• 专利附录
  • 专利说明
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  • 类似技术
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    • 专利摘要:
    1. A method for producing a polymer coating on a metal substrate by applying a composition comprising a polyolefin, an epoxy resin and a hardener, characterized in that, in order to increase the adhesion of the coating to the substrate, a composition is used that contains a polyolefin resin resin containing an index index by the polymer, with the index index. g / 10 min; and a particle diameter of 15–40 µm, a modified polyolefin resin with a melt index of 2–4 g / 10 min, containing hydroxyl or carboxyl groups in an amount of 0.81.3 mol, per 1000 g of modified polyolefin , and composition based on epoxy resin with an average mop.m. 1000-2700 and an epoxy equivalent of 650-1800 and a hardener taken at a ratio of
    公开号:SU1136750A3
    申请号:SU813276194
    申请日:1981-04-28
    公开日:1985-01-23
    发明作者:Мията Нобуйоси；Мурасе Хейхати
    申请人:Кансаи Пейнт Ко,Лтд (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to the application of polymeric coatings on metal substrates and can be used when applying corrosion-resistant coatings.  There is a known method of applying a polymer coating to a metal substrate, which involves applying a coating of epoxy resin followed by curing and then applying a coating of olefin resin with preliminary preparation of an intermediate layer of modified polyolefin containing an adhesion functional group.  The disadvantage of this method is multistage.  The closest in technical essence and the achieved effect to the present invention is a method of obtaining a polymer coating on a metal base; "ke by applying a composite, containing a polyolefin and an epoxy resin, and using a film-forming composite capable of forming a multi-layer film consisting of the bottom a layer made of epoxy resin and a surface layer made of olefin resin.  The known method uses the phenomenon of phase separation of various types of polymers 2.  The disadvantage of the known method is the relatively low adhesion of the polymer coating to the metallic substrate.  The purpose of the invention is to increase the adhesion of the polymer coating to the metal substrate.  This goal is achieved by the fact that according to the method of obtaining a polymer coating on a metal substrate by applying a composition containing a polyolefin, an epoxy resin. and a hardener, use composition S containing PS powder olefin resin with an index of c.  1.5–20 g / 10 min and a particle diameter of 15–40 µm, a modified olefin resin with a melt index of 2–4 g / 10 min, containing hydroxyl or carboxyl groups in an amount of 0.8–1.3 mol per 100 g of modified polyolefin, and composition.  on the basis of epoxy resin with an average mol.  m  1000-2700 and an epoxy equivalent of 650-1800 and hardened bodies taken at a ratio of (33-35): (2-5) :( 37-75) May. h  respectively, and after applying the composition, an ethylene polygon coating with a melt index of 0.25-1 g / 10 min and a density of 0.9250, 947, or is additionally applied. ethyl acetate copolymer with a melt index of 1.7 g / 10 min and a density of 0.930.  Moreover, before applying the composition, the substrate can be treated with a 1% solution in a mixture of water and isopropanol, taken at a ratio of 9: 1, chloride, phosphonium triphenylbenzyl, or a 0.5% aqueous solution of trimethyl-2-bromo ethyl ammonium.  bromide.  Thus, according to the invention, the method of manufacture. olefinic resin films on a metal substrate include: A) making a multilayer film using a composition forming a multilayer film, comprising:.   a) solid powder containing olefin resin with a melt index of 0.3-80 g / 10 min-, b | solid powder containing modified olefin resin with a polar group with a melt index of 0.3-80 g / 10 min; c) the formation of a film is a resinous material comprising an epoxy resin with an average mol. m  350-4000 and with epoxy equivalent 1503800 and curing agent; B1 is the subsequent binding, when the material of the surface coating of olefin resin is heated, with the top layer (of olefin resin) of a multilayer coated film.  .  The composition is coated to form a multilayer film.  The coating composition used that forms the multilayer film includes a hard film; o powder, hardened powder b and resinous material with as the main resinous components.  When this coating composition is applied to the surface of a metal substrate in one operation and fired, a multi-layer coated film is formed in which the layer providing the film of cured epoxy resin is located. on the surface of the metal substrate, t. e.  is a lower layer, a layer of olefin resin is located on the surface and is bound to the lower layer through a modified olefin resin containing a polar group.  This composition, g} of an opener, forming a multilayer film, can be of any shape, depending on the conditions of the coatings, for example, it can be in the form of a powder composition, consisting of solid powder, solid resinous material, in powder form, like a full suspension. obtained by dispersing solid powder a, solid powder b and resinous material c in a powdery state in a weak solvent of all these components or a form of paint coating such as incomplete suspension uu obtained by dispersing or dissolving solid powder x, b and a solid powder of a resinous material in a powdery state in the organic compound, the poor solvent is yuschems organichesksy and modified olefin resins, but a good solvent in epoxy resinous material s.  Solid powder  The olefin resin that is included in the solid powder may be a homopolymer of olefin, a copolymer of two or more olefins, and a mixture of such homopolymers or copolymers in arbitrary ratios.  Olefin includes not only those hydrocarbons that contain only the ethylene double bond (mono-olefins), but also hydrocarbons that contain two or more ethylene / double bonds (diolefins, etc. d. ).  The ethylene, propylene, butene, isobutylene, pentane, butadiene and isoprene are the boilers of such olefins.  Typical examples of olefinic resins that can be used for solid powder are polyethylene, polypropylene and low, medium and high density ethnpen-propylene copolymer, with polyethylene being particularly preferred.  These olefin resins may be used alone or in combination with one another.  Thus, for example, using low-density polyethylene and high-density polyethylene in combination with one another, it is possible to regulate the hardness or flexibility of the resulting coated film.  It is important that the olefin resins used have a melt index of 0.3-80 g / 10 min, preferably 1.5-60 g / 10 min.  If the melt index of the olefin resin is less than 0.3 g / 10 min, the flowability of the coated film at the time of coating and calcining the coating composition is insufficient and the formation of a multilayer coated film is impeded, which makes it difficult to obtain a uniform coated film.  If the melt index of the olefin resin exceeds 80 g / 10 min, the melt flow of the coated film becomes extremely large, making it difficult to obtain a multilayer film with good adhesion between the layers, and the coated film may have poor properties.  