Hybrid reinforced plastic structural parts

FIELD: construction.

SUBSTANCE: invention refers to a structural part that comprises a metal component and a plastic component, which are connected to each other by means of a linkage system that may withstand long-term load of connection between part components, and to the method for manufacturing of such a structural part. The linkage system that connects the metal component and the plastic component comprises a binding substance based on plastic or a binding substance based on plastic in combination with a primer. At the same time the plastic-based binding substance is an epoxide modified by means of covalent attachment of 1,3-diene. Besides, the binding substance contains a hardener.

EFFECT: manufactured structural parts have high bending strength and torsional stiffness, are able to withstand dynamic and static load, may be applied in corrosion media.

23 cl, 1 dwg, 1 tbl

 

The present invention relates to structural parts, comprising a metal component and the plastic component, which are connected to each other through the binder.

Composite plastic parts must combine the positive qualities of the respective metal and plastic designs. In the present description details includes two distinct components - metal and plastic, called "hybrid" parts. However, the properties and working characteristics of metals and plastics vary greatly, and thus, obtaining long-lasting and able to withstand the load of the connection between such parts is not a simple task.

In DE 3839855 C2 describes a composite part, comprising reinforcing ribs are made of plastic, which injectively in the main body is made of metal. The main metal housing includes holes into which Inuktitut plastic parts. This means that a positive connection, in which plastic parts as it were fixed in the metal. Alternatively, as is known, to obtain a positive connection perform the corresponding flared grip metal component. These types of positive connection n is suitable for the manufacture of parts, working under load, because it does not provide the necessary strength of the resulting structure. In addition, these parts can corrode under the influence of moisture seeping as a result of capillary forces between the metal component and the plastic component.

One of the known methods of joining metal component coated with an adhesive varnish, with plastic component is a method for continuous co-extrusion (co-extrusion). Metal component, which in this case represents the foil is subjected to preliminary heating, in which the binder is activated and during the extrusion process promotes the formation of connections between the metal component and the printed plastic component. Activation of the binder requires heating the component to a temperature exceeding a certain temperature, depending on the nature of the corresponding applied binder. If this temperature is not reached, the connection formed between the two components of composite parts, is fragile. Because metals are good conductors of heat, in some cases achieving a sufficient temperature, it is difficult, in particular in the case of the use of large and vol is x parts.

In the application WO 2005/032793 this method was improved by the introduction of the binder, which can be activated on subsequent heating, i.e. at first make the composite part by injectionem (molding pressure) of the plastic component to the metal component, and then the metal component is again heated to the activation layer of the binder. In this way connect the material of the metallic component with the material of the plastic component.

The method proposed in the application WO 2005/032793, results in a stable connection between metal and plastic, which is strong enough to bond the components are not exposed to severe mechanical loads, for example for the manufacture of purely decorative items. Composite parts can also be used as products that are subjected to certain mechanical load, but the possible collapse of such products does not lead to tragic consequences.

However, in the case of structural parts, in particular load-bearing elements, moving parts and/or significant for the security part of the vehicle, equipment or any other device, the durability and reliability of connection of metal and plastic must meet certain requirements, which which do not comply with the details manufactured using methods that are applied on the existing level of technology.

Thus, the present invention is to provide structural parts, comprising a metal component and the plastic component, which are connected to each other through strong connections capable of withstanding the load.

In particular, the present invention is to provide structural parts, which are capable of withstanding the dynamic and static load.

Another objective of the present invention is to provide structural parts with high resistance to bending and torsional rigidity.

Another objective of the present invention is to provide structural parts, which can be used in corrosive environments.

The present invention relates to structural parts, including a metal component, a plastic component and a binder system, connecting the metal component and the plastic component; however, the binder system consists of a plastic binder or plastic binder in combination with the primer, with the plastic binder is a polyester, polyurethane or epoxide-modified diene and/or what yenom.

Structural detail, proposed according to the present invention, can be obtained in accordance with the method including the following operations:

a) providing a metal component, and on one side or on both sides of the specified metal component, a coating of pre-utverzhdenii binder system, i.e. the linking system, subjected to preliminary operations education cross-links;

b) placing the metal component, on which a coating of pre-utverzhdenii binder system, a mould for casting under pressure so that the layer of pre-cured binders facing surface to the free volume of the mold;

C) forming under pressure a plastic component to a metal component, which is further curing binder systems; however, the binder system consists of a plastic binder or plastic binder in combination with the primer, with the plastic binder is a polyester, polyurethane or epoxide-modified diene and/or polirom.

In accordance with the present description, the term "one" should be understood as "at least one".

Distinctive prize is ACOM present invention is a binder system. She is a thermosetting (capable of forming cross-linkage) system, cured in two stages, which due to its composition, in particular modification of danami and/or polyene, can be optimally adapted to the specific plastic used for injection molding. This allows previously inaccessible joint strength between the metal and plastic material.

As the metal component can be applied to almost any metal, in particular metals commonly used in the art for the manufacture of structural parts, such as various grades of steel with different strength, stainless steel, tin, light metals, such as aluminum and magnesium, etc. or alloys of metals, for example, carbon, chromium, Nickel and molybdenum. Preferably use steel, not containing coatings or lubricants.

The metal component is usually used in the form of sheet metal or sheet metal, made in the form of molded parts.

The preferred materials used for the manufacture of a plastic component, is chosen depending on the temperature range of intended use and depending on the requirements to mechanical properties. The use of plastic materials, armirovannykh fiber, for example, glass fiber-reinforced or reinforced with carbon fiber, ensures a particularly high strength of the product. Also for the manufacture of parts can be used polymeric materials with low surface energy, such as PE, PP and PA.

As plastic materials may be used homopolymers, such as polyvinyl PE, PP or PA, polyamine, polystyrene, polyethersulfone (PES), polyethylenimine (PAYS), polyetherketone (PEK) or polyetheretherketone (Cape peek).

The plastic material may be reinforced with fibers and/or fillers and/or they may be added other additives such as dyes, flame retardants or amplifiers fluidity.

If the plastic material is reinforced with a fiber, the fiber content can reach 60 wt.%.

Typical plastic materials used for molding under pressure, include: polypropylene (PP), for example PP vers 30, polyamide (PA), for example PA 6 ST. and PA 6.6 SV, a mixture of polyamide-polyphenyleneoxides (a mixture of PA-PFD), a mixture of polyamide-polystyrene (syndiotactic) (mixture of PA-PCA), a mixture of polyamide copolymers-Acrylonitrile-butadiene-styrene (mixture of PA-ABS), polyphthalamide (APF), polyster (SFC) and polysulfone (POC).

In a preferred example implementation of the plastic material used for molding under pressure is m, is a PA 6 ST or PA 6.6 SV, in which the fiber content in each case is 30 wt.%.

