Adhesive composition

Abstract: An adhesive composition particularly useful for bonding a heat-recoverable polymeric sleeve around a cable splice to form a cable splice case comprises a polyamide and a copo­ lymer of ethylene and an ester of an ethylenically unsa­ turated carboxylic acid, said copolymer having a melt flow index of at least 40 as measured according to ASTM D12380-70; the amount of copolymer being at least 38% based on the weight of the polyamide.

Description: The present invention relates to an adhesive composition, particularly to a hot-melt adhesive composition containing polyamide and being suitable for use in the cable accessories or pipe line industry, particularly for adhesion to non-flame-brushed polyethylene and/or lead. Environmental protection frequently has to be provided around substrates such as cables to protect them from contaminants such as moisture. An excellent way of providing such protection is to surround the substrate with an adhesive composition, conveniently applied as a coating on a dimensionally-recoverable, preferably heat-shrinkable sleeve. Such a sleeve may be positioned around the substrate and heated causing the adhesive composition to become molten or softened and causing the sleeve to shrink, driving the adhesive into bonding engagement with the substrate. The sleeve itself may of course provide environmental protection, and the quantity of adhesive required may be reduced by coating the sleeve at only its edges to provide a bond to the substrate. A specific instance where environmental protection is required is around a cable splice, particularly in a multi-core telecommunications cable, where missing cable sheath (removed in order to form the splice) has to be made good. This may be done by installing a liner around the splice, the liner preferably being shaped to provide a smooth transition between the bulky splice and the smaller diameter cable or cables that enter and leave it. The liner is then surrounded by a heat-recoverable sleeve that extends past each end of the liner down onto intact cable jacket. The sleeve is internally coated with a hot-melt adhesive composition and, when heated, it shrinks down and becomes bonded to each cable jacket and to the liner between them. In this way leak paths from the outside environment into the now-formed splice case are avoided, and the conductors of the cable protected from moisture etc. Such splice cases may be expected to provide an environmental barrier for the life-time of the cable, say at least twenty-five years. The cable, and splice case, may be subjected to temperature variations ranging from say -40°C in winter to say +70°C in the case of a cable exposed to direct sunlight, and the cable may be internally pressurized. As will be appreciated, these requirements of life-time, temperature and pressure put severe demands on the performance of the adhesive. The problem is made more difficult because, for practical purposes, a given product may have to be suitable for many different environments, for example around buried cables in cold countries, and aerial cables in hot-countries. These performance requirements are themselves difficult to achieve at an acceptable price, but the difficulty can be seen to be particularly acute when one considers installation conditions. Installation is at present carried out by heating the sleeve and consequently the adhesive with an open-flame torch, although electrical heating may be used. It is clearly desirable that the amount of heat required to soften the adhesive be kept to a minimum. The weather may be cold, there may be little room in a man hole for vigorous heating, an electrical heater may have limited power, and the cable or the sleeve may be damaged by high temperatures etc. Thus, there is a maximum acceptable installation temperature. Also, as noted above there is a wide temperature range over which the adhesive must retain its adhesive power. Unfortunately, the maximum allowable installation temperature is not very much higher than the minimum acceptable upper limit to the range of service temperatures. We have found therefore that our adhesive should have a sharp melt transition. In addition to a sharp melt transition, the adhesive should have a high peel strength to polyethylene, preferably both flame-brushed and non-flame-crushed, and to lead, it should have good low temperature impact strength, and low temperature flexibility, and it should have low viscosity at the installation temperature say at 160°C. Attempts have been made to formulate adhesive compositions that combine, for example, high impact strength and high peel strength over a wide temperature