MXPA97006097A - Laminates of plastic / metal improvement - Google Patents

Abstract

Plastic / metal laminates, for example, protective or plastic-coated cable shield tapes having improved friction, adhesion and heat sealing properties, which comprise at least one metallic substrate having directly adhered thereto at least one surface thereof a layer of thermoplastic adhesive containing an amount of etchant sufficient to substantially reduce the coefficient of friction of the laminate and sufficient to emboss the surface of the plastic laminate / met

Description

IMPROVED PLASTIC / METAL LAMINATES This invention relates generally to improved plastic / metal laminates with improved adhesion to various substrates, improved heat sealing capacity and lower Friction Coefficient ("DOF"). The improved plastic / metal laminates of the present invention also exhibit reduced rupture rates and substantially reduced flaking and dusting during the manufacture of cables and other mixed plastic / metal articles formed using the plastic / metal laminates of the present invention. . Additionally, the present invention relates to mixed plastic / metal or laminate articles that can reasonably be expected to be installed and / or in some way used as communication and electrical cables, metal / plastic / metal laminates for potential use. as electrical equipment housings, for heating ducts, in various automotive applications, etc. In the manufacture of cables and other mixed plastic / metal articles formed of various rolled articles involving one or more metallic layers or substrates having one or more layers or coatings of a thermoplastic polymeric material adhered thereto, a "timing" control factor frequent or consideration that regulates its suitability for various end-use applications is the degree by which the plastic / metal laminate can be shaped and formed and the degree of adhesion between the various polymeric and metallic layers in said laminate or mixed articles. Particularly useful for plastic / metal laminates of the present invention are in electric cables In the design and construction of electric cables, especially telecommunication cables such as telephone cables, it is known to assemble insulated conductors or glass fibers in a matrix and surround it by lining and shirt components. The protective lining is often referred to as a "protective lining, screener, protective tape or armor tape". In general, the process by which laminated plastic / metal materials (eg, protective tape or shell) are formed into cables, generally consists of a non-reel stand which supplies the plastic / metal laminate, typically having a width of 1.27 cm to 20.32 cm to a corrugator (if you want cable with uniform finish, the corrugator is drifted). From the corrugator, the plastic / metal laminate is advanced forward to a preformer, a forming tray which initiates the configuration of the laminate in a tube. The preformed laminate is then advanced forward to at least one forming die, at which point the laminate is formed in a tube having overlapped seam. In the die (s) of formation, the die is fed into the plastic / metal tube. From the forming die (s), the plastic / metal tube containing the die is advanced forward in at least one dimensioning die which dimension the plastic / metal tube to the appropriate dimension of the wire wanted. A heating source can be used to promote the adhesion of the overlapped seam. After a jacketed resin is extruded into the plastic / metal tube. After extrusion of the jacket into the plastic / metal tube, the final cable is cooled in a Water bath and it is usually wound in a coil. Depending on the final cable size and type of cable desired, the line speed of this cable manufacturing process can vary from 244 m / min to 91 44 In the present art, normally the energy of the contact surface of the plastic / metal laminate to the surface of the preforming, die (s) of formation and given (s) sizing, is sufficient to cause blocking of the plastic / metal laminate which results in some shaking movement of the plastic / metal laminate as it is pulled out of the cable manufacturing process. The locking and shaking movement occasionally results in the breaking of the plastic / metal laminate. The resulting shaking is due to the narrow clearances of the forming and sizing dies and the normally high COF of the plastic / metal laminates of the present technique since the contact energy of substantial high surface area as the laminate is removed from the plastic / metal through the cable manufacturing process, the surface of the thermoplastic polymer wears out significantly, causing the formation of flakes and dust of the thermoplastic polymer specifically around the preformer, die (s) of formation and die (s) of dimness, but more usually after the given (s) ) dimensionador (es). The resulting dust and flakes can accumulate around the manufacturing process, promoting the reduction of process time. Additionally, there is a corresponding increase in the temperature of the die (s) given as the plastic / metal tube formed is pulled through the dimensioning die (s). In order to decrease abrasion, flaking, dusting, die temperature and rolling rupture rate, a preferred mode of operation in the industry is to apply an oil lubricant to the surface of the plastic / metal laminate before of the preforming operation of the manufacturing process. The intended purpose of the oil lubricant is to decrease the COF of the plastic / metal sheet surface which is brought into contact with the preformer, formation die (s) and dimensioning die (s). However, the use of an oil lubricant can sometimes substantially reduce the adhesion performance of the plastic / metal laminate to the jacket component as well as reduce adhesion in the lap seam. The use of an oil lubricant can also sometimes cause some guiding problems between the plastic / metal laminate and the affected process surfaces. Therefore, there is a need in the industry for plastic / metal laminates that exhibit reduced rupture regimes, exhibit flake and reduced powder formation, maintain or increase adhesion to jacket components and maintain or increase adhesion at the seams of overlap while substantially eliminating or reducing the amount of oil