CN1173845A - Improved plastic/metal laminates - Google Patents

Abstract

Plastic/metal laminates (for example, plastic-coated cable shielding or armoring tapes) having improved friction, adhesion, and heat-sealability properties which comprise at least one metallic substrate having directly adhered to at least one surface thereof a thermoplastic adhesive layer containing an amount of embosser sufficient to substantially lower the coefficient of friction of the laminate and sufficient to emboss the surface of the plastic/metal laminate.

Description

Improved Plastic/Metal Laminates

The present invention relates broadly to improved plastic/metal laminates wherein the material has improved adhesion to various substrates, improved heat sealability and has a lower coefficient of friction ("COF"). The use of the improved plastic/metal laminates of the present invention also exhibits low breakage rates and a substantial reduction in debris and dust in the production of electrical cables and other shaped plastic/metal composite articles. In addition, the present invention relates to plastic/metal composite articles or laminates, which are expected to be suitably installed and/or used in wireline telecommunication cables, and potentially used in the manufacture of electrical instrumentation housings, heat transfer conduits , and metal/plastic/metal laminates for various automotive applications.

Production of electrical cables and other shaped plastic/metal composite articles from various laminates comprising one or more metallic layers or substrates to which one or more coating layers of thermoplastic polymer material are adhered on metal substrates. Often controlling factors or considerations for suitability for various applications are the extent to which the plastic/metal laminate may be molded and formed and its use in laminated or composite articles between the various polymer layers and the degree of adhesion between the metal layer.

A particularly useful use of the plastic/metal laminates of the present invention is in electrical cables, in the art of designing and constructing electrical cables, especially in telecommunications such as telephone cables. It is known to assemble insulated conductors or glass fibers in the core part and surround it by the sheath and jacket parts. The protective layer portion is often referred to as "protective screen, protective tape or armor tape".

The production process for cables generally made of plastic/metal laminates (e.g., protective tape or armor tape), usually delivered by an unwinding device, typically 0.5 inches (1.27 cm) in width ) to 8.0 inches (20.32 cm). The conveyed material enters the corrugation mill (if smooth coated cable is required to be produced, it does not have to go through the corrugation mill). After the corrugator, the plastic/metal laminate enters a pre-press or forming channel, where the laminate begins to form a tube, and then the preformed laminate enters at least one forming die, where a jointed joint is formed. tube. In the forming die, the cable core is fed into the formed plastic/metal tube, and then the plastic/metal tube containing the cable core enters at least one compression die, where the plastic/metal tube is pressed into the appropriate size cable as required. Use a heat source to promote bonding at the joints. Next a jacket resin is extruded onto the plastic/metal tube. Afterwards, the finished cable is cooled in a water bath and typically wound on a reel. Depending on the type and size of cable required, the production speed of the cable production line can range from 8 ft/min (2.44 m/min) to 300 ft/min (91.44 m/min).

According to the current typical process, the contact surface energy of the plastic/metal material to the surface of the pre-press, forming die and pressing die is enough to cause the laminated material to be blocked, which occurs when the plastic/metal laminated material is pulled during the cable production process. The jerking action, this jamming and jerking action can sometimes cause breakage of the plastic/metal laminate. This jamming and resulting jerk action is believed to be due to the tight clearances of the forming and compression dies in the current art and the typical high friction relationship of the plastic/metal laminates used in the current art. Due to the rather high surface contact energies that exist when the plastic/metal laminate is pulled during cable production, the surface of the thermoplastic polymer is significantly abraded and causes fragmentation and dusting of the thermoplastic polymer, especially during pre-compacting Around the machine, forming dies and press dies, but more typically after the press dies. The resulting debris and dust can accumulate during the production process, forcing the production process to shut down. In addition, when the formed plastic/metal is drawn through the die, the temperature of the die increases considerably.

In order to reduce wear, fragmentation and dusting, reduce the temperature of the mold and the proportion of laminate fracture. The industry preferred method of operation is to apply a lubricating oil to the surface of the plastic/metal laminate prior to the preforming operation of the production process. The intended purpose is to reduce the coefficient of friction of plastic/metal laminate surfaces in contact with various molds. However, the use of lubricating oils sometimes greatly reduces the adhesion properties between the plastic/metal laminate and the casing components and reduces the adhesion at the joint. The use of lubricating oils also sometimes causes control problems between the plastic/metal laminate and the affected operating surface.