In the above notation means ST. fiberglass, vers means of long fiber, and the number after vers means of mass percentage of long fiberglass in plastic.

Long fiber is used because of its dimensional relationships (length to height). This fiber improves the impact strength and dimensional stability (dimensional stability) when heated in plastics, such as polypropylene. Currently, even the plastics material reinforced with short glass fiber (ST), can exhibit good dimensional stability when heated and the degree of shrinkage; plastic reinforced with long glass fiber, can be even higher thermal and mechanical parameters. Such indicators PP vers, as strength and stiffness, exceed those of polypropylene compounds in which as fillers using ST (short fiber), 30%, and their impact strength exceeds the corresponding value for SV polypropylene almost 300%.

In the temperature range +100°C, i.e. for structural parts, bearing only a small thermal load, can be used, for example, PP vers 30, i.e. a polypropylene containing 30 mA is.% long fiberglass.

In the temperature range from -40°C to +120°C or +140°C, i.e. for structural parts, bearing more significant thermal load, depending on the requirements of mechanical strength is used high-quality plastics such as polyamide, such as PA 6 ST or PA 6.6 SV. Polyamide (PA) type of amino acids derived from a single monomer by polycondensation or polymerization (ε-lactam), and polyamides type diamine-dicarboxylic acid derived from two monomers by polycondensation. Polyamides derived from unbranched aliphatic monomers, designate in accordance with the number of carbon atoms, i.e. PA 6 made from aminohexanoic acid (or ε-caprolactam), and PA 6.6 prepared from diamine and adipic acid.

Alternatively, PA 6th ST. and PA 6.6 SV can be used a mixture of PA-PFD and a mixture of PA-PCA, in which the VFD means Polyphenylene oxyde, and the PCA means syndiotactic polystyrene.

In the temperature range from -40°C to more than +140°C, i.e. for structural parts, bearing a significant thermal load, depending on the requirements of mechanical strength and chemical resistance applied engineering plastics with improved performance characteristics, such as PFA, PPS. The APF means polyphtalamide and SFC means polyster. In the General case, the AE, alternatively can be used partially aromatic polyamides and the dog. Dog means polysulfone (poly[oxy-1,4-phenylene-sulfonyl-1,4-phenylene-oxy-(4,4'-isopropylidenediphenol)]).

Thanks to its lightness, strength and secure structural parts are offered in accordance with the present invention, especially suitable for the manufacture of parts of enclosures of vehicles. United one-piece connection of the parts of the vehicle must withstand temperatures ranging from -40°C to +120°C. In the manufacture of the vehicle specified components must pass all stages of the painting, but in this case the operation, geometry, surface finish and other parameters of the details should remain unchanged. These operations are performed under the following conditions: when the catalytic coating by immersing items usually maintained at 200°C for 20 minutes; for the application of the filler items was kept at 160°C for 30 minutes and for painting details is maintained at 150°C for 30 minutes. Accordingly, it is necessary to apply a plastic material, for example polyamide, such as PA 6 ST, PA 6.6 ST.

Parts attached to the main body detachable way, need not comply with the requirements catalyti the definition of coating by immersion. These parts attach to the body later. For the manufacture of such parts from a suitable plastic, for example, PP vers.

In addition, the plastic must meet the requirements of mechanical strength, in particular the parameters of bending and torsion, as well as other requirements such as chemical resistance, electrical conductivity, no smell, etc.

The linking system is a system cured in two stages, i.e. a binder system that fully utverjdayut if two successive operations. The formation of cross-links is carried out with the help of thermal activation. The binder system includes "actual" binder, which is a plastic binder, which may be used alone or in combination with primer, which is used to enhance the activation of the metal surface. The binder system is applied to the sheet material or metal component and is subjected to partial formation of cross-links in the first stage with the formation of a dry surface that is stable from damage when carrying out further operations. During or after the operation of applying the plastic molding spend the final blended binder system with the formation of the finished isdel who I am. Full cross-linked binder system can be carried out, for example, when carrying out the subsequent curing operation or during the operation of the catalytic coating by immersion. The catalytic coating by immersion, which is carried out at a temperature of from 165 to 215°C., preferably from 190 to 200°C, increasing the strength and glass transition temperature TD binder system.

The binder system should, on the one hand, contact with a metal material, and on the other hand, with a plastic material. Accordingly, the composition of the material system chosen depending on the nature of the metal component and the plastic component structural parts, in particular depending on the nature of the plastic component.

If the linking system includes a primer, then apply traditional types of primers known in the art. The primer includes metallovedenie groups, which provide a compound material with a metal, and an organic group capable of contact with the plastic material or the base material plastic, for example with a matrix binder. Primers are organic compounds containing hydroxyl, tirinya, amino group or carboxyl group capable of contact with the metal. In addition, for this purpose can be used metal salts and, more preferably, the ORGANOMETALLIC compounds, for example functionalityand cyclopentadienyl iron. Functional groups in the primer contact with the metal, while the organic portion of the molecule is connected with a plastic binding agent.

Alternatively, or in addition to the above primers may be used alkoxysilane with organic functional fragments, for example 3-(trimethoxysilyl)-1-propanamine, 3-(trimethoxysilyl)-propylbetaine, N-1-[3-(trimethoxysilyl)propyl]-1,2-amandemen, 3-(triethoxysilyl)-propanenitrile), 3-glycidylmethacrylate etc. are applied to the metal surface in diluted condition, such as alcohol or water solution concentration from 1 to 10%; the above-mentioned compounds, in particular, are characterized by this provides a particularly strong connection between the components. CNS group of the silane binds to the metal surface and the complementary functional group of the organic part of the molecule will bind to the matrix plastic binder.

Additionally, there may be used a mixture of silanes with prepolymers, such as carbamates. The appropriate ratio of components in the mixture (mass relations) silane:prepolymer range from 1:50 to 1:1.

Non-limiting examples of compositions g is UNEVOC can be the following: 3 to 8 wt.% 3-glycidoxypropyl-methyldiethanolamine or 1-[3-(trimethoxysilyl)propyl]urethane or 3-(trimethoxysilyl)prophylatically plus from 2 to 5 wt.% N-(2-amino-ethyl)-3-(trimethoxysilyl)Propylamine, or 3-(trimethoxysilyl)Propylamine, 3-(trimethoxysilyl)-1-propanethiol in alcohol or mixture of alcohols in which preferred are ethanol, methanol and isopropyl alcohol. Also suitable solution of the hydrochloride of N-[3-(trimethoxysilyl)propyl]-N'-(4-vinylbenzyl)Ethylenediamine concentration from 5 to 15 wt.%, for example, in methanol.