lubricant necessary during manufacture in articles such as electric cables. The present invention substantially solves the problems of abrasion, flaking, dusting and rupture of plastic / metal laminates (e.g. , plastic coated cable protection tapes) during the forming and forming of these laminates into cables and other plastic / metal articles formed while reducing or substantially eliminating the need to use an oil lubricant. In general, the Applicant has found that these problems are solved substantially incorp by praying in the plastic layer of the plastic / metal laminate, a sufficient embossing amount to substantially reduce the coefficient of friction of the laminate and to emboss the surface of the plastic layer When it is formed and incorporated into mixed articles of plastic / metal of the present invention also exhibit improved heat sealing capability and adhesion to external jacket components. Accordingly, in one aspect the present invention is a plastic / metal laminate comprising a metal substrate and, at least, a surface layer adhered to said substrate either directly or via an intermediate polymer layer or layers, said surface layer essentially consisting of a base adhesive polymer or polymer mixture and an amount of embossing sufficient to substantially reduce the coefficient of friction of the laminate and sufficient to emboss said surface layer. In another aspect, the present invention is a more finished plastic / metal composite article, such as an electrical or communication cable, comprising a matrix of at least one insulated conductor or fiberglass, a cover surrounding said matrix and an outer plastic jacket that surrounds and adheres to said cover, said cover comprising: a metal substrate; a surface layer adhered to said metal substrate either directly or via an intermediate polymer layer or layers, said surface layer consisting essentially of a base adhesive polymer or polymer mixture and a relief embosser, wherein said protective cover exhibits a resistance to the top joining of said outer plastic jacket in relation to a similar cover differing only in the absence of the embossing of said cover and wherein said cover exhibits higher values of heat sealing in relation to a similar protective cover that differs only in the absence of a relief engraver of said protective cover. Figure 1 is a graphical representation of heat seal capability test results for embodiments of the present invention. In one embodiment, the present invention is a single layer or multiple layer thermoplastic adhesive system. The adhesive systems of the present invention contain at least one layer consisting essentially of a base adhesive resin and an amount of embossing sufficient to reduce the coefficient of friction ("COF") of the adhesive system and sufficient to emboss the adhesive system. Generally, the adhesive systems of the present invention have a thickness of 2.54 μm to 127 μm. Adhesive systems with a thickness of 5.08 μm to 127 μm are preferred, and adhesive systems with a thickness of 145.4 μm to 63.5 μm are preferred. Another embodiment of the present invention is a plastic / metal laminate formed by applying adhesive systems of the present invention to one or both sides of a metal substrate in the form of a strip or tape. Adhesive systems are applied via techniques well known in the art (eg, extrusion coating or lamination). Generally, the plastic / metal laminates of the present invention have a thickness of 50.8 μm to 635 μm and preferably, of 101.6 μm to 381 μm. Yet another embodiment of the present invention is a mixed structure comprising a matrix component, a protective component surrounding the matrix and a thermoplastic jacket component surrounding and adhering to the cover component, wherein the protective cover component consists of essentially of a plastic / metal laminate of the present invention. The adhesive systems of the present invention must be capable of adhering to both the metal substrate of the plastic / metal laminate and the jacket component of any mixed article in which the laminate can be incorporated. In a multi-layer adhesive system, the outer or surface layer (ie, the layer to be bonded to the jacket component) must contain the required amount of the embossing apparatus required. In a multi-layer adhesive system, layers other than the surface layer do not necessarily contain embossing and may comprise the base adhesive resin the same or different than the surface layer. The thermoplastic polymers suitable for use in the base adhesive resin of the present invention ("base adhesive polymers") are generally those known in the art for producing laminates useful for making communication cables. Preferred base adhesive polymers include the commonly known solid random copolymers of a higher proportion of ethylene with a minor proportion (eg, usually from 1 to 30, preferably from 2 to 20 weight percent based on the weight of said copolymer) of an ethylenically unsaturated carboxylic acid monomer. Specific examples of said suitable ethylenically unsaturated carboxylic acids (the term of which includes mono and polybasic acids, acid anhydrides and partial esters of polybasic acids, as well as the different metal salts thereof) are acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid itaconic acid. maieic anhydride, monometic maleate. monoethyl monoline fumarate, monoethyl fumarate, tripropylene glycol monomethyl ether acid maleate, or ethylene glycol monophenyl ether acid moleate. The carboxylic acid monomer is preferably selected from alpha / beta-ethylenically unsaturated mono and polycarboxylic acids and acid anhydrides having from 3 to 8 carbon atoms per molecule and partial esters of said polycarboxylic acid the acid portion, has at least a carboxylic acid group and the alcohol moiety have from 1 to 20 carbon atoms. Said copolymers may consist essentially of ethylene and one or more said ethylenically unsaturated anhydride or anhydride or may also contain a small amount of another monomer copolymerizable with ethylene. Therefore, the copolymers may contain other copolymerizable monomers including esters of acrylic acid, methacrylic acid and the like. The random copolymers of said type and method for forming them are easily known in the art.