Accordingly, there is a need in the industry for a plastic/metal material that exhibits a low rate of breakage, low fragmentation and dusting, maintains or improves adhesion to jacket components, maintains and improves joint adhesion, and at the same time In the production process such as cable products, the amount of lubricating oil must not be used or greatly reduced.

This invention has actually solved the problem of abrasion, fragmentation, dusting and breakage of plastic/metal laminates such as protective tapes for plastic jacketed cables when we mold these laminates into cables, At the same time, the use of lubricating oil is greatly reduced or eliminated. In summary, the applicants of the present invention have discovered that these problems can be substantially solved by incorporating something into the plastic layer of the plastic/metal laminate. Incorporating a sufficient amount of embosser can greatly reduce the coefficient of friction of the laminate and emboss patterns on the surface of the plastic layer. The plastic/metal laminates of the present invention also exhibit improved heat sealability and adhesion to the outer jacket components when formed and assembled into plastic/metal composite articles such as electrical cables.

Thus, in one aspect the invention is a plastic/metal laminate comprising a metallic substrate and at least one surface layer adhered directly or via one or more intervening polymer layers onto the above substrate. The above-mentioned surface layer is basically composed of a basic adhesive polymer or a mixture of polymers and an appropriate amount of embossing material. Embossed flowers on the surface.

In another aspect, the present invention is a more complete plastic/metal composite article, such as an electric or telecommunication cable. A cable core comprising at least one insulated conductor or glass fiber, a protective layer surrounding said cable core and an outer plastic sleeve surrounding and adhered to said protective layer. The above-mentioned protective layer comprises: a metal substrate; a surface layer adhered to the above-mentioned metal substrate directly or through one or more intermediate polymer layers; the above-mentioned surface layer is basically composed of a The base adhesive polymer or polymer blend and an embossing material. The protective layer mentioned here exhibits a greater bond strength to the outer plastic sleeve relative to a similar protective layer, the only difference being the absence of embossing material. The protective layer mentioned here exhibits a greater heat seal value than a similar protective layer, the only difference being the absence of embossing material.

Fig. 1 is a graphical representation of the results of a heat-sealability test in an embodiment of the present invention.

One embodiment of the present invention is a single layer or multilayer thermoplastic adhesive system. The adhesive system of the present invention comprises at least one layer consisting essentially of a base adhesive resin and an amount of embossing material sufficient to reduce the coefficient of friction of the adhesive system and to compress the adhesive system. flower. Typically, the adhesive systems of the present invention have a thickness of 0.1 mil (2.54 microns) to 5 mils (127 microns). Preferred adhesive systems have a thickness of 0.2 mil (5.08 microns) to 5 mils (127 microns), and most preferred adhesive systems have a thickness of 1 mil (25.4 microns) to 2.5 mils (63.5 microns).

Another embodiment of the invention is a plastic/metal laminate formed by applying the adhesive system of the invention to one or both sides of a metal substrate in sheet or strip form. The present adhesive system can be applied by techniques known in the art (eg extrusion coating or lamination). Typically, the plastic/metal laminates of the present invention have a thickness of 2 (50.8) to 25 mils (635 microns), preferably 4 (101.6) to 15 mils (381 microns).

Yet another embodiment of the present invention is a composite structure comprising a cable core component, a sheath component surrounding the cable core and an outer thermoplastic sleeve component surrounding and adhering on the protective layer components. The protective layer component here essentially consists of the plastic/metal laminate according to the invention.

The bonding system of the present invention must be capable of bonding to the metal substrate of the plastic/metal laminate and to the outer casing component of any composite article so that the laminate formed will be integral. In a multilayer adhesive system, the outer or face layer (ie, the layer that adheres to the outer sleeve component) must contain the required sufficient amount of embossing material. In a multilayer adhesive system, the layers other than the face layer need not contain embossing material, but may contain any of the same or different base adhesive resins except the face layer.

