Olefin-based resin composition

Abstract: There is provided an olefin-based resin composition applied to the coatings of electrical cables used in automobiles. The coatings have neatly balanced properties to satisfy product requirements, such as wear and flame resistance, tensile strength, flexibility, and heat and freeze resistance. The olefin-based resin composition comprises: (i) a polymeric material in an amount of 100 parts by weight which includes: (a) a propylene-type polymer portion (b) a polyolefin portion treated with maleic acid anhydride; and (c) an olefin-type polymer portion; and (ii) a metal hydroxide product. The propylene-type polymer portion (a) comprises at least one propylene polymer having a melt flow rate of 5g/10 min. at the most, and accounts for a proportion of 50 to 95% by weight of the polymeric material (i). The polyolefin portion treated with maleic acid anhydride (b) comprises at least one polyolefin, a proportion of 0.1 to 10% by weight of which is structurally modified through maleic acid anhydride treatment, and the polyolefin portion accounts for a proportion of 1 to 20% by weight of the polymeric material (i). The olefin-type polymer portion (c) comprises at least one ethylene-α-olefin copolymer, and accounts for 5 to 40% by weight of the polymeric material (i). The metal hydroxide product (ii) comprises at least one metal hydroxide in an amount of 30 to 200 parts by weight relative to the polymeric material (i).

Description: The present invention relates to olefin-based resin compositions, and more particularly halogen-free olefin-based resin compositions. These compositions are used for the coatings of electrical cables used in the automobile industries. These compositions therefore must satisfy prerogatives of the car industry, such as wear resistance, flame resistance, tensile strength and flexibility, among others. Poly (vinyl chloride) has mainly been used as a coating material for electrical cables in automobile applications. The reason is that this polymer has a good mechanical strength, formability at extrusion with electrical cables, flexibility and paintability. The poly (vinyl chloride) also provides an inexpensive material. Recently, however, global environmental concerns have compelled the auto industry to reconsider the choice of product types used for automobile parts, including coating materials for electrical cables. As a result, poly (vinyl chloride) is currently being replaced by halogen-free resin materials. As a consequence, there has been search into wear-resistant resin compositions that do not generate toxic gases, such as halogen gases, when they are burned. Such compositions include halogen-free compositions containing a polyolefin-based polymer and a metal hydroxide as a flame retardant, as disclosed in Japanese patent applications published under Nos. HEI 7-176219 and HEI 7-78518. Further, Japanese patent application published under No. HEI 7-182930 describes a composition containing a polymeric material mixture consisting of a polypropylene-type resin, a polyethylene treated with an unsaturated carboxylic acid, and an ethylene-type copolymer, on the one hand, and a metal hydroxide, on the other. US-A-4 863 995 describes a polypropylene composition comprising at least 40 % by weight of a crystalline polypropylene having a melt flow index of from 0.01-100 g/10 min, preferably from 0.2-70 g/10 min, 10-100 parts by weight of a modified propylene polymer which has been treated with maleic acid anhydride. The ratio of anhydride per 100 parts by weight of the polypropylene is in the range of 0.02-10 parts by weight. 5.0-30 % by weight of a ethylene copolymer comprise vinyl acetate. Fillers like magnesium hydroxide have been employed in a range of from 15 to 45 parts by weight. EP-A-0 972 803 describes a flame and wear resisting resin composition comprising 45-90% of a propylene-ethylene copolymer, 10-55 % by weight of an ethylene-vinyl acetate copolymer, 30-300 parts by weight of a metal hydroxide especially magnesium, aluminium and calcium hydroxide which has been treated with an amino-containing silane-based coupling agent. However, when the disclosed compositions supra are used in order to retard combustion or perform auto-extinction of the flame, a large amount of metal hydroxides must be added to the compositions. The compositions then acquire extremely low mechanical properties, such as a low wear resistance and tensile strength. In order to avoid the drop in mechanical strength, it has been contemplated to add polypropylene or a high-density polyethylene which are relatively hard resins. However, electrical cables coated with such compositions then become less flexible and less formable. An