylic surface, again producing a water-insoluble and very smooth coating.

Example 16 A styrene-butadiene tube was coated with a stabilizing and adhesive polymer with the following solution and dried at 80 ° C. for 5 minutes. Nitrocellulose 32.3gm Polyurethane 10.0gm Dibutyl phthalate 12.2gm Camphor 9.0gm Polyvinyl butyral 11.2gm Acetone 25ml Ethanol 264ml Butyl acetate 226.3ml Ethyl acetate 439.2ml Toluene 467.8ml Isopropanol 13.8ml Dimethylformamide 100ml The solution was coated and dried at 80 ° C. for 5 minutes. PVP 1.0 gm ethanol 9.0 ml dimethylformamide 2.0 ml water 0.5 ml This sample was insoluble in water and was smooth when wet.

Example 17 This example illustrates how solvent (s) can be added to enhance adhesion by attacking or interacting with a layer that can be coated. Multiple samples of polyurethane tubing were coated with the following stabilizing polymer solutions. Nitrocellulose 64.6gm Dibutyl phthalate 24.3gm Camphor 17.9gm Polyvinyl butyral 22.5gm Acetone 28.4ml Ethanol 306.1ml Butyl acetate 257.0ml Ethyl acetate 499.2ml Toluene 552.8ml Isopropanol 27.5ml Dimethylformamide 200.0ml The sample coated as above was Were coated with any of the following solutions containing varying amounts of dimethylformamide or acetic acid that interact with the surface to be coated to enhance adhesion: (a) coated with the following hydrophilic polymer solution: Then 70 ° C
Dry for 5 minutes. PVP 1.0 gm ethanol 9.0 ml dimethylformamide 3.0 ml This hydrophilic coating adhered well, was insoluble in water, and was very smooth. (B) hydrophilic polymer in ethanol, 10% (w / v)
And then dried at 70 ° C. for 5 minutes. (C) coated with the following hydrophilic polymer solution,
Dry for 5 minutes. PVP 1.0gm Ethanol 9.0ml Dimethylformamide 1.0ml This sample resisted peeling when wet, but 3ml
Was not as resistant to wet abrasion as the above sample containing dimethylformamide. (D) coating with the following hydrophilic polymer solution,
Dry for 5 minutes. PVP 1.0 gm ethanol 9.0 ml acetic acid 3.0 ml This hydrophilic coating was well adhered, insoluble in water and very smooth.

Example 18 In this example, a hydrophilic polymer and a stabilizing polymer were combined in a single solution, which was coated on a polyurethane tube and then dried at 80 ° C. for 5 minutes. PVP 0.5 gm nitrocellulose 0.056 gm methyl ethyl ketone 13.7 ml isopropanol 0.024 gm acetic acid 1.0 ml This resulted in a single layer coating that was smooth when wet and resistant to wet abrasion.

Example 19 The following solution was coated on a polyurethane tube and then dried at 80 ° C. for 5 minutes. PVP 1.5 gm Polyethylene glycol 2.7 gm Ethanol 68.8 gm Isopropanol 18.0 gm 4-butyrolactone 8.0 gm In this example, the hydrophilic polymer is dissolved in a solution containing at least one solvent that swells the substrate on which the coating is to be applied. Combined. By swelling the substrate, some of the hydrophilic polymer molecules were trapped in the surface of the substrate after the solvent had evaporated. Because some of the hydrophilic polymer was firmly adhered into the substrate surface, it was made resistant to wet abrasion, thus resulting in a monolayer coating that was smooth when wet.

Examples 20 to 24 The following solutions were prepared, applied by dip coating on an 8 French polyurethane tube, and then dried at 80 ° C. for 10 minutes. Ingredient Example 20 Example 21 Example 22 Example 23 Example 24 10% PV Pin 4.0g 4.0g 4.0g 4.0g 4.0g Benzyl alcohol ─ 24.4g 16.0g 16.0g 16.0g N, N, dimethylacetamide ─ ─ 7.5g ─ 氷 Glacial acetic acid ─ ─ ─ 7.5 g ─ N-methyl-2-pyrrolidone ─ ─ ─ ─ 7.5 g Denatured alcohol 25.3 g ─ 1.8 g 1.8 g 1.8 g

The following test methods were used to evaluate the performance of this coated lubricating layer for wet lubricity and wet abrasion resistance. After drying the film to remove the organic solvent,
Gentian Violet (eg, Ricca Chemical) is applied to the coated surface using a brush or swab.
Company catalog No. 3240) was applied. The dye was strongly absorbed into the lubricating layer but not into the plastic substrate. The stained sample was then kept under cold, gentle running water. After rinsing the samples with water, they were rubbed vigorously while squeezing between the thumb and forefinger of one hand. When the adhesion to the plastic substrate is very weak, this coating layer can be washed off completely from the surface (this is demonstrated by washing out virtually all the dye). The dyeing should be very strong after rinsing if the coating layer has penetrated too far into the coating and / or has cured due to too much polymerizable or cross-linking agent in the coating. Can be. During the finger rub test, most or all of such coatings remained on the plastic substrate, which was largely evidenced by dye retention, however, they did not have a very smooth feel. Between these two extremes is a coating that has a more desirable balance of smooth feel and resistance to peeling due to wet friction. The ability to make such quality assessments is rapidly developed by those familiar with the physical properties of various plastics or other materials.

The coating of Example 20 completely washed off when kept under cold running water, indicating little or no penetration of the polyurethane or hardening of the coating. This is expected because ethanol exhibits very low solvent activity on the polyurethane surface.

