• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A surface coated article comprising a substrate with a cured polyethylene oxide-based coating thereupon. The essential features of the article are that the coating essentially consists of polyethylene oxide chains, with one free end and one end that has been cross-linked to other chains via a special cross-linking agent, that the cross-linking has been performed by radiation, and that the substrate has been swollen prior to cross-linking. The article can be prepared by applying to the substrate a solution containing the polyethylene oxide, the cross-linking agent, a swelling solvent and optionally a radical initiator, evaporating the solvent and cross-linking the coating by radiation curing. A suitable coating composition comprises per mole of the polyethylene oxide, 0.1-10 moles of the cross-linking agent, 0-500 moles of the solvent and optionally 0.0001-0.5 moles of the radical initiator. The article is especially useful within the biomedical field.
    公开号:SU1729284A3
    申请号:SU874202428
    申请日:1987-03-17
    公开日:1992-04-23
    发明作者:Густав Геландер Карл；Сонни Йенссон Эрик；Г.Владкова Тодорка
    申请人:Иткемиска Институтед (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to biomedicine, to a method of applying hydrophilic coatings on articles and compositions for these coatings.
    The aim of the invention is to obtain a coating with improved hydrophilic properties and simplify the process technology.
    In polyethylene oxide, each chain has one free and unmodified end, the other end of the chain has at least one ethylenically unsaturated group. This means that during irradiation, only one end of the polyethylene oxide chain contains a reactive group that can participate in a crosslinking reaction, while the other end of the chain does not contain any group that can participate in this reaction. The reactive end of the chain should contain only one ethylenically unsaturated group, however, there may be cases when two, three or more unsaturated groups are present. Such reactive groups should be so
    close to the end of the chain so that they could not form cycles during irradiation, i.e. There must always be a free mobile polyethylene oxide chain hanging from the surface of the base and directed towards the aqueous phase in contact with the coated article.
    Examples of suitable unsaturated ethylene groups are acrylic and methacrylic groups. However, there may be groups of an unsaturated ethylene compound that can be polymerized and crosslinked by the use of radiation-induced radicals. A subgroup of ethylene groups is formed by polarized ethylene groups, among them acrylic and methacrylic. However, it is necessary that the unsaturated groups be derived from a low molecular weight unsaturated carboxylic acid, for example less than 1000, especially less than 200.
    One end of the polyethylene oxide should not contain a double bond that may be involved in the crosslinking reaction. Usually it means esterified.
    (L
    WITH
    VI Yu Yu
    S 00 4
     WITH
    in the ordinary way, the end of polyethylene oxide. The other end, i.e. reactive polyethylene oxide can be obtained, for example, by reacting a chemically unmodified hydroxyl end of polyethylene oxide by esterification with a compound containing an ethylene group. The compound may contain various functional groups depending on the end use of the product to be produced.
    Another method for preparing polyethylene oxide is as follows. The compound containing an ethylene group is ethoxylated by a known method. The resulting polyethylene oxide chains are a mixture of chains with a molecular weight distribution within a desired range, for example, a so-called normal distribution.
    A crosslinking agent is a reactive substance with two or more radiation-curable ethylene groups that react with ethylene groups of polyethylene oxide chains. This means that ethylene groups are of the same nature as the corresponding polyethylene oxide chain groups. Groups of the crosslinking agent are allyl, acrylic and methacrylic. In addition, the crosslinking agent should have a low molecular weight, for example, less than 1000, preferably less than 300.
    The crosslinking agent contains, in addition to unsaturated ethylene groups, one or more ethylene oxide targets containing 5-500 (preferably 3-200) ethylene oxide units having a free, unreacted end. The number of ethylenically unsaturated crosslinker groups is 2 or 3.
    An example of a crosslinking agent is hexamethylenediol diacrylate.
    Polyethylene oxide and crosslinking reagents are used, of course, in such proportions and molar ratios, so that a dried, durable coating (adhered) to the base is obtained with the desired properties required for the final use of the product. These ratios depend on the specific nature of the polyethylene oxide and crosslinking reagents, but they can be determined by a series of experiments for each specific case.