object of the present invention is therefore to provide an olefin-based resin composition which is substantially free of halogen and has well-balanced properties required for the coatings of electrical cable used in automobiles. These requisite properties include wear resistance, flame resistance, tensile strength, flexibility, heat resistance and low-temperature (freeze) resistance. To this end, there is provided an olefin-based resin composition comprising: (i) a polymeric material in an amount of 100 parts by weight which includes: (a) a propylene-type polymer portion (b) a polyolefin portion treated with maleic acid anhydride; and (c) an olefin-type polymer portion; and (ii) a metal hydroxide product. The propylene-type polymer portion (a) comprises at least one propylene polymer having a melt flow rate of about 5g/10 min. at the most, and accounts for a proportion of 50 to 95% by weight of the polymeric material (i). The polyolefin portion treated with maleic acid anhydride (b) comprises at least one polyolefin, a proportion of 0.1 to 10% by weight of which is structurally modified through maleic acid anhydride treatment, and the polyolefin portion accounts for a proportion of 1 to 20% by weight of the polymeric material (i). The olefin-type polymer portion (c) comprises at least one ethylene-α-olefin copolymer, and accounts for 5 to 40% by weight of the polymeric material (i). The metal hydroxide product (ii) comprises at least one metal hydroxide in an amount of 50 to 200 parts by weight relative to the polymeric material (i). Preferably, the polyolefin portion treated with maleic acid anhydride (b) accounts for 5 to 20% by weight of the polymeric material (i), the olefin-type polymer portion (c) accounts for 5 to 30% by weight of the polymeric material, and the metal hydroxide product (ii) comprises at least one metal hydroxide in an amount of 50 to 150 parts by weight relative to the polymeric material (i). More preferably, the metal hydroxide product (ii) comprises at least one metal hydroxide in an amount of 70 to 90 parts by weight relative to the polymeric material. Suitably, the propylene-type polymer portion (a) comprises at least one polymer selected from the group consisting of a propylene-ethylene block copolymer in which propylene constitutes at least 50% by weight of the block copolymer, a propylene-ethylene random copolymer in which propylene constitutes at least 50% by weight of the random copolymer, and a propylene homopolymer. Preferably, the polyolefin portion treated with maleic acid anhydride (b) comprises at least polypropylene structurally modified through maleic acid anhydride treatment. Further, the olefin-type polymer portion (c) may comprise at least one polymer selected from the group consisting of an ethylene-vinyl acetate copolymer and an ethylene-ethyl acrylate copolymer. Preferably, the metal hydroxide product (ii) comprises magnesium hydroxide. Suitably, the metal hydroxide product (ii) is treated with a silane-type coupling agent. In a preferred embodiment, the silane-type coupling agent comprises an aminosilane-type coupling agent. As understood from the above, the present invention provides an olefin-based resin composition which is substantially free of halogen. The invention concerns also an electrical cable coated with, or clad in, such an olefin-based resin composition. The above and the other objects, features and advantages of the invention will be made apparent from the following description of the preferred embodiments, given as non-limiting examples. The propylene polymer portion (a) having a melt flow rate (MFR) of 5g/10 min. at the most, preferably ranging from 0.1 to 5g/10 min., includes, for example, propylene homopolymer, and a block or random copolymer of propylene and ethylene in which propylene accounts for at least 50% by weight of the corresponding block or random copolymer. Examples of such propylene-type polymer portion include RB610A (block copolymer), RB410 (random copolymer) and RB110 (homopolymer), manufactured and commercialized by TOKUYAMA CORP.. When the proportion of such propylene polymer portion (a) exceeds the above-mentioned upper limit of 95% by weight in the polymeric material (i), the composition obtained becomes less flexible and less formable. Conversely, when its proportion is less than the lower limit of 50% by weight, the composition becomes less resistant to wear. In the above embodiments, the MFR is measured according to the method based on Standard JIS K 6921-2. An organic acid anhydride used for treating the polyolefin portion (b) is maleic acid anhydride. Preferably, 0.1 to 10 % by weight of the polyolefin portion (b) are treated with it. Examples of such polyolefin