CN106334219A - Hyaluronic acid modified hydrophilic lubricating coating, preparation method and applications thereof - Google Patents

Hyaluronic acid modified hydrophilic lubricating coating, preparation method and applications thereof Download PDF

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Publication number
CN106334219A
CN106334219A CN201610724993.6A CN201610724993A CN106334219A CN 106334219 A CN106334219 A CN 106334219A CN 201610724993 A CN201610724993 A CN 201610724993A CN 106334219 A CN106334219 A CN 106334219A
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CN
China
Prior art keywords
hyaluronic acid
cross
acid modified
linking agent
lower floor
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Pending
Application number
CN201610724993.6A
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Chinese (zh)
Inventor
韩寿彭
姚修权
杜世杰
孙家永
付道安
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Shanghai Xuan Yi medical science and technology company limited
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Berno Austria Medical Technology (suzhou) Co Ltd
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Priority to CN201610724993.6A priority Critical patent/CN106334219A/en
Publication of CN106334219A publication Critical patent/CN106334219A/en
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08Materials for coatings
    • A61L31/10Macromolecular materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/24Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246Intercrosslinking of at least two polymers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00Materials characterised by their function or physical properties
    • A61L2400/10Materials for lubricating medical devices
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2420/00Materials or methods for coatings medical devices
    • A61L2420/02Methods for coating medical devices
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2405/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/08Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof

Abstract

The present invention discloses a hyaluronic acid modified hydrophilic lubricating coating, which comprises an upper layer and a lower layer, wherein the lower layer comprises a substance and a cross-linking agent, the substance contains at least two groups being subjected to a cross-linking reaction with the cross-linking agent, the upper layer comprises hyaluronic acid or sodium hyaluronate and the cross-linking agent, and the upper layer and the lower layer are subjected to cross-linking through the cross-linking agent. The invention further discloses a preparation method and applications of the hydrophilic lubricating coating. According to the present invention, the lower layer substance physically adsorbed or chemically bonded to the substrate and the upper layer hyaluronic acid (sodium hyaluronate) are linked by using the covalent grafting of the cross-linking agent, such that the lubricity of the coating is retained, the firmness of the coating is improved, the good biocompatibility is provided, and the obtained coating is non-toxic and harmless to human body, and does not have cytotoxicity.

Description

Hyaluronic acid modified hydrophilic lubrication coating and preparation method and application
Technical field
The invention belongs to medical bio coatings art, it is related to a kind of hyaluronic acid modified hydrophilic lubrication coating and its preparation Method and application, particularly to by the way of a kind of grafting using cross-linking agent covalent bond by physical absorption or be chemically bound in base material The hyaluronic acid (sodium) on lower floor's material and upper strata couples together, formed hydrophilic lubrication coating, this coating have good fastness, The advantages of lubricity and biocompatibility.
Background technology
With scientific and technical continuous development, medical field also constantly presents new, effective treatment meanss, minimally invasive handss Art is exactly the therapeutic modality more than a comparison clinically, accordingly matingly, the minimally invasive handss of these interventions or natural cavity Art apparatus also obtains very big development, such as catheter, the conduit of cardiovascular and cerebrovascular, prosthese carrier, and artificial intraocular lensess are defeated Send device, various calculus Minimally Invasive Surgery apparatuses etc..When being performed the operation, due to factors such as the coarse of operating theater instruments surface or corner angle, And these operating theater instruments are entered human body and will be contacted with blood vessel, tissue or organ, therefore body can be caused to damage;In actual behaviour When making, give people, in order to reduce the operating theater instruments entering human body, the wound that body causes, and improve the controllable performance of doctor, typically all Need the surface-coated lubricant of operating theater instruments.Traditional method is to carry out operation consent, in the surface-coated one of operating theater instruments Layer greasing substance, such as silicone oil, glycerol etc., but this type coating be easy to come off it is impossible to keeps operating theater instruments entering, perform the operation and The lubricity of the whole process such as removal.
At present, commercially available lubricant coating lubricity is good, but its fastness is poor, easily de- from the base materials such as apparatus Fall, be difficult to keep lasting lubricity, have in prior art by using the degree of cross linking increasing lubricating layer, strengthening the jail of lubricant Solidity, but, with the increase of the degree of cross linking, the lubricity of coating is just corresponding to be deteriorated, so occurring in that fastness and lubricity The problem that can not get both.Describe a kind of hyaluronic acid modified porous titanium coating and its system in a Chinese cn103785067b Preparation Method, by the medical metal surface spraying porous titanium coating such as titanium alloy, then hyaluronic acid being fixed on titanium coating, To improve the biological activity of bone implant material, promote the healing of osseous tissue.