Thermoplastic polymers suitable for use in the base bonding resins of the present invention ("base bonding polymers") are generally those known in the art of producing laminates for making telecommunication cables. Preferred base binding polymers include known common solid random copolymers which are a major proportion of ethylenic and a minor proportion of ethylenically unsaturated carboxylic acid monomer (e.g., typically a copolymer containing 1% to 30% of the total amount, preferably 2% to 20%) are obtained by copolymerization. Such suitable ethylenically unsaturated carboxylic acids (a term which includes monobasic or polybasic acids, anhydrides and partial esters of polybasic acids, and the various metal salts of those acids) are acrylic acid, methacrylic acid, crotonic acid, fumaric acid, Maleic acid, itaconic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monomethyl fumarate, monoethyl fumarate, tripropylene glycol monomethyl ether Ethylene glycol monophenyl ether maleate or acid ester. Preferred carboxylic acid monomers are selected from the group consisting of α/β ethylenically unsaturated mono- and polycarboxylic acids and anhydrides having 3 to 8 carbon atoms per molecule and partial esters of such polycarboxylic acids, such carboxylic acid esters, The acid moiety has at least one carboxylic acid group and the alcohol moiety has 1 to 20 carbon atoms. Such copolymers may consist essentially of ethylene and one or more ethylenically unsaturated carboxylic acids or anhydrides thereof comonomers or may also contain minor amounts of other monomers copolymerizable with ethylene. Accordingly, such copolymers may contain other copolymerizable monomers including acrylates, methacrylates, and the like. Such random copolymers and methods of making them are readily understood in the art.

Other thermoplastic polymers suitable for use in the present invention include known olefin polymers, generally olefinic olefin polymers, for example, the various known ethylene homopolymers (e.g., ultra-low, linear low , low, medium and high density polyethylene, having a density ranging from 0.82 to 0.96 g/cc), a copolymer having a major proportion of ethylene with a minor proportion of known copolymerizable monomers such as high (e.g., C3 to C12) α-olefins, ethylenically unsaturated ester monomers (for example, vinyl acetate, ethyl acrylate, etc.) and grafted modifications of such ethylenic homopolymers and copolymers (for example, with acrylic acid, horse to acid anhydride grafted, etc.). Olefin polymers, copolymers and chemically modified olefins of this type and/or copolymers of this type and methods for their manufacture are readily understood in the art.

In one embodiment of the present invention, the base binder resin is a blend of (a) and (b), (a) a random copolymer of ethylene and ethylenically unsaturated carboxylic acid monomers, and (b) ) a copolymer of at least one different olefinic olefin and/or a olefinic olefinic polymer resin that is not a random ethylene/unsaturated carboxylic acid copolymer. A preferred base binder resin comprises, by weight, from 5% to 95% of (a), more preferably from 50-95%, most preferably from 65-95% of (a), preferably The base binder resin also contains 0-95% by weight of (b), more preferably 0-50%, most preferably 5-20% (b).

Furthermore, it should be understood that references to "a random copolymer of ethylene with an ethylenically unsaturated carboxylic acid" are intended to include partially or fully neutralized variations thereof known in connection therewith, and in the art, Attributed to "ionic polymers". Further, it should be understood that reference to "a copolymer of a different olefinic olefin and/or a olefinic olefin polymer resin other than a random ethylene/unsaturated carboxylic acid copolymer" is intended to include olefinic olefin polymers, Such polymers use an anhydride or anhydride precursor of an ethylenically unsaturated dibasic acid, an ester of an ethylenically unsaturated dibasic acid, and rubbery modified derivatives of the above compounds by copolymerization or grafting. Modified body obtained by branch copolymerization reaction technology.

Typically, the embossing materials used in the present invention are known in the art and are organic or inorganic fillers. Embossing materials suitable for use in the present invention are desirably incompatible in nature, chemically inert, and insoluble in the base binding polymer. The incompatibility is due to the actual lack of chemical (eg polymeric) bonding with the base adhesive polymer, and preferably with any other species involved in the film coating. Chemical inertness is due to being virtually insoluble in the base adhesive polymer, or preferably insoluble to any other components in the base adhesive resin. Insolubility is attributed to insolubility in the base binding polymer to such an extent that the physical integrity of the embossed surface is virtually maintained.

The amount of embossing material must be sufficient to substantially lower the coefficient of friction (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 means that there are many raised parts on the surface, and its raised height range is 1/100-1/4 of the thickness of the adhesive layer, and the larger raised parts make the surface Too rough and adversely affects the strength and other properties of the film layer. Smaller protrusions are generally less effective at reducing the coefficient of friction of plastic/metal laminates. The evaluation of surface protrusion here is by determining the difference in the contact measurement value of thermoplastic polymers, as specified in the American material testing standard D374 (ASTMD374), and the difference in the gravimetric measurement value of thermoplastic polymers, according to the American material testing standard D374 (ASTMD374). Test standard E252 (ASTME252).

Preferably the surface layer contains 0.1-16% by weight of embossing material, more preferably 2-16% by weight, most preferably 4-8% by weight.