Other thermoplastic polymers suitable for use in the present invention include the known olefin polymers which are, as a rule, the ethylene olefin polymers such as, for example, the various known ethylene homopolymers (e.g., ultra low density polyethylene). , linear low, low, medium, high, having a density scale of 0.82 to 0.96 g / cm2), copolymer having a higher proportion of ethylene with a lower proportion of known copolymerizable monomers such as higher alpha olefins (e.g. from C3 to C12). ethylenically unsaturated ester monomers (eg, grafted with acrylic acid, maleic anhydride, etc.). Olefin polymers, copolymers of said type and chemically modified olefin and copolymers of said type and method for forming them are readily known in the art. In one embodiment of the present invention, the base adhesive resin is a mixture of (a) a random copolymer of ethylene with an ethylenically unsaturated carboxylic acid monomer with (b) at least one ethylenic olefin homopolymer and a copolymer of a Ethylene olefin polymer resin is not an ethylene / random unsaturated carboxylic acid copolymer. Preferably, the base adhesive resin comprises from 5 percent to 95 percent of (a), more preferably from 50 percent to 95 percent and even more preferably from 6 percent to 95 percent, based on the weight of the adhesive base resin. Preferably, the base adhesive resin also comprises from 0 percent to 95 percent of (b), more preferably from 0 percent to 50 percent, and even more preferably from 5 percent to 20 percent, based on weight of the base adhesive resin. In addition, it should be understood that when reference is made to "Random copolymers of ethylene with an ethylenically unsaturated carboxylic acid", is intended to include with it the partially or completely neutralized known versions thereof, which are commonly referred to in the art as "lonomers". it should be understood that when the "ethylene olefin homopolymer or a copolymer of an ethylenic olefin polymer resin which is not an ethylene / random unsaturated carboxylic acid copolymer" salt being referenced, it is intended to include ethylene olefin polymers which can be modified by copolymerization or graft copolymerization techniques employing an ethylenically unsaturated dicarboxylic acid anhydride or anhydride precursor, esters of an ethylenically unsaturated dicarboxylic acid and modified rubber derivatives thereof Generally, the embossers in the present invention are known from some way in the technical ica as organic or inorganic fillers. Embossing etchers suitable for use in the present invention are desirably non-compatibilized, chemically inert and insoluble in the base adhesive polymers. Being non-compatibilized refers to a substantial lack of chemical bonding (eg, polymeric) bonding with the base adhesive polymers and preferably such a deficiency with respect to any other substance in the film, being chemically inert refers to a substantial inability to dissolving the base adhesive polymers, or preferably any other component in the base adhesive resin. Being insoluble refers to the substantial inability to dissolve in the base adhesive polymers to a degree such that the physical integrity of the embossed surface is substantially maintained.