Content of the invention
The first object of the present invention is to provide a kind of hyaluronic acid modified hydrophilic lubrication coating, by cross-linking agent covalent bond Lower floor's material that the mode of grafting by physical absorption or is chemically bound in base material and the hyaluronic acid (sodium) on upper strata couple together, shape Become hydrophilic lubrication coating, both maintained the lubricity of coating, improve the fastness of coating again.
The second object of the present invention is to provide a kind of preparation method of above-mentioned hyaluronic acid modified hydrophilic lubrication coating, By physical absorption or be chemically bound in lower floor's material of base material and the hyalomitome on upper strata by way of cross-linking agent covalent bond is grafted Sour (sodium) couples together, and forms hydrophilic lubrication coating, had both maintained the lubricity of coating, improves the fastness of coating again.
The third object of the present invention is to provide a kind of application of above-mentioned hyaluronic acid modified hydrophilic lubrication coating, passes through The mode of cross-linking agent covalent bond grafting by physical absorption or is chemically bound in lower floor's material of base material and the hyaluronic acid on upper strata (sodium) couples together, and forms hydrophilic lubrication coating, had both maintained the lubricity of coating, improves the fastness of coating again.
Technical scheme is as follows:
A kind of hyaluronic acid modified hydrophilic lubrication coating, including upper and lower two-layer, described lower floor includes at least containing two Individual and cross-linking agent crosslinks the material of group of reaction and described cross-linking agent, and described upper strata includes hyaluronic acid or transparent Matter acid sodium and described cross-linking agent, described cross-linking agents are passed through with lower floor in described upper strata.
Further preferred, the weight portion crosslinking the material of reaction in described lower floor is 30~100, described friendship The weight portion of connection agent is 0.1~10.0.
Further preferred, in described upper strata, the weight portion of hyaluronic acid or hyaluronate sodium is 0.1~1.0, described Cross-linking agent weight portion be 0.01~5.0.
Further preferred, the group participating in cross-linking reaction in described lower floor is unsaturated carbon-carbon double bond, hydroxyl, amine Base, carboxyl, nitrine, diazonium, isocyano, silicon methoxyl group, the group that carbon is alkene or nitrogen is alkene can be produced.
Further preferred, the material crosslinking reaction in described lower floor is the polyurethane with carboxyl, hydroxyl Polyurethane, the polyacrylate with carboxyl, hydroxyl polyacrylate, the homopolymer of 2-(Acryloyloxy)ethanol, acrylic acid hydroxyl second The copolymer of ester, the acrylate copolymer with isocyanate group, the Voncoat R 3310 with isocyanate group, carry methoxyl group The acrylate copolymer of silane group or the one or more of which of the Voncoat R 3310 with methoxy silane groups.
Further preferred, described cross-linking agent is isocyanates or aziridine class cross-linking agent.
Further preferred, described cross-linking agent is n75, bl116, basonat hw1000 or neocryl cx100's One or more.
The invention also discloses a kind of preparation method of above-mentioned hyaluronic acid modified hydrophilic lubrication coating, including following Step: take a base material, first coat described lower floor's solution, after solidification, be coated with described upper solution, finally cured again To the base material being coated with described hydrophilic lubrication coating.
Further preferably, the preparation process of described lower floor's solution: in the water of 0~70 weight portion, add 30~100 The material of participation cross-linking reaction described in weight portion and the cross-linking agent described in 0.1~10.0 weight portion, and mix homogeneously;Described The preparation process of upper solution: in the water of 99~99.9 weight portions, add 0.1~1.0 weight portion described in hyaluronic acid or Cross-linking agent described in hyaluronate sodium and 0.01~5.0 weight portion, and mix homogeneously.
Further preferred, described substrate surface is after solvent or corona treatment, coating more successively is described Lower floor's solution and upper solution;The solidification temperature of described lower floor's solution and upper solution is 50 DEG C~100 DEG C, hardening time It is 1~3h.
Further preferred, the material of described base material is metal material, nonmetallic materials or macromolecule organic material.
The invention also discloses a kind of application of above-mentioned hyaluronic acid modified hydrophilic lubrication coating, described hydrophilic profit Sliding coating is coated in the surface of operating theater instruments, for increasing the lubricity on operating theater instruments surface, reduces operating theater instruments to body Loss.