Examples of organic embossing materials suitable for use in the present invention include particulate polyester, polytetrafluoroethylene ("PTFE"). Nylon, polystyrene, high-impact polystyrene ("HIPS"), styrene-acrylonitrile ("SAN"), acrylonitrile-butadiene-styrene ("ABS"), polycarbonate wait. Suitable inorganic embossing materials include particulate graphite, mica, chalk, calcium sulfate, calcium silicate, calcium carbonate, talc, bentonite, barite, kaolin, magnesium aluminosilicate, magnesium silicate, inorganic colloids, Pyrophyllite, serite, silica, gypsum powder, etc. Preferred embossing materials are non-compatible, non-hygroscopic and non-microporous in the base adhesive polymer. The most preferred embossing material is mica, which not only has the ability to be effectively distributed onto the plastic/metal laminate to give a uniform embossed surface, but also improves the adhesion properties of the plastic/metal laminate.

A substantial reduction in the coefficient of friction of the plastic/metal laminate means the effect that the static or initial coefficient of friction and the resulting dynamic or sliding dynamic coefficient of friction are substantially equivalent to those of the plastic/metal laminate, The difference is only that the material without any embossing material has a lower static and dynamic coefficient of friction than that. The static and dynamic coefficients of friction of plastic/metal laminates were determined using a modified American Standard for Testing Materials D1894 (see Example I). Preferred plastic/metal laminates have a static coefficient of friction of at most 0.40, more preferably at most 0.30, most preferably at most 0.2, as determined according to ASTM D1894, modified. Preferred plastic/metal laminates have a dynamic coefficient of friction of at most 0.40, more preferably at most 0.30, and most preferably at most 0.20, also measured according to AMTSD1894, modified.

The plastic/metal laminates of the present invention exhibit improved adhesion. The evaluation of adhesion performance is to determine the tear strength of plastic/metal laminates according to the standards and methods specified in the revised ASTMB736 (see Example II). Adhesion of plastic/metal laminates to materials usually on jacket components is determined using the standard and method developed by ASTM 1876, modified (see Example v). Furthermore, it should be understood that references to improved adhesion herein mean that the adhesion is improved relative to the adhesion observed when utilizing substantially equivalent plastic/metal laminate or composite articles, the difference being only that In the latter there is no embossing material.

The interlayer adhesion of the preferred multilayer adhesive system of the present invention is at least 5 lbs/in, more preferably at least 8 lbs/in (142.86 kg/m), most preferably at least 12 lbs/in (214.30 kg/m) m), these data are determined according to the standards and methods stipulated in the revised ASTMB736. Preferably the adhesion between the coating (i.e. the outer insulating jacket layer of a cable) and the plastic/metal laminate of the present invention is at least 8 lbs/in, more preferably at least 10 lbs/in ( 178.56 kg/m) and most preferably at least 15 lb/in (267.86 kg/m), as determined by ASTM 1876, modified.

The thickness of the metal substrate (eg, sheet, strip, foil, etc.) used in the present invention is not critical, and may be less than 1 mil foil or relatively thick sheet. Typical metal substrate thicknesses are from 3 (76.2) to 25 mils (635.00 microns). 4 mil (101.60) to 15 mil (381.00 microns) is preferred. Metal substrates can be composed of a wide variety of metal raw materials such as aluminum, aluminum alloys, alloyed aluminum, copper, surface-modified copper, bronze steel, tin-free steel, tin-plated steel, aluminized steel, clad Aluminum steel, stainless steel, copper-clad stainless steel, copper-clad mild steel, lead-plated steel, galvanized steel, chrome-plated or chromium-treated steel, lead, magnesium, tin, and the like. Of course, these metals may be surface treated or have a conversion coating on the surface of the metal if desired. Particularly preferred metal substrates for this application include those consisting of chromium/chromium oxide coated steel (generally referred to in the art as tin-free steel), stainless steel, aluminum and copper.