The amount of embossing should be sufficient to substantially reduce the COF of the plastic / metal laminate and to emboss the surface of the plastic / metal laminate. By embossing the surface of the plastic / metal laminate, it is understood that there are reliefs on the surface that vary in height from 1/100 to V * of the thickness of the adhesive layer (s). The larger reliefs result in a very rough surface and adversely affect film strength and other properties. Smaller reliefs are generally less effective in reducing the COF of the plastic / metal laminate. Embossing of the surface was evaluated herein by measuring the difference in contact measurements of the thermoplastic polymer as defined in ASTM D374 and measurement in weight of the thermoplastic polymer as defined in ASTM E252. Preferably, the surface layer contains from 0.1 weight percent to 16 weight percent embossed etchant, more preferably from 2 weight percent to 16 weight percent and even more preferably from 4 weight percent to 8 percent in weigh. Examples of organic embossing ethers suitable for use in the present invention include particulate polyesters. polytetrafluoroethylene ("PTFE"), nylon, polystyrene. high impact polystyrene ("PEAP"), styrene-acrylonitrile (EAN "), acrylonitrile-butadiene-styrene (" ABE "), polycarbonate, etc. Inorganic relief engravers include mica gis particulate graphite, calcium sulfate, calcium silicate, calcium carbonate, talc, bentonites, barytes, kaolin, aluminum and magnesium silicates, magnesium silicate, mineral colloids, pyrophyllite, septa, silicas, gypsum, etc. The preferred embossing engravers are not compatible, non-hygroscopic and not microporous forming in the base adhesive polymers A more preferred embossing is mica, which has the ability to not only effectively impart a uniform embossed surface to the plastic / metal laminate, but also to improve the adhesion properties of the plastic / metal laminate. Substantially decrease the COF of the plastic / metal laminate, it is understood that both the resulting static or starting COF as kinetic or slip COF The result is less than the static COF and kinetic COF of an essentially identical plastic / metal laminate that differs only by the absence of any embossing recorder. The static and kinetic COF's of the plastic / metal laminate were measured using a modified ASTM D1894 (see Example 11) Preferably, the static COF of the plastic / metal laminate is at most 040, more preferably when much of 030, and even more preferably, as much as 020 as measured by the modified ASTM D1894 The plastic / metal laminates of the present invention exhibit improved adhesion. The adhesion properties were evaluated by measuring the plastic / metal laminate release strength according to a modified ASTM B736 (See Example li) The adhesion of the plastic / metal laminate to Materials commonly found in protective jacket components were measured using a modified ASTM 1876 (See Example V). In addition, it should be understood that when improved adhesion is referred to herein, adhesion is understood to be improved in relation to adhesion. observed when using essentially ethylenic plastic / metal laminates or mixed articles differing only in the absence of a relief embosser. Preferably, the adhesive bond strength between the layers of a multilayer adhesive system of the present invention is at least 8929 μm, more preferably at least 142 86 kg / m and even more preferable of at least 21,430 kg / m as measured by the modified ASTM B736 Preferably, the adhesion between a coating layer (i.e., such as an outer insulating jacket layer on an electric cable) and plastic / metal laminates of the present, at least 14286 kg / m, more preferably 17858 kg / m and even more preferably, at least 16787 kg / m measured by the modified ASTM 1876 The thickness of metal substrates (eg, sheets, strips, sheets, etc.) used in the present invention is not critical Sheets of less than 254 μm can also be used as relatively thick sheets Normally, metal substrates have a thickness of 76 2 μm to 655 00 μm and preferably 101 60 μm to 381 00 μm The metallic substrate can be composed of a wide variety of metallic materials such as, for example, aluminum, aluminum alloys, coated aluminum alloy, copper, copper with modified surface, steel bronze, tin-free steel, tin-plated steel, aluminized steel, aluminum-coated steel, stainless steel, copper-clad stainless steel, low-carbon steel coated with copper, tin / lead alloy steel and silver, galvanized steel , steel plated with chromium or treated with chromium, lead, magnesium, tin and the like Said metals, of course, may have treated surface or have conversion coatings on the surface thereof, if desired The metal substrates particularly preferred for use in the present include those compounds of chrome-coated steel / chromium oxide (also commonly known in the art as tin-free steel), stainless steel, aluminum and copper. The adhesive systems of the present invention can be applied to metal substrates in any form desirable that could be desired For example, conventional extrusion coating techniques are p They can be used to apply the adhesive system to the chosen metal substrates. Alternatively, conventional film lamination techniques can also be suitably employed to adhere to a film system of adhesives to the desired metal substrate. A combination of coextrusion technologies can also be used. conventional film lamination For example it may be convenient to first extrude or co-extrude an adhesive system such as a film and laminate the film to one or two surfaces of a metal substrate. EXAMPLES The present invention is further illustrated, but it is not understood that it is in any way limited to the following examples. In one of the following examples, all parts and percentages are based on weight unless otherwise indicated. Example 1 In this example, adhesive films of a 40.64 μm thick layer were created. The adhesive film contained a mixture of a base adhesive resin and Micafil 40 (a mixture containing 40 percent by weight high density polyethylene and mica)., available from DuPont Canada). The base adhesive resin was a mixture of a random ethylene / acrylic acid copolymer ("EAA") and an olefin polymer. The EAA copolymer contained 6 weight percent acrylic acid based on the weight of the copolymer and had a melt index of 5.5. The olefin polymer used was a polyethylene having a melt index of 5.5 and a density of 0.916 g / cm 3 ("HDPE-1"). The amounts of EAA, LDPE-1, HDE-1 and Micafil 40 used in various samples as shown in Table 1. The different film samples were laminated on one side of a 190.5 μm thick aluminum sheet. In the preparation of said samples, the indicated monolayer film was laminated by preheating the metal for one minute in an air circulation oven heated to 148.89 ° C. The resulting post-heated laminate was allowed to equilibrate in air at 22.78 ° C having a relative humidity of 50 percent for at least 12 hours before any testing was performed. The resulting laminate samples were cut using pieces of a mixed material at 6.99 cm by 10.16 cm, with the largest dimension in the machine direction. Sheet samples were subjected to coefficient of friction (COF) test in accordance with ASTM D1894 (except 12.7 cm per minute cross-linked speed, a 200 gram load cell, a # 7 gloss stainless steel plate High, and a 1 kg sled were used, the conditioning is at least 12 hours in air of relative humidity at 50 percent at 22.78 ° C, and the test is carried out on at least 5 specimens of test) under normal constant laboratory conditions. The results of the COF test are shown in Table 1. TABLE I%%%% Static Kinetic Example # E E..AA..AA L LDDPPEE - 11 HDPE-1 Micafil 40 COF COF 91.00 5.00 0.5429 0.5257 1-2 40.00 56.00 0.3320 0.3120 I-2 67.20 16.80 12.00 0.2313 0.2099 I-3 60.80 15.20 20.00 0.2005 0.1696 I-4 5880 2520 1200 0 1757 0.1518 I-5 53.20 2280 20.00 0.1796 0.1532 I-7 46.20 19 80 30.00 0.1449 0.1289 I-8 55.20 10 80 30.00 0.1428 0.1359 I-9 79.00 5.00 12.00 0.3400 0.3150 1-10 71.00 5.00 20.00 0.2727 0.2509 1-11 61.00 5.00 30.00 0.1940 0.1657 1-12 94.00 2.00 0.4520 0.4152 1-13 84.00 12.00 0.3300 0.3150 1-14 76.00 20.00 0.2795 0.2572 * The remainder of the film composition contained approximately equal weight percentages of antiblocking agent and heat stabilizing / antioxidant agent. A sample was created and tested in the same manner as the previous examples except that the mica was not incorporated into the adhesive film used to make the laminates. The results in Table 1 show that laminates using relatively high levels of high density polyethylene exhibit reduced COF values relative to the COF values exhibited by the control (Sample 1-1 vs. control). However, the results in Table I also show that the addition of mica in the sample laminates results in more significant reductions in COF values. EXAMPLE II The laminates were prepared in the same manner as the laminates in Example I. In addition to the olefin polymers used in Example I (ie, LDPE-1 and HDPE-1), an additional low density polyethylene was used. , which has a melt index of 1.9 and a density of 0.926 g / cm2 ("LDPE-2"). Laminates were cut into samples that were 2.54 cm wide by 15.24 cm, with the largest dimension in the machine direction. Samples were tested for 90 ° heat seal capacity in accordance with ASTM B736 (except that a cross rate of 30.48 cm per minute, a 25 kg loaded cell, a heat seal temperature of 148.89 ° is employed. C, a heat sealing pressure of 275790.4 Passes, a dilation time of 2 seconds, the conditioning is at least 5 minutes in air with relative humidity at 50 percent at 22.78 ° C and the test is carried out in, At least 5 test specimens, under normal laboratory conditions For comparison purposes, a control sample was created and tested in the same way as other samples, the control did not contain either HDPE-1 or Micafil 40. The results of heat sealing capacity test for each sample are shown in Table II.