Compared with prior art, beneficial effects of the present invention are as follows:
A kind of hyaluronic acid modified hydrophilic lubrication coating of the first, present invention, using the side of cross-linking agent covalent bond grafting Lower floor's material that formula by physical absorption or is chemically bound in base material and the hyaluronic acid (sodium) on upper strata couple together, hyaluronic acid (sodium) by lower floor's material be combined with base material more firm, thus difficult for drop-off, improve the firm of hyaluronic acid (sodium) Property, hyaluronic acid (sodium) is grafted on lower floor's material by cross-linking agent simultaneously, decreases the degree of cross linking of hyaluronic acid, to improve The lubricity of hyaluronic acid;
A kind of hyaluronic acid modified hydrophilic lubrication coating of the 2nd, present invention, by using hyaluronic acid (sodium) conduct Hydrophilic lubrication layer is so that have good biocompatibility to human body, and, no cytotoxicity nontoxic to human body.
Certainly, implement arbitrary product of the present invention or method it is not absolutely required to reach simultaneously all the above excellent Point.
Brief description
Fig. 1 is the principle schematic that is bonded with base material of a kind of hyaluronic acid modified hydrophilic lubrication coating of the present invention;
Fig. 2 is the structural representation of the cone-shaped bag of the embodiment of the present invention 2;
Fig. 3 is the prosthese extrusion way schematic diagram of the embodiment of the present invention 2.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this Bright, rather than limit protection scope of the present invention.Those skilled in the art are according to changing that the present invention makes in actual applications Enter and adjust, still fall within protection scope of the present invention.
As shown in figure 1, a kind of hyaluronic acid modified hydrophilic lubrication coating of the present invention, including upper and lower two-layer, described Lower floor includes at least crosslinking the material of the group of reaction and described cross-linking agent with cross-linking agent containing two, described upper strata Including hyaluronic acid or hyaluronate sodium and described cross-linking agent, described cross-linking agents are passed through with lower floor in described upper strata.
The weight portion crosslinking the material of reaction in described lower floor is 30~100, the weight portion of described cross-linking agent For 0.1~10.0, in described upper strata, the weight portion of hyaluronic acid or hyaluronate sodium is 0.1~1.0, described cross-linking agent Weight portion is 0.01~5.0.
The group participating in cross-linking reaction in described lower floor is unsaturated carbon-carbon double bond, hydroxyl, amido, carboxyl, nitrine, Diazonium, isocyano, silicon methoxyl group, the group that carbon is alkene or nitrogen is alkene can be produced, those skilled in the art are according to actual needs Different selections can be made, the lower floor of the present invention crosslinks the material of the reaction more preferably polyurethane with carboxyl, hydroxyl Polyurethane, the polyacrylate with carboxyl, hydroxyl polyacrylate, the homopolymer of 2-(Acryloyloxy)ethanol, acrylic acid hydroxyl The copolymer of ethyl ester, the acrylate copolymer with isocyanate group, the Voncoat R 3310 with isocyanate group, carry methoxy The acrylate copolymer of base silane group or the one or more of which of the Voncoat R 3310 with methoxy silane groups.
Described cross-linking agent is isocyanates or aziridine class cross-linking agent, and the cross-linking agent of the present invention is specially One or more of bayer n75, bl116, basf basonat hw1000 or dsm neocryl cx100.
The invention also discloses a kind of preparation method of above-mentioned hyaluronic acid modified hydrophilic lubrication coating, including following Step:
(1) first, in the water of 0~70 weight portion, add the material of the participation cross-linking reaction described in 30~100 weight portions With the cross-linking agent described in 0.1~10.0 weight portion, mechanically or magnetically power stir 1~2h to mix homogeneously, then through filter, deaeration process Obtain described lower floor's solution;
(2) and then, in the water of 99~99.9 weight portions, add 0.1~1.0 weight portion described in hyaluronic acid or transparent Cross-linking agent described in matter acid sodium and 0.01~5.0 weight portion, mechanically or magnetically power stir 1~2h to mix homogeneously, then through filtering, de- Bubble processes and obtains described upper solution, and the present invention is in order that the upper solution holding time of preparation more long, described cross-linking agent More stable, the ph of upper solution can be adjusted to 9-10;
(3) take a base material, clean through organic solvents such as ethanol or isopropanols first, the oils and fatss removing substrate surface are done Defecate clean base material, be then coated with described lower floor's solution, after solidification, be coated with described upper solution, finally cured again To the base material being coated with hydrophilic lubrication coating, finally sealed is packed, and prevents the moisture absorption.