"Actually" binding agent representing a plastic binder, applied to the primer, so that, on the one hand, it binds to the primer, and on the other hand, provides a compound material with plastic. In the alternative case, primer and plastic binder can be mixed. After curing the "proper" binder is a plastic material. Usually it also includes metallovedenie group or contains components, including metallovedenie group, and thus can be applied without primer, and the connection material, the metal will be provided with a plastic binder. When this plastic binder is applied directly on the metal.

Plastic binder, which provides a compound material with plastic and the connection to the primer and/or a metal surface, preferably is a complex polyester, polyurethane or epoxide particularly preferred is an epoxy resin, based on bisphenol a and/or bisphenol a and/or bisphenol a and/or bisphenol F and/or novolak.

Bisphenol a is a 2,2-bis-(4-hydroxyphenyl)-propane, bisphenol represents a 2,2-bis-(4-hydroxyphenyl)-butane, bisphenol s, is a 1,1-bis-(4-hydroxyphenyl)-cyclohexane, bisphenol F represents 2,2-methylenediphenol. Especially preferred are bisphenol a and bisphenol Century If they are used in the form of a mixture, the mass ratio of bisphenol a:bisphenol In preferably is in the range from 1:1 to 1:10.

The binder system can be adapted to the respective plastic attached to metal by modifying the binder system danami, in particular 1,3-danami, or modifications to the system a polyene, such as natural rubber or synthetic rubber; dieny and/or polyene can be covalently linked to the resin (polymerized in a matrix binder) and/or physically introduced (added) into the matrix of the binder. The proportion of the diene and/or the share being in a binder system is preferably from 1 to 30 wt.%, particularly preferably, from 3 to 10 wt.%.

Modified elastomers, adhesive binders based on epoxides include, for example, a substance obtained by the polymerization of 1,3-butadiene (covalent bond) or to relax is of rubber (physical introduction by).

The plastic binder is preferably a single binder. In epoxy systems epoxy group can be, for example, applied for the activation of metal and attach the material to the metal.

Another way of adapting the linking system to the corresponding plastic attached to metal, and may include the addition of alkyl - and/or allmodifications silanes that meet the General formula HO-Si(R)(R')(R"), in which groups R, R' and R" may be the same or partly or differently modified alkyl and/or aryl groups, and alkyl and/or aryl groups contain functional groups such as COOH, HE, NH2. Silanes ensure the formation of cross-links (at the expense of functional organic groups) and the connection to the metal (due to hydroxyl group at silicon). However, the presence of silanes is not an absolute necessity, since joining the metal may also be provided with functional groups of the plastic binder.

When connecting material according to the present invention there is no capillary action (i.e., the penetration of moisture between the plastic material and metal material) due to the presence of solid bonding of plastics material and a metal material is through the linking system. This allows you to fill in the open, i.e. unprotected surface section and other unprotected metal surface with a layer of plastics material. Since both sides of detail is provided a solid bonding, there is no penetration of moisture to the exposed surfaces except for diffusion, which provides sufficient corrosion resistance. Of course, the binder is as resistant against corrosion and against hydrolysis.

The binder can also provide protection against corrosion, particularly if you use a system based on the plastic material, for example epoxy system, a system based on a complex of the polyester or polyurethane. With this choice of binder in the finished product utverjdenie binder forms on the surface of the metal material corrosion-resistant layer in places that were not coated with plastics material. Thus, the binder system it is important to apply a continuous layer.

Optionally, the binder may be suitable for catalytic application by immersion (PNC). To do this, it must have sufficient thermal stability and electrical conductivity.

Conductive binder receive the user is receiving electrically conductive ingredients. Suitable electrically conductive ingredients include organic bases include, for example, carbon black and graphite, and inorganic bases are metal powders such as zinc dust.

In some implementations of the binder should be suitable for welding, i.e. metal parts coated with the binder should be suitable for welding.

Necessary conditions for this must be, on the one hand, electrical conductivity, and on the other hand, thermal stability. In addition, the substance must be non-combustible. Thermal stability preferably provides the use of epoxy resin systems with a high density of cross-links, based on bisphenol a and/or bisphenol Century

The resistance is provided by the introduction of halogenated bisphenols. For example, the binder can be prepared from 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane and/or tetrabromobisphenol or optionally contain these bisphenola. Alternatively, or in addition to binding substance can be added flame retardant agents (halogenated or halogen-free).

In particular, when applying the binder method of roll coating, it is necessary that after performing the first operation frequent knogo formation of cross-links obtained binder had sufficient flexibility or formability thus, to the binder completely covers the metal material after molding even in areas with high curvature. The elasticity of the binder can be increased, for example, by linking elastomer (1,3-butadiene) with a binder or by adding a binder of rubber.

To enhance the adhesion of the material with metal, enhanced protection from corrosion, electrical conductivity, thermal stability, Flammability and elasticity to the substance can be added to the above materials either separately or in combination depending on which property should be obtained.

In addition, the additives may be used dyes.

In one of the preferred implementations of the present invention when carrying out the first operation of the curing reactions occur epoxy resins, additives that improve impact strength, and amines used as curing agents, preferably responsive amines that allows you to adjust the adhesive strength of the film (operation).

Preferably, the final curing is carried out at elevated temperature in the second curing operation. For this operation it is preferable to use a curing agent in slow motion. If necessary, the curing speed specified is tergites delayed action can be controlled by adding accelerators.

Following are preferable examples of the implementation of the epoxy resin, additives that improve impact strength, hardener, hardener slow motion and other optional ingredients of the binder.

Epoxy resin

The content of the epoxy resin in the binder substance is preferably from 20 to 80 wt.%, more preferably from 50 to 70 wt.%.

Essentially, for the manufacture of binders, proposed according to the present invention can be any epoxy resin, known in the technical field of epoxy resins. Can also be used a mixture of epoxy resins.

Examples of epoxy resins include:

I) Complex polyglycidyl and poly(ss-methylglycerol) ether obtained by the reaction of the compounds, the molecule of which contains at least two carboxyl groups with epichlorohydrin and ss-methylephedrine. The reaction is conveniently carried out in the presence of bases.

As compounds, the molecule of which contains at least two carboxyl groups, can be used aliphatic polycarboxylic acid. Examples of such polycarboxylic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, timelineview acid, cork acid, azelaic acid or dimenisonal or three is erusovanou linoleic acid.

In addition, can be used and cycloaliphatic polycarboxylic acids, for example tetrahydrophtalic acid, 4-methyltetrahydrophthalic acid, hexahydrophthalic acid or 4-methylhexahydrophthalic acid.

Additionally, there may be used aromatic polycarboxylic acid such as phthalic acid, isophthalic acid or terephthalic acid.

II) Simple polyglycidyl or poly(P-methylglycerol) ether obtained by the reaction of compounds containing at least two free alcoholic hydroxyl groups and/or phenolic hydroxyl groups with epichlorohydrin or p-methylephedrine under alkaline conditions or in the presence of an acid catalyst with subsequent alkali treatment.