TABLE II *%%%%% Sell to Sell to Heat Heat Example # EAA LDPE-1 LDPE-2 HDPE-1 Micafil 40 Max Prom ika / m, (kq / m) 91 00 5 00 11-1 40 00 56 00 18 54 1745 II-2 67 20 16 80 12 00 10343 6041 eleven - . 11 - 3 60 80 15 20 20 00 96 15 4627 II-4 58 80 25 20 12 00 73 27 3588 II-5 53 20 22 80 20 00 89 70 3720 II-6 40 00 54 00 2 00 17 84 17 18 II-7 40 00 44 00 12 00 27 32 2466 II-8 40 00 36 00 20 00 31 56 3075 II-9 61 00 30 00 42 93 3761 11-10 94 00 500 2 00 10184 86 02 11-11 84 00 12 00 73 74 49 77 11-12 76 00 20 00 16794 14794 * The remainder of the film composition contained approximately equal weight percentages of antiblocking agent and heat stabilizing agent / antioxidants. The results in Table II show that the addition of a relatively high level of high density polyethylene in a mixture with EAA It significantly reduces the adhesion properties of the sample compared to the control sample. Furthermore, it is observed that the addition of mica in mixtures with low density and high density polyethylene can also substantially reduce the adhesion properties of the laminate. However, given the proper balance of mica and high density polyethylene in blends (eg, via Micafil 40) with the random ethylene / carboxylic acid copolymer, the best significant in adhesion properties with heat sealing capability can be obtained compared to the control laminate (for example, 11-12 vs control). Example III Samples were prepared and tested in a manner similar to the samples in Examples I and II. In addition, the adhesive film used to prepare the samples was a two-layer adhesive film with 58.42 μm thickness, each layer having an equal thickness. The adhesive film was prepared by a conventional film casting process opposite to the film blowing process. For comparison, a control sample was prepared using a layer film of 58.42 μm in thickness. Each sample in Example II had a layer in contact with the metal having the same composition as the control. The composition of the other layer (surface layer) in each sample is shown in Table III. The samples were tested in the same manner as the samples in Examples II and II 6 and the test results are also shown in Table III.