The solid powder used may consist solely of the olefinic resin mijH may additionally contain a coloring pigment (such as titanium dioxide, carbon black, iron oxide, aluminum powder, and phthalocyanine blue), a pigment filler (such as calcium carbonate, barium sulfate, talc and clay) anti-rust pigment (such as lead red lead, basic lead chromic acid, zinc chromate, zinc molybdate, aluminum phosphate, and zinc powder), reinforcing filler (such as asbestos, thin glass l nnye flakes and glass fibers) and other components.  In addition, it may contain additives that are embraced in powdered coating compositions, such as dispersing agents, ultraviolet absorbers, flow control agents, and thixotropic agents.  The inclusion of such additives makes it possible to achieve such effects as coloring a solid powder, improving its mechanical, chemical and electrical properties and reducing its cost.  The grinding of olefinic resin can be carried out by known methods, for example by chemical spraying, by introducing a jet of a solution containing o finum resin into a weak solvent, which results in the precipitation of the olefinic resin in powder form, and by mechanical spraying, which results in pulverization.  under the influence of extremely low temperatures.  These additives should preferably be thoroughly mixed and dispersed in the olefin resin prior to the spraying operation.  The number of added prizes is not critical.  But these amounts can be up to 150 wt. %, preferably up to 120 wt. % based on. weight of olefin resin.  The particle size of the solid powder is not strictly limited and may vary widely depending on the type of resin used in the solid powder a and other factors.  If the particle size is too large, then a uniform film cannot be obtained.  In connection with ethyl, it is desirable that the solid powder should have an average particle diameter, usually not more. more than 74 microns, preferably not more than 44 microns.  If the particle size is too small, there may be a risk of explosion or a harmful effect on human health.  For this reason, a lower limit of 10 microns is desirable.  Solid powder b.  The modified olefin resin containing - the polar group used in the solid powder B is a resin obtainable by administration. polar group to olefin smile.  Such a resin includes, for example, copolymer of at least one olefin, considered in the description of solid powder, with another copolymerized r ;; iMC vinyl monomer containing a sex group, resins obtained by graft polymerization of the monomer of vinal, containing a polar the group with the olefin resins described for solid powder, or the resins obtained by introducing polar pears in such ways as halogenation, chlorine sufirming, sulfonation, and ozone oxidation.  The polar group, which may be contained in a modified 0, 6 olefin resin, includes, for example, atoms or groups of atoms that have a good affinity for enoxide resin, containing resin material C, and consisting, for example, of heteroatoms, such as oxygen , nitrogen, sulfur. and halogen atoms, especially chlorine and fluorine atoms, and include groups of atoms containing these heteroatoms, for example, a hydroxyl group (-OH) hydroxy group (0), a carbonyl group (5 G-0), a carboxylic acid group (-COOH) acids {-COOR, where R is preferably a lower alkyl), a carboxylic anhydride group (-sulfonyl group,.   h (-SOg), sulfo group (-SOjH), nitrile (-CN) and amide groups (-CONC}, These polar groups can cyniectBoV individually or in combination with one another.  The content of the polar group may vary depending on the type of polar group and other factors.  An excessively high content of the polar group prevents the formation of a coated multilayer film.  If the content of the polar group is too low, a sufficient adhesion between the upper layer of olefin resin and the lower layer of epoxy cannot be achieved. resin.  Preferably, such a polar group content is such that the surface tension of the modified olefin resin containing field | In the course of hot Ylavleni, the Bbmie will be the surface tension of the olefinic resin in the solid powder during hot melting and lower than the surface tension of the resinous material during hot melting.  The definite limit of the content of the polar group is not easy to establish, however, the content of the polar group, calculated as the content of heteroatrums belonging to this semi-polar group, is 0.2–15 wt. % preferably 0.55 wt. -% of the weight amount of the modified olefin resin.   The field used by the practical groups of the process are carboxy.  group 7 and a group of carbonic anhydride, it is desirable that these groups be present in an amount of 0.052, 5 mol, preferably 0.11, 5 mol 5 per 1000 g of modified olefin resin.  In the preparation of a modified olefin resin containing a polar group, vinyl monomers containing a polar group can be used, which serve as dL copolymerization with an olefin or dp graft polymerization with an olefin resin.  .  Examples of vinyl monomers containing a polar group include layered vinyl esters of organic kilotones, for example, vipylacetate and vinyl propionate, non-saturated carboxylic acids and anhydrides or their esters such as acrylic acid, methacrylic acid: acid, methyl acrylate, ethyl acrylate, propylacrylate, n-butyl acrylate, isobutyl acrylate lat, 2-ethylhexane 1 acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, non-acyl acetate Excellent polar vinyl monomers, such as acrylonitrile, methacrylonyl, allyl vinyl ether, nil chloride and vinylidene chloride.   Typical examples of a modified olefin resin containing a field group I that can be used in a solid powder are ethylene-vinyl acetate copolymer Ta, ethesta-acrylic acid copolymer, fluorinated polyethylene, chlorinated polyethylene, chlorosulphated polyethylene, sulfonated polyethylene, polyethylene, ozone oxidation, polyethylene with grafted maleic anhydride, polyethylene with grafted acrylic acid, polyethylene with grafted acrylonitrile acid, and polyethylene with grafted acrylamide.  Preferred are ethylene-vinyl acetate copolymer, ethylene acrylic acid copolymer, ozone-oxidized polyethylene, maleic acid anhydride grafted polyethylene, and acrylic acid grafted polyethylene.  In the case where the modified olefin resin is a 750 polymer containing molecular resin.  links derived from the vinyl ester of said organic acid or unsaturated carboxylic ester, it may be subjected to saponification to convert the ester group to a polar group, such as carboxyl or hydroxyl, before using this resin in solid powder b.  Modified olefin resins containing a polar group can be used individually or in. as a mixture of two I. T1I more pitches.  Modified olefin. the resin containing the polar group should have a melt index of 0.380 g / 10 min, preferably 1.560 g / 10 min, which is greater than the index. the olefinic resin melt used in the solid powder. The solid powder b used may consist either solely of said modified olefinic resin containing a polar group, or additionally include additives such as coloring agents, pigment fillers rust-preventing pigments, reinforcing fillers, dispersants, ultraviolet absorbers, co-flow agents and thixotropic agents.  The powdering of an olefinic resin containing polar groups can be carried out by known methods, for example, by chemical bleaching, which consists of the introduction of a jet of a solution containing said modified olefin resin into a weak solution of this resin, as a result of which it precipitates in powder form, or by mechanical spraying, consisting in powdering at extremely low temperatures.  