The present invention also can use plasma method to process the surface of base material, and the clean effect of its cleaning is more preferable;Under described Layer solution and upper solution are all passed through electricity, microwave or the mode of heating such as infrared and are solidified, and described solidification temperature is 50 DEG C~100 DEG C, hardening time is 1~3h.The material of described base material is metal material, nonmetallic materials or macromolecule organic material, tool Body be pp, pe, ptfe, metal, pa, pu or pebax, the present invention when actually used, if the material of base material be pp, pe or Pvc, then lower floor's material be combined with base material by way of physical absorption, if the material of base material be pu, pebax or pi, under Layer material is combined with base material by way of chemical bonding or/and physical absorption;Described base material is specially outside the internal diameter of pipe Footpath, seal wire, support or film;The coating method of the present invention has dip-coating, brushing and spraying, but is not limited to three of the above, specifically Coating method selects according to the shape of base material, if by the way of dip-coating and spraying, upper solution and lower floor's solution can use and fits When the solvent dilution of ratio, but the relative amount of its component keeps constant.
During use, the base material being coated with hydrophilic lubrication coating is placed in pure water or normal saline immersion 1min, after taking-up, should Coating on base material shows good lubricity and fastness.
The invention also discloses a kind of application of above-mentioned hyaluronic acid modified hydrophilic lubrication coating, described hydrophilic profit Sliding coating is coated in the surface of operating theater instruments, for increasing the lubricity on operating theater instruments surface, reduces operating theater instruments to body Loss.
The lower floor preparing solution is coated on substrate surface by the present invention first, and cured rear formation one is not hydrophilic Thin film, this thin layer is by the surface of physical absorption or chemical bonding and base material so that this thin layer is difficult to take off from substrate surface Fall, there is preferable fastness;Then upper solution is coated in lower floor after hardening, under the mode of crosslinked dose of grafting is incited somebody to action Layer is coupled together with the hyaluronic acid (sodium) on upper strata, hence in so that upper strata has preferable lubricity.One kind of the present invention is transparent The modified hydrophilic lubrication coating of matter acid, by physical absorption or be chemically bound in base material by the way of the grafting of cross-linking agent covalent bond The hyaluronic acid (sodium) on lower floor's material and upper strata couples together, and hyaluronic acid (sodium) is combined more with base material by lower floor's material Firmly, thus difficult for drop-off, improve the fastness of hyaluronic acid (sodium), hyaluronic acid (sodium) is grafted to by cross-linking agent simultaneously On lower floor's material, decrease the degree of cross linking of hyaluronic acid, to improve the lubricity of hyaluronic acid.
Embodiment 1
The present embodiment 1 is the pipe of external diameter 0.9mm, and the material of this base material is pebax:
The preparation method of the hyaluronic acid modified hydrophilic lubrication coating of embodiment 1, concrete preparation condition as shown in Table 1, Concrete substance classes including component each in the upper and lower and its weight portion, solidification temperature and time, concrete operation step is such as Under:
(1) weight portion of each component as described in the upper and lower of table one respectively, is taken in two containers, mechanically or magnetically Power stirs 1~2h to solution mix homogeneously, then respectively through filter, deaeration process, prepared upper solution and lower floor's solution;
(2) take above-mentioned base material, first through ethanol purge, remove the base material that the oils and fatss of substrate surface are totally cleaned, so Coat described lower floor's solution afterwards, after solidification, be coated with described upper solution, finally cured again obtain being coated with hydrophilic profit The base material of sliding coating, packs, prevents the moisture absorption.
Table one
1.1 greasy properties and firm performance test
The base material being coated with hydrophilic lubrication coating is placed in pure water or normal saline immersion 1min, after taking-up, uses harland Fts friction tester equipment testing friction power, grip force 600g, every pipe is tested 20 times, and 20 times frictional force increases tiltedly Rate is less than 0.1g/ time, altogether tests 10 pipes, and frictional force meansigma methodss are 8.4g, as shown in Table 2.
Table two
1.2 chemical property tests
According to gb/t14233.1-2008 standard testing chemical property, it is to be more than 2ml, the present embodiment 1 that standard requires The test value of the coating of preparation is 0.8ml, as shown in Table 3.Therefore, the chemical property of the coating of the present embodiment 1 preparation meets The requirement of gb/t14233.1-2008.