portion (b) treated with an organic acid anhydride include polyethylene, polypropylene, polybutene, ethylene-vinyl acetate copolymers (EVA), ethylene-ethyl acrylate copolymers (EEA), ethylene-methyl acrylate copolymers (EMA), ethylene-methyl methacrylate copolymers, ethylene-propylene rubber and ethylene-butene copolymers. A preferred example is polypropylene treated with maleic acid anhydride, since it gives an inventive composition having a sufficient level of hardness and wear resistance, without performing cross-linking. The proportion of polyolefin portion (b) treated with maleic acid anhydride in the polymeric material (i) ranges from 1 to 20, preferably from 5 to 20% by weight. When its proportion exceeds the upper limit of 20% by weight, the polyolefin reacts strongly with the metal hydroxide, so that tensile elongation (elongation rate at breaking point) of the composition becomes reduced, and the composition becomes less flexible. Conversely, when its proportion is less than the lower limit of 1% by weight, wear resistance of the composition cannot be improved. Preferred examples of an ethylene-α-olefin copolymer of the olefin-type polymer portion (c) include an ethylene-vinyl acetate copolymer (EVA) and an ethylene-ethyl acrylate copolymer (EEA). The proportion of α-olefin in the above ethylene-α-olefin copolymer is not particularly limited. EVA used in the Examples of the present invention had either 25% or 46% by weight of vinyl acetate, as shown in the Tables. EEA used in the Examples of the invention had 15% by weight of ethyl acrylate, as also shown in the Tables. The proportion of ethylene-α-olefin copolymer of the olefin-type polymer portion (c) in the polymeric material (i) ranges from 5 to 40, preferably 5 to 30% by weight. When its proportion exceeds the upper limit of 40% by weight, the composition obtained becomes less resistant to wear. Conversely, when its proportion is less than the lower limit of 5% by weight, the composition obtained becomes hard and less formable. Examples of the metal hydroxide product (ii) include magnesium hydroxide and aluminum hydroxide, preferably in their particle form. Suitably, metal hydroxide particles used in the invention are treated with a coupling agent, preferably a silane coupling agent and a higher fatty acid. The silane coupling agent includes e.g. an aminosilane-type coupling agent, a vinylsilane coupling agent and an epoxysilane coupling agent. Examples of higher fatty acids include stearic acid and oleic acid. Among the above examples, magnesium hydroxide treated with an aminosilane-type coupling agent is most preferably used . The part of metal hydroxide product (ii), added to 100 parts by weight of the polymeric material (i), ranges from 50 to 200, preferably from 50 to 150, more preferably from 70 to 90 parts by weight. When the part of metal hydroxide product (ii) is too high, the composition obtained suffers deterioration in elongation rate, wear resistance, flexibility and formability. On the other hand, when its part is too low, flame resistance of the composition is impaired. The olefin-based resin composition of the present invention may further contain an appropriate amount of usual additives, such as anti-oxidants, copper-damage inhibitors and lubricants, so far as they do not impede the above described product features. The inventive olefin-based resin composition can be prepared by mixing and kneading the polymeric material (i) and the metal hydroxide product (ii) supra according to a known method. When the composition is applied to the coatings of electrical cables used in automobiles, these coatings satisfy required wear resistance, flame resistance, tensile strength, flexibility, heat resistance, freeze resistance, etc.. Above all, these coatings generate no halogen gas. The aminosilane-type coupling agents contain, in their molecule, functional groups reacting with inorganic compounds and those reacting with organic compounds. Accordingly, when a metal hydroxide is treated with an aminosilane-type coupling agent, the former is bound to the latter through those functional groups reacting with inorganic compounds. When the thus-treated metal hydroxide is added to the composition, the metal hydroxide becomes firmly bound to an organic acid anhydride maleic acid anhydride) combined with the polyolefin portion (b) or the olefin-type polymer portion (c) through the aminosilane's functional groups which react with organic compounds. As a result, wear resistance of the composition is markedly improved. When an amino group (as in the above case) and/or an epoxy group is (are) present at the oleophilic group side of the silane coupling agent, that (those) group(s) react(s) with the