TABLE *%%%% Static Kinetic Sell. Sell. al Example E.A.A LDPE-1 HDPE-1 Micafil COF COF Heat Heat # 40 Max. Prom. (Kq / m) (ka / m) 91. 00 5.00 0.7834 0.7386 273.23 116.43 111-1 45.60 30.40 20.00 0.1900 0.1734 170.72 141.08 III-2 57.60 38.40 0.6150 0.6064 237.87 140.19 III-3 45.60 30.40 20.00 0.3015 0.3440 118.04 92.33 III-4 57.60 38.40 0.4375 0.2773 176.26 101.25 III-5 91.00 5.00 0.4235 0.4356 263.94 121.61 III-6 45.60 38.40 12.00 0.2682 0.2764 159.29 110.54 III-7 76.00 20.00 0.2934 0.2595 255.01 233.23 III-8 45.60 38.40 12.00 0.4398 0.3788 191.26 88.93 III-9 72.33 10.46 13.21 0.1900 0.1700 239.30 179.47 111-10 57.41 24.38 14.21 0.1200 0.1080 202.33 160.19 * The balance of the surface layer composition contained approximately equal weight percentages of antiblocking agent and heat stabilizing / antioxidant agent. Example IV Two groups of samples were prepared in the same manner as the samples in Example III. The samples in one group had a thickness of 40.64 μm and the samples in the other group had a thickness of 58.42 μm. Each group of samples contained samples made in accordance with both Sample 11 I-control and Sample III-7. Samples were cut into 2.54 cm and 15.24 cm pieces with the longest dimension in the machine direction. The samples were subjected to heat sealing test according to the same modified ASTM B736 of Example III (except that the heat seal temperatures of 102.22 ° C, 127,775 ° C, 148.89 ° C, 178.885 ° C and 204.44 were employed. ° C). The results of these tests were graphically described in Figure 1. From the results described in Figure 1, it is observed that a substantial improvement in heat sealing capacity was achieved at low temperatures of heat sealing capacity. The results in Figure 1 also show that the thickness of the samples has very little effect, if any. Example V Samples were prepared in the same manner as the samples in Example III except that the two-ply adhesive film had a total thickness of 40.64 μm instead of 58.42 μm to test adhesion to normal protective jacket materials. , these samples were compression molded into two different groups of sheets of 1 905 μm polyethylene thickness to form mixed structures. The first group of sheets was prepared from a high density polyethylene (UC3479 available from Union Carbide) and the second group of sheets was made from a medium density polyethylene (UC8864 available from Union Carbide). Both groups of sheets also contained approximately 2.6 weight percent carbon black. In the compression molding operation to form these mixed structures, a platinum press was employed. The laminar samples were placed in contact with the sheets in the press and compression molding was achieved at 230 ° C and 103421.4 Passes for three minutes. The resulting mixed structure was then cooled to room temperature in the plated press, removed from the press and subsequently cut into strips 2.5 cm wide by 15.24 cm with the largest dimension in the machine direction.