It is desirable that these additives be thoroughly mixed and dispersed in the modified olefin resin prior to the spraying operation.  The amount of these powders is not critical, but it is desirable that these amounts be up to 150 wt. %, preferably up to 120 wt. % by weight of modified olefin resin.  The particle diameter of the solid powder b is not strictly limited and may vary widely depending on the type of resin used in the solid powder b and other factors.  If the particle size is too large, then a thin, uniform film cannot be obtained.  For this reason, it is desirable that the average particle diameter of the solid powder B be not more than 74 µm, preferably not more than 44 µm.  If the particle size of the powder is too small, there may be a risk of explosion or a harmful effect on human health.  Therefore, the size limit is 10 µm.  Resinous material with; .  The epoxy resin, constituting the resinous material t, is found in a solid or liquid state at room temperature and has an average mol. m  350-400Q, preferably 900 - 3000, and. epoxy equivalent of 150-3800, preferably 450-2100.  The epoxy resin can be soluble or insoluble in the dispersing medium described below, or it can be wetted with this medium.  However, if the epoxy resin is almost insoluble in the dispersing medium, the type of epoxy resin used in the resinous material c is limited due to the fact that the resinous material must be dispersed in a powdery state in the dispersing medium.  Therefore, in this case, it is desirable to use epoxy resins, which are in a solid state at room temperature and have an average mol. m  700-4000, preferably 900-3000, and epoxy equi 1. .  iHT 150-3300, preferably 45. -2100.  If average mol. m  epoxy resin is less than 350, then the fluidity of the molten curing. After evaporation of the solutions from the resulting coated film, the agent usually becomes too high, and a multilayer film that does not have a good adhesion between the layers cannot be obtained.  Thus, the coated film formed tends to sag.  If average mol. m  epoxy resin exceeds 4000, the fluidity of the molten coated film is insufficient and it is difficult to obtain a uniform film or film in which the epoxy layer has an excellent ability to coat the substrate.  If the epoxy equivalent of an epoxy resin is less than 150, then the crosslink frequency of the cured film becomes extremely large and its adhesion to the metal substrate can be reduced by creating internal stress, the coated film becomes brittle.  If the zpoxy equivalent is greater than 3800, the frequency of cross-links becomes too low and there is a tendency to lower the mechanical strength, water resistance, chemical resistance and Other properties of the coated film.  From the point of view of improving the mechanical properties of hardened plastic; Coated coatings, adhesion bonding of these films to a metal substrate, corrosion resistance of films and other characteristics suitable epoxy resins for use in resinous material c are, for example, polyhydric phenol epoxy resins, for example of the type of condensation product of bisphepol with epihalohydrin, epoxy resin the type of product of phenol phenol with formaldehyde and epoxy resins of the type of polymerized fatty acid.  Examples of polyatomic phenol / epihalohydrin condensation product type epoxy resins are the condensation products of bisphenol A, bisphenol F or halogenated bisphenol A and epichlorohydrin.  Examples of epoxy resins of the formaldehyde condensation product type phenol are epoxy resins of the glycidyl simple ebiopvolovac type.  Examples of epoxy resins of the polymerized fatty acid type are epoxy resins of the dimeric acid type.  The most suitable are epoxy resins, such as a condensation product of a polybasic phenol with epigalsphydrin.  These epoxies can be used individually or in. combinations with one another
    As curing agents that serve to open these epoxy resins, it is preferable to use such substances that practically do not interact with epoxy resins during the manufacture and storage of resinous compositions, as described below, and quickly react with epoxy resins only under conditions firing film as described below. These curing agents include, for example, polycarboxylic acids and their anhydrides (such as ddipinova, sebacic, phthalic, trimellitic acid, anhydrides of maleic, phthalic, trimel LTL, itaconic, tetrahydrophthalic, and pyromellitic acid), amides of carboxylic acid. (For example, the addition product of the dimeric acids with triethylenetatramine), methylated melamines (such as etherification with methyl hexamethylolmelamine), protected isocyanates (such as isophorone diisocyanate, protected with -caprrolactam, and the product p isoedineni tolipendiizotsig .anata with trimethylolpropane, cresol zaschischenny) dicyandiamide and its derivatives (such as 2,6-ksilenkl-diguanidin) dihydrazides carboxylic acids (such as adipic acid dihydrazide), 1shidazolyn, imidazole, and salts of imidazoline or imidazole. Preferred are dicyandiamides, carboxylic acid dihydrazides and imidazoline salts. These curing agents can be used alone or in combination with one another.
    The amount of the hardening agent may vary widely depending on the epoxy resin and / or curing agent used. In order to achieve the desired Mechanical properties, water resistance, corrosion resistance and other characteristics of the required coated film, it is necessary that the amount of curing agent be at least 0.7 equivalent, preferably 0.8-1.2 equivalent, per epoxy group in the cured epoxy resin .
    An epoxy resin may also include additives, such as coloring pigments, pigment fillers, dispersing agents, ultraviolet absorbers, flow control agents, and thixstropes, as in the case of solid powders q and b. The amount of additives may be up to 150% by weight, preferably up to 120% by weight, of the total amount of epoxy resin and curing agent.
    In the case where the coating composition forming the multilayer film is to be prepared in powder form or as a complete suspension, resinous material made of epoxy resin, curing agents, etc. can be prepared by methods used to make ordinary powder epoxy resin coating compositions. For example, they can be prepared by combining hot rolling or extrusion using conventional chemical or mechanical spraying, or using dispersing agents, or by i extrusion method solvent. It is desirable that the particle diameter of the resinous material at the moment is the same as the diameter of the particles of solid powder 1 or b. The average particle diameter of the resinous material with usually is not more than 74 µm, preferably not more than 44 µm, and not less than 10 µm.
    In the case where a coating composition, a composite multilayer film, is prepared as a partial suspension, resinous material can be obtained by mixing an epoxy resin, a hardening agent and other components with an epoxy resin solvent and dispersing them in a solvent in the same way, as in the case of solvent-based paint coatings, using a ball, roller or sand mill. ,
    Dispersion (5) common environment.