Table three
Sequence number Blank Hyaluronic acid coatings sample
Potassium permanganate liquor capacity ml Potassium permanganate liquor capacity ml
Duplicate Samples 1 9.1 7.9
Duplicate Samples 2 9.0 8.8
Duplicate Samples 3 9.1 8.2
Duplicate Samples 4 9.3 8.3
Duplicate Samples 5 9.1 8.2
Average 9.1 8.3
Reducing substances 9.1-8.3=0.8, less than 2
1.3 cytotoxicity test
According to iso10993-5:2009 standard testing cytotoxicity, standard requires to be greater than 70%, prepared by the present embodiment 1 Coating test result be 85.7%, as shown in Table 4.Therefore, the cytotoxicity of the coating of the present embodiment 1 preparation meets The requirement of iso10993-5:2009.
Table four
Blank Hyaluronic acid coatings sample
100% concentration 100% concentration
Duplicate Samples 1 0.782 0.71
Duplicate Samples 2 0.786 0.706
Duplicate Samples 3 0.817 0.667
Duplicate Samples 4 0.806 0.682
Duplicate Samples 5 0.769 0.704
Average 0.792 0.6938
Toxicity ratio 87.50%
Embodiment 2
The present embodiment 2 is the cone-shaped bag of thickness 0.3mm, and the material of base material is pu material, this cone-shaped bag structural representation As shown in Figure 2:
The preparation method of the hyaluronic acid modified hydrophilic lubrication coating of embodiment 2, concrete preparation condition as shown in Table 4, Concrete substance classes including component each in the upper and lower and its weight portion, solidification temperature and time, concrete operation step is such as Under:
(1) weight portion of each component as described in the upper and lower of table five respectively, is taken in two containers, mechanically or magnetically Power stirs 1~2h to solution mix homogeneously, then respectively through filter, deaeration process, prepared upper solution and lower floor's solution;
(2) take above-mentioned base material, first through ethanol purge, remove the base material that the oils and fatss of substrate surface are totally cleaned, so Coat described lower floor's solution afterwards, after solidification, be coated with described upper solution, finally cured again obtain being coated with hydrophilic profit The base material of sliding coating, finally sealed is packed, and prevents the moisture absorption.
Table five
It is coated with the cone-shaped bag of hydrophilic lubrication coating, be placed in pure water or normal saline soaks 1min, extrude grand after taking-up The prosthese of breast operation, prosthetic surface frosted, volume is 300ml, and cone-shaped bag opening 5.0cm is according to extrusion side as shown in Figure 3 Formula, extrudes more than 10 times, it therefore follows that, the lubricity of the present embodiment 2 cone-shaped bag is good, and can keep the profit of coating the long period Slip.
Present invention disclosed above preferred embodiment is only intended to help illustrate the present invention.Preferred embodiment is not detailed Describe all of details, also do not limit the specific embodiment that this invention is only described.Obviously, the content according to this specification, Can make many modifications and variations.This specification is chosen and is specifically described these embodiments, is to preferably explain the present invention Principle and practical application so that skilled artisan can be best understood by and utilize the present invention.The present invention is only Limited by claims and its four corner and equivalent.

Claims (12)

1. a kind of hyaluronic acid modified hydrophilic lubrication coating it is characterised in that include upper and lower two-layer, described lower floor include to Crosslink the material of group of reaction and described cross-linking agent containing two with cross-linking agent less, described upper strata includes hyalomitome Acid or hyaluronate sodium and described cross-linking agent, described cross-linking agents are passed through with lower floor in described upper strata.
2. a kind of hyaluronic acid modified hydrophilic lubrication coating according to claim 1 is it is characterised in that described lower floor In crosslink reaction the weight portion of material be 30~100, the weight portion of described cross-linking agent is 0.1~10.0.
3. a kind of hyaluronic acid modified hydrophilic lubrication coating according to claim 1 is it is characterised in that described upper strata The weight portion of middle hyaluronic acid or hyaluronate sodium is 0.1~1.0, and the weight portion of described cross-linking agent is 0.01~5.0.
4. a kind of hyaluronic acid modified hydrophilic lubrication coating according to claim 1 is it is characterised in that described lower floor The middle group participating in cross-linking reaction is unsaturated carbon-carbon double bond, hydroxyl, amido, carboxyl, nitrine, diazonium, isocyano, silicon methoxy Base, the group that carbon is alkene or nitrogen is alkene can be produced.