organic acid anhydride combined with the polyolefin portion (b) or the olefin-type polymer portion (c), so that the hydrophilicity of such groups is suppressed. As a result, the composition becomes mechanically stronger and more waterproof. The present invention will be described hereafter with reference to examples and comparative examples. Examples 1 to 5 and Comparative Examples 1 to 6 The components indicated in the upper part of the corresponding columns in Tables I and II were mixed in indicated amounts. The resultant mixtures were kneaded in a biaxial extruder at 250°C. The obtained compositions were extruded around a conductive cable regulated by ISO as 0.5sq (7/0.32 soft copper wires, indicating 7 wires respectively having a diameter of 0.32mm, and forming a conductor with a cross-section area of 0.5mm 2 ), to yield a coating thickness of 0.3mm. The extrusion was performed in dies having a diameter of 1.6mm and 1.0mm, respectively, and nipples; at a die temperature of 210 to 230°C and a cylinder temperature of 200 to 240°C; and at a line speed of 100m/min. The terms in Tables I and II are defined as follows. "Propylene BP" indicates: a propylene-ethylene block copolymer of MFR 0.5g/10 min.. "RB610A" manufactured by TOKUYAMA CORP. is used for Examples 1 to 9 and Comparative Examples 1 to 10, except for Comparative Example 6; a propylene-ethylene block copolymer of MFR 6.5g/10 min. "MK640" manufactured by TOKUYAMA CORP. is used for Comparative Example 6. "MAH-PP" indicates polypropylene, 1% by weight of which is treated with maleic acid anhydride. "EVA" indicates ethylene-vinyl acetate copolymers. "EEA" indicates ethylene-ethyl acrylate copolymers. "MAGNIFIN H5IV" indicates magnesium hydroxide treated with an aminosilane-type coupling agent, manufactured by ALUSUISSE MARTINSWERK GmbH. The anti-aging agent used is a hindered phenol type compound, for example, "TOMINOX TT", manufactured by YOSHITOMI FINECHEMICALS, Ltd.. The coated electrical cables of Examples 1 to 5 and Comparative Examples 1 to 6 were subjected to tests for flame resistance, tensile strength, elongation rate and wear resistance according to JASO D611 (Japanese Automobile Standard Organization). To test heat resistance, a length of about 220mm was cut out from a coated electrical cable, to obtain a sample. The conductive portion was then removed from the sample, thereby yielding a sample coating. The sample coating was hung in a gear oven set to 150°C. After 100 hours, the sample coating was allowed to stand at room temperature for 24 to 48 hours. The tensile strength and the elongation rate were then measured as indicated above. An elongation at breaking point (elongation rate) exceeding 125% was judged as good. To test freeze resistance, a length of about 38mm was cut out from the coated electrical cable to obtain an sample. The sample was then subjected to a testing device comprising a sample grip, a hitting bar and a thermostatic bath. The sample was firmly held by the sample grip. They were then dipped into the thermostatic bath frozen by using ethanol. After 2 and a half minutes, frozen solvent temperatures were registered. The sample was then hit by the hitting bar, and the sample was inspected to detect whether the coating had a crack. The temperature at which the crack was formed was considered as the brittle temperature (fragilisation temperature). When the brittle temperature was less than -20°C, the result was considered as good. To test wear resistance, an abrasion frequency exceeding 300 times, averaged on 3 samples, was considered as good. Flexibility was evaluated by hand feeling, when the coated electrical cable was bent. Formability was evaluated by observing whether or not whiskers were formed, when coatings was stripped off from the end portion of coated electrical cable. The results of the tests are shown in Tables I and II. Ex.1 Ex.2 Ex.3 Ex.4 Ex.5 Ex.6 Ex.7 Ex.8 Ex.9 Propylene BP 60 65 68 60 60 85 85 80 70 MAH-PP 10 5 2 10 10 10 5 10 20 EVA(VA25%) 30 30 30 5 10 10 10 EVA (VA46%) 30 EEA(EA15%) 30 MAGNIFIN H5IV 90 90 90 90 90 70 70 70 70 Anti-aging agent 1 1 1 1 1 1 1 1 1 Total 191 191 191 191 191 171 171 171 171 Flame resistance Good Good Good Good Good Good Good Good Good Tensile strength (Mpa) 45.2 43.7 42.1 41.0 41.8 40.4 37.1 40.8 38.3 Elongation rate (%) 387 383 450 403 390 543 598 480 372 Heat resistance Tensile strength (MPa) Tensile elongation (%) 36.8 35.2 34.4 33.5 31.9 193 187 207 198 175 Freeze resistance Good Good Good Good Good Wear resistance (frequencies) 1424 923 747 565 1849 1290 314 521 648 Flexibility Good Good Good Good Good Good Good Good Good Formability Good Good Good Good Good Good Good Good Good Abbreviations: Ex.: Example. Com. Ex.1 