    In the case where the coating composition is powdered, no dispersion medium is required. In the case when this composition is a complete or incomplete suspension, volatile organic solvents should be used as the dispersing medium. Such an organic solvent may be a volatile organic liquid containing at least 90%, preferably at least 95%, of a weak solvent of these solid defects. The term weak solvent refers to an agent that does not dissolve and (or) does not substantially moisten the olefin resin in the solid powder and the modified olefin resin in the solid powder b. In particular, a weak solvent. is such an agent that, when immersed in the powder of the specified resin at room temperature for 1 week, evaporates, does not detect particle deformation due to fusion or swelling on the surface of the resulting powder when observed with a microscope. Organic solvent may be weak or strong solvent epoxy resin in resinous material c. . When the organic solvent is a poor solvent of resinous material, t, the resulting coating composition is an incomplete suspension. Nepalna suspension has the advantage over the full one, as it allows the viscosity to be easily adjusted, and the metal substrate can be completely coated with epoxy. However, evaporation of the solvent occurs slowly and there may be defects in the event that the coating composition is applied in the form of a thick layer. 6 therefore, incomplete and complete suspensions should be selected according to the intended use. The weak solvents used are non-polar organic liquids, especially liquid hydrocarbons, varying depending on the types of solid powder I, solid powder b and resinous material o. Examples of such non-polar organic liquids are aliphatic hydrocarbons such as alkanes containing 5-16 carbon atoms, such as N-pentane, y-hexane, isohexane, n-heptane, H-ca. an, isooctane, n-decane I-dodecane, H-hexadecane and 2,2-di0 methylbutane, and alkenes containing 5 -16 carbon atoms, such as 1-pentene, 1-octene, 1-d price 1-dodecahe-. prices and 1-hexadecene, alicyclic hydrocarbons containing 6 to 12 carbon atoms, such as hlhlohexane, methylcyclohexane, dimethylcyclohexane. hexane, ethylcyclohexane and methylisog amnpcyclohexane, and mixed hydrocarbons, such as petroleum ether, light petroleum gasoline, gasoline, kerosene, white spirit, and special gasoline solvent. Thermodynamically nonpolar weak solvents, due to their properties, cannot easily dissolve epoxy resins. Therefore, these dispersing media can be used to prepare coating compositions in the form of a complete suspension in which solid powders, o (and fc resinous material is dispersed without solvent. Solvents that dissolve poorly d and fe powders, but do well resinous material c are typically high-polar solvents. Examples of such high-polar solvents are esters such as methyl acetate, ethyl acetate, isopropyl acetate and n-butyl acetate, ketones such as acetone, methane ethyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone, and ethers such as methyl cellosolve, ethyl celloolol., butyl cellosolve and cellosolve acetate. These solvents can be used individually or as a mixture of two or more solvents. do not wet or dissolve powders "and b. In connection with this, solvents that do not dissolve solid powders a and b poorly can be used individually as a dispersing medium. Alcohols and aromatic hydrocarbons can be used as an auxiliary or diluent solvent when epoxy resin is to be used in a dissolved state. Examples of such alcohols are methanol, ethanol, propanol, butanol and amyl alcohol, examples of aromatic hydrocarbons are benzene, toluene, xylene and these 1 benzene. .15 Preparation of coating composition. The coating composition used can be prepared as follows using solid powder O (and b, resinous material C, if necessary, dispersing medium. The coating composition in powder form can be obtained by uniform mixing of finely divided powders of the individual components jTOB. Mixing can be carried out by known methods In the case of preparing a coating composition in the form of a complete or incomplete suspension, the solid powder is -o (, solid powder is fc, resinous material C and others are necessary The e ingredients are dispersed in a volatile organic solvent of the indicated Type or dispersed and partially dissolved in this solvent. To obtain a complete suspension, it is desirable that all solid powder and all solid powder material be crushed to prepare a suspension from them. In order to obtain an incomplete suspension, you must first. prepare a solution of resinous material with, using partially or fully organic solvent in the final composition. Dispersing or dissolving itself can be carried out by known methods, for example, using a homogenizer or a device of this type. In preparing the coating composition, one type can be used. Each of the solid materials “and b and resinous material, as well as two or more types of powder of powders“ and / or b and / or resinous material, c. The ratios of solid powder, solid powder b and resinous material c are not critical} and can vary within wide limits. If the sum of the actual volumes of solid powders b is extremely small compared to the actual volume of resinous material c, then the layer of olefin resin forms a continuous film as the upper layer, and the chemically inert lower layer of epoxy resin is exposed from the surface in one, then in. 750 elsewhere, causing deterioration of various properties. Conversely, if the sum of the actual volumes of solid powders cx and b is significantly greater than the actual volume of resinous material c, then the coating of the metal substrate with a layer of epoxy resin is incomplete and the layer of olefin resin is partially in contact with the metal substrate, resulting in weakened adhesion or reduced corrosion resistance coated films. In this connection, the sum of the actual volumes of solid powder and solid powder should be 5-300%, preferably 20-200%, of the actual volume of resinous material, c. The term “reap volume”, referring to solid powder w, solid powder b and resinous material c, refers to the volume of solid powder excluding the spaces between individual particles when these particles are maximally compacted. In the case where the resinous material is in the form of a solution, the real volume refers to the volume of the resinous component remaining after removal of the solvent. Preferably, the solid powder b is mixed in a specific ratio with the solid powder W. Usually, the mixing is carried out in such a way that the real volume of the solid powder V is t-30%, preferably 3-20%, of the real volume of the solid powder. " When preparing a complete or incomplete suspension type coating composition, the ratio of dispersing medium to solid powder, solid powder B and resinous material C can vary over a wide range, taking into account the ability of the composition to form a coating, etc. Typically, the ratio of dispersion medium is 50-300 wt.h. preferably 80-200 mash. Mainly 100-180 mac. on 100 ma.ch. solid powder ", solid powder b and resinous material c, taken in total. The composite composition prepared in this way is applied as an intermediate adhesive layer to the surface of the metal substrate if it is necessary to obtain a thick film coated with olefin resin on the surface of such a metal substrate as steel pipes, tanks and ordinary steel structures.
    Obtaining a multilayer coated film.
    The application of this coating composition, forming a multilayer film, to these metal substrates does not require any special methods, and can be carried out using ordinary methods, such as air-jet spraying, bezvo fluidizing the coating with a roller. The total thickness of the coated film after drying and firing is 30-250 microns, preferably
    50-200 μm, the surface layer of oleic resin has a thickness of 30150 μm, preferably 30-120 μm, of the total thickness of the coated film.