Some of the resulting strips were then subjected to 180 ° peel-off with reinforcement plate test according to ASTM D1876 (except that a cross rate of . 08 cm per minute, a load cell of 25 kilograms, the conditioning is for 12 to 48 hours in air with relative humidity at 50 percent at 22.78 ° C, the unit and unbound lengths of this polymer layer are 6.35 cm and of 1.25 cm respectively and the test was carried out in at least 3 specimens of preuba instead of ten). Other strips were immersed (ie, "aged") in water at 60 ° C for 7, 30, 60 and 120 days, allowed to equilibrate and dried in air at 22.78 ° C with 50 percent relative humidity, during the night and then also underwent the 180 ° detachment test mentioned above.

For comparison purposes, a control sample was prepared and tested in the same manner as other samples except that the adhesive film used was a layer film of 58.42 μm thickness. The release test results for each sample were shown in Table V-A for the HDPE-2 sheets and Table V-B for the MDPE sheets. As can be seen from the results in Table V-A and Table V-B, the Examples of the present invention exhibit improvements in aged adhesion. TABLE V-A ADHESION OF HDPE SHIRT ENCLACE (kg / m) *%%% Dep. Desp. Desp. Desp. Desp.

Sample EAA LDPE-1 Initial Micafil 7 days 30 days 60 days 120 days 40 control 91.00 5.00 13.46 16.12 17.03 16.91 17.00 V-A-1 75.60 8.40 12.00 11.58 20.65 20.90 20.89 20.90 V-A-2 58.80 25.20 12.00 11.68 18.08 19.15 18.67 19.00 * The balance of the surface layer composition contained approximately equal percentages by weight of anti-blocking agent and heat stabilizing agent / antioxidant.

TABLE V-B ADHESION OF MDPE SHIRT ENCLACE (kg / m)%%% Dep. Desp. Desp. Desp. Desp.

Sample EAA LDPE-1 Initial Micafil 7 days 30 days 60 days 120 days 40 control 91.00 5.00 13.77 15.29 16.29 16.27 16.20 VB-1 75.60 8.40 12.00 11.92 19.71 21.81 21.83 21.80 VB-2 58.80 25.20 12.00 12.35 18.49 18.88 18.33 18.25 The balance of the surface layer composition contained approximately approximately equal weight percentages of anti-blocking agent and heat stabilizing agent / antioxidant Example VI In this example, the laminates were prepared in the same manner as Example III. The resulting laminates were slotted to a strip with a width of 4.29 cm and were configured and formed into electrical or communication cables using a conventional cable manufacturing process as described in this application. The laminates used to form the cables are shown in Table VI-A and some resulting cable processing data are shown in Table VI-B. TABLE VI TO ADHESION OF HDPE SHEET LACE (kg / m) * Superfi- Sample%%%% COF No. EAA LDPE-1 HDPE-1 Static Kinetic Laminar Micafil 40 control 91.00 5.00 0.7834 0.7386 smooth VI-1 57.60 38.40 0.4136 0.2814 smooth VI-2 58.80 25.20 12.00 0.2700 0.2800 in relief VI-3 67.20 16.80 12.00 0.3200 0.2400 in relief VI-4 76.00 20.00 0.2600 0.2200 in relief * The balance of the surface layer composition contained approximately equal percentages by weight of anti-blocking agent and heat stabilizing agent / antioxidant. From the results in Table Vl-B, it is noted that substantial improvement in the manufacture of plastic / metal laminates in electrical and / or communication cables can be achieved with laminates of the present invention. While the present invention has been illustrated herein by reference to particular embodiments and examples thereof, said fact is not to be understood as limiting in any way to the scope of the present invention.