Simple glycidyloxy esters of the specified type receive, for example, from acyclic alcohols such as ethylene glycol, diethylene glycol or higher poly(oksietilenom)glycols, propane-1,2-diol or poly(oxypropylene)glycols, propane-1,3-diol, butane-1,4-diol, poly(oxytetracyline)glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, pentaerythritol or sorbitol, and from polyepichlorohydrins.

Other simple glycidyloxy esters of the specified type derived from cycloaliphatic alcohols, for example of 1,4-cyclohexanedimethanol, bis(4-hydro is bicyclohexyl)methane or 2,2-bis(4-hydroxycyclohexyl)propane, or of alcohols containing aromatic groups and/or other functional groups, for example N,N-bis(2-hydroxyethyl)aniline or p,p'-bis(2-hydroxyethylamino)-difenilmetana.

Simple glycidyloxy esters can also be derived from mononuclear phenols, such as resorcinol or hydroquinone, or multi-core phenols, for example bis(4-hydroxyphenyl)methane, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)sulfone, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane or 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane.

Other hydroxycodone suitable for cooking simple glycidyloxy esters are novolak, produced by condensation of aldehydes, such as formaldehyde, acetaldehyde, chloral or furfuraldehyde, with phenols or bisphenolate, as containing or not containing chlorine atoms and the other substituting group, for example, phenol, 4-chlorophenol, 2-were-or 4-tert-butylphenol.

III) Derivatives, poly(N-glycidyl)obtained by the reaction of dehydrochlorinating the reaction products of epichlorohydrin with amines which contain at least two hydrogen atoms at the amine nitrogen atom. Such amines include, for example, aniline, N-butylamine, bis(4-AMINOPHENYL)methane, m-xylylenediamine or bis(4-methylaminophenol)methane.

Derivatives of poly(N-glycidyl) also include three is glycidylester, N,N'-diglycidylether of cycloalkylation, such as etilenmocevina or 1,3-propylenimine, and diglyceride hydantoins, such as 5,5-dimethylhydantoin.

IV) Derivatives of poly(3-glycidyl), such as di-3-glycidylester derived from developed, such as, for example, ethane-1,2-dithiol or a simple bis(4-mercaptoethanol) ether.

V) Cycloaliphatic epoxy resins, for example, a simple bis(2,3-amoxicillinbuy) ether, a simple 2-amoxicillingeneric ether, 1,2-bis(2,3-amoxicillinamoxil)ethane or 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate.

However, it is also possible to use epoxy resins in which the 1,2-epoxypropyl linked to different heteroatoms or functional groups; these compounds include, for example, N,N,O-tripyridyltriazine 4-aminophenol, simple glycidyloxy ester complex glycidyloxy esters of salicylic acid, N-glycidyl-N'-(2-glycidyloxy)-5,5-dimethylhydantoin or 2-glycidyloxy-1,3-bis(5,5-dimethyl-1-glycidylester-3-yl)propane.

Preferably use a simple diglycidyl ether of bisphenol a or Apeksimova.

Especially preferred are simple diglycidyl ether of bisphenol a or epoxyketone novolak.

Supplements that increase impact strength

Additives that increase the shock about the activity, described in the following patent applications: EP 0308664, EP 0338985, EP 0353190, EP 0358603, EP 0365479 or EP 0381625.

As additives that improve impact strength, it is preferable to use a copolymer of diene and/or a polyurethane containing terminal phenolic group, and/or a polyurea, or a combination of these compounds. In another preferred example of implementation as additives that improve impact strength, use butadienestyrene, including terminal amino group or carboxyl group.

The hardener

The content of the curing agent in the binder substance is preferably from 1 to 15 wt.%, more preferably, from 2 to 4 wt.%.

The hardeners of epoxy resins, optionally used in accordance with the present invention, preferably are responsive amines, such as aliphatic, cycloaliphatic, analiticheskie or aromatic amines may aminoamide containing imidazoline groups, and their adducts with derivatives of glycidol, which on average contain more than two reactive hydrogen atoms on the amine nitrogen atom in one molecule. These compounds are well known in the art and described, for example, Lee &Neville, "Handbook of Epoxy Resins", MC Graw Hill Book Company, 1987, Chapters 6-1 to 10-19.

Especially preferred is the use of pole is raminov.

Hardeners delayed action

The content of the hardener slow steps in the binder substance is preferably from 1 to 15 wt.%, more preferably, from 5 to 11 wt.%.

In General, in accordance with the present invention may be used any compound which, as is well known, is used as a hardener slow motion and that meets the requirements of the present invention, i.e. any compound that is inert with respect to the epoxy resin at a temperature below the restrictive temperature equal to 70°C (measured using differential scanning calorimetry (DSC = differential scanning calorimetry) at a heating rate of 10°C/min), and which, however, quickly reacts formation of cross-links at a temperature exceeding the restrictive temperature. Restrictive temperature hardener slow steps used according to the present invention, is preferably at least 85°C., in particular at least 100°C.

Examples of suitable hardeners delayed actions include dicyandiamide, cyanoguanidine, for example the compounds described in patents US 4859761 or EP-A-306451, aromatic amines such as 4,4'- or 3,3'-diaminodiphenylsulfone, or guanidine, for example, 1-O-tolylboronic, or modified poly is mine, for example Ancamine@ 2014 S (Anchor Chemical UK Limited, Manchester).

Other examples of suitable hardeners delayed actions include N-illimitably, for example 1-(2',4',6'-trimethylbenzoyl)-2-phenylimidazol or 1-benzoyl-2-isopropylimidazole.

Such compounds are described, for example, in U.S. patents US 4436892, US 4587311 or Japanese patent 743212.

Other suitable hardeners are complexes of metal salts with imidazoles, for example, described in U.S. patent US 3678007 or US 3677978, hydrazides of carboxylic acids, for example dehydrated adipic acid, isophthalic acid hydrazide or hydrazide Anthranilic acid, triazine derivatives, for example 2-phenyl-4,6-diamino-s-triazine(benzoguanamine) or 2-lauryl-4,6-diamino-s-triazine(EuroGeoNames), as well as melamine and its derivatives. The last of these compounds are described, for example, in U.S. patent US 3030247.

Other suitable hardeners delayed actions include derivatives of cyanoacetyl described, for example, in U.S. patent 4283520, such as neopentylglycol, N-isobutylacetate, 1,6-hexamethylenediisocyanate or 1,4-cyclohexanedicarboxylate.

Other suitable hardeners slow-acting derivatives include N-cyanoacetamide, for example N,N'-dicyandiamide. Such compounds are described, for example, in U.S. patents US 4529821, US 4550203 and US 4618712.

p> Other suitable hardeners delayed action include alltoofamiliar and urea derivatives described in U.S. patent US 3386955, for example, toluene-2,4-bis(N,N-dimethylcarbamyl).