The outermost portions of the coatings of Examples 21 and 23 rubbed off when wet, but left a very smooth thin layer. The residual dye strength was moderate. These samples were determined to have a very good balance between resistance to wet wear and lubricity.

The coatings of Examples 22 and 24 were not very smooth when wet rubbed, and the coatings did not feel water swollen compared to Examples 21 and 23. The samples were very resistant to scuffing when wet, which was evidenced by a stronger residual dye stain after wet rubbing when compared to Examples 21 and 23. These are examples in which the activity of the solvent is too high and a slight lubricity is obtained. These samples were used alone or in combination with solvents to provide a sufficient degree of activity, and how the performance of the lubricating layer was adjusted to balance resistance to wet friction and lubricity. Shows what can be done.

Example 25 The following solution was prepared. Polyvinylpyrrolidone 0.4 g Denatured ethanol 19.6 g Benzyl alcohol 10.0 g

This solution was dip-coated on a polyurethane tube, and then dried at 80 ° C. for 22 minutes. A solution of gentian violet was applied to the coated surface as detailed in Examples 20-24. When tested, the coating was fairly resistant to wet rub-off and was very smooth. Compared to the coating of Example 21, this was slightly smoother, but slightly less resistant to wet rub-off.

Example 26 The following solution was dip-coated on a polyurethane tube and dried at 80 ° C for 12 minutes.
A solution of gentian violet was applied to the coated surface as detailed in Examples 20-24. Polyvinylpyrrolidone 0.4 g Benzyl alcohol 10.5 g Denatured ethanol 3.6 g N, N dimethylacetamide 5.0 g The coating was very smooth and a lubricating layer remained on the surface after intense wet rubbing and did not peel .

Example 27 The following solution was dip coated on a tube of polyvinyl chloride and dried at 80 ° C for 12 minutes. Polyvinylpyrrolidone 0.9 gm methylin chloride 5.0 gm N-methyl-2-pyrrolidone 10.0 gm

Example of Gentian Violet Solution
Applied to the coated surface as detailed in 20-24. After cooling, the coating was tested for lubricity and wet rub resistance by utilizing the gentian violet test method described above.

The coating was very smooth and a lubricating layer remained on the surface after intense wet rubbing, which did not peel.

The embodiments provided above are not meant to be exclusive. Numerous other modifications of the present invention, including the use of other co-solvents and polymer mixtures, will be apparent to those skilled in the art and are considered to be within the scope of the claims.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ identification code FI G02B 1/10 A61F 5/43 G02C 7/04 G02B 1/10 Z (58) Fields surveyed (Int.Cl. ⁷ , DB name) ) B32B 1/00-35/00

Claims (12)

(57) [Claims] 1. A lubricating composite coating comprising: an outer layer having an exposed outer surface, wherein the outer layer comprises a hydrophilic polymer selected from the group consisting of polyvinylpyrrolidone, polyvinylpyrrolidone-polyvinyl acetate copolymer and mixtures thereof. Wherein the hydrophilic polymer is free of silane compounds; and from the group consisting of cellulose esters, copolymers of polymethyl vinyl ether and maleic anhydride, esters of the copolymers, nylons and mixtures of any of the foregoing. An inner layer comprising a selected water-insoluble stabilizing polymer, wherein the composite is substantially smoother when wet than when dry, resistant to peeling by wet abrasion, and comprises an aqueous solution. Essentially insoluble in the hydrophilic polymer, The wet lubricity of the ratio of stabilizing polymer is a composite article, Ru changing the degree of resistance and insolubility in peeling, lubricating composite coating. 2. The composite coating of claim 1, wherein said stabilizing polymer comprises a hydrophilic polymer. 3. The composite coating of claim 1, wherein said outer layer comprises a stabilizing polymer. 4. The composite coating according to claim 1, wherein the hydrophilic polymer is selected from the group consisting of polyvinylpyrrolidone and polyvinylpyrrolidone-polyvinyl acetate. 5. The method according to claim 1, wherein the stabilizing polymer is selected from the group consisting of cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose nitrate, ethyl cellulose and hydroxyethyl cellulose. Composite coating. 6. The method of claim 1, wherein said coating further comprises a plasticizer.
The composite coating according to any one of claims 5 to 5. 7. The composite of claim 6, wherein said plasticizer is selected from the group consisting of camphor, polyvinyl butyral, dibutyl phthalate, castor oil, dioctyl phthalate, acetyl tributyl citrate, dibutyl sebacate, sebacic acid and an alkyl resin. Coating. 8. The composite coating according to claim 1, wherein said coating further comprises an adhesive polymer. 9. The composite coating of claim 8, wherein said adhesive polymer is selected from the group consisting of polyester, polyurethane, styrene polybutadiene, acrylic resin, polyvinylidene chloride, polycarbonate, and polyvinyl chloride. 10. A product having thereon the lubricating composite coating according to claim 1, wherein an inner layer of the composite coating adheres to the product. 11. The substrate may be a metal substrate, a glass substrate, or a polyurethane, polyvinyl chloride, polyacrylate,
Polycarbonate, polystyrene, polyester resin,
The article of claim 10, wherein the article is a polymer substrate selected from the group consisting of polybutadiene-styrene copolymer, nylon, polypropylene, polybutylene, Teflon, silicone, and polyvinyl acetal. 12. The product according to claim 12, wherein said product is a catheter, a condom,
12. The product according to claim 10 or 11, wherein the product is a medical device selected from the group consisting of a contact lens, a peristaltic pump chamber, an arteriovenous shunt, a gastrointestinal tract supply tube and an endotracheal tube.