JPH03503379A - Low friction coefficient surface - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] name of invention Low friction coefficient surface The present invention relates to molded structures having low wet friction surfaces.

background U.S. Pat. No. 4,585,666 describes polymeric surfaces that have low friction under wet conditions. A method of coating with a hydrophilic paint is disclosed. The same method applies 0.05 to the polymer surface. or 40% of at least 2 unreacted incyanates per molecule. , evaporate the solvent, and prepare a solution containing 0.5 to 50% polyvinylpyrrolidone. is applied to the treated polymer surface, the solvent is evaporated, and the coated material is heated to a high temperature. It consists of curing with

U.S. Pat. No. 4,503,111 consists of a hydrophobic support material and a polymeric coating. Discloses recording material. A typical example is “Mylar” film (polyester). Polyvinyl pyrrolidone with a molecular weight of 360,000 is Dissolved in a mixed solvent (volume ratio): 50:50 (volume ratio); Applied as a solution. . The product is air dried and tested on an inkjet printer.

U.S. Patent No. 4,119.094 and U.S. Patent No. 4,100.309 coating the polyvinylpyrrolidone-polyurethane homogeneous copolymer; disclosing the support; ing. In the same way, polyisocyanates and polysaccharides in a solvent such as methyl ethyl ketone are used. urethane is applied to the support, and the solvent is evaporated. The support is made of polyurethane. When tanning, use only polyisocyanates. The above-treated support is then coated with , apply a polyvinyl-rubyridone solution dissolved in a solvent, and evaporate the solvent. .

The support may be, for example, a tube, such as a catheter, a condom, or a pump tube. be.

U.S. Pat. No. 4,055,682 discloses silicone catheters in bulk or solution form. contact with N-vinyl pyrrolidone (NVP) and place the catheter and NVP in high Discloses a method of making the material hydrophilic by ion irradiation at a high irradiation dose.

Adjust the ion dose and NVP concentration to allow MVP to penetrate beyond the thin surface layer. and prevent it.

U.S. Pat. No. 3,892,575 discloses that a support, e.g. a plastic film material, A method of modifying surface properties is disclosed. Apply a very thin layer of the modifier mixture to the support. The modified material is bonded to the support by UV irradiation.

In a typical example, a 1% solution of polyvinyl pyrrolidone with saponin added to Apply a thin layer onto a polyethylene terephthalate sheet. Approximately 1 wet sheet Heat to 00°C and irradiate with an ultraviolet germicidal lamp for 1 minute.

The resulting wood-loving layer has moderate abrasion resistance and can be peeled off with adhesive tape. There isn't.

U.S. Pat. No. 4,589,873 discloses a method for coating a polymeric support, viz. , polyvinyl pyrrolidone, dimethylformamide, butanone, methanol, selected from tetrahydrofuran, and dimethylacetamide; in a coating solvent. Apply a solution dissolved in polyvinyl pyrrolidone to the support and apply the same solvent to the polyvinyl pyrrolidone paint. evaporates so that it remains on the surface of the support, and when the same surface comes into contact with an aqueous liquid, the coated support A method for imparting lubricity to the surface of a holding body is disclosed.

The above literature describes solid molded structures with low friction and durable surfaces under wet conditions. It teaches absolutely nothing about using hydrophilic cross-linked polymers to make I don't have it, and I'm not suggesting it.

Related applications This application is filed concurrently with U.S. Patent Application No. 07/172.183 by the inventor. Continuous.

Summary of the invention The present invention has a surface coated with at least one hydrophilic crosslinked polymer; The coating surface is durable and has low friction for a long time under wet conditions, e.g. tubes, pipes, etc. It relates to solid molded structures such as films, containers, or fibers.

Wetting means that the support is not limited to water, but also low molecular weight alcohols, such as methane. Contact with liquid substances such as tanol and ethanol, salt solutions, blood and body fluids means state.

The present invention also provides a solid surface comprising at least 0.1% by weight of an uncrosslinked hydrophilic polymer. Radical initiators selected from peroxides and ultraviolet (UV) activated radical initiators. Apply a solution containing a radical initiator, air dry the coated solid surface, and dry; by heating to the decomposition temperature of the radical initiator or by using a UV-activated radical initiator. In some cases, durable hydrophilic cross-linked polyester can be produced by irradiating the coated surface with ultraviolet light. Relating to a method of providing a solid surface coated with a mer coating, The method of the present invention further comprises modifying the solid surface by at least 0.1% by weight of an uncrosslinked woody polymer. The coated solid surface is air-dried and then heated to an electric current of 1 to 20 megarads. It can also be carried out by irradiating with a sub-beam or by corona discharge.