    Such a coated film may be dried and fired by conventional means, for example with
    7
    RZ-Y-KI
    RS
    I where Y is a nitrogen atom, phosphorus or a mouse; RI, Rj and K are the same or different and each represents a hydrogen atom or an organic group containing no more than 8 carbon atoms, X is an anion. In the above formulas (1) and (11), the organic groups R ,,,, Rg and R can be any organic group that does not significantly impede the ionization of bnium compounds and adversely affect the affinity of onium compounds with the surface of the substrate. The organic group typically includes hydrocarbon groups containing no more than 8, preferably no more than 7 carbon atoms, which may include a hetero atom,
    using hot-dried dryers, infrared and student's furnaces, electromagnetic induction heaters and other devices. 06bWHO Firing is carried out at 150-250 ° C for 5-40 minutes. In this way, a coated multilayer film is obtained which has an extremely good adhesion between the layers (as between
    metal substrate and the bottom layer of cured epoxy resin, and between the bottom layer of epoxy resin and the top layer of olefin resin}
    It has been established that if, in the manufacture of a multilayer film, the surface of a metal substrate is pretreated with a solution of at least
    at least one onium compound
    (i.e. compounds with a complexing atom that has electron pairs capable of forming salt-like compounds), then
    multilayer film with. a coating having a smooth surface and good interlayer adhesion.
    Examples of compounds having such ability are compounds of the general formulas

    E.2 3
    0
    X
    m such as an oxygen atom, in the form of a hydroxyl group, an alkoxy group (i.e. ether oxygen), etc. and / or may be substituted by a halogen atom. Thus, an organic group may be a hydrocarbon group containing not more than 8, preferably not more than 7 carbon atoms, which may include at least one, preferably 1-3, and preferably only one heteroatom selected from among hydroxyl and ether (ether) oxygen atoms and halogen atoms. Such hydrocarbon groups include aliphatic, alicyclic, and aromatic hydrocarbon groups, such as alkyl, cycloalkyl, 1uchloalkylalkyl, aryl, and aralkyl groups, may have a linear or branched carbon chain and contain 1-6 carbon atoms. Such alkyl groups include, for example, methyl, ethyl p-yl, or a reagent or tert-butyl, pentyl, heptyl, and octl. The cycloalkyl and cycloheptyl alkyl groups preferably contain 5-8 carbon atoms, for example cyclopentyl, cyclohexyl, cyclohexylmethyl and diclohexylethyl. - Examples of aryl groups are phenyl, tolyl and xylyl, a preferred aryl group is phenyl. Examples of aralkyl goopps are benzyl and phenethyl groups, with the benzyl group being preferred. Preferred examples of a hydrocarbon group containing a heteroatom selected from the oxygen atoms of the hydroxyl group and the ether group and halogen atoms are oxyalkyl groups containing 1-8 carbon atoms (especially lower oxyalkyl groups, such as hydroxymethyl, hydroxyethyl, hydroxybutyl , hydroxypentyl, ox heptyl, and hydroxyoctyl; alkoxy groups containing 2–8 carbon atoms (especially lower alkoxy, lower alkyl groups), such as methoxymethyl, methoxyethyl, ethoxymethyl, n-propoxyethyl, iso-propoxyme l, I -butoxymethyl, isobutoxyethyl and tert.butoxyethyl, and alkyl groups containing 1-6 carbon atoms, such as chloromethyl, chloroethyl, chloropropane, chloropentane, bromoethyl and bromine propane. Examples of anion X are radicals of inorganic acids, such as P0 | ® ° and halogen (for example, C1®, Brf Jt S0 | f HSO® and NO®, hydroxyl ion (OH) and organic acid radicals, such as CjHjCOO®, CHjCH (OH) COO® and CfcHsSOa.) the lower one, which belongs to groups of compounds or to compounds, means such groups and compounds that contain no more than 6 carbon atoms Lerode, preferably not more than 4. Onium compounds can be used either Alki 5020, individually or in combination with one another. Since the onium compound has the property of providing a thermodynamic affinity between the surface of the substrate and the lower layer of the multilayer film, a very small amount of a thin film, one to seven molecules thick, the onium compound can have a significant effect on the formation of a multilayer coating. The action of alkyl groups as substituents R is greatest in the case of lower alkyl groups, especially methyl, and tends to be gradually weakened as the number of carbon atoms of alkyl groups increases. This effect is significant in the case of aryl and afalkyl groups, such as the phenyl or benzyl group. . In connection with this, substituents. are preferably alkyl groups with a content of 1-4 carbon atoms, oxyalkyl groups with a content of 1-4 carbon atoms, alkoxyapkyl groups with a content of 2-4 carbon atoms, haloalkyl groups with a content of 1-4 carbon atoms, phenyl group and a benzyl group. The central elements of onium compounds are nitrogen atoms and phosphorus, preferably a phosphorus atom. The beneficial effect of the blue compound is somewhat reduced in the case of arsenic and sulfur atoms. The X® anions are halogen ions, with chlorine ions being preferred, followed by bromine and iodine ions. Thus, the preferred onium compounds are ammonium and phosphonium compounds of the general formula K.21 where 2 nitrogen or phosphorus is preferred, the ni 4i phosphorus atom is the same or different and each represents a lower alkyl group with a content of 1-4 atoms carbon (especially a met1-sha or ethyl group), an alkoxyalkyl group with a content of 2-4 carbon atoms, an alkoxyalkyl group with a content of 2-4 carbon atoms, a haloalkyl group with a content of 1-4 carbon atoms, a phenyl group or a benzyl group, Xf - halogen ion especially Br® or 3® When treating the surface of a metal substrate, the onium compound is applied to it from the solution. Since the onium compound is usually soluble in water, it can be used in an inert water solution. Any solvent which is capable of dissolving the onium compound can be used, since the coating composition forming the multilayer film is usually applied after drying the previously applied onto the onium compound and the solvent type of the pretreatment solution does not affect the film-forming ability of the composition. coating forming a multilayer film. Thus, an organic solvent can be used to improve the drying performance of the pretreatment solvent or the wettability characteristics of the substrate surface, a mixture of water with water-miscible organic solvent can also be used. Examples of organic solvents that can be used for this purpose are as acetone, methyl ethyl ketone, methyl isobutyl ketone, alcohols, such as methanol, ethanol and isopropanol, esters such as methylated acetate, ethyl acetate and isopropyl acetate; and high boiling solvents, such as ethylene glycol monoethyl ether and ethylene glycol monoethyl ether acetic acid. These solvents can be used individually or in combination with one another. In some cases, at least one of them can be used in a mixture with water. Type out. The solvent or solvent mixture is determined taking into account the solubility of the onium compound, the wettability of the surface of the substrate (to be coated), the drying characteristics of the onium compound, the hazard} 1 of the solvent ignition and so on. The concentration of the onium compound and the solvent is not critical and is usually 0.0103% by weight, preferably 0.3-5% by weight. If the concentration of the onium compound is less than 0.01% by weight, the effect of pretreatment is reduced and the lower the layer of the multilayer film cannot completely cover the surface of the metal substrate. If the concentration exceeds 30% by weight, the solution of the onium compound for pretreatment of the substrate becomes viscous and its ability to coat the surface is reduced. In