The adhesive system of the present invention may be applied to the metal substrate by any convenient method desired. For example, conventional extrusion lamination techniques can be used to apply the adhesive system to the selected metal substrate. In addition, conventional film lamination techniques may be used appropriately to adhere the adhesive film system to the desired metal substrate. A combination of conventional coextrusion and film lamination techniques can also be used. For example, an adhesive system may first be extruded or coextruded into a film as desired, and the film then laminated to one or both sides of a metal substrate.

example

The invention may be further illustrated by the following examples, which are not to be construed in any way as being limited to these examples. In the following examples, all parts and percentages are by weight unless otherwise indicated.

example 1

In this example, a 1.6 mil (40.64 micron) thick single layer adhesive film was produced using conventional blown film procedures. The adhesive film comprised a base adhesive resin and a blend of high density polyethylene and 40% by weight mica (ie, Micafil 40, available from DuPont Canada). The base adhesive resin is a mixture of a random ethylene/ethylene acid ("EAA") copolymer and an olefin polymer. The EAA copolymer contained 6% acrylic acid in total copolymer and had a melt index of 5.5. The olefin polymer used was polyethylene with a melt index of 5.5 and a density of 0.916 g/cc ("LDPE-1") or polyethylene with a melt index of 5.0 and a density of 0.958 g/cc ("HDPE-1"). Table I shows the amount of EAA, LDPE-1, HDPE-1 and Micafil 40 used in various samples.

Various film samples were laminated to one side of a 7.5 mil (190.5 micron) thick aluminum sheet. When preparing such samples, the metal sheet is preheated in a circulating air oven heated to 300°F (148.89°C) for one minute, then laminated with the desired monolayer film, and then the preheated metal sheet is drawn, The desired monolayer film was passed through a set of rubber rollers, and the resulting laminate was post-heated for one minute in a circulating air oven heated to 300°F (148.89°C). The resulting post-heated laminate should be allowed to equilibrate for at least 12 hours in air at 73°F (22.78°C) and 50% relative humidity prior to any testing.

The resulting laminate samples were template cut into pieces 2.75 inches (6.99 cm) wide by 4.00 inches (10.16 cm) long, with the larger dimension in the machine direction. Laminate samples, in accordance with the standards and methods established by ASTM D1894, are subjected to the coefficient of friction test under standard constant laboratory conditions. (except when using a crosshead speed of 5 inches per minute, a 2000 gram load cell, a #7 high finish stainless steel plate, and a 1 kg tractor, at least 73°F (22.78°C) and 50% relative humidity Conditioned under conditions for 12 hours, and the test was carried out on at least 5 test samples). The test results for the coefficient of friction are listed in Table I.

表I*    ％       ％        ％       ％               静态      动态试样#  EAA      LDPE-1    HDPE-1   Micafil40        摩擦系数  摩擦系数对照   91.00    5.00                                0.5429    0.5257I-1    40.00              56.00                     0.3320    0.3120I-2    67.20              16.80    12.00            0.2313    0.2099I-3    60.80              15.20    20.00 0.2005    0.1696I.4    58.80              25.20    12.00            0.1757    0.1518I-5    53.20              22.80    20.00            0.1796    0.1532I-6    46.20              19.80    30.00            0.1449    0.1289I-7    43.20              10.80    30.00            0.1428    0.1359I-8    79.00    5.00               12.00            0.3400    0.3150I-9    71.00    5.00               20.00            0.2727    0.2509 I-10 61.00 5.00 30.00 0.1940 0.1657i-11 94.00 2.00 0.4520 0.4152i-12 84.00 12.00 0.3150i-13 76.00 20.00 0.2795 0.2572

*Balance of film composition contains approximately equal weight percentages of antiblock and heat stabilizer/antioxidant.

A set of control samples was prepared and tested in the same manner as the above examples except that no mica was incorporated into the adhesive film used to make the laminate.

The results in Table I show that laminates using relatively high levels of high density polyethylene exhibit reduced coefficient of friction values compared to those exhibited by the corresponding control (Sample 1-1 vs. Control). However, the data in Table I also show that the addition of mica to the laminate samples resulted in a more pronounced reduction in the coefficient of friction values.

Example II

Laminates were prepared in the same manner as in Example 1, except for the olefin polymers used in Example 1 (i.e. LDPE-1 and HDPE-1), an additional low-density polyethylene was used with a melt Index 1.9 and density 0.925 g/ml ("LDPE-2"). Laminates were cut into 1 inch (2.54 cm) wide, 6 inch (15.24 cm) samples with the larger dimension in the machine direction.