Extending the above outline, the present invention includes: (1) Apply solid acid to the surface of the structure for at least 1 second to contain the following components, i.e. (a) (b) (i) thermally or (ii) a radical initiator activated by ultraviolet radiation. contact with a solution containing an initiator, (2) dry the coated surface, e.g. in air, and (3) remove the hydrophilic polymer from the dry coated surface. , further crosslinked as described below, Implemented by

When using thermally activated radical initiators in the coating solution, the coating surface is Crosslinking of the hydrophilic polymer is carried out by heating to the decomposition temperature of the cal initiator. Application chart The length of time that the surface is exposed to elevated temperatures is determined by the half-life of the initiator. The exposure time is The length must be such that substantially all of the initiator is consumed.

When using UV-activated radical initiators in the coating solution, the coating surface crosslinks the hydrophilic polymer by irradiating it with ultraviolet light. Duration of exposure of coated surface to UV light is determined by the intensity of the light source and the half-life of the initiator.

The exposure time must be long enough to consume substantially all of the initiator.

The method of the invention comprises a thermally activated initiator and a UV activated initiator. It is also possible to use and implement both in combination.

The number of moles of initiator (both thermally or UV activated) used in the process of the invention is , 0.0002 to 0.0040 or less per gram of uncrosslinked hydrophilic polymer. However, some supports, such as supports made of "E5tane" or "Lycra" In the carrier, the molar ratio can be made even higher. These supports are described in Examples. explain. More generally, the effective amount of the initiator is used, and the effective amount is the crosslinkable amount. By crosslinking the necessary amount of highly functional wood-philic polymer, it exhibits a low coefficient of friction when wet and is highly durable. The amount is sufficient to form a coating film with

Alternatively, the method of the present invention involves treating a solid surface with a solution consisting of an uncrosslinked hydrophilic polymer. The coated surface is air-dried, then irradiated with an electron beam of 1 to 20 megarads. Alternatively, corona discharge is carried out for 10 to 5 minutes to effect crosslinking of the polymer.

Cross-linking of wood-philic polymers can be carried out in air or in an inert atmosphere, such as nitrogen, helium, It can be carried out in Rougon or carbon dioxide gas. The degree of crosslinking is important and the operating conditions Select and adjust. Too much crosslinking will reduce or completely reduce the low friction properties of the surface. - Excessive crosslinking reduces the durability of the coating film. Should pay more attention cross-linking must be carried out on relatively dry wood-philic polymers. That is. Hydrophilic polymers cross-linked in the presence of water provide contact rather than low-friction surfaces. It was discovered that it forms an adhesive surface.

Crosslinkable hydrophilic polymers that can be used in the present invention include, for example, poly(N-vinyl resin). lolidones), such as poly(N-vinyl-2-pyrrolidone). clear and preferred, and poly(N-vinyl-3-pyrrolidone): one on the ring or One or more hydrogen atoms are ~CH1,'-CtHs, -0C Substituted poly(N-vinyl) substituted with a substituent selected from 1(s, -QC, H$) -2 and 3-pyrrolidone): poly(N-vinyl-2-piperidone); poly(N -vinyl-3-piperidone); poly(N-vinyl-4-piperidone); One or more hydrogen atoms are 10H3, -C2 Substituted poly(N -vinyl-2-13- and 4-piperidone); poly(methyl vinyl ether) ); polyacrylic acid; polymethacrylic acid; polyethylene oxide; partial esthetics polymethacrylic acid: polymethacrylamide; partially esterified polyacrylic Polyacrylic acid; Polyacrylamide; Methylcellulose; Poly(2-hydroxyethylmethyl) acrylate); and a mixture of the above polymers. However, only the above polymers It is not limited to.

The crosslinkable hydrophilic polymers of the invention can be coated, e.g. with a paint, before being applied to a solid support. Can be blended with hydrophobic polymers in solution. Hydrophilic and hydrophobic polymers The proportion of water should be such that ultimately a hydrophilic surface is formed on the solid support. This will be readily apparent to those skilled in the art. hydrophilic Preferably, the polymer makes up the majority of the blend. Useful hydrophobic polymers is polyurethane.

Thermally activated radical initiators that can be used in the present invention include, for example, peroxide initiators. agents such as benzoyl peroxide, peracetic acid, perbenzoic acid, hydrogen peroxide, t-butylpe peroxide, bis(4-t-butyl peroxydicarbonate)% t-butyl Peroxypivalate, t-butyl peroctoate, diisopropylbenzene Hydroperoxide, succinic peroxide, potassium persulfate, and persulfate Examples include ammonium. However, it is not limited to these. Please refer to the explanation below. There is no reason to believe that thermally activated radicals can generate stabilized free radicals. A radical initiator, e.g. 10N or -COOR ester, adjacent to the radical generating site. A radical initiator with a group has sufficient energy to crosslink the woody polymer. - is believed not to have it.