    For example, different molar ratios are needed if the crosslinking agent contains or does not contain ethylene units.
    The solvent, which besides the property of dissolving (well wetted) and evaporating, contributes to the swelling of the substrate to be coated. This type of method is related to
    mainly with cases where a polymer base is used, and means that an improved anchoring effect can be obtained. When using a solvent having such a swelling capacity,
    0, in a subsequent cross-linking reaction, bridges or crosslinks can be created that are more or less mechanically attached to the swelling base.
    5 The main functions of the solvent are that it must dissolve polyethylene oxide and a crosslinking agent, wet the surface of the base in order to achieve a homogeneous spreading of oxide
    0 polyethylene, to promote the swelling of polyethylene oxide to the surface of the base, and also to have such a rate of evaporation that there is enough time to swell the surface of the base to obtain
    5 of a homogeneous coating film (this is promoted by slowly evaporating the solvent without complete sorption of the polyethylene oxide inside the polymer).
    In the proposed method is required
    0 mixture of solvents that must be compatible with each other, because another function is needed, namely, dissolving power. For polyvinyl chloride, a mixture of equal parts of tet5 rahidrofuran (contributes to the swelling of polyvinyl chloride), toluene and ethanol (dissolves polyethylene oxide, wets the surface and has a suitable evaporation rate) is suitable.
    0 The curing of the coating composition is achieved by irradiation-initiated polymerization, as this is a quick and effective way of obtaining the desired results. The initiators used5 are initiators activated by radiation using gamma x-rays, electron beams or ultraviolet reactions. Ultraviolet radiation is particularly preferred and can be carried out at ordinary room temperature. UV polymerization requires the presence of a photoinitiator, which is desirable to be of the so-called photo-fragmentation type, for example, 25 hydroxy-2-propiophenone (with two reactive radicals being formed directly at the beginning of irradiation), or H-extracting type (with radicals by removing hydrogen from the added tertiary amine containing acidic-hydrogen atoms, for example thioxanthone plus trimethylamine). The initiator can take hydrogen atoms to a certain extent also from polyethylene oxide and from the polymer base, adhesion to the polymer base can be improved as a result of the formation of chemical bonds with the base.
    According to the described embodiment, the crosslinking is carried out in two stages, namely, partial crosslinking in air for a short time before the formation of a polyethylene oxide gel that is poorly soluble in water, but in which the polyethylene oxide chains retain some mobility, and the final irradiation of the gel in the aqueous phase, wherein the polar, polyethylene oxide chains are oriented in the aqueous phase. This is an important advantage compared with the known methods, since the structure of the coating according to the proposed method is such that the polyethylene oxide chains are highly concentrated on the surface of the product being manufactured, i.e. all chains are directed towards the aqueous phase.
    Practically, the proposed method can be carried out by rolling or spraying on the surface of the base or dipping the base in a solution containing polyethylene oxide, a crosslinking agent and a radical initiator. After this, excess solvent is allowed to settle or evaporate from the surface. Finally, a dry or at least current coating is cured by irradiation, for example, by passing a substrate with a coating applied on it on a conveyor past a radiation source.
    This means that the proposed process is carried out in two stages, simple and fast.
    The ratios between the various components of the composition are as follows: 0.1 to 10, preferably 0.3 to 3 mol of the crosslinking agent is used per 1 mole of polyethylene oxide, if the said agent does not contain a significant portion of ethylene oxide units, and 0.002 to 50 mol of the mentioned cross-linking agent if it contains such ethylene oxide units of 0-500, preferably 50-150 mol of solvent and, if desired, 0.0001-0.5, preferably 0.001-0.01 mol of a radical initiator. So, in the case where significant amounts of ethylene oxide units are not present in the crosslinking agent, the ratio of polyethylene oxide / crosslinking agent should usually be 1: 10-10: 1, but to obtain optimal
    properties, the preferred ratio is 1: 3-3: 1. For lower molecular weight polyethylene oxides, the molar ratio is particularly preferred.
    1: 1 or close to this ratio, and the higher the molecular weight of polyethylene oxide, the more the ratio approaches 1: 3.