range. The following adhesive compositions based on polyamides may be noted. US 4018733 (Lopez, Glover and Lyons) discloses a hot-melt adhesive composition comprising a compatible mixture of: (a) an acidic polymer of ethylene having an acid number ranging from about 3 to about 80 selected from the group consisting of a terpolymer of ethylene, and ethylenically unsaturated mono-or di-carboxylic acid and a vinyl ester of C₁ to C₆ aliphatic carboxylic acid and a copolymer of ethylene and a C₂ to C₂₀ aliphatic ester of a monoethylenically mono-or di-carboxylic acid wherein a portion of the carboxlic acid moieties of the said mono-or di-carboxylic acid component are not esterified, and (b) a polyamide having an amine number ranging from about 70 to about 400 with a tackifying agent wherein said tackifying agent is present in an amount ranging from about 3 to about 20 parts by weight per 100 parts of (a) and (b) together, components (a) and (b) being present in a relative proportion by weight ranging from about 40:60 to 60:40. EP 0040926 (Raychem) discloses a hot-melt adhesive composition comprising a polyamide based in one or more dimeric fatty acids and an ethylene/acrylic acid/butyl acrylate terpolymer containing free carboxylic acid groups. The acid terpolymer is preferably present at an amount of less than 20% by weight based on the weight of the polyamide. GB 1563030 (Allied Chemical Corporation) discloses a hot-melt adhesive composition comprising a compatible admixture of: (a) 15 to 99 weight percent of a polyamide adhesive based component; and correspondingly (b) 85 to 1 weight percent of a normally solid, homogenous component of ethylene and an unsaturated carboxylic acid having an acid number of at least 70 and a number average molecular weight between 500 and 5000, said copolymer containing at least a major proportion of ethylene by weight, said percentages being by weight of (a) plus (b). EP-A-0195218 discloses a hot melt adhesive based on a polyamide and a copolymer of ethylene. However, although esters are optional comonomers, the pressure of an internal anhydride of an ethylenically unsaturated dicarboxylic acid is essential. The anhydride-containing polymers react by ring opening. Such copolymers containing internal anhydrides are outside the scope of the present invention and are expressly excluded from its scope. GB-A-2104800 discloses a hot melt adhesive comprising a thermoplastic polyamide with reactive amine groups, a polymer of ethylene and an ethylenically unsaturated ester of an alkanol epoxy resin. The epoxy resin reacts with the other components when the composition is heated. Such compositions containing reactive epoxy resins are not part of the present invention and are expressly excluded from its scope. We have now formulated an adhesive composition that can provide excellent peel strength to polyethylene, can have excellent low temperature impact strength and flexibility, and can be produced at reasonable cost. The new adhesive also can allow good installability due to low viscosity at installation temperatures. We have found that an ethylene copolymer of high melt flow index can be blended with suitable quantities of one or more polyamides to produce the desired properties. Thus, the present invention provides an adhesive composition comprising a blend of (a) a polyamide having a ring and ball softening point according to ASTM E28 of from 80-120°C, a molecular weight of from 2000-10000 a viscosity at 210°C according to ASTM D3236 of 2-8 PaS and an amine number from 50-400, and (b) a second polymer characterised in that the second polymer is a copolymer of ethylene and an ester of an ethylenically unsaturated carboxylic acid, said copolymer having a melt flow index of at least 40 as measured according to ASTM D1238-70, the amount of the copolymer being at least 38% based on the weight of polyamide, but excluding any composition: (i) wherein the copolymer comprises an internal anhydride of ethylenically-unsaturated dicarboxylic acid and (ii) which contains a thermoplastic epoxy resin. The composition may additionally comprise other components for example for controlling viscosity or flow temperatures or adhesive strength. A preferred further component comprises a polyethylene acrylic acid copolymer, (which can help control viscosity or flow temperature), which is preferably present up to 57% based on the weight of the polyamide, and is preferably less than 20% based on the weight of the composition, more preferably less than 15%, especially less than 10%, say 3-7% particularly when low acidity is desired. Other components may comprise versamid 100 (trade mark for polyamide of