Other suitable hardeners delayed action also include imidazoles such as imidazole, 2-ethylimidazole, 2-phenylimidazole, 1-Mei, 1-cyanoethyl-2-ethyl-4-Mei or 2-ethyl-4-Mei.

Other suitable hardeners delayed action also include tertiary amines, such as benzyldimethylamine or 2,4,6-Tris(dimethylaminomethyl)phenol.

Preferred hardeners delayed action include diaminodiphenylsulfone, dicyandiamide, phenylimidazol and 2,4,6-Tris(dimethylaminomethyl)phenol.

Especially preferred is the use of dicyandiamide.

Accelerators, hardeners delayed action

You can use the accelerator, the content of which in the binder substance is from 0 to 8 wt.%, more preferably, from 2 to 4 wt.%.

It is advantageous if the mixture is proposed according to the present invention, also contain accelerators for the formation of cross-links, flowing under the action of the hardener slow motion. Suitable accelerators include, for example, derivatives of urea, for example N,N-dimethyl-N'-(3-chloro-4-were)urea (chlortoluron), N-dimethyl-N'-(4-chlorophenyl)urea (monuron) or N,N-dimethyl-N'-(3,4-dichlorophenyl)urea (Diuron), 2,4-bis(N',N'-dimethylurea)toluene or 1,4-bis(N',N'-dimethylurea)benzene. The use of these compounds is described, for example, in the above-mentioned patent US 4283520. Suitable accelerators include, for example, derivatives of urea, as described in the application GB 1192790.

Other suitable accelerators include imidazoles such as imidazole, 2-ethylimidazole, 2-phenylimidazole, 1-Mei, 1-cyanoethyl-2-ethyl-4-Mei or 2-ethyl-4-Mei.

Other suitable accelerators include tertiary amines, their salts or Quaternary ammonium compounds, such as benzyldimethylamine, 2,4,6-Tris(dimethylaminomethyl)phenol, 4-aminopyridine, phenolate of triphenylamine, chloride of Tetramethylammonium or bromide or chloride of benzyltrimethylammonium; or alkali metal alcoholate, such as sodium alcoholate and 2,4-dihydroxy-3-hydroxymethylene.

Other suitable accelerators include solid solutions of nitrogen-containing bases and phenol/aldehyde resins described in the application EP-A-200678, and Mannich bases of polymeric phenols described in the application EP-A-351365.

Preferred accelerators are chlortoluron, imidazoles and derivatives of urea.

Especially preferred accelerator is chlortoluron.

Thermoplastic powder

You can use thermoplastic powder, the content of kotorogo binder substance is from 0 to 7 wt.%, preferably from 0.5 to 3 wt.% and more preferably from 1 to 2 wt.%.

So, as an ingredient in binders, as filler and/or toughness modifier can be used thermoplastic powder, preferably amorphous thermoplastic powder, melting point which is below the melting temperature of the injected plastic component. As thermoplastic powder may be used homopolymers and/or copolymers, including polypropylene, polyamides, alloys polyamides, polyethylene (high or low density), (PE), Polyphenylene oxyde, PBT or PS. Preferably use low-density polyethylene. The average particle size d50 of the powder should not exceed 50 microns and preferably no greater than 30 microns.

Solvent

It is possible to use solvent content in the binder substance is from 0 to 66 wt.%, more preferably from 40 to 60 wt.%.

The solvent can be used in polar or nonpolar solvents. In particular, there may be used solvents containing group OR in which R represents H, alkyl or aryl, or solvents, including group N(R1)(R2), in which R1=N, R2=H; R1=N, R2=alkyl; R1=N, R2=aryl; R1=R2=Alky and/or R 1=R2=aryl. Alkyl in R, R1and R2contains from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms. The solvent preferably is a reactive solvent, and it improves the adherence to the metal substrate.

In addition, the binder may contain halogenated or halogen-free flame retardants. In addition, the binder can be added coloring matter.

Preferably the compositions of the binders listed in the Table below. Binder, proposed according to the present invention may contain one or more ingredients that are listed in the Table at the specified concentrations. Particularly preferably, if the binder contains all the above ingredients in the indicated concentrations.

Preferred compositions of the binders
The binderConcentration
PreferredEspecially preferred
Epoxide (for example, bicheno is A, bisphenol F, system of a novolak or a combination thereof)20-80%
The hardener1-15%2-4%
Diglycidyl ether of butanediol2-15%
Copolymers of diene and/or polyurethane based on phenol and/or polyurea, or a combination thereof5-40%7-15%
Butadienestyrene containing end amino group1-15%4-8%
Butadienestyrene containing end carboxyl group1-15%4-8%
Dicyandiamide1-15%5-11%
Chlortoluron0-8%2-4%
Thermoplastic powder0-7%0.5 to 3%
The solvent (polar or nonpolar)0-66%
Agnesa any composition (halogenated and/or halogen-free) 0-30%
The dye0-3%

The connection of metal and plastic used for the manufacture of reinforced plastic structural parts, perform applying the plastic molding on the metal component, on which a coating of pre-sewn binder.

The coating of the binder system can be deposited on a metal component before or after attaching the metal component forms. Usually forming metal component is produced by stamping and deep stretching of sheet metal. Possible coating methods include a so-called coating method "roll coating (coating prior to molding, spray painting, coating, immersing, coating, spraying of powder materials (coating after molding). It is also possible coating with a brush. Alternatively use a combination of several methods of coating.

For coating as solvents can be used above solvents. The solvent allows you to adjust the viscosity of the solution used in accordance with the selected method of coating, as reactive solvents can reduce the curing time. In addition, when using solvents containing functional groups can be achieved a higher density of cross-links. During the formation of polar groups to the substrate increases the value of a power margin.

If the binder system is applied prior to stamping and deep drawing of sheet metal, using a roll coating method, the cut edges of the stamped metal parts and parts subjected to deep drawing, without a binding substance. If possible, the binder is not applied to areas subjected to strong deformation.

To ensure corrosion resistance is necessary either to apply the binder to areas that do not have a coating binder, or to put on these parcels plastic material so that the plastic material was completely glued binding material along the periphery of the uncovered plots. In areas that are spatially remote from areas subjected to stamping and deep drawing, the coating can be applied by roll method. Sheet metal with coating method, roll coating, and then heated to a temperature and for a time sufficient to obtain a dry and solid structure connecting the system. The binder system should be subjected to partial formation of cross-links to such an extent, in which is formed a dry surface that is stable for further processing. Then the sheet metal is cut into pieces of the desired size and shape or stamp and subjected to deep drawing. Then sheet metal degreasing and then using an appropriate method of molding under pressure on the material can be applied to the plastic component. If necessary, the remaining unprotected areas can then be protected from corrosion by the application of paints or similar method.