Table II* % % % % % Heat Sealed Heat Sealed Specimen# EAA LDPE-1 LDPE-2 Average HDPE-1 0 Mica fil 4 Max

(KG/m) (kg/m) compare 91.00 5.00 150.36 112.76ii-40.00 56.00 18.54 17.45ii-2 67.20 16.00 103.43 60.41ii-3 60.80 20.00 96.27II-4 52.00 73.2735.8.8.88i 35.88III. 22.80     20.00       89.70   37.20II-6   40.00              54.00              2.00        17.84   17.18II-7   40.00              44.00              12.00       27.32   24.66II-8   40.00              36.00              20.00       31.56   30.75II-9   61.00    5.00                         30.00       42.93   37.61II-10  94.00                                 2.00        101.84  86.02II-11  84.00                                 12.00       73.74   49.77 II-12 76.00 20.00 167.94 147.94

*Balance of film composition contains approximately equal weight percentages of antiblock and heat stabilizer/antioxidant.

The samples were subjected to a 90° heat sealability test according to ASTM B736 and under standard laboratory conditions (except using a crosshead speed of 12 inches per minute, a 25 kg load cell, and a heat seal at 300°F (148.89°C) Temperature, 40 pounds per square inch (psig) heat seal pressure, 2 second dwell time, at least 5 minutes of conditioning at 73°F (22.78°C) and 50% relative air humidity, at least 5 tests tested on the sample).

For the purpose of comparison, a control sample was made and tested in the same way as other samples. Control samples did not contain any HDPE-1 or Micafil40.

The results of the heat sealability test for each sample are listed in Table II.

The test results in Table II show that the addition of relatively high levels of HDPE in blends with EAA significantly reduced the adhesive properties of the samples compared to the control samples. Furthermore, it was seen that the addition of mica in blends with low and high density polyethylene can also substantially reduce the adhesion properties of the laminate. However, giving the right balance of the amounts of mica and HDPE in blends with random ethylene/carboxylic acid copolymers (e.g. Micafil 40) significantly improved heat seal adhesion performance compared to control laminates (II-12 compared with control sample).

Example III

Samples were prepared and tested in a manner similar to the samples in Examples I and II. However, the adhesive film used to prepare the samples was a 2.3 mil (58.42 micron) thick two-layer adhesive film, each layer being the same thickness. In contrast to the blown film process, the conventional cast film process was used in this example to prepare the adhesive film. For comparison, a 2.3 mil (58.42 micron) thick monolayer film was used to prepare a control sample. Each sample in Example III had a layer of contact metal having the same composition as the control. The composition of the other layer (surface layer) of each sample is shown in Table III. The sample is tested in the same way as the sample in Example I and Example II, and the test results are also listed in Table III.

Table III

* % % % % % Static Friction Dynamic Friction Heat Seal Heat Seal Specimen# EAA LDPE-1 HDPE-1 Micafil40 Friction Coefficient Friction Coefficient Maximum Average

(kg/m) (kg/m)对照     91.00  5.00                       0.7834   0.7386 273.23 116.43III-1    45.60         30.40  20.00        0.1900   0.1734 170.72 141.19III-2    57.60  38.40                      0.6150   0.6064 237.87 140.19III-3    45.60  30.40         20.00        0.3015   0.3440 118.04 92.33III-4    57.60 38.40              0.4375   0.2773 176.26 101.25III-5    91.00                5.00         0.4235   0.4356 263.94 121.61III-6    45.60  38.40         12.00        0.2682   0.2764 159.29 110.54III-7    76.00                20.00        0.2934   0.2595 255.01 233.23III-8  45.60  38.40  12.00         0.4398 0.3788  191.26 88.93III-9  72.33         10.46  13.21  0.1900 0.1700 239.30 179.47III-10 57.31 24.38 14.21 0.1200 0.1080 202.33 160.19

*Balance of film composition contains approximately equal weight percentages of release agent and heat stabilizer/antioxidant.

Example IV

Two sets of samples were prepared in the same manner as the samples in Example III. One set of samples had a thickness of 1.6 mils (40.64 microns) and the other set of samples had a thickness of 2.3 mils (58.42 microns). Each set of samples contained samples made according to Sample III-Control and Sample III-7. The test specimens were cut into 1 x 6 inch pieces with the larger dimension in the machine direction.

The test specimens were tested for heat sealability in the same manner as the modified ASTM B736 of Example III (except that the heat seal temperatures used were 200, 250, 300, 350 and 400°F (204.44°C)). The results of these experiments are graphically depicted in panel 1. From the results depicted in Fig. 1, it can be seen that the heat-sealing performance is substantially improved at lower heat-sealing temperatures. The results in Figure 1 also show that the thickness of the samples has very little, if any, effect on the heat sealability.