Schering), tackifiers, such as a terpene phenol, for example that known by the trade mark SP553 (Schenetady Corp.) or, polyisobutylene and antioxidants such as that known by the trade mark Irganox 1010 (Ciba Geigy). We prefer that the composition has substantially no vinyl acetate nor vinyl acetate copolymer content. A preferred composition comprises: (a) from 35-65, preferably 50-60, especially 53-56 parts by weight of one or more polyamides as defined above; (b) from 25-44, preferably 25-35, especially 27-31 parts by weight of one or more copolymers as defined above of ethylene and an ester, particularly polyethylene ethylacrylate and/or polyethylene butylacrylate; (c) from 5-20, preferably 10-15, especially 12-15 parts by weight of polyethylene acrylic acid copolymer; and (d) from 0-4, preferably 1-4, especially 1-3 parts by weight of a vinyl terminated rubber, particularly vinyl terminated butadiene nitrile rubber; and excludes any composition wherein the copolymer comprises an internal anhydride of an ethylenically-unsaturated dicarboxylic acid and any composition containing a thermoplastic epoxy resin. The or each polyamide preferably has a ring and ball softening point according to ASTM E28 of from 90-110°C, and a viscosity at 210°C according to ASTM D3236 of 3-5 Pa.S. Suitable polyamides include those known by the trade marks Macromelt 6735 (Henkel), Macromelt 6766 (Henkel) and Macromelt 6301 (Henkel). In general, a polyamide (or blend of polyamides) may be chosen that has the desired physical and chemical properties (for example melt flow index, softening point, viscosity, and adhesive strength) substantially similar to those of the quoted examples. Two (or more) polyamides may be chosen particularly where low temperature flexibility is required, especially in combination with low cost. The copolymer of ethylene and an ester preferably contains only two comonomers, and we substantially exclude terpolymers from the composition. Preferred copolymers have a ring and ball softening point according to ASTM E28 of 80-125°Cm especially 95-120°C. Examples of preferred copolymers include: polyethylene ethylacrylate, such as those known by the trade marks EA 89821 (USI) and Alathon 704 (DuPont); and polyethylene butylacrylate, such as that known by the trade mark Lotader HX 8280 (Companie de France). As with the polyamide, other copolymers can be used having similar physical and chemical properties to those quoted. Where a polyethylene acrylate acid copolymer is used, we prefer that known by the trade mark Alathon 5120 (DuPont) or AC5120 (Allied Chemical Corporation) or equivalents. We have identified a problem that may occur when using some prior art adhesives, and that may be solved with the present invention. Adhesion may be poor to certain materials, particularly metals, such as that used for lead cables in Belgium. We have noticed that the lead used for Belgian cables is substantially pure and therefore soft. As a result of this softness, and as a result of a disparity between the thermal coefficient of expansion of adhesives and of lead, thermal cycling may cause cohesive failure of the lead : a very thin surface layer of the lead may peel away from the bulk. The problem is less likely to occur with harder lead compositions, for example those containing impurities or additives such as antimony, copper, silver or tin. The skilled man will be able to determine where there is a risk that this problem will occur, but typically at risk are lead compositions having a melting point as determined by differential scanning calorimetery at 8 degrees centigrade per minute of at least 322 degrees centigrade. An alternative indication (which applies to lead and to other metals and other materials) is hardness : a Vickers hardness of less than 5.5, preferably less than 5.0 microns may lead to poor bonding, the measurement being made on Leitz Miniload equipment using a 100 gm core. Recognition of this possible failure mode has led us to reduce the acidity of our adhesive composition and thereby reduce stress on cycling at the adhesive/lead interface. This may be done by, for example, reducing the acidity of say AC 5120, or by replacing or reducing the amount of the AC 5120 itself. In one embodiment AC 5120 may be at least partially replaced by SP 553 (a trade mark of Schenectady, France, for a tackifier), and/or by AC 540 (a trade mark for a polyethylene acrylic acid copolymer of Allied Chemical Corporation). AC 540 has a lower concentration of acid functionality than AC 5120. Often components which may be added include Oppanol B-12 (a trade mark for polyisobutylene of BASF). Peel strengths at room temperature of at least 