In one modification of the above method for stamping and deep drawing of sheet metal can be used foil for deep drawing. Foil for deep drawing can be fixed after applying roll coating (after the preliminary formation of cross-links in a binder system or just prior to stamping and deep drawing of sheet metal. After stamping and deep drawing sheet metal foil for deep drawing are removed. In this case, to carry out degreasing sheet metal is not required. Then put the plastic component in a suitable mold. In this case it may not be bodymist education cutting edges or other uchastochkah open metal treated for protection against corrosion, for example, by means of special staining, if these parts can corrode.

If the binder system is applied after forming the metal component, for example, paint spraying, coating, immersing, coating, spraying of powder materials or catalytic coating by immersion, it allows more efficient use of corrosion protection in a binder system. Thus, there are no unprotected cutting edge of or damage to the layer of binder in the molding. When this corrosion protection provided by the binder system is used not only in the areas of connection with the plastic component, but also in areas not in contact with the plastic component. Thus can be eliminated additional technological painted metal component. In addition, if necessary, areas that should not be applied binder system may be intentionally left unprotected.

The adhesion of the binder with respect to the metal can be strengthened by appropriate pretreatment of the metal surface, such as degreasing and/or cleaning, mechanical processing, such as processing the rigid sandblasting apparatus or brush, the passivation, electrical or physical activation.

To enhance the adhesive bonding with the metal surface can be performed drying carried out in a period of time of 10 to 180 minutes at a temperature of from ordinary to 150°C, preferably for at least 20 minutes at 110°C. During drying, the evaporation of solvents used for coating, and begins the first operation of the formation of cross-links. In this case, can be applied hardener preferably amine type. Function hardener consists in initiating the polymerization reaction of the epoxide. In addition, there is a decrease in the adhesion strength of the adhesive layer/coating, which improves the stability of the material during the further processing. In addition, there is a strong adhesion to the substrate (e.g., metal). Specified clutch is large enough to prevent flushing when injection molding parts (e.g., injection molding). In addition, there is a temporary anti-corrosion layer. Polymerization can occur with the participation of polar groups, such as the polar groups of the solvent, or by disclosure of the cycle and the formation of ties, for example, between diepoxides and diamine.

After coating of the binder system useful to carry out subsequent the General processing of the coating of the binder, for example, by draining, drying or rinsing. Then perform the linking of the binder, i.e. its partial crosslinking to obtain a strength sufficient for further processing. The required temperature and duration depend on the type of binder system and comprise, for example, 100°C for 30 seconds, or 140°C for 40 seconds, or 120°C for 20 seconds. In the General case, suitable temperature, comprising from 80 to 160°C and a duration from 10 seconds to 1 minute.

Depending on the method of pre-curing (microwave, induction furnace or an oven with hot air, in particular an oven with hot air) the duration of the pre-curing is from 20 seconds to 40 minutes. The metal to which applied binder, can then be cooled to normal temperature and sent to storage or sent for further processing in a hot state. At this stage floor already provides protection against corrosion.

Then the metal component coated with a partially cross-linked binder system is introduced into a suitable mold for injection molding. Shape design will adapt so that it is, on the one hand, approached the design of the metal component, and on the other hand, corresponded to the desired design plastics the new component; the metal component is placed in a mold so that the binder facing the inside free volume form. The shape can be designed, for example, so that the reinforcing structure made of plastic injections in a metal component. It is useful to heat to a certain temperature, the value of which depends on the type of binder system. Preheating helps thermosetting behavior the linking system. Alternatively or additionally, the metal component may be pre-heated to the activation temperature binder system. This pre-heating can be produced, for example, using an external heat supply using induction heating, infrared emitter, furnace, etc. or from within the form (during or after the depositing of the metal component in the form, for example using IR emitters. Then Inuktitut source material for the manufacture of a plastic component. High temperature liquid melt causes thermal activation and, as a rule, the completion of the reaction-curing binder systems. Plastic is forever fixed on the metal component. Then the resulting hybrid structural detail and shape preferably cooled to accelerate the lowering of the temperature is s and ready hybrid structural detail is extracted from the form.

If you use a binder system with a high temperature of activation, after carrying out injection molding logical to release transaction (hardening) construction details for complete curing binder systems and thus ensure a stable adhesion between the plastic component and the metal component. This also applies to areas that bear the binder system, but not injection plastic that allows you to provide corrosion protection by using a binder system.

In a preferred example implementation using dicyandiamide in combination with a solvent having a polar group, which enables to produce place for fixing the plastic component made, for example, from PA, which is then molded under pressure. The dicyandiamide curing is preferably carried out at 150°C.

Typically, the binder system is applied on the entire surface or only on some areas and, in addition, or on one side or on both sides of the metal component. One of the special advantages of the binder system proposed according to the present invention, is that even if the plastic component is applied only on one side of the metal component, get strong and permanent connection capable of N. the load. The connection between materials and additional security measures, including positive connection between metal and plastic, are not required. Of course, such a positive connection can be created additionally, if the manufacturer mate is not straightforward, for example, injection box, plastic material in the holes of the metallic component.

Because a one-way connection of metal and plastic using the linking system is strong enough, then the appearance of the surface of the metal component, which is missing the plastic coating does not deteriorate. Thus, the surface of the metal component can be left open, for example, for decorative purposes, require the presence of metal or varnished surface. When processing such structural parts, in which there is an open metal surface indicated the open surface of the metal (in all cases the back side of a metal component handle binder) may be at different stages of processing. The open surface can be, for example, brushed pressing the polishing, polished, covered with a transparent scratch lacquer or manolakos; the surface may be subjected to the Uta finishing applying the lacquer coating or it can be covered with a layer of primer. In this case, the finished structural part is subjected to finish processing the application of the lacquer coating. This helps protect against corrosion of the cutting edge. To protect open the metal surface during further processing, for example when carrying out injection molding, it is useful to close the open surface of the metal protective film. The protective film is not removed before molding.

Some examples of applications of hybrid structural parts, proposed according to the present invention include the manufacture of vehicles as well as used in aircraft construction, the construction of space ships and submarines, in the manufacture of small buildings motor vehicles.

In particular, the present invention relates to pressurized parts of vehicles intended for the manufacture of shells of vehicles, including hybrid structural parts are offered in accordance with the present invention. It should be noted that the individual characteristics of the components discussed below in relation to Cabinet parts of the vehicle, which, in particular, relate to the construction of Cabinet parts of the vehicle and the corresponding structural parts, are exclusively related to the present invention and, in particular, the e include the characteristics of claim 1 or claim 8 or include only a portion of the above characteristics. Weight plays an important role in the manufacture of structural parts and, in particular, body parts of vehicles. On the other hand, the load on these parts also significant, and, in addition, these items must be durable enough. So, despite the above advances in existing technology, the design of the buildings vehicles and, in particular, in passenger cars almost exclusively used traditional double-hulled sheet metal. For many years this design is used, despite its considerable weight, thanks to such useful qualities, such as low price, stability and reliability. At the same time when using the construction details of the offer in accordance with the present invention, can be manufactured piece body, the vehicle of comparable value and reliability with a body part of a vehicle manufactured from double sheet metal, but allowing greatly facilitate the mass of the resulting product.