addition, the drying performance is deteriorated. The application of the pretreatment solution prepared in this way, containing at least one onium compound, is carried out by known coating methods, such as spraying, brush or roller application, by dipping. The amount of pretreatment solution varies depending on. the type or concentration of onium compound used. Typically, this number, calculated as the weight amount of the onium compound in the pretreatment solution, is about 0.0011, 5 g / m. Preferably, 0.010.5 g / m. The drying of the pretreatment solution applied to the surface of the SUB-RAY can be performed at room temperature or at elevated. It is sufficient to evaporate the solvent only. In the case when the pretreatment solution has a high water content, its evaporation is slow and drying. occurs at elevated temperatures. Preferably, the drying is carried out in a heating furnace with hot air circulating through it, the drying temperature is 50-140 ° C. The duration of the drying process is not strictly limited, since the ultimate goal is evaporation of the solvent. In the case of drying at room temperature, a drying time of 5-715 minutes is sufficient, and in the case of drying at 100 ° C, 2-3 minutes. If desired, approximately 0.1-3 can be added to the pretreatment solution containing the onium compound. ma.ch. MONO-, di-, or tri- (hydroxy- (lower) alkyl) amine,. such as monoethiolamine, diethanol amine, triethanolamine, or about 0.05-0.2 h of phosphoric acid per 100 mash. pretreatment solution. It improves corrosion resistance. Then, a coating composition forming a multilayer film is applied to the surface of the substrate, which has been pretreated with a solution of the onium compound, in the same way as prepared above Surface coating of the olefin resin on the film. Since the top layer of the coated multilayer film formed, consisting of a cured epoxy resin and olefin resin, is a thermoplastic olefin resin, the latter is additionally bonded in the molten form to the top layer of the multilayer film while it is still in the molten state due to preserved roasting heat or after the coated multilayer film is cooled and reheated to give a softened or melted state. As a result, an olefinic resin coated film is formed which adheres firmly to the metal substrate, forming a single unit with it. So it can be semi. A surface coating of olefin resin, which has greater adhesion to the metal substrate. The olefin resin surface coating material, which adhesives are bonded in a hot polished form, includes, for example, homopolymers or copolymers of olefins, such as ethylene, propylene, bylene, isobutane, pentene, butadiene and isoprene, copolymers of these olefins with vinyl monomers containing a polar Group, described in 5024 of the type (e.g., vinyl acetate, acrylic acid and tetrafluoroethylene) with an olefin content of at least 75% by weight, which are known as surface coating materials based on olefin resin. Typical examples of such olefin resin based surface coating materials are polyethylene (low, medium or high density), polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer and ethylene-acry. New copolymer, polyethylene to sew polyethylene is a polyethylene. The olefins. The resins may be used individually or as a mixture comprising two or more resins. The melt index of the olefin resin is not more than 1 g / 10 min, preferably not more than 0.5 g / 10 min. The olefin resin-based surface coating material may contain, if necessary, a coloring pigment (such as titanium dioxide and carbon black), a pigment filler (such as calcium carbonate, barium sulfate, and clay), a reinforcing agent (such as glass fiber, asbestos, and thin glass flakes) , and other additives (for example, dispersants, such as silane bonding agents, ultraviolet absorbers, and antioxidants), as well as olefin resin. The inclusion of these additives can lead to various effects, such as coloring the surface coating material based on olefin resin, improving its mechanical, chemical, electrical properties, increasing durability and reducing cost. In the case of adhesive bonding in the form of a melt, the epoxy resin based surface coating material is heated with the olefin resin surface coating material in various forms upon heating to the surface of the multilayer coated film, depending on the coating method. For example, it can be applied to the surface of a substrate in the form of powder, small granules of tapes, flax and sheets. The methods for applying an olefin resin-based coating material are different and depend on
    25
    the shape or heat capacity of the metal substrate on which the coated multilayer film is formed, on the scale of production and other factors. So, for example, a push-pull coating method can be used with a transverse extrusion head or a T-shaped extrusion head, typically used for polyethylene coating, an adhesive method of applying a molten powder, for example a coating method in a fluidized bed, a spray coating method, a plug, the method of coating by electrostatic spraying of the powder and spo (j6 spraying of the powder in the flame. The method of applying the coating by extrusion has the advantage in the case where the metal substrate to which the coating J is applied has a simple shape (cylinder, hollow cylinder or flat plate). Methods for applying the molten powder to the adhesive have the advantage that the substrate has a complex shape or small size.
    The surface of the applied epoxy resin coating layer, which forms a single whole with the top layer of the coated multilayer film, varies depending on the coated metal substrate, the conditions in which the coated metal substrate is used, the desired service life and other factors and is 0, 5-5 mm.
    The coated multilayer film made according to the invention, consisting of a thermoplastic olefin resin, has high adhesion to the metal substrate and between the layers. The proposed method makes it possible to easily obtain a film coated with olefin RESIN; having a very large crowd and possessing high adhesion to the metal substrate.
    The preparation of the composition is covered with-. tee forming a multilayer film.
    Coating Composition A. Solid Powder a-1. 35 parts of polyethylene with an average particle diameter of 20 µm, obtained by chemical spraying of polyethylene with a bottom 26
    36750
    This density, pmekdeho melt index of 20 g / 10 mg - and density of 0.920
    Solid powder b-1. 5 parts of modified polyethylene powder having an average particle diameter of 21 μm, obtained by xiimiic pulverization of low-density polyethylene with grafted acrylic
    0 acid, having a melt index of 4 g / 10 min, density 0.930, acid number 60, degree of modification 1.0 mol / 1000 g of modified 1 resin.
    5 Resinous material s-1. 75 parts, enamels, obtained by dispersing 100 parts of bisphenol type A epoxy resin, having an average mol, m. About 1400 and an epoxy equivalent of about 900; .4h. adipic acid dihydrazide and 20 parts of red iron oxide at 40 h, ethylene glycol monoethyl ether (short name
    5 ethyl cellosolve) and 20 h, toluene is stirred in a ball mill for 24 hours.
    These ingredients (q-1, b-1 and c-1 are mixed thoroughly and
    Q is dispersed in a mixture of 26 parts of methyl isobutyl ketone and 13 hours of toluene using a dispersant, resulting in a coating composition A, forming a multilayer film, as an incomplete suspension. Composition pokrp and B. Solid powder d-2. 35 h. Poly. olefin powder having an average particle diameter of 40 microns, which
    is obtained by melt mixing 85 parts of polypropylene having a melt index of 7.02 / 10 minutes and a density of 0.91J 15 parts of ethylene-o-olefin copolymer in the form
    with an elastomer having a melt index of 5.0 g / 10 min and a density of 0.88, and 10 parts of carbon black in a twin-screw extruder.