Example V

Samples were prepared in the same manner as the samples in Example III, except that the total thickness of the two adhesive films was 1.6 mils (40.64 microns) instead of 2.3 mils (58.42 microns). To test adhesion to typical jacket component materials, the samples were molded onto two different sets of 75 mil (1,905 micron) thick polyethylene sheets to form composite structures. The first set of sheets was made from high density polyethylene (UC3479, available from Union Carbide). The second set of sheets was made from medium density polyethylene (UC8864, available from Union Carbide). Both sets of sheets contained approximately 2.6% by weight carbon black.

To form these composite structures in a molding operation, a stamping press is used. The laminate sample was placed in intimate contact with the sheet under pressure, and the compression molding was performed at 230°C and 15 psig for three minutes. The resulting composite structure was cooled to room temperature in the press. Remove from press and cut into strips 1 inch wide by 6 inches long with the larger dimension in the machine direction.

Some of the prepared strips were tested for 180° tearing from the base plate in accordance with the standards and methods established by ASTM D1876 (except for the use of a crosshead speed of two inches per minute, a load cell of 25 kg, and a sample It needs to be conditioned at 73°F (22.78) and the air humidity is 50% for 12 to 48 hours. The lengths of the bonded and unbonded polymer layers are 2.5 inches and 0.5 inches, respectively. The test is carried out on at least 3 test samples instead of 10). The other strips were immersed (i.e. "aged") in water at 140°F (60°C) for 7, 30, 60 and 120 days, allowed to equilibrate, and at 73°F (22.78) at 50% relative humidity Dry in air overnight, and then perform the aforementioned 180° tear test.

For comparison, a control sample was prepared and tested in the same manner as the other samples, except that the adhesive film used was a single layer film having a thickness of 2.3 mils (58.42 microns).

The tear test results for each sample using the HDPE-2 sheet are listed in Table V-A, while the test results using the MDPE sheet are listed in Table V-B. As can be seen from the results in Table V-A and Table V-B, the examples of the invention show improvements in aged adhesion performance.

Form V-A

HDPE coat bonding (kg/meter)* % % % % % peeling and stripping divesticking and stripping off sample#EAA LDPE-Micafil40 Initial 7 days, 30 days, 60 days, 120 days, 91.00 5.00 13.46 16.03 16.00V-A-75.60 8.40 12.00 11.58 20.65 20.90 20.89 20.90V-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 contains approximately equal weight percentages of antiblocking agent and heat stabilizer/antioxidant.

Form V-B

    Adhesion of MDPE jacket bonded (kg/m)

* % % % Percent Dipping Dipping Dipping Dripping Detmixing Sample#EAA LDPE-Micafil40 In the first 7 days, 30 days, 60 days, 120 days, 91.00 5.00 13.77 15.39 16.27 16.20V-B-1 75.60 11.92 19.71 21.83 21.80V-2 5-2 5-2 12.00 12.35 18.49 18.88 18.33 18.25

*The balance of the surface layer composition contains approximately equal weight percentages of antiblocking agent and heat stabilizer/antioxidant.

Example VI

In this example, a laminate was prepared in the same manner as in Example III. The resulting laminate was cut into 111/16 inch (4.29 cm) wide tapes and fabricated into electric cables and or communication cables using conventional cable manufacturing procedures described in this application. The laminate materials used to make the cables are listed in Table VI. Process data for several produced cables are listed in Table VII.

Table VI

Applying layer pressure materials for manufacturing cables* % % % % % % Static Modeling Mooth Material Sample#EAA LDPE-1 HDPE-MiCafil40 Ruby coefficient surface Facial surface Two-compare 91.00 5.00 0.7834 0.7386 smooth VI-57.60 38.40 0.4136 0.2814 smooth VI-2 58.80 25.20 12.00 0.2700 0.2800 Vi-3 67.20 16.80 12.00 0.3200 0.2400 Pressure Vi-4 76.00 20.00 0.22200 Pressure

*The balance of the surface layer composition contains approximately equal weight percentages of antiblocking agent and heat stabilizer/antioxidant.

From the results in Table VII, it is observed that substantial progress can be made in the manufacture of electrical and/or telecommunication cables from plastic/metal laminates using the laminates of the present invention.

While the invention has been illustrated by reference to specific embodiments and examples, these facts should not be construed in any way as limiting the scope of the invention.