Case part of the vehicle may be a structural part, proposed according to the present invention, or turn constructional detail, produced according to the present invention, it is which is a hybrid bearing design Cabinet parts of the vehicle.

Case part of the vehicle or structural detail may be made in accordance with traditional manufacturing methods, in which the visible surface of the sheet metal lacquer finish. However, it is cheaper to use another way in which on the visible side of the device has no metal component or sheet metal. Thus it is possible to make the appropriate component in which the metal component is only needed to create the desired strength (stability). This reduces the mass of the products.

To hybrid bearing design can be attached to the covering element. The covering element can be made of plastics material, in particular, formed by injection molding. The covering element can then be covered with a varnish, for example, when the lacquer Cabinet parts of the vehicle together with all the vehicle body; for this purpose can be used as the plastic material of suitable color.

The covering element may also be a structural part with an open metal surface. In this construction details with an open metal surface suitable metal material may be relatively thin, which allows you to make cuts in eastwoodiae body parts of the vehicle, who in appearance does not differ from traditional body parts of the vehicle, but, nevertheless, have less weight. In General, the hybrid bearing structure of Cabinet parts of the vehicle may be inside the product, that is, it may not be visible or partially visible. In particular, the coating can be applied on both sides of the part. When such internal fastening hybrid load-bearing structure of the injection box through the sheet metal material can be made only on the visible areas. Accordingly, the metal component or sheet metal piece hybrid carrier structure may be made in the form of component intended for the manufacture of the visible part of the product. The establishment of the stiffness by elements made by molding a plastic material under pressure, can be carried out only from the side opposite to the visible surface of the product or only in areas that have a floor, which can also be fixed injected patterns. In this case, the sheet material can be located on the outer surface, and the coating is on the inner side of the part. In addition, the sheet material can be located on the inner surface, and the coating is on the outer side of the part. To appropriate castke sheet metal before injectionem plastic material or after injection box, plastic material may be a lacquer finish. If the lacquer is applied before injectionem plastics material, on the treated area, it is useful to apply a protective film which is removed after application of plastic material by molding under pressure or after Assembly of Cabinet parts of the vehicle.

In a plastic structural component parts can be manufactured jacks for connection to other parts. Similar nests can be manufactured in a hybrid carrier structure and/or cover element. In particular, the socket for connection of the respective parts are preferably securely fastened after joining the cover elements to hybrid bearing structure, since it does not require the production of additional fasteners. This is especially preferable to make the contact elements, which, if appropriate to the design of the grooves and/or recesses can create pre-tension in places of fastening parts, so that the fixed parts tightly stand in their designated sockets.

The drawing shows a top view of the structural parts are offered in accordance with the present invention.

The drawing shows a sheet metal (1), in which method an injection molding attached plating (2) roofs, made in the form of a plastic component

1. Structural part including the metal component, a plastic component and a binder system, connecting the metal component and the plastic component, wherein the binder system consists of binders on the basis of plastic or of a binder based on plastics in combination with primer and binder-based plastics is an epoxide, modified by the covalent joining of 1,3-diene, this binder also contains a curing agent.

2. Structural part according to claim 1, characterized in that the binder-based plastic is an epoxy resin manufactured on the basis of bisphenol a and/or bisphenol a and/or bisphenol a and/or bisphenol F.

3. Structural part according to claim 1, characterized in that the binder-based plastic is an epoxy resin manufactured on the basis of simple diglycidylether ether of bisphenol a or epoxyketone of novolak.

4. Structural part according to any one of claims 1 to 3, characterized in that the binder system is modified by the physical insertion of the diene and/or acted upon, in particular rubber.

5. Structural part according to any one of claims 1 to 3, characterized in that the proportion of the diene and/or acted upon in a binder system is from 1 is about 30 wt.%, preferably from 3 to 10 wt.%.

6. Structural part according to any one of claims 1 to 3, characterized in that the binder system further modified alkyl - and/or allmodifications silanes of General formula HO-Si(R)(R')(R"), and the groups R, R' and R" may be the same or some or all groups can be variously modified alkyl and/or aryl groups, and alkyl and/or aryl groups contain functional groups such as COOH, HE, NH2.

7. Structural part according to any one of claims 1 to 3, characterized in that the binder system contains a hardener.

8. Structural part according to any one of claims 1 to 3, characterized in that the binder system contains an additive that increases impact strength.

9. Structural part according to any one of claims 1 to 3, characterized in that the binder system contains a hardener slow motion.

10. Structural part according to claim 9, characterized in that the binder system contains the accelerator hardener slow motion.

11. Structural part according to any one of claims 1 to 3, characterized in that the binder system contains powdered thermoplastic material.

12. Structural part according to any one of claims 1 to 3, characterized in that the binder system comprises a solvent OR, where R represents H, alkyl or aryl, or the solvent is N(R1 )(R2), in which R1=N, R2=H; R1=N, R2=alkyl; R1=N, R2=aryl; R1=R2=alkyl; and/or R1=R2=aryl.

13. Structural part according to any one of claims 1 to 3, characterized in that the plastic component is composed of a plastic material selected from polypropylene, polyamide, blends of polyamide and polyphenyleneoxides, mixtures of polyamide and polystyrene, polyphthalamide, polipropilenonvye and polysulfone.

14. Structural part according to any one of claims 1 to 3, characterized in that the plastic component is a plastic material, reinforced with fiber.

15. Structural part according to any one of claims 1 to 3, characterized in that the specified item includes open (visible) metal surface with metallic luster or having a view of the lacquered surface.

16. A method of manufacturing a structural part including the metal component and the plastic component, comprising the following operations:
a) providing a metal component and a metal component on one or both sides has a coating of pre-utverzhdenii binder system;
b) introducing a metal component having a coating of pre-utverzhdenii binder system, in the mold for injection molding so that the th pre-cured binders facing surface to the free volume of the mold;
c) injection molding a plastic component to a metal component with further curing binder system;
characterized in that, as a binder systems use a binder system of a plastic binder or plastic binder in combination with a primer, and a plastic binder is a complex epoxide, modified by covalent joining 1,3-diene.

17. The method according to item 16, characterized in that prior to the operation (a) on the metal component are coated with a binder system by paint spraying, or coating, dipping, or coating of powder or catalytic coating, dipping, or coating roll coating.