5. a kind of hyaluronic acid modified hydrophilic lubrication coating according to claim 4 is it is characterised in that described lower floor In crosslink reaction material be the polyurethane with carboxyl, hydroxyl polyurethane, the polyacrylate with carboxyl, hydroxyl Polyacrylate, the homopolymer of 2-(Acryloyloxy)ethanol, the copolymer of 2-(Acryloyloxy)ethanol, the acrylate with isocyanate group Copolymer, the Voncoat R 3310 with isocyanate group, the acrylate copolymer with methoxy silane groups or band methoxy The one or more of which of the Voncoat R 3310 of base silane group.
6. a kind of hyaluronic acid modified hydrophilic lubrication coating according to claim 1 is it is characterised in that described crosslinking Agent is isocyanates or aziridine class cross-linking agent.
7. a kind of hyaluronic acid modified hydrophilic lubrication coating according to claim 6 is it is characterised in that described crosslinking Agent is one or more of n75, bl116, basonat hw1000 or neocryl cx100.
8. the preparation method of the hyaluronic acid modified hydrophilic lubrication coating as described in a kind of any one as claim 1~7, it is special Levy and be, comprise the following steps: take a base material, first coat described lower floor's solution, after solidification, be coated with described upper solution, Last cured again obtain being coated with the base material of described hydrophilic lubrication coating.
9. a kind of hyaluronic acid modified hydrophilic lubrication coating according to claim 8 preparation method it is characterised in that The preparation process of described lower floor's solution: in the water of 0~70 weight portion, add the participation described in 30~100 weight portions crosslinked Cross-linking agent described in the material of reaction and 0.1~10.0 weight portion, and mix homogeneously;The preparation process of described upper solution: To in the water of 99~99.9 weight portions, add hyaluronic acid described in 0.1~1.0 weight portion or hyaluronate sodium and 0.01~ Cross-linking agent described in 5.0 weight portions, and mix homogeneously.
10. the preparation method of a kind of hyaluronic acid modified hydrophilic lubrication coating according to claim 8, its feature exists In described substrate surface is after solvent or corona treatment, then the lower floor's solution described in coating successively and upper solution; The solidification temperature of described lower floor's solution and upper solution is 50 DEG C~100 DEG C, and hardening time is 1~3h.
A kind of 11. preparation methoies of hyaluronic acid modified hydrophilic lubrication coating according to claim 8, its feature exists In the material of described base material is metal material, nonmetallic materials or macromolecule organic material.
The application of the hyaluronic acid modified hydrophilic lubrication coating as described in a kind of 12. any one as claim 1~11, its feature It is, described hydrophilic lubrication coating is coated in the surface of operating theater instruments, for increasing the lubricity on operating theater instruments surface, reduce The loss to body for the operating theater instruments.
CN201610724993.6A 2016-08-25 2016-08-25 Hyaluronic acid modified hydrophilic lubricating coating, preparation method and applications thereof Pending CN106334219A (en)

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EP3459571A1 (en) * 2017-09-22 2019-03-27 Covidien LP Compliant hydrophilic coatings for medical devices
CN109646716A (en) * 2018-12-28 2019-04-19 深圳大学 Artificial cornea optical centre portion and preparation method thereof and artificial cornea
CN110743043A (en) * 2019-12-05 2020-02-04 苏州恒瑞宏远医疗科技有限公司 Hydrophilic coating for catheters and devices
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Publication number Priority date Publication date Assignee Title
EP3459571A1 (en) * 2017-09-22 2019-03-27 Covidien LP Compliant hydrophilic coatings for medical devices
CN109535799A (en) * 2017-09-22 2019-03-29 柯惠有限合伙公司 Submissive hydrophilic coating for medical device
US10759957B2 (en) 2017-09-22 2020-09-01 Covidien Lp Compliant hydrophilic coatings for medical devices
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CN112584879A (en) * 2018-08-22 2021-03-30 小太阳公司 Lubrication method
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CN109646716A (en) * 2018-12-28 2019-04-19 深圳大学 Artificial cornea optical centre portion and preparation method thereof and artificial cornea
CN109646716B (en) * 2018-12-28 2021-04-20 深圳大学 Artificial cornea optical center, preparation method thereof and artificial cornea
CN110743043A (en) * 2019-12-05 2020-02-04 苏州恒瑞宏远医疗科技有限公司 Hydrophilic coating for catheters and devices
CN115040699A (en) * 2021-03-09 2022-09-13 上海硕创生物医药科技有限公司 Heat-cured sodium hyaluronate coating, medical catheter and instrument

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