TABLE Vl-B Sample Vel. line use of temp breaks. final Num. Of lubricant cable of flakes and tapes in (° C) in given meters / min oil powder in point of dimensiona- formadores and welding dor dyes control 40 no yes yes 29.44 50 no yes yes 30 60 no if yes 31.11 control 40 yes yes 25 50 yes yes yes 25.56 60 yes yes yes 26.11 VI-1 40 no yes no 27.78 50 no yes no 27.78 60 no yes no 28.35 VI-2 40 no no no 28.89 50 no no no 27.22 60 no no no 27.22 VI-3 40 no no no 26.67 50 no no no 26.67 60 no no no 26.67 VI-4 40 no no no 27.22

Claims (14)

1. CLAIMS 1. A laminate comprising: a) a metal substrate: b) a surface layer adhered to said substrate either directly or via an intermediate polymer layer or layers; said surface layer consisting essentially of a base adhesive resin and an amount of embossing sufficient to substantially reduce the coefficient of friction of the laminate and sufficient to emboss said surface layer. A laminate according to claim 1, wherein the laminate has a maximum seal with heat of at least 89.29 kg / m and a seal with average heat of at least 89.29 kg / m. 3. A laminate according to claim 1, wherein the laminate has a maximum heat seal of at least 142.86 kg / m and an average heat seal of at least 142.86 kg / m. A laminate according to claim 1, wherein the base adhesive resin consists essentially of a mixture of (a) a random copolymer of ethylene with an ethylenically unsaturated carboxylic acid monomer with (b) at least one homopolymer of ethylenic olefin or a copolymer of an ethylenic olefin polymer resin that is not an ethylene / random unsaturated carboxylic acid copolymer. A laminate according to claim 4, wherein the ethylene olefin polymer resin is selected from the group consisting of ethylene homopolymers and copolymers having a higher proportion of ethylene with a minor proportion of a comonomer which is polymerizable and or it reacts with it. 6. A laminate according to claim 1, wherein the ethylene olefin polymer is a high density polyethylene. 7. A laminate according to claim 1, wherein the embossed engraver is mica. 8. A plastic / metal laminate, comprising: a) a metal substrate; b) an intermediate thermoplastic polymer layer adhering to at least one surface of said metal substrate, said intermediate layer comprising a random copolymer of ethylene with an ethylenically unsaturated carboxylic acid monomer; c) a surface layer adhered to said intermediate layer, consisting essentially of: i) a random copolymer of ethylene with an ethylenically unsaturated carboxylic acid monomer; ii) at least one olefin polymer resin which is not a random copolymer of ethylene with an ethylenically unsaturated carboxylic acid monomer: iii) an amount of etchant sufficient to substantially decrease the coefficient of friction of the laminate and sufficient to record in relief said surface layer. 9. A laminate according to claim 8, wherein the laminate has a maximum seal with heat of at least 89.29 kg / m and an average heat seal of at least 89.29 kg / mm. 10. A laminate according to the rievindication, where the laminate has a maximum seal with heat of at least 142.86 kg / m and an average heat seal of at least 142.86 kg / m. A laminate according to claim 8, wherein the ethylenic olefin polymer resin is selected from the group consisting of ethylene homopolymers and copolymers having a higher proportion of ethylene with a minor proportion of a comonomer that is polymerizable and / or is reacted with it. 12. A laminate according to claim 8, wherein the ethylene olefin polymer is a high density polyethylene. 13. An article comprising a matrix of at least one insulated conductor, a protective covering surrounding said matrix and an outer plastic jacket surrounding and adhering to said protective cover, wherein said protective cover consists essentially of a laminate according to any claim 1 or claim 8. 14. An article according to claim 13, wherein the resistance to bonding said protective cover to said outer jacket is at least 142.86 kg / m.