    For crosslinking agents containing
    0 ethylene oxide units, the variation in molar ratios is greater or variable, since some of the desired properties attributed to ethylene oxide units can be transferred to the product through a crosslinking agent. The general limits of the ratios can be expressed respectively from 1:50 to 50: 1, and it is difficult to specify a narrower total interval, since it depends on the flexibility of this type of invention. But
    0 sometimes also in this case the 1: 100-10: 1 and 1: 3-3: 1 intervals are applicable.
    The invention may be used as an anti-inflammatory or antistatic product or as a product with
    5 friction reducing properties. It has been found that the product has excellent properties for preventing protein adsorption, which open up wide possibilities for its use in the field of
    0 biomaterials, especially in the biomedical field. Biocompatibility is particularly pronounced for polyethylene oxide chains of at least 10 or more, preferably at least 25 or 30 ethylene oxide units.
    In addition, the surface coating according to the invention makes the hydrophobic surfaces completely hydrophilic and
    0 wettable with water and facilitates cleaning of contaminated and contaminated areas. It also prevents static surfaces from charging with static electricity, repels oil and various dispersed particles. Another important property that can be used for special applications is the property of reducing friction between surfaces. The product may be applied in medicine, for example, to obtain biocompatible tissue surfaces; which can be used inside the human body, for example, for vascular and bone
    5 prostheses, to prevent incompatibility reactions, to obtain blood-biologically compatible surfaces to prevent blood coagulation and protein deposition, for example, using catheters and when circulating outside blood
    an organism, for example, in the case of using oxygen generators and an artificial kidney; by applying bandages to absorb tissue fluid, by soaking the composition with iodine / potassium iodide, a healing effect is achieved and wound healing is accelerated.
    In addition, it can be used to prevent the development of bacteria on surfaces (antibacterial effect), for example for medical catheters, for contraceptives, as a coating that kills sperm.
    In connection with the use of the product in medicine, according to the proposed method, radiation-curing has a significant advantage, since in this case the sterilization of the object is also achieved.
    PRI me R 1. Monoethyl esterified polyethylene glycol (PEG) mol. mass 550 monoacrylate with acrylic acid. After evaporation, to obtain the product, designated as PEG-A-550, 0.02 mol of hexamethylene-diol-diacrylate (GDDA) (bifunctional cross-linking agent), 0.002 mol 2 is added to the said product. -hydroxy-2-propiophenone (photoinitiator) and a solvent mixture consisting of 1.5 mol of ethanol, 0.75 mol of toluene and 1.0 mol of tetrahydrofuran (TTF).
    Three different samples were prepared: Sample A containing 0.005 mol PEG-A-550, Sample B containing 0.002 mol of this compound and Sample C containing 0.4 mol of the indicated compound.
    Each of the described solutions is dripped onto a polyvinyl chloride plate, the solvent is evaporated, and then the applied coating is cured using irradiation from a UV apparatus (Primare, USA), in which there are two mercury lamps giving a power of 100 W / cm at a speed of 6 m / min .
    Samples are washed with water for 60 s. Only for sample B a fully hydrophilic water wetted surface was obtained.
    Example 2: To 0.02 mol of PEG-A-1900, 0.02 mol of GDDA and 0.0002 mol of 2-hydroxy-2-propiophenone were added. The solvent used is pure para-xylene (0.2 mol) to swell polyethylene. This solution D, as well as solution B, from example 1 (prepared with PEG-A-1900 instead of PEG-A-550) is applied with a thin layer onto a polyethylene surface. The solvent evaporates and the coating cures as in Example 1.
    The resulting coatings are washed with water for 60 seconds.
    Only product D was completely hydrophilic, coating B peeled off after a while.
    Samples coated dip after
    This into a vessel with heavy fuel oil. A black oil film was observed on both samples. If the samples are dipped into water again, the oil is removed from the coating D, it is completely cleared of oil. Sample B
    0 remains coated with oil and is not cleaned when washed with water.
    PRI me R 3. Covering compositions prepared according to C in example 1 and containing, respectively, PEG-A-550.
    5 PEG-A-1900, PEG-A-5000 is applied on a polyvinyl chloride film, the solvent is evaporated, after which the samples are cured by UV irradiation as in Example 1.