    Solid powder L -2. 2 parts of modified 5 polystyrene powder having an average particle diameter of about 45 microns, which is obtained by cooling and dissolving an adhesive resin having a melting index of 3.0 g / 10 min, density O, 96, and so on. obtained by grafting acrylic acid to subjected to partial saponification of co27
    the polymer of ethylene - vinyl acetate, the degree of modification of 0.8 mol / 1000 g of the modified resin,
    Resinous material s-2. 37 parts of a powder having an average particle diameter of 30 microns, which is obtained by uniformly spraying and mixing 100 parts of bisphenol type A epoxy resin having an epoxy equivalent of about 1800, m.p. approximately and mol. m. 2750, 20 parts of barite (BaO), 15 m. of chromate chromate, 8 parts of carbon black and 5.5 parts of 2 b-xylenyldiguaniline in a mixer with the addition of 100 hours. methyl ethyl ketone, followed by dispersion of the mixture in a ball mill for 18 hours, and final spray drying of the resulting em. or at 80 ° C.
    All of the listed ingredients (c-2, b-2 and c-2) are thoroughly mixed in a mixer, resulting in a powdered coating composition B, forming a multi-layer film.
    Coating Composition C.
    Solid powder "KZ. 33 to 4, of polyethylene powder having an average particle diameter of 15 µm, which is obtained by chemical spraying of a medium density polyethylene having a melt index of 1.5 r / f O min and a density of 0.944.
    Solid powder L-3. 3 parts of a powder having an average particle diameter of 40 µm, which is obtained by ochalodeni and spraying the resin, which is partially saponified ethylene-vinyl acetate copolymer resin containing HE as a polar group, having a melt index of 2 g / 10 min links in the molecular chain of 75%. The content of hydroxyl groups in the resin is 1.3 mol per 1000 g of resin.
    Resin material s-3. 64 parts of powder, which is obtained by stirring 50 parts of bisphenol type A epoxy resin having an average mol. m; 1000 and an epoxy equivalent of 650, 50 parts epoxy resin based on bisphenol type A, having an average mol. m. 1400 and epoxy equivalent 900; 4 parts of dicyandiamide, 10 parts of red iron oxide and 5 hours of titanium white
    3675028
    in a twin-screw extruder with the subsequent spraying of the mixture using a device of fine spray 5 with simultaneous drying with ice
    5 and sieving the powder through a 250 mesh (0.063 mm) sieve to remove coarse particles.
    Perezylennye ingredients (a-W,
    0 b-3 .and c-3). dispersed in 120 parts of a mixed weak solvent, s, consisting of 40 -h. dimethylcyclohexane, 55 parts of a mixed aliphatic solvent and 5. parts of xylene,
    15 which results in a coating composition C in the form of a complete suspension, forming a multilayer film.
    Example 1. The coating composition A is applied by spraying a compressing
    air on the surface of the steel plate (dimensions 3,2150 x 3 mm), sand-blasted, and cured
    25 at room temperature. The coated film is then fired using a hot air dryer at 200 ° C for 20 minutes, resulting in a multilayer
    30 coated film having a thickness of 120 microns. Then, while the upper part of this multilayer film is still in the molten state, polyethylene is melted under the influence of heat (at 230 ° C) (melt index 0.25 g / 10 min, density 0.947) applied to it surface thickness
    4Q multi-coated film. 2. MM using single-screw extruder equipped with a T-shaped extrusion HEAD. The coated steel plate is immediately cooled with water, and thus a sample is obtained for testing the surface coating of olefin resin.
    , Example 2. The same steel plate as in example 1, the sandblasted stripped by sandblasting, is preheated before and pseudo. the freezing layer of coating composition B, and then burned with a hot-air dryer for 15 minutes, resulting in a multi-layer film with
    29
    a coating having a thickness of 150 microns. The coated plate is pre-heated to 280 ° C using an electromagnetic induction heater and then immersed in a fluidized bed of polyethylene powder (having a melt index of 1 g / 10 min, a density of 0.925 and an average particle diameter of 75 mesh (or 0.2 mm) and heated to for 5 minutes at a surface temperature of 220 ° C, using an infrared heating oven. As a result, a coating having a thickness of 1.5 mm is obtained. The coated steel plate is cooled in air and a sample is prepared for testing from ole Finnish resin.
    Example 3. The coating composition was applied with a squeegee onto the same steel plate as in example 1, which was sandblasted, then it was cured at room temperature and burned for 12 minutes, resulting in a coated multilayer film. having a thickness of 175 microns. This coated steel plate is preheated in an infrared heating furnace so that the surface temperature of the coated film reaches 220 ° C, and a layer of ethylene vinyl acetate is applied to this multilayer film using a rubber roller (melt index 1.7 g / 10 min, density 0.93, vinyl acetate content 8%, thickness 3 mm). The laminated steel plate is heated at 240 ° C for 1 minute and then cooled with water, as a result of which a sample is obtained for testing the surface coating of olefin resin.
    Example 4 A treatment solution is prepared by dissolving 1% phosphonium trifuylbenzyl chloride in a mixed solvent consisting of 90 parts of water and 10 parts of isopropanol. The treatment solution is sprayed onto the surface of the same steel plate as in Example 1, sandblasted, and dried for 5 minutes.
    Then the steel plate is additionally coated in the same manner.
    An OCR as described in Example 1, resulting in a sample being prepared for testing an olefin resin surface coating. Example 5. A 0.5% aqueous solution of trimethyl-2-bromo-ethyl ammonium bromide is prepared and used to surface it with the same steel plate as
    in Example 1, iodized stripping by sandblasting, dipping method. The steel plate treated in this cut is dried at room temperature for -.
    10 i-iOHH and then deposited on it in the same manner as described in Example 2, resulting in a sample for testing an olefin resin surface coating.
    Example 6 (comparative). 20 hours of styrene-butadiene block copolymer and 20 hours of pure asphalt bitumen are mixed with
    hot rolls, resulting in the main batch. Then 40 hours of air-filled asphalt bitumen (20/30), 40 hours of air flow are introduced into the main batch.
    asphalt bitumen (30–40) and 10 parts of tar ester (hydrogenated rosin ester) and all ingredients are moved while heating the mixture at 130 ° C. Then
    the mixture is stirred at 130 ° C to
    as long as it does not melt evenly to form an adhesive composition.