Com. Ex.2 Com. Ex.3 Com. Ex.4 Com. Ex.5 Com. Ex.6 Com. Ex.7 Com. Ex.8 Com. Ex.9 Com. Ex.10 Propylene BP 70 90 40 90 60 60 100 90 100 60 MAH-PP 30 10 5 10 10 10 EVA (VA25%) 10 30 10 30 EVA (VA46%) 30 30 EEA(EA15%) 35 MAGNIFIN H5IV 90 120 90 70 300 90 70 70 70 70 Anti-aging agent 1 1 1 1 1 1 1 1 1 1 Total 191 221 191 171 401 191 171 171 171 171 Flame resistance Good Good Good Bad Good Good Good Good Good Good Tensile strength (Mpa) 26.5 22.2 33.9 22.6 21.3 31.4 32.3 38.4 32.7 Elongation rate (%) 650 437 107 43 76 293 665 715 417 Heat resistance Tensile strength (MPa) 27.5 25.4 34.5 20.6 20.1 31.7 Tensile elongation (%) 230 150 86 40 50 110 Freeze resistance Good Good Good Good Good Bad Wear resistance (frequencies) 570 4726 4341 10000 103 2208 2131 128 2862 93 Flexibility Good Bad Bad Bad Bad Good Bad Good Bad Good Formability Good Bad Good Bad Bad Good Bad Good Bad Good Abbreviations: Com. Ex.: Comparative Example. Comparison of the results for Examples 1 to 5 with those for Comparative Example 1 indicates that the addition of a small quantity of polypropylene, treated with maleic acid -anhydride, to the propylene block copolymer and ethylene-α-olefin copolymer improves the wear resistance of the composition obtained greatly. This addition, besides, does not impede the flexibility and formability of the composition. This phenomenon can be explained by the fact that, as an aminosilane-type coupling agent (having amino groups) was used for treating magnesium hydroxide, these amino groups have reacted with the maleic acid anhydride groups of the anhydride-treated polypropylene. According to the results obtained for Comparative Example 2, when contents of a hard resin are increased, instead of adding polypropylene treated with maleic acid anhydride, the resultant composition is not flexible enough. Manufacture of coated electrical cables thus becomes more difficult. The results obtained for Comparative Example 3 show that when the polypropylene treated with maleic acid anhydride is added in a great quantity, magnesium hydroxide becomes bound to the resin too firmly, so that the tensile elongation and flexibility of the composition are degraded. The results obtained for Comparative example 4 indicate that, unless ethylene-α-olefin copolymers are added, coated electrical cables become too hard, and their formability and flame resistance deteriorate. According to the results obtained for Comparative Example 5, when magnesium hydroxide is added in a large amount, the elongation rate, wear resistance, flexibility and formability of the composition are degraded. As indicated from the results obtained for Comparative Example 6, when the propylene polymer used has a MFR exceeding 5g/10 min., the heat and freeze resistance of the composition is not good. Examples 6 to 9 and Comparative Examples 7 to 10 The components shown in the upper part of the corresponding columns in Tables I and II were mixed in indicated amounts, and kneaded at 250°C. The compositions obtained were respectively extruded around an electrical cable (ISO conductor, 0.5sq, 7/compressed 0.32 soft copper wires, as mentioned above), to yield a coating having a thickness of 0.2mm. The extrusion was performed by using dies having a diameter of 1.3mm and 0.88mm, respectively, and nipples; at a die and a cylinder temperature of, respectively, 210 to 230 and 200 to 240°C; and at a line speed of 100m/min.. The flame resistance, tensile strength, tensile elongation, wear resistance, flexibility and formability of the obtained compositions were tested, as described for Examples 1 to 5 and Comparative Examples 1 to 6. It can be concluded from the results obtained for Comparative Examples 7 and 9 that, unless ethylene-α-olefin copolymers are added, coated electrical cables become too hard and hardly formable. The results obtained for Comparative Example 8 show that, when the amount of ethylene-α-olefin copolymer is increased, instead of adding polypropylene treated with maleic acid anhydride, the compositions obtained are sufficiently flexible and formable, but less resistant to the wear. According to the results obtained for Examples 7 to 9, as the quantity of anhydride-treated polypropylene added increases, the wear resistance of the compositions improves, but their elongation rate becomes somewhat reduced. As can be deduced from the results obtained for Example 6, when the amount of ethylene-α-olefin copolymer added is reduced, the wear resistance of the compositions improves. According to the results obtained for Comparative Example 10, the wear resistance of the compositions deteriorates as the amount of ethylene-α-olefin copolymer increases, in spite of the addition of the anhydride-treated polypropylene.