    All samples are processed within 6
    0 h of 1% albumin bovine serum (BSA) dissolved in saline sodium chloride, after which the surfaces are washed in pure saline sodium saline for 60 minutes,
    five
    Samples are dried and the surface analyzed by electron spectroscopy for chemical analyzes. ESCA for protein nitrogen.
    0 For all glycols, protein adsorption is less compared to adsorption of untreated polyvinyl chloride. The amount of protein adsorbed decreases with increasing molecular weight.
    5 PEG as follows; mol% of nitrogen on the surface: untreated polyvinyl chloride 5; PEG-A550 2; PEG-A-1900 0.9; PEG-A-5000 is less than 0.5.
    PRI me R 4. A coating composition prepared as in Example 1, but with PEG-A-1900, is applied to two stainless steel plates that are precoated with a thin polyvinylchloride film obtained as a result.
    5 evaporation of a 0.5% solution of polyvinyl chloride in tetrahydrofuran deposited on a steel plate. The coating composition is left in the air to dry, and then from the sample plates it is opened in the normal way — in one stage in the air and the other plate is dried in two stages: first, partially and very quickly (less than 0.5%). m / min) by UV irradiation in air, then the coating composition is coated with a layer of water under which the final is performed at a speed of 5 m / min by UV irradiation,
    Samples are treated with 1% BSA solution followed by washing as described in Example 3.
    The protein content, determined using ESCA, is the following, mol% of nitrogen on the surface: one-step curing 0.9; two-stage curing less than 0.5.
    The percentage of PEG on the surface, determined using ESCA as CHaO - carbon is the following, mol.% PEG: one-step curing 60; two-stage curing more than 90.
    EXAMPLE 5 Trimethylpropane (TMP), ethoxylated with 20 ethylene oxide units on TMP, is diacrylated by the introduction of 2 mol of acrylic acid per 1 mol of TMP.
    The following components are added to 0.003 mol of the dry product (TMP- (EO) 20-A), mol: 2-hydroxy-2-propyonone 0.0001; ethanol 0.78; toluene 0.50; tetrahydrofuran 0.25.
    The coating composition is applied to Plexiglas (R) (PMMA) and the film by a two-step method as described in Example 4. One treated and one untreated PMMA Plexiglas plates are treated with a powdery mixture of iron oxide (Pv20) and colloidal carbon, taken in equal mass parts, when rocking in the test chamber at a relative humidity of 70% for 15 minutes.
    After the test, the raw plate has a durable red-black coating, while the treated sample is completely free of particles from the mixture after being removed from the chamber.
    EXAMPLE 6 A silicon wafer is coated with a polyvinyl chloride film by dipping and a 0.5% solution of polyvinyl chloride in tetrahydrofuran. After that, a film with the following composition is applied to the wafer, mol: PEG-A-500 0.02; trimethylolpro p a ntriacrylate 0.04; 2-hydroxy-2-prothiophenone 0.02; ethanol 2; toluene 2; tetrahydrofuran 2.
    Films are obtained by rotating on a rotary plate at 100 rpm, dried and cured in one step. Protein adsorption is measured by ellipsometry. The following results are obtained for the base thickness A: silicon polyvinyl chloride 20-30; silicon polyvinyl chloride-PEG-A-SOOO less than 2.
    Apply p.7. The accumulation of cells and red blood cells.
    Equimolar amounts (0.01 mol) of monoacrylated PEG 1900 and hexanedol diacrylate are dissolved in a mixture of toluene-cyclohexanone-ethanol (1 part by weight each) and diluted to a final solids concentration of 0.5% by weight. %
    The resulting solution is applied to PVC films and PMMA plates each 3x3 cm in size using an applicator with a spiral rod applying a layer
    1 mm thick (group a), the inner part (lumen) of almost transparent tubules made of PE (polyethylene) with a length of 1 m and an inner diameter of 2 mm, which are treated by passing the solution through the lumen
    0 pipettes Before. by applying a PEG film, PE tubes are made hydrophilic by keeping for 2 minutes in concentrated sulfuric acid containing 2 mg / l of potassium permanganate, followed by careful
    5 by washing with water (group B).