Suitable solvents for dissolving woody polymers include, for example, water, methylene chloride, Chloroform, low molecular weight alcohols such as methanol, or ethanol, di Methylformamide (DMF), dimethylacetamide, ethyl acetate, methyl ethyl Thirketone, ethylene dichloride, acetone, lactic acid esters, e.g. ethyl lactate , diacetone alcohol, N-methylpyrrolidone, pyridine, and mono- and di- Examples include ethylene glycol ethers. However, it is not limited to these.

The concentration of uncrosslinked woody polymer in the coating solution is not critical. The higher the concentration used, It will be readily appreciated that the coating thickness of the hydrophilic crosslinked polymer can be increased.

Similarly, the molecular weight of the uncrosslinked hydrophilic polymer is not important; Tomo 1,000. More preferably at least 10,000 uncrosslinked hydrophilic polymers. Preferably, a reamer is used.

In the above explanation, it is assumed that the wood-philic polymer is in the form of a solution, but this is essential. There isn't. More specifically, the uncrosslinked hydrophilic polytwo can be prepared in any way possible. can also be applied to solid surfaces. For example, uncrosslinked hydrophilic polymers can be It can be applied by spraying or spray applied to the surface, all of which require skill in the art. It is obvious to those who

The present invention is a coating in which the crosslinked coating has low friction when wet and adheres to the support with good durability. It will be understood that the present invention relates to support structures and methods of making the same. hydrophilic crosslinking The adhesion of the polymer to the surface of the support depends on the ratio of the radical initiator to the polymer described above. When chosen correctly, hydrophilic cross-linked polymers can be strongly bonded to metal surfaces, e.g. steel and aluminum. physical rather than chemical bonding, as evidenced by the fact that it adheres to It is believed that this is due to the power of However, I am not bound by this explanation. coating The durability of the hydrophilic crosslinked polymer on the surface of an object can be determined by immersing the same coating in water at 37°C. , can be determined by periodically measuring the coefficient of friction of the surface when wet. 1 hour later If the coefficient of friction remains unchanged, the coating is considered durable. 1 hour time are arbitrarily selected, and those with the same coating that are not durable are considered irrespective of their type. Most of them will be destroyed within an hour.

The low coefficient of friction of a coated surface when wet can be determined by rubbing a wet sample with a human finger and uncoating it. It can be quantitatively determined by comparing the feel of a wet support. The coefficient of dynamic friction is Standard test methods, e.g. ASTM D 1890-61T or ASTM D 189 4-78 can be used for quantitative measurement. The coefficient of friction measured using these test methods The values show quantitative differences depending on whether the coating material being tested is dry or wet. . Mixtures of uncrosslinked hydrophilic polymers with other miscible hydrophobic polymers are It can be used to carry out the method of the invention. Added to uncrosslinked woody polymers The amount of miscible polymers that can be mixed can be easily determined experimentally and the present invention The advantages achieved by the coating are durable coated solid surfaces with a low coefficient of friction when wet. The upper limit may be set to an amount slightly less than the amount that has a substantial negative effect on the formation of the surface. .

The solid support whose surface can be coated according to the invention can be an organic or inorganic material and can be a heavy Includes coalescent, metal, wood, natural fibers and synthetic fibers. More specifically these The support is a polymer, such as Mylar", Rynite".

Fluoropolymers such as “Tefzel” (modified ETFE fluorinated hydrocarbon) and "ViLon" fluorinated elastomers, perfluoropolymers such as "Kalrez" per Fluoroelastomers and 'Teflon' fluorinated hydrocarbon resins, polyacetal examples For example, 'Delrin' acetal resin, polyamide, polyimide, polyolefin , polyvinyl halide, polycarbonate, cellulose, effect epoxy resin, natural and synthetic rubbers, and silicones; metals include steel, stainless steel, etc. natural fibers such as cotton and wool; The synthetic fiber is, for example, "Dacron" polyester fiber. Oropolymers and perfluoropolymers are mono- or co-polymer of tetrafluoroethylene. It is a polymer. Other preferred fluoropolymers include monovinylidene fluoride. and copolymers. Non-polar surfaces, e.g. polyolefins, must be coated Before treatment, e.g. corona discharge, flame treatment, or permanganate or triacid It must be made polar by chemical etching using chromium chloride.