Claims: An olefin-based resin composition comprising: (i) a polymeric material including: (a) a propylene-type polymer portion (b) a polyolefin portion; and (c) an olefin-type polymer portion and (ii) a metal hydroxide product comprising at least one metal hydroxide, characterized in that said propylene-type polymer portion (a) comprises at least one propylene polymer having a melt flow rate of 5g/10 min. at the most, said propylene-type polymer portion accounting for a proportion of 50 to 95% by weight of said polymeric material (i); said polyolefin portion (b) is treated with maleic acid anhydride and comprises at least one polyolefin, a proportion of 0.1 to 10% by weight of which is structurally modified through maleic acid anhydride treatment, said polyolefin portion accounting for a proportion of 1 to 20% by weight of said polymeric material (i); said olefin-type polymer portion (c) comprises at least one ethylene-α-olefin copolymer, said olefin-type polymer portion accounting for 5 to 40% by weight of said polymeric material (i); and said metal hydroxide product (ii) comprises at least one metal hydroxide in an amount of 50 to 200 parts by weight relative to 100 parts by weight of said polymeric material (i). The olefin-based resin composition according to claim 1, wherein said polyolefin portion treated with maleic acid anhydride (b) accounts for 5 to 20% by weight of said polymeric material (i), said olefin-type polymer portion (c) accounts for 5 to 30% by weight of said polymeric material, and said metal hydroxide product (ii) comprises at least one metal hydroxide in an amount of 50 to 150 parts by weight relative to said polymeric material (i). The olefin-based resin composition according to claim 1 or 2, wherein said metal hydroxide product (ii) comprises at least one metal hydroxide in an amount of 70 to 90 parts by weight relative to said polymeric material. The olefin-based resin composition according to any one of claims 1 to 3, wherein said propylene-type polymer portion (a) comprises at least one polymer selected from the group consisting of a propylene-ethylene block copolymer in which propylene constitutes at least 50% by weight of said block copolymer, a propylene-ethylene random copolymer in which propylene constitutes at least 50% by weight of said random copolymer, and a propylene homopolymer. The olefin-based resin composition according to any one of claims 1 to 4, wherein said polyolefin portion treated with maleic acid anhydride (b) comprises at least polypropylene structurally modified through maleic acid anhydride treatment. The olefin-based resin composition according to any one of claims 1 to 5, wherein said olefin-type polymer portion (c) comprises at least one polymer selected from the group consisting of an ethylene-vinyl acetate copolymer and an ethylene-ethyl acrylate copolymer. The olefin-based resin composition according to any one of claims 1 to 6, wherein said metal hydroxide product (ii) comprises magnesium hydroxide. The olefin-based resin composition according to any one of claims 1 to 7, wherein said metal hydroxide product (ii) is treated with a silane-type coupling agent. The olefin-based resin composition according to claim 8, wherein said silane-type coupling agent comprises an aminosilane-type coupling agent. An olefin-based resin composition defined by any one of claims 1 to 9, which is substantially free of halogen. An electrical cable coated with the olefin-based resin composition defined by any one of claims 1 to 10.

Inventors: FUJIMOTO HIROSHI, HASE TATSUYA, SATO MASASHI, FUJIMOTO, HIROSHI, HASE, TATSUYA, SATO, MASASHI
Applicants: SUMITOMO ELECTRIC INDUSTRIES, SUMITOMO WIRING SYSTEMS, SUMITOMO ELECTRIC INDUSTRIES, LTD., SUMITOMO WIRING SYSTEMS, LTD.
Application year: 2001
Main classification: C08K3
IPC codes: C08L23, C08K3, C08L51, H01B7, C08K9, C08L53, H01B3