18. The method according to item 16 or 17, characterized in that prior to the operation (a) a binder system is subjected to preliminary curing at a temperature of from 100 to 140°C, during the time from 20 to 40 C.

19. The method according to item 16 or 17, in which the mold is preheated to a predetermined temperature before operation (b) and/or metal component is heated to a predetermined temperature prior to the operation (s).

20. The method according to item 16 or 17, in which the transaction (s) done is give a complete curing binder systems.

21. The method according to item 16 or 17, in which to fully cure the binder system of structural detail after operation (C) is subjected to the operation of the vacation.

22. The method according to item 16 or 17, in which the plastic component is subjected to injection molding to form the coating.

23. The method according to item 16 or 17, in which the plastic component is subjected to injection molding to form the structures stiffness.



 

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7 cl, 2 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to coat and method of coating outer surfaces. Proposed method of coating pipeline outer surfaces by polymer capable of forming cross-links under action of water comprises the following stages: a) pipeline outer surface is coated by, at least, one polymer that forms cross-links under action of water. Note here that said polymer represents HDPE grafted by alkoxy silane. b) Polymer is cross linked on subjecting it to water at increased temperature to produce cross-linked polymer layer unless cross linking degree makes ≥30% to ≤80%. c) Polymer is cross linked that can form cross links under action of water at ≥50°C to ≤350°C, preferably at ≥150°C to ≤300°C, more preferably at ≥200°C to ≤260°C. Note here that during these stages, pipeline is heated to ≥170°C to ≤230°C, preferably to ≥180°C to ≤220°C, more preferably to ≥190°C to ≤210°C. Powder ionic spraying method is used epoxy resin layer is applied with thickness of ≥0.08 to ≤0.16 mm, preferably of ≥0.10 to ≤0.13 mm, more preferably, 0.125 mm. Method of envelopment extrusion is used to apply a layer of glue with thickness of ≥0.15 mm to ≤0.30 mm, preferable of ≥0.22 mm to ≤0.27 mm, more preferably of 0.25 mm. By method of extrusion, applied is upper layer of HDPE with thickness of ≥2.8 mm to ≤3.2 mm, preferably of ≥2.9 mm to ≤3.1 mm, more preferably of 3 mm. Extrusion is used to apply layer of HDPE cross linked by silane with thickness of ≥0.8 mm to ≤1.2 mm, preferably of ≥0.9 mm to ≤1.1 mm, more preferably of 1 mm. Now, pipeline is treated by water with temperature of ≥10°C to ≤40°C, preferably of ≥20°C to ≤30°C, more preferably of 25°C. Coat is made as described above. Invention covers also coated pipeline.

EFFECT: improved operating performances and expanded applications.

11 cl, 2 tbl, 3 dwg, 2 ex

FIELD: process engineering.

SUBSTANCE: invention relates to multilayer metallised biaxially-oriented polypropylene films used for food packing and to method of their production. Said film comprises main layer A made from crystalline home- or copolymers of propylene comprising bonds C2-C10 of alpha-olefine, one top layer B made from propylene copolymer containing 3 to 6 wt % of the bonds of linear C4-C10-1-alkene, and metal layer M applied on the surface of top layer B. Propylene copolymer of layer B has fraction soluble in xylene at 23°C, less than 4.0 wt %, Vick softening point above 135°C indenter depth in Vick test smaller than or equal to 0.05 mm at 120°C. Method of film production comprises co-extrusion of layers A and B, biaxial orienting of co-extruded layer A and B, treatment of top layer B surface and metal deposition on said layer.

EFFECT: multilayer metallised biaxially-oriented polypropylene films with high oxygen and steam barrier properties.

FIELD: process engineering.

SUBSTANCE: invention relates to multilayer metallised biaxially-oriented polypropylene films used for food packing and to method of their production. Said film comprises main layer A made from crystalline home- or copolymers of propylene comprising bonds C2-C10 of alpha-olefine, one top layer B made from propylene copolymer containing 3 to 6 wt % of the bonds of linear C4-C10-1-alkene, and metal layer M applied on the surface of top layer B. Propylene copolymer of layer B has fraction soluble in xylene at 23°C, less than 4.0 wt %, Vick softening point above 135°C indenter depth in Vick test smaller than or equal to 0.05 mm at 120°C. Method of film production comprises co-extrusion of layers A and B, biaxial orienting of co-extruded layer A and B, treatment of top layer B surface and metal deposition on said layer.

EFFECT: multilayer metallised biaxially-oriented polypropylene films with high oxygen and steam barrier properties.

FIELD: personal use articles.

SUBSTANCE: unit of external panels comprises front panel made of transparent polyethylene terephthalate, which forms front surface of refrigerator, back surface of which has printed area with specified colour and/or print, and back surface made of polyvinyl chloride, which is installed on back surface of front panel. Unit of external panels is installed outside refrigerator. Refrigerator door comprises door unit, which comprises external door that forms front surface of refrigerator door, and inner lining of door, which is connected to back surface of outer door, unit of panels, which comprises front panel made of transparent polyethylene terephthalate, forming front surface of refrigerator that has back surface with printed area, which has specified colour and/or print, and back panel made of polyvinyl chloride installed in back surface of front panel. Unit of panels is installed on front surface of refrigerator.

EFFECT: simplified manufacturing of refrigerator.

6 cl, 4 dwg

FIELD: metallurgy.

SUBSTANCE: metal tube has polymer coat with low surface energy. At least a part of said polymer coat is activated. A part of said polymer coat of the mainline constructed by area adjoining each uncoated section has activated surface. Fixation-prone coat with high surface energy is applied on said part with activated surface.

EFFECT: possibility to decontaminate surfaces in-situ prior to erection welding.

25 cl, 8 dwg, 3 tbl, 1 ex

FIELD: metallurgy.

SUBSTANCE: sheet has insulating coating containing composite resin consisting of polysiloxane and polymer containing carbon element. Method involves application of composite resin and burning at temperature of 150 to 350°C till the coating with weight of 0.05 g/m2 to 10 g/m2 is formed.

EFFECT: obtaining the sheet with insulating coating providing high corrosion resistance and formability, which are equivalent to or higher than those properties of chrome-containing insulating coating.

16 cl, 6 tbl, 1 ex

FIELD: process engineering.

SUBSTANCE: method of producing capsule 1 containing drink ingredients to be forced into drink making device wherein fluid is forced into capsule to interact with ingredients and force prepared drink outward. Capsule comprises case 4 with sealing component 8 attached thereto. Proposed comprises step whereat at least one sealing material is injected onto the surface of said case 4 to produce sealing component 8 by injection moulding. Said component is tightly attached to case 4. Case inner space is filled with food ingredients and tightly closed by membrane 5.

EFFECT: better tightness, ease of use.

41 cl, 15 dwg

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