When the solid support is a polymer, the polymer can be crystalline, semicrystalline, or glassy amorphous. And elastic polymers can be mentioned. However, it is not limited to that. same Polymers contain additives such as fillers, pigments, antioxidants, antiozonants, etc. It can contain.

Solid supports can also include surfaces coated with coatings, such as paint. child In the case of Ru.

If it is difficult to coat a surface and make it slippery, first coat the surface with the desired coating of the invention. The advantageous effects of the present invention are realized when applied with materials known to give desirable results. It was discovered that it can be done. For example, P el 1 ethane” 1 The reason for this is unclear. However, it is difficult to make polyurethane slippery using the method of the present invention. , in this case, the method of the present invention is applied after applying "E5tane".

The present invention has a durable hydrophilic coating that has a low coefficient of friction under wet conditions. Provide a solid support surface. Additionally, some coatings of the present invention are biocompatible, blood compatible, etc. It exhibits antifouling properties, antifouling properties, and antifogging properties, and its large It was found that the changes in dimensions (width, thickness, etc.) were minimal. like this The coating is used for applications in the medical field, such as catheters, scopes such as endoscopes and throats. Cephaloscopes, tubing such as feeding, drainage and endotracheal catheters, wound dressings, contours lenses, eye patches with modified cleaning properties, transplant materials, condoms, extracorporeal blood conduits , suitable for use as hemodialysis membranes, hemofilters, and circulatory support devices.

Other uses include food packaging, ship hulls, razor blades, fishing nets, electrical conduit, and torpedo surfaces. low-friction coatings, internal coatings for pipes or tubes where large volumes of liquid are transferred, separation membranes , glass products, sports/recreational equipment, cosmetic additives (spreading agents), release agents. Mention may be made of molding agents, fishing line and renewable cooking utensil paints.

The invention will be illustrated by the following examples. In Examples and Comparative Examples, PVP is as above. Poly(N-vinyl-2-pyrrolidone), a preferred hydrophilic polymer such as ) means.

Example 1 Put the polyurethane film [Tex1nT&I480 API into the watch glass, 5 g benzoyl peroxide, 48 g methylene chloride and 1.5 y PVP [molecules 36,000] for 10 minutes. 25 pieces of the obtained film Air dried at 0C for 10 minutes, placed in an approximately 1Q jar, and purged with nitrogen for 3 hours. Next The jar was sealed and heated at 90° C. for 1 hour.

The resulting film exhibited low friction in water. Low friction at least 3 days at 37°C It remained unchanged even after being kept in water for a while.

Example 2 Polyurethane film rTexin" 480 API with PVP [molecular weight 36. 0001 was dissolved in methylene chloride and immersed in a 3% solution for 30 minutes. Film? The liquid was removed and air-dried for several hours. The obtained film was then placed under an argon atmosphere. I put it in the watch glass in my glove box. The same film lO Megarad's electric Treated by irradiating with rays.

The resulting film exhibited low friction in water at 37°C. Low friction in water is 37℃ It remained undecreased for at least 6 days.

Example 3 3 g (7) PVP [benzoyl peroxide with a molecular weight of 36.0001.1 g, and 96 A coating solution consisting of g of methylene chloride was prepared. test material by half its length It was immersed in the same solution and taken out. Excess solvent was drained.

After air drying, the film was cured by heating in air at 110°C for 1 hour. coated t ;the material is, ■, Steel plate panel [for paint testing] 2. Mylar” [polyethylene terephthalate film] 3. Aluminum It is a thick foil [thickness 1 mil (0,0254 mm)].

All specimens showed a low coefficient of friction in water. The coating was placed in water at 23°C for 4 days. It remained slippery. Uncoated steel panels; areas are widely spaced It rusted, but the area coated with cross-linked PVP did not.

After 4 days, the aluminum foil was dried and the thickness of the coating film was approximately 0.1 mil (0,0 0254). Mylar? Rinse the 1″ film, dry it, and remove it from the polyethylene film. The mixture was placed in a plastic bag and cooled to 0°C. Quickly remove the same film from rental Then blow air.

This example shows that the present invention can be applied to metals and plastics without polymer penetration on solid surfaces. has been shown to be useful.

There is therefore no need to associate the two polymers with a grafted polymer support. .

Example 4 Molecular weight dependence of Hirifune polymer There appears to be no molecular weight dependence, as shown in the experiments below.

3g PVP, 96g methylene chloride, 96g methylene chloride and 1g peroxide Add a solution consisting of benzoyl to 1 mil (0-0254 am) of aluminum foil. It was applied on top of the . Dry and cure at 110'C for 1 hour, then soak in water at 23'C. Pickled.