100 N/25mm, generally at least 150 N/25mm especially at least 170 N/25mm to Belgian lead can be achieved after 10 temperature cycles from -40 degrees centigrade to +60 degrees centigrade. The primary components selected, and their relative amounts, and any further components such as viscosity or flow modifiers are preferaby such as to achieve a peel strength to non-flame brushed polyethylene, preferably also to lead, of at least 100 N/25mm at room temperature (test QAPK027), a ring and ball softening temperature of 90-110°C (test ASTM E28), a viscosity at 160°C of 40-110 Pa.S (test ASTM D3236), a low temperature mandrel flexibility of -30°C or lower, and an impact brittleness of -30° of lower (test ISO 974). The adhesive composition may be provided with, preferably as a coating on, a dimensonally-recoverable, preferably heat-shrinkable article. The article may comprise a sleeve, which may be tubular or of the wrap-around type, such as that disclosed in UK Patent 1155470 (Raychem). We particularly prefer that the sleeve or other recoverable article comprises a recoverable composite material recoverable by virtue of a recoverable fabric component thereof. The recoverable fibre may be part of a recoverable fabric, such as one that comprises a weave of recoverable fibres in one direction and dimensionally stable fibres in another direction. We prefer that the recoverable fibres comprise polyethylene and that the stable fibres comprise glass. The composite material may comprise recoverable fibres and a matrix material, such as polyethylene, by means of which the composite is rendered substantially impermeable. The matrix material is preferably such that the adhesive composition is able to bond thereto. Where a branched cable splice is to be environmentally sealed by means of a sleeve, a branch-off clip may be applied to an end of the sleeve to hold together circumferentially-spaced portions of the sleeve between the branching cables. The use of such a clip to bring together such portions of a recoverable sleeve is disclosed in GB 1604981. Such a clip may have three legs, the outer two lying outside the sleeve, and an inner lying within the sleeve, generally between the branching cables. The branch-off seal formed using such a clip may be enhanced if an inner leg of the clip comprises an adhesive, and the adhesive of the invention may be used for such purpose. The adhesive may provide substantially the whole of the inner leg, or may provide a coating over a heat-conducting or other support. The adhesive of the invention may be supplied separately from any sleeve instead of or in addition to the sleeve coating as mentioned above. For example, such adhesive may be supplied in strip form for wrapping around a cable prior to installation of a recoverable sleeve or other cable enclosure. The invention is further illustrated by the following examples. Example 1 An adhesive composition was made by mixing in a blend mixer the following materials: Polyamide Macromelt 6301 93 parts by weight VTBNX 5 parts by weight Antioxidant 2 parts by weight Sixty parts by weight of the resulting first blend were mixed with 35 parts by weight of ethylene ethylacrylate (Alathon 704) and 5 parts by weight of polyethylene acrylic acid (AC5120). The resulting adhesive composition was then laminated onto a heat-recoverable composite comprising a weave of recoverable high density polyethylene in the weft and glass fibres in the warp having a matrix material of low density polyethylene. The lamination was carried out to a thickness of 0.4mm using a belt laminator. A wrap-around sleeve was formed from the resulting coated composite by forming at edge regions thereof closure members that could be held together by a C-shaped channel, as disclosed in EP 0116392 (Raychem). The sleeve was then heat-shrunk around a polyethylene cable splice of 1 in 3 out configuration, using a branch-off clip between the branching cables. The size of the sleeve was that known by Raychem's trade mark VASM 4/6. The sleeve was tested for leaks on a pressure/temperature cycle at 40 KPa from -40°C to +60°C at 3 cycles per day. Excellent performance was noted. The adhesive composition of this example had a viscosity at 160°C of 80.7 Pa.S, and a ring and ball softening point of 102°C. Viscosity was determined according to ASTM D-3236-1978, using a Brookfield Model HBT, Spindle SC-27 at 160°C at a shear rate of 5rpm. The softening point was determined by the ring and ball method according to ASTM E28-1977. The sample preparation being by the pour method, at a heat-up speed of 5°C/minute. Example 2 Example 1 was repeated, but using the following components: First blend 42.5 