    For both types of bases, the solvent is evaporated before curing to dryness. All items are cured in a Mi nicure machine for 15 minutes. Special
    For a long time, the inner surface of the tubes is cured due to scattering and absorption of radiation by the tube material.
    The basics of group A, subjected to pre-sterilization with ethanol, are treated with 75 ml of a culture of fibroblast cells containing 1 million cells in 1 ml. The suspensions are made for 1 hour to settle onto the base, after which the objects are transferred to
    0 germ-sensitive calf serum and incubated for up to 48 hours at 37 ° C. The surfaces are then visually inspected and photographed under a microscope. Untreated PMMA visible after 48 hours
    5, the corresponding layers of cells completely covering the surface by forming a network of cell mounds tightly bound to the surface. Separate cells of spherical shape are visible for PEG-treated PVC and PMMA surfaces, which indicates the intactness of these cells and the absence of their growth on the surface. Conducted tests show that, in contrast to conventional polymeric
    5 basics of PEG treated surfaces do not favor cell growth and show a very low propensity for cell adhesion.
    The treated tubes of group B are tested for platelet adhesion. Fresh citrate human blood is circulated through the tubes for 20 minutes, and then washed in the usual manner with brine. Ultimately, ATP (adenosine triphosphate) is extracted from adherent platelets with a buffer solution, the amount of which is determined. The following results were obtained, mmol ATP / cm2: untreated polyethylene 1500x10 11; polyethylene treated with PEG-acrylate 13x10 11.
    The results show that the surface of the substrate (polyethylene) is completely covered with repulsive platelets with a PEG film.
    Example Antistatic properties.
    Video screens cover a series of films corresponding to examples 1-3.
    Changes in the strength of the electrostatic field are measured using an Eltex O 475 / A, C electrostatic field strength meter.
    The experiments were carried out under the following conditions: the thickness of the PEG-acrylate coating is less than 5 mm, the curing of the PEG-acrylate coating is carried out on a rotating disk by irradiating 4x300 W UV lamps with Osram ultra vitalux.
    Video screens run for 1 hour.
    Video screens are turned off and at a fixed distance from the 30 cm screen, the dependence of the change in the electrostatic field intensity on time is measured.
    The tests carried out clearly show that PEG acrylate films significantly reduce the strength of the electric field, i.e. are effective antistatic coatings.
    Antistatic characteristics are given in table 1; Comparative data on the hydrophilicity of the coating are given in Table 2.
    权利要求:
    Claims (2)
    [1]
    1. A method of obtaining a surface coated product by applying a mixture of modified polyethylene oxide, a bifunctional cross-linking agent, initiator and solvent to the product surface, evaporating the solvent and curing the coating, characterized in that, in order to obtain an improved hydrophilic properties, and simplify process technologies, monoacrylated polyethylene oxide with mol.m. is used as polyethylene oxide. 550.1900, 5000, as an initiator - photoinitiator in the following ratio of components, mol: the specified polyethylene oxide is 0.002-0.4; bifunctional crosslinking agent 0.02-0.04; photoinitiator 0,00001-0,002; the solvent is 0.2-3.25.
    [2]
    2. A composition for coating an article comprising a modified polyethylene oxide, a bifunctional crosslinking agent, an initiator, a solvent, characterized in that, in order to increase the hydrophilicity of the composition, it contains monoacrylated polyethylene oxide mol.m. as modified polyethylene oxide. 550, 1900, 5000, as an initiator, photoinitiator in the following ratio of components, mol: the specified modified polyethylene oxide is 0.002-0.4; bifunctional crosslinking agent 0.02-0.04; photoinitiator 0.00001-0.00 2; the solvent is 0.2-3.25.
    Coverage I Time, Mineral Density of electric PPL, kV / m
    Table 2
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    同族专利:
    公开号 | 公开日
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    SE8404866A|SE444950B|1984-09-28|1984-09-28|COVERED ARTICLE, PROCEDURES AND METHODS OF PRODUCING THEREOF AND USING THEREOF|
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