1. Molecular weight 10. ooOOノP VP 2. PVP with a molecular weight of 24.000 3. Molecular weight 40.000 (7) P V P4, molecular weight 160,000 nopv All films were smooth in water, ie, exhibited a low coefficient of friction.

Example 5 Friction coefficient data A commercially available polyurethane, Estane” film measuring 4 inches x 12 inches ( It was hot pressed into a steel plate panel measuring 10-2 x 30.5 cm). Obtained polyurethane The tongue surface was treated with 1g of benzoyl peroxide, 3g of PVP [molecular weight 360.000], and 20 seconds of immersion in a solution consisting of 96 g of methylene chloride I; under nitrogen atmosphere After drying overnight, the panels were heated in air at 110°C for 1 hour and then at 37°C. Washed in water for 1 hour.

Rub the coated surface with soft paper to remove crumbled debris, and then apply polyurethane as the second surface. The coefficient of friction was tested using a f-[A S T M D 1894-78].

The above test was carried out using polytetrafluoroethylene and polyvinyl chloride instead of steel plates. Repeated using.

Dynamic friction coefficient of untreated E5tane When dry When wet 2.35 0.59 Dynamic friction coefficient of cross-linked PVP coating E 5tane when dry and when wet 0.30 0.09 Coefficient of kinetic friction of untreated E5tane on polytetrafluoroethylene When dry When wet 0.27 0.17 Crosslinked PVP coating on PTFE E　5taneTI″ dynamic friction coefficient When dry When wet 0.20 0.10 Dynamic friction coefficient of untreated E5tane on polyvinyl chloride (PVC) when dry When wet 0.55 0.39 Dynamic friction coefficient of cross-linked PVP coating E 5tane on PVC dry and wet 0.22 0.10 3 g of PVP [molecular weight 360.000], 2 g of t-butyl peroctoate and and 95 g of methylene chloride. stainless steel plate and Mylar” 500D polyester film with 10ml of the same solution (0, 254+nm) doctor knife. After air drying, the coating was Cure for 1 hour at temperatures ranging from 110°C to 110°C. The paint film is less slippery in water at 37°C. It was maintained without decreasing for at least 7 days.

Example 7 Cross-linked polyvinyl pyrrolidone (PVP) coated on LycraTM film A, 10+n1l (0,254mm+) doctor on Lycra” film - A PVP solution with the following composition [molecular weight 360.0001] was applied using a knife. .

1) 39 PVP, l 9 benzoyl peroxide, 96 g methylene chloride, 2) 3 9 pvp, 2 g benzoyl peroxide, 95 g methylene chloride, 3) 39 P VP, 3 g benzoyl peroxide, 94 g methylene chloride.

After evaporating the solvent, the coating Lycra'' was cured at 110° C. for 1 hour. 3 types The entire film remained slippery in water for at least one day.

B. The same balloon made of "Lycra" was treated in the same way with solution 1, and the other one was treated with the same amount of solution. Treated with solution 1 diluted with methylene chloride. Both balloons are very slippery in the water. It was great.

Example 8 A, containing 3% PvP and methylene chloride, and further containing 1) 1% benzoyl peroxide, methylene chloride, 2) Add two types of solutions containing 3% benzoyl peroxide to Mylar" 500D 7 (applied to lume, air dried, and cured at 110°C. Solution 1 was slippery in water. Solution 2 did not give a slippery surface in water.

B. Solution 2 also gives a slippery coating on aluminum foil or stainless steel. There wasn't.

Excessive crosslinking gives an uneven surface.

Example 9 30% by weight Ba5O, 1% by weight titanium dioxide, and 0.5% by weight green Catheter tubing made of polyurethane filled with colored pigments was treated with 19% benzene peroxide. 3 g of PVP [from methylene chloride with molecular weights 360.0001 and 969] The coating treatment was carried out by immersing it in a solution for 20 seconds. - After drying overnight under nitrogen atmosphere , heat the catheter tube in air at 110°C for 1 hour, then rinse with water at 37°C for 1 hour. did. The friction coefficient of the cladding is improved by using plasticized polyvinyl chloride on the opposing second surface. It was tested using the method of ASTM D-1890-617. The result It is shown below.

dynamic friction coefficient When dry When wet Average value measured for 5 samples 0.22 0.03 Example 10 3 g of polyacrylic acid [solution 1: molecular weight 90,000, solution 2: molecular weight 250 ゜0001.0.5% amber peroxide and 96.59% water. A coating solution was prepared. Mylar D-E 5tane” and the above on aluminum foil Two types of solutions were applied. Excess solvent was removed. After air drying, the film is kept at 100℃ It was heated for 1 hour to harden it. The surface of the coated material exhibits a low temperature at room temperature when in contact with water. It showed a low coefficient of friction for at least 7 days. The above experiment was carried out using L 2 and 3% by weight amber. Similar results were obtained by repeating the addition of acid peroxide to the coating solution.