parts by weight Alathon 704 40 parts by weight AC 5120 17.5 parts by weight Viscosity at 160°C was 44 Pa.S, and the softening point was 98°C. Example 3 Example 1 was repeated, but using the following components; First blend 50 parts by weight Alathon 704 38 parts by weight AC 5120 12 parts by weight Viscosity at 160°C was 67 Pa. S, and softening point was 105°C. Peel strength at room temperature to non-flame-brushed polyethylene averaged 167 N/25mm determined according to QAPK 027. Example 4 Example 1 was repeated, but using the following components: Macromelt 6301 46.5 parts by weight VTBNX 2.5 parts by weight Antioxidant 1 part by weight Alathon 704 38 parts by weight AC 5120 12 parts by weight. Viscosity at 160°C was 56.5 Pa.s, and the softenng point was 104°C. Peel strength at room temperature to non-flame-brushed polyethylene averaged 120 N/25mm. Example 5 Example 1 was repeated, but using the following components: Macromelt 6301 46.5 parts by weight Antioxidant 1 part by weight Lotader HX 8280 38 parts by weight AC 5120 12 parts by weight VTBNX 2.5 parts by weight Viscosity at 160°C was 63.1 Pa.s, and the softening point was 99°C. Peel strength at room temperature to non-flame-brushed polyethylene was 301 N/25mm. Example 6 Example 1 was repeated but using the following components Macromelt 6301 54.4 parts by weight VTBNX 2 parts by weight Antioxidant 1 part by weight Lotader HX 8280 29 parts by weight AC 5120 13.6 parts by weight Viscosity at 160°C was 58 Pa.s, and softening point was 99°C. Peel strength at room temperature to non-flame-brushed polyethylene was 386 N/25mm. Example 7 Example 1 was repeated but using the following components. Macromelt 6301 50 parts by weight VTBNX 2 parts by weight Antioxidant 1 part by weight Lotader HX 8280 37 parts by weight AC 5120 10 parts by weight Viscosity at 160°C was 89 Pa.S, and the softening point was 96°C. Peel strength at room temperature to non-flame-brushed polyethylene was 277 N/25mm. Example 8 Example 1 was repeated but using the following components. Macromelt 6301 60 parts by weight Antioxidant 1 part by weight Lotader 8600 B 19 parts by weight Oppanol B-12 10 parts by weight SP 553 5 parts by weight AC 540 5 parts by weight (Lotader 8600 B is a trade mark of Companie de France for polyethylene butyl acrylate copolymer.) The resulting composition, which can be seen to contain no AC 5120, had a viscosity at 160°c of 77.5 Pa.S, and at 200°C of 28.1 Pa.S. Its ring and ball softening point was 101.4°C. Peel strength to flame-brushed polyethylene at room temperature was 438.2 N/25mm. Peel strenth to Belgian lead cable at room temperature after temperature cycling of 10 cycles from -40°C to +60°C was 183 N/25mm, and before cycling it was 192 N/25mm. Such values are surprisingly different from those for compositions containing large quantities of AC 5120, where the peel strength to Belgian lead drops substantially to zero. The quantity of these components may, of course, be varied. The Oppanol B-12 is preferably present from 5-10 parts, the SP 553 from 0-7 parts, and the Lotader from 15-25 parts. Preferably the relative amounts are as follows : Lotader/Oppanol/SP 553 3.8 - 4.2: 1.8 - 2.2 : 0.8 - 1.2. Example 9 Example 1 was repeated but using the following components. Macromelt 6301 60 parts by weight Antioxidant 1 part by weight Lotader 8600 B 19 parts by weight Oppanol B-12 10 parts by weight SP 553 5 parts by weight AC 5120 5 parts by weight The resulting composition, which can be seen to contain less AC 5120 than the early examples, had a viscosity at 160°C of 64 Pa.S and at 200°C of 19.2 Pa.S. Its ring and ball softening point was 99.8°C. Peel strength to flame brushed polyethylene at room temperature was 400°C. Peel strength to Belgian lead cable at room temperature after temperature cycling of 10 cycles from -40°C to +60°C was 175 N/25mm, and before cycling it was 201 N/25mm. The retention of some AC 5120 may be desirable in order to achieve a low viscosity and high peel strength to lead. For the avoidance of doubt, it is here stated that the invention provides an adhesive composition, and an article particularly a recoverable article having such a composition, that exhibits the properties mentioned herein as desirable. Any of the components mentioned herein may be selected to achieve these properties, particularly the selection of an acid copolymer with a high melt flow index, together with a polyamide, the high melt flow index of the copolymer allowing it to be used at high relative amounts based on the amount of the polyamide, and inclusion of other components such as viscosity or melt flow temperature modifiers, rubbers and antioxidants, etc.