    The same steel plate as
    in the described examples, sandblasted, preheated to. 100 ° C. The resulting adhesive composition, melted at 150 ° C, is applied to the steel plate with a knife device to a coating thickness of 500 µm. After that, a polyethylene sheet 2 mm thick (melt index 0.25 g / 10 min, density 0.947) is applied to a steel plate coated with the indicated composition. The sheet is pressed using a rubber roller. The resulting steel plate was held at 100 ° C for 10 minutes, and then cooled with air, resulting in a sample for comparative analysis. 31P p and measures (comparative). A steel plate as described in example 1, which was subjected to sandblasting, was coated by spraying it with epoxy enamel (resin S-1). The coated film is cured at room temperature and then burned at 200 ° C for 20 minutes, resulting in an epoxy base layer having a thickness of 55 µm. Then low-density polyethylene with grafted polyacrylic acid, having a melt index of 4 g / 10 min and a density of 0.930, and high density pr-ethylene, having a melt index of 0.25 g / 10 min and an apidity of 0.947,: is forced out of separate extruders at 180 and 230 C accordingly, they are introduced into a T-shaped extrusion die with the formation of a multilayer sheet type extrudate with separate layers with a thickness of LLP and 2 mm cooTBfeTCTBeHHO. After that, a multi-layered sheet is applied to the main epoxy layer of a coated steel plate (preheated to 18 ° C), so that the polyethylene layer with acrylic acid grafted firmly adheres to the primary epoxy layer. Then, the obtained steel plate is cooled with water and thus the sample is crawled for comparative analysis. Example 8 (comparative). Sample. Phase Test of the olefinic resin surface coating of the prostrate: Pour in the same manner as described in Example E1, with the exception that instead of the coating composition A, a coating composition in the form of an incomplete suspension, obtained by removing solid powder b-g from coating composition A. Samples obtained in the described examples are subjected to the test. The test results are presented in the table .. Types and methods of testing. Adhesive strength. A 10 mm wide olefin resin surface layer is cut. Part of it is removed, bent at 180 ° C and stretched from 5032 at a speed of 10 mm / min to measure adhesion strength. Shear resistance An excess of the coating material located at the ends of the test specimen is scraped off, and the specimen is held for 3 hours in a tank at 90 ° C so that its longitudinal axis is at an angle of 70. The slip width of the olefin resin surface coating material is measured. Shrinkage of the sample in the longitudinal direction ... An excess of the coating material located at the ends of the test specimen, held horizontally for 60 minutes in an oven at 80 ° C, is scraped off, then the sample is cooled to room temperature outside the furnace and heated again. The heating heating cycle is repeated 10 times and measured in Descent of the material of the surface coating of polyolefin resin (in the longitudinal direction of the sample). Impact resistance. Using the Gardener's impact device, the maximum impact force is measured, at which neither cracking, nor peeling of the epoxy resin layer and the olefin resin surface coating layer occurs. Resistance to cathodic decay. The end part and the back surface of the sample are coated with colorful pokryshayup51m material such as epoxy resin and dried, so that these parts were coated. Then in the surface layer of olefin resin a hole is drilled with a diameter of 2 mm, which passes. to a steel sheet serving as a metal substrate. After that, the sample is dipped into a 3% aqueous solution of sodium chloride. Further, using this Sample as a cathode and using a platinum anode, a direct current of 6 V is passed through both electrodes. After passing for 30 days. the electric current measures the diameter of that portion of the coated film that peels off the steel plate when scraped with a knife. Corrosion resistance.
    33
    in the test specimen, a 1-mm-wide breadth reaching the steel sheet is made, and a 5% aqueous solution of sodium chloride is sprayed onto the specimen for 1000 hours using a salt spray device. Measure the width of the corroded part of the metal substrate from the cut part
    The results presented in the following table show that the surface coating of olefino34
    136750
    This resin obtained according to the proposed method has a high adhesion, low temperature change, high impact resistance at low temperature and high corrosion resistance.
    Thus, as the analysis of the table shows, the coating obtained by the proposed method has a high interlayer and improved physicomechanical properties as compared to the coating obtained in a known manner.
    A; 1; hesion strength 10 / 9.5 20/40 ° С, kg / cm Shear strength.
    Shrinkage of the sample in the longitudinal direction, mm Impact resistance 20 / -, 20 ° С, kg / cm 2.3 / 3.0
    Cathodic resistance
    10.5 peeling, mm
    Corrosion resistance.
    0.7
    mm
    0.2
    2.0
    9.0
    12.5
    15
    35
    0.8
    2.2 1.4
    0.5 10 / 8.5 8.0 / 6.5 3.5 / 1.0 6.0 / 3.5 2.0 / 2.5 3.2 / 4.5 1.5 / 0.1 2.1 / 2.8
    权利要求:
    Claims (2)
    [1]
    1. METHOD FOR PRODUCING A POLYMER COATING ON A METAL SUBSTRATE by applying a composition containing a polyolefin, an epoxy resin and a hardener, characterized in that, in order to increase the adhesion of the coating to the substrate, a composition containing a powdery polyolefin resin with a melt index of 1.5-20 is used g / 10 min 'and a particle diameter of 15-40 μm, a modified polyolefin resin with a melt index of 2-4 g / 10 min, containing hydroxyl or carboxyl groups in an amount of 0.81.3 mol. per 1000 g of modified polyolefin, and in based on epoxy resin with an average mol.m. 1000-2700 and an epoxy equivalent of 650-1800 and hardener, taken at a ratio of (33-35) :( 2-5) :( 37-75) parts by weight respectively, and after applying the composition, an additional polyethylene coating with a melt index of 0.25-1 g / 10 min and a density of 0.925-0.947 or a copolymer of vinyl acetate with ethylene with a melt index of 1.7 g / 10 min and a density of 0.930 is additionally applied.
    [2]
    2 ,. The method of claim 1, wherein the substrate is treated with a 12th solution in a mixture of water and isopropanol taken at a ratio of 9: 1, triphenylbenzyl phosphonium chloride or 0.52th before applying the composition. aqueous solution of trimethyl-3-bromoethylammonium bromide.
    类似技术:
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    同族专利:
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    DE3117302C2|1990-04-19|
    CA1151520A|1983-08-09|
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    申请号 | 申请日 | 专利标题
    JP55056229A|JPS6210703B2|1980-04-30|1980-04-30|
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