Example 11 From 3 g methylcellulose, 5 g succinic peroxide, and 969 g water A coating solution was prepared. Apply the above solution to "Estane" and aluminum foil. did. Discard excess solvent; After air drying, the film was heated in air at 100℃ for 1 hour. Heat and harden. The surface of the coated material will remain in contact with water for at least 2 hours. showed a low coefficient of friction. The above experiment was carried out with the above coating solution of 1:1 g, 2 g and 3 g. It was repeated using a solution with added succinic peroxide with similar results.

Example 12 3 g poly(methyl vinyl ether), (L5 g benzoyl peroxide, A coating solution was prepared consisting of and 96.5 g of toluene. E 5tane” The above solution was applied to aluminum foil. Excess solvent was removed. After air drying, fill The film was cured by heating it in air at 100°C for 1 hour. The surface of the coated material is exposed to water. Upon contact, a low coefficient of friction was exhibited for at least 2 hours. The above experiment, the above coating Repeat using a solution with 19.26 and 3 g of succinic peroxide added to the solution. I repeated it and got the same result.

Example 13 Triple ply to smooth, gel-coated polyester/fiberglass port hull material board % of PVP [molecular weight 360,0001, and 2% by weight of benzoyl peroxide as salt] A solution dissolved in methylene chloride was applied to the board by dipping it in the same solution for 30 seconds. excess Fill the plate with methylene chloride vapor; stand it vertically in a large beaker. and remove it. Steam is allowed to evaporate slowly until the coating is dry, then It was cured by heating at ℃ for 20 minutes. The raised areas in the finish have very fine grains. Removed with a light layer of sandpaper.

When the coated plate thus obtained was brought into contact with water, it exhibited a low coefficient of friction.

Example 14 Mylar” film coated with cross-linked PVP was treated with methanol and ethanol as wetting agents. The coefficient of friction was measured using tanol. Obtained: The film was immersed in ethanol or showed a low coefficient of friction when brought into contact with methanol.

Example 15 3% PVP [molecular weight 360.000] and 2% benzoyl peroxide were dissolved in methyl chloride. A solution was obtained. 2@ silicone tube samples, one untreated The other one was plasma treated and immersed in the above solution for 30 seconds.

The resulting tube was sparged with nitrogen and then air-dried for 3 days. Paint film 110° Crosslinking was achieved by heating at C for 70 minutes. Even when heated for 2 hours with stirring in a water bath at 38°C, both The silicone tube on the other hand was slippery when wet.

Example 16 "Delrin" 100ST acetal resin (DuPo A strip sample (commercially available from NT) was immersed in a PVP solution. After air drying, The same sample was heated at 110°C for 70 minutes. Heat in a 38°C water bath for 2 hours with stirring. However, the sample surface was still slippery.

Example 17 Hytrel 4056 polyester elastomer (DuPo A sample (commercially available from NT) was immersed in the PVP solution for 5 seconds. - After evening air drying , and heated at 110° C. for 70 minutes. Even after stirring for 2 hours in a water bath at 38°C, the sample remained non-active. It was always slippery.

Kago Uchiura In the same procedure as in Example 15, a perfluoroelastomer (DuPon (commercially available from Company T) was immersed in the PVP solution for 5 minutes. -Late air drying After that, it was heated at 100'o for 70 minutes. Even if immersed for 2 hours in a stirred water bath at 38°C, The sample was slippery.

Example 19 "Rynite" 530-NC-10 polyester ene was prepared in the same manner as in Example 15. A sample of Genialing thermoplastic resin was immersed in the PVP solution for approximately 4 minutes. “Ryni te"530-NC-10 (commercially available from DuPont) is 30% by weight poly(ethylene terephthalate) containing glass fibers. After air drying for 30 minutes, 1 Heat at 00°C for 70 minutes. obtained; the sample remains very slippery even when wet with distilled water. It's easy.