Claims: An adhesive composition comprising a blend of (a) a polyamide having a ring and ball softening point according to ASTM E28 of from 80-120°C, a molecular weight of from 2000-10000 a viscosity at 210°C according to ASTM D3236 of 2-8 PaS and an amine number from 50-400, and (b) a second polymer characterised in that the second polymer is a copolymer of ethylene and an ester of an ethylenically unsaturated carboxylic acid, said copolymer having a melt flow index of at least 40 as measured according to ASTM D1238-70, the amount of the copolymer being at least 38% based on the weight of polyamide, but excluding any composition: (i) wherein the copolymer comprises an internal anhydride of ethylenically-unsaturated dicarboxylic acid and (ii) which contains a thermoplastic epoxy resin. An adhesive composition according to claim 1, which additionally comprises a polyethylene acrylic acid copolymer. An adhesive composition according to claim 2, in which the amount of the polyethylene acrylic acid copolymer is less than 20% based on the weight of the polyamide. An adhesive composition according to claim 1, which additionally comprises a tackifier. An adhesive composition according to claim 3, comprising: (a) from 35-65 parts by weight of polyamide; (b) from 25-44 parts by weight of copolymer of ethylene and an ester; and (c) from 5-20 parts by weight of polyethylene acrylic acid copolymer. An adhesive composition according to any preceding claim, in which said copolymer of ethylene and an ester comprises polyethylene ethylacrylate or polyethylene butylacrylate. An adhesive composition according to any preceding claim in which polyamide (a) comprises a blend of two or more different polyamides. An adhesive composition according to any preceding claim, in which the melt flow index of copolymer (b) is at least 70. An adhesive composition according to claim 8, in which the melt flow index of copolymer (b) is from 100-300. An adhesive composition according to any preceding claim, in which copolymer (b) has a ring and ball softening point according to ASTM E28 of 80-125°C. An adhesive composition according to any preceding claim, which additionally comprises a vinyl-terminated rubber. An adhesive composition according to claim 11, in which the amount of said rubber is from 4-8% by weight of the weight of polyamide (a). An adhesive composition according to claim 11 or 12, in which said rubber comprises a vinyl-terminated butadiene nitrile rubber. An adhesive composition according to any preceding claim, having substantially no vinyl acetate nor vinyl acetate copolymer content. An adhesive composition according to any preceding claim, having a viscosity according to ATM D3236 at 160°C of from 40-110 Pa.S. An adhesive composition according to any preceding claim, having a ring and ball softening point according to ASTM E28 of 90-110C. An adhesive composition according to any preceding claim having a peel strength at room temperature to non-flame-brushed polyethylene according to QAPK027 of at least 100 N/25mm. An adhesive composition according to any preceding claim having a peel strength at room temperature after 10 temperature cycles from -40 to +60C to substantially pure lead of at least 100 N/25mm. An adhesive composition according to any preceding claim which comprises: (a) from 50-60 parts by weight of polyamide; (b) from 25-35 parts by weight of polyethylene butyl acrylate copolymer; (c) from 10-15 parts by weight of polyethylene acrylic acid copolymer; and (d) from 1-4 parts by weight of a vinyl terminated rubber. An adhesive composition according to any preceding claim which additionally comprises one or more viscosity or melt flow index modifiers. A heat-shrinkable article having an adhesive composition according to any preceding claim at a surface thereof. An article according to claim 21, being a recoverable composite material recoverable by virtue of a recoverable fibre component thereof. An article according to claim 22, in which said composite material comprises recoverable fibres and a polyethylene matrix material the adhesive composition being bonded to the matrix. An article according to any of claims 21-24 in the form of a tubular or wraparound sleeve. A method of environmentally protecting a cable or a pipe which comprises (a) providing an adhesive composition according to any of claims 1-20; (b) heating the composition; (c) allowing or causing the composition to flow around a surface of the cable or pipe; (d) allowing or causing the composition to cool. A method according to claim 25, in which the composition is provided as part of a heat-recoverable article. A method according to claim 26, in which the cable or pipe comprises a material having a Vickers hardness of less than 5.5 microns. A method according to claim 27, in which the material comprises substantially pure lead.

Inventors: DIERICKX ETIENNE LOUIS, OVERBERGH NOEL MARCEL MICHIEL, DIERICKX, ETIENNE LOUIS, OVERBERGH, NOEL MARCEL MICHIEL
Applicants: RAYCHEM SA NV, N.V. RAYCHEM S.A.
Application year: 1989
Main classification: C09J177
IPC codes: B29C61, C08L77, H01B3, C09J177, C09J123