Table VII

Specimen of process data for laminated materials for making cables# Cable production Lubricants in forming tools At welding points Pressing dies

Use of Line Speed and Tape Break in Die Final Temperature °C

m/min Fragment and powder control 40 no yes yes yes 29.44

50 No Yes Yes 30

60 No Yes Yes Yes 31.11 Comparison 40 Yes Yes Yes Yes 25

50 Yes Yes Yes 25.56

60 Yes Yes Yes Yes 26.11VII-1 40 No Yes No 27.78

50 No Yes Yes No 27.78

60 No Yes No 28.33VII-2 40 No No No No 28.89

50 None None None 27.22

60 No No No No 27.22VII-3 40 No No No No 26.67

50 None None None 26.67

60 No No No No 26.67VII-4 40 No No No No 27.22

Claims (14)

1. a laminated material comprises:

A) a kind of ground of metal:

B) a kind of superficial layer directly or through the polymeric layer in the middle of one or more layers adheres on the above-mentioned ground; Above-mentioned superficial layer is made up of a kind of basic binder resin and an amount of embossing material basically, and the consumption of embossing material will be enough to substantially reduce the coefficient of friction of laminated material and be enough to embossing on above-mentioned superficial layer.

2. a kind of laminated material of claim 1, wherein laminated material has the maximum heat sealing value of 5 pounds/inch (89.29 kilograms/meter) and the evenly heat sealing value of 5 pounds/inch (89.29 kilograms/meter) at least.

3. a kind of laminated material of claim 1, wherein laminated material has the even sealed value of maximum heat sealing value and 8 pounds/inch (142.86 kilograms/meter) of 8 pounds/inch (142.86 kilograms/meter) at least.

4. a kind of laminated material of claim 1, basic binder resin wherein is the random copolymer by (a) a kind of ethene and a kind of alkene class unsaturated carboxylic acid monomer basically, with the alkene of (b) at least a different alkene class and/or a kind of copolymer of alkene class olefin polymer resin, it is not random ethene/copolymers of unsaturated carboxylic acids, a kind of mixture that both form.

5. a kind of laminated material of claim 1, wherein alkene class olefinic polymerization resin is selected from Alathon and copolymer, the ethene that ethylene copolymer has a larger proportion with have gathering property and an or comonomer that can react therewith than small scale.

6. a kind of laminated material of claim 1, alkene class olefin polymer wherein is a high density polyethylene (HDPE).

7. a kind of laminated material of claim 1.Embossing material wherein is a mica.

8. plastic/metal laminated material.Comprise:

A) a kind of ground of metal.

B) a kind of thermoplastic polymer layer of centre adheres at least one surface of above-mentioned metal substrate.Above-mentioned intermediate layer comprises the random copolymer of a kind of ethene and alkene class unsaturated carboxylic acid monomer.

C) a kind of superficial layer that adheres to above-mentioned intermediate layer, it is made up of following several materials basically:

I) random copolymer of a kind of ethene and a kind of alkene class unsaturated carboxylic acid monomer.

Ii) at least a olefinic polymerization resin, it is not the random copolymer of ethene and a kind of alkene class unsaturated carboxylic acid monomer.

Iii) an amount of embossing material, its consumption are enough to substantially reduce the coefficient of friction of laminated material and be enough in above-mentioned superficial layer embossing.

9. a kind of laminated material of claim 8, wherein laminated material has and is the heat seal maximum of 5 pounds/inch (89.29 kilograms/meter) at least and is the heat seal mean value of 5 pounds/inch (89.29 kilograms/meter) at least.

10. a kind of laminated material of claim 8, wherein laminated material has and is the heat seal maximum of 8 pounds/inch (142.86 kilograms/meter) at least and is the heat seal mean value of 8 pounds/inch (142.86 kilograms/meter) at least.

11. a kind of laminated material of claim 8, alkene class olefinic polymerization resin wherein is selected from Alathon and copolymer, the ethene that ethylene copolymer wherein has a larger proportion with have gathering property and an or comonomer that can react therewith than small scale.

12. a kind of laminated material of claim 8, alkene class olefin polymer wherein is a kind of high density polyethylene (HDPE).

13. goods; this goods have comprised the cable core of the conductor of at least a insulation; a kind of round above-mentioned cable core protective layer and a kind of around and stick to outer layer plastic cover on the above-mentioned protective layer, this protective layer is that any laminated material by claim 1 or claim 8 constitutes basically.

14. a kind of goods of claim 13, wherein above-mentioned protective layer is 8 pounds/inch (142.86 kilograms/meter) to the bond strength of above-mentioned overcoat at least.

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