Comparative experiment I Pour P V P [20% aqueous solution] into a watch glass, place it in a polyethylene bag, The interior was purged with nitrogen. The bag was sealed and passed under an electron beam. , 1 megarad When irradiated with , the viscosity increased. After irradiation with 2 megarads, the solution turned into a gel. 2 ．． Gels irradiated with electron beams of 5, 10 or 20 megarads are strongly sticky and wettable. Even when I was wearing it, it stuck strongly to my fingers. This means that a film that is cross-linked in a dry state becomes non-functional when wet. This is in contrast to the fact that it was always slippery. A cover coated with PVP cross-linked in the presence of water. The tater was so sticky that it was impossible to insert it into the body.

Comparative experiment 2 In this experiment, PVP was mixed with polyurethane to facilitate the swelling of the coating and allow the coating to continue. so that it is in close contact with the immersing water.

Combine the following two types of solutions.

Dissolve 2g of PVP [molecular weight 360.0001] in 1.13I+l12 DMF. 2 g of Tex1n” 480 [polyurethane] in 2.13 ml of DMF Solution of 1 The final solution increased in viscosity but no phase separation occurred. Heat the same solution to 145℃. A film was prepared by casting. No phase separation occurred. The same film When immersed in water at 25℃ for 7 hours, the weight increases by 99.6%, and after 72 hours, It increased by 118% by weight.

When dry, the film is extracted and loses 3% weight due to f knee P V P. ;.

This experiment shows how much swelling occurs when selecting a hydrophilic polymer depending on the application. This shows that it is possible to take into account the

Comparative experiment 3 The following experiments show that coatings made of uncrosslinked PVP are not durable and the importance of PVP crosslinking. It is a thing.

The polyurethane film was made of PVP [3% by weight methylene chloride with a molecular weight of 360.0001] It was coated with a paint solution. The film was dried at 25°C for 24 hours, then heated to 100°C for 1 hour. heated for an hour. The surface of the coated material exhibits a low coefficient of friction when in contact with water. Ta. However, when the same film was immersed in water at 37°C for about an hour, the low coefficient of friction decreased. It has been shown that the uncrosslinked polymer is not durable.

international search report “”””””””””””””PCT/US89100720 International Search Report

Claims (1)

[Claims] 1. The surface is coated with a hydrophilic cross-linked polymer, and the coating is durable and A solid molded structure characterized by a low coefficient of friction when hot and wet. 2. The crosslinked polymer is poly(N-vinyl-3-pyrrolidone), one or more The hydrogen atom on the upper ring is from -CH3, -C2H5, -OCH3, and -OC2H5 Poly(N-vinyl-2- and 3-pyrroli substituted with selected substituents) Poly(N-vinyl-2-piperidone), Poly(N-vinyl-3-piperidone) peridone), poly(N-vinyl-4-piperidone), on one or more rings Where hydrogen is selected from -CH3, -C2H5, -OCH3, and -OC2H5 Poly(N-bicol-2-, 3-, and 4-piperidone) substituted with substituents ), poly(methyl vinyl ether), polyacrylic acid, polymethacrylic acid, polyethylene oxide, partially esterified polymethacrylic acid, polymethacrylate Acrylamide, partially esterified polyacrylic acid, polyacrylamide , methylcellulose, poly(2-hydroxymethacrylate), and their Solid molded structure according to claim 1, characterized in that it is selected from a mixture. . 3. Blending the crosslinked hydrophilic polymer with a non-hydrophilic polymer before coating. The structure according to claim 1, characterized in that: 4. The polymer is poly(N-vinyl-2-pyrrolidone). A molded structure according to claim 1. 5. A molded structure according to claim 1 in the form of a tube. 6. A molded structure according to claim 1 in the form of a fiber. 7. A molded structure according to claim 1 in the form of a storage container. 8. A molded structure according to claim 1 in the form of a film. 9. Claim 1 comprising an organic support coated with a cross-linked hydrophilic polymer. Molded structure. 10. Claim 1 comprising an inorganic support coated with a cross-linked hydrophilic polymer. molded structure. 11. The molding according to claim 9, characterized in that the organic support is a polymer. Structure. 12. Claim 9, characterized in that the organic support is polyurethane. molded structure. 13. The molded structure according to claim 10, wherein the inorganic support is metal. thing. ! 4. The composition according to claim 13, characterized in that the metal is aluminum. type structure. 15. Claim 13, characterized in that the metal is stainless steel. Molded structure. 16. Claims characterized in that the hydrophilic polymer constitutes a major portion of the blend. The structure described in scope item 3. 17. Claim 1, wherein the non-hydrophilic polymer is polyurethane. Structure according to item 6. 18. Claim 1, characterized in that the organic support is a perfluoropolymer. The molded structure according to item 9. 19. Claim 9, characterized in that the organic support is a fluoropolymer. Molded structure as described. 20. Claim 9, characterized in that the organic support is polyacetal. molded structure. 21. The solid molded structure is contacted with a cross-linkable hydrophilic polymer and coated with the necessary If so, dry the resulting coated surface and avoid crosslinking the polymer. How to do it. 22. The crosslinkable polymer is poly(N-vinyl-3-pyrrolidone), one or more or more hydrogen atoms on the ring are -CH3, -C2H5, -OCH3, and -OC2H5 poly(N-vinyl-2- and 3-pyrin substituted with substituents selected from lolidone), poly(N-vinyl-2-piperidone), poly(N-vinyl-3 - piperidone), poly(N-vinyl-4-piperidone), one or more ring hydrogen is selected from -CH3, -C2H5, -OCH3, and -OC2H5 Poly(N-vinyl-2-, 3-, and 4-piperi) substituted with substituents Don), poly(methyl vinyl ether), polyacrylic acid, polymethacrylic acids, polyethylene oxide, partially esterified polymethacrylic acid, poly methacrylamide, partially esterified polyacrylic acid, polyacrylic acid mido, methylcellulose, poly(2-hydroxymethacrylate), and 22. The method according to claim 21, characterized in that the method is selected from a mixture of: 23. The crosslinkable hydrophilic polymer is a solution, and the resulting coated surface is dried to form a solution. 22. A method according to claim 21, characterized in that the solvent is removed. 24. Crosslinking is carried out with 1 to 20 megarads of electron beam radiation or corona discharge. 22. The method according to claim 21, characterized in that: 25. Claim 24, characterized in that the crosslinking is carried out in an inert atmosphere. How to put it on. 26. The inert atmosphere is selected from nitrogen, argon, helium, and carbon dioxide. 26. A method according to claim 25, characterized in that: 27. The method according to claim 24, characterized in that the crosslinking is carried out in air. . 28. A solution of crosslinkable hydrophilic polymer is thermally activated and treated with UV light. comprising an effective amount of a radical initiator selected from activated radical initiators; 24. The method of claim 23, characterized in that: 29. The number of moles of initiator per gram of polymer is from 0.0002 to 0.004 29. The method according to claim 28, wherein the value is 0 or less. 30. Claim 2, characterized in that the thermal radical initiator is a peroxide. The method described in Section 8. 31. The initiator is a thermally activated radical initiator and the crosslinking is inert Claim No. 1, characterized in that the radical initiator is decomposed in an atmosphere. The method according to item 28. 32. Inert atmosphere selected from nitrogen, argon, helium, and carbon dioxide 32. A method according to claim 31, characterized in that: 33. The method according to claim 28, characterized in that the crosslinking is carried out in air. . 34. The radical initiator is benzoyl peroxide, peracetic acid, perbenzoic acid, hydrogen peroxide, t-Butyl hydroperoxide, bis(4-t-butylcyclohexyl)per Oxy-dicarbonate, t-butylperoxypivalate, t-butylperoxypivalate kutoate, diisopropylbenzene hydride peroxide, succinic acid peroxy The claim is characterized in that it is selected from hydrogen persulfate, potassium persulfate, and ammonium persulfate. The method according to item 31. 35. The radical initiator is benzoyl peroxide, peracetic acid, perbenzoic acid, hydrogen peroxide, t-Butyl hydroperoxide, bis(4-t-butylcyclohexyl)per Oxy-dicarbonate, t-butylperoxypivalate, t-butylperoxypivalate kutoate, diisopropylbenzene hydride peroxide, succinic acid peroxy The claim is characterized in that it is selected from hydrogen persulfate, potassium persulfate, and ammonium persulfate. The method according to item 33. 36. A radical initiator is an initiator that is activated by ultraviolet light, and the crosslinking is initiated by ultraviolet light. The radical initiator is activated by irradiation with radiation. 29. The method of claim 28. 37. Claim 36, characterized in that the crosslinking is carried out in an inert atmosphere. How to put it on. 38. Inert atmosphere selected from nitrogen, argon, helium, and carbon dioxide 38. A method according to claim 37, characterized in that: 39. The method according to claim 36, characterized in that the crosslinking is carried out in air. . 40. The radical initiator is benzoin or benzoin methyl ether. 37. The method of claim 36, characterized in that: 41. Furthermore (1) Spray the surface of the solid molded structure for at least 1 second with the following components, namely (a) at least 0.1% by weight of a crosslinkable hydrophilic polymer; and (b) (i) thermally active. or (ii) a radical initiator that is activated by ultraviolet radiation. contact with a solution containing (2) Dry the coated surface, and (3) Cross-linking the hydrophilic polymer on the dry coating surface. 22. The method according to claim 21.