Patent GB-1148382-A (GB)
Title: Split films of polymer material
Inventor: RASMUSSEN OLE-BENDT
IPC: D01D5/42
Filed: 1965-02-23
Abstract: 1,148,382. Film fibrillation. O. RASMUSSEN. 23 Feb., 1966 [23 Feb., 1965; 10 July, 1965], Nos. 7870/65 and 29332/65. Headings B5B and B5N. [Also in Division D1] A sheet product comprises a high molecular weight polymeric material, A, in the form of needle-like or thread-like crystalline formations having an average diameter of 0À5-10 microns which are oriented predominantly in one direction and are linked together across the intervening spaces by connections of colloidal dimensions, which connections are of the same material as that of the crystalline formations and are integral therewith, the intervening spaces being partially filled with another polymeric material, B, consisting of a polymer or a polymer mixture which is chemically different from the polymeric material A, and in which some of the needle-like or thread-like crystalline formations are deflected out of the said direction, to form an open network of the said formations, by transverse stretching. The polymeric material A may be a polyamide or a polyester, or may consist of isotactic or syndiotactic polypropylene, polyformaldehyde, an isotactic or syndiotactic polyvinyl compound, or highly crystalline polyethylene, or of a segmented polymer with alternating crystalline and elastomeric segments, e.g. crystalline segments consisting of polypropylene or polyethylene and elastomeric segments consisting of a copolymer of propylene and ethylene. Suitably the melt index of the polymeric material A is between 0À05 and 1À0 as determined according to ASTM No. D1238-57T(E) at a temperature 50 C. above the crystalline melting point of the polymeric material A. The polymeric material B may be polyethylene, or may be a water-soluble polymeric material, e.g. polyoxyethylene. Thus the polymeric material A may be a polyamide or a polyester and the polymeric material B may be polyoxyethylene. In another preferred embodiment, the polymeric material A consists of iso- or syndiotactic polypropylene and the polymeric material B consists of an ethylene polymer or copolymer having a melt index, determined at the same temperature as for material A, which is 5 to 200 times greater than that of the polymeric material A. In order to obtain an unhindered development of the thread-like crystal formations of the A material it is preferred that the B material is either crystalline with a crystalline melting point substantially lower than that of the A material or amorphous. The sheet product is made by colloidally mixing while molten the crystallizable high molecular weight polymeric material A with the polymeric material B, which is chemically different from A and has a lower melting point and a higher melt index than A, extruding the melt mixture as a sheet and phase orientating the sheet by strongly stretching the sheet in the direction of extrusion while the sheet is still molten, cooling the stretched sheet first to make the polymeric material A crystallize and agglomerate while keeping the polymeric material B in fluid state, swelling or partially leaching out the polymeric material B and splitting the sheet material thus formed by stretching it in a direction transverse to the direction of orientation. In this method, the melt mixture to be extruded consists suitably of 60 to 80% by weight of polymeric material A and 40 to 20% by weight of polymeric material B, and the latter is preferably of a substantially lower viscosity than that of the polymeric material A, determined in the molten state at the same temperature. During the movement towards the extruder die, and owing to the change in velocity when the product leaves the die, a further stretching of the structural shape of the A material in the direction of movement takes place to give a phase orientation in the melted state. This orientation can be enhanced by stretching the sheet immediately after leaving the die and while still in the melted state, and/or by using a long and narrow die for the extrusion. Cooling of the sheet is suitably effected by a medium which is kept at a temperature slightly below the crystalline melting point of the polymeric material A. The sheet material may further be molecularly orientated by stretching the solidified sheet material in the direction of extrusion before stretching the material transversely. In this method the sheet after solidification and before or after the transverse stretching may be treated with a swelling agent or with a solvent for the polymeric material B, to remove the major part thereof. Before the transverse stretching, the crystalline formations are all oriented predominantly in one direction, i.e. parallel to one another. The transverse stretching results in an open network of the crystal formations being formed and in this network some of the crystal formations are deflected out of their original direction of orientation. The network may be split into fibres in known manner. Such treatments can also be effected after the transverse stretching. In another embodiment the splitting into fibres is carried out by subjecting the film to a rolling transversely to the longitudinal direction of the thread-like crystal formations while the B material is still present, subsequently washing out the latter. The B material thus helps in separating the future fibres of the A material so that the resulting sheet product gets a particularly bulky structure. In Example 1, a paper-like material is made from an A-phase consisting of isotactic polypropylene (75%), and a B-phase consisting of a low density polyethylene (25%). The polymers are mixed and repeatedly extruded and cooling of the extruded film is immediately followed by a longitudinal stretching for molecularly orienting the polypropylene. The main part of the polyethylene is removed from the oriented film by solution in xylene at 80 C. While still in the hot xylene bath, the film is drawn laterally to a 5-10 times greater width, thus producing a 3-dimensional flat network of fibres, in which the average width of the fine meshes was far below 1 mm., the product being of paper-like character in the dry state. The remaining residue of polyethylene forms membranes surrounding the fibres and to some extent acting as a binder for the fibres at their points of contact. The surface character of the paper is very hydrophobic because of the polyethylene, and this property makes the material useful for surgical dressings in direct contact with the wound. As both polymers are resistant to almost all chemicals at room temperature, the material is also suitable for filtration. The dissolved polyethylene can easily be precipitated by cooling of the solution and recovered by centrifuging. In Example 2, a paper-like material having a hydrophilic surface is made using polypropylene as the A- phase (75%), and an ethylene-vinyl acetate copolymer as the B-phase (25%). The said copolymer consisted of 29% vinyl acetate and 71% ethylene. The phases are mixed, extruded and cooled, and the extrudate longitudinally stretched for molecular orienting of the polypropylene. The product is then treated in a xylene bath at room temperature, to remove about 30% of the admixed copolymer, and whilst still moist with xylene, the material is laterally stretched to form a homogeneous paper-like material. While the material is still wet and sticky from the xylene, it is cut into short lengths, and cross-laminated by means of a set of rollers. No extra adhesive is necessary as the swollen copolymer acts as an adhesive upon drying. The surface of the laminated material shows satisfactory adhesion of ink and printing ink, and the product is highly water resistant. It is thus useful as a paper substitute. In Example 3, the procedure of Example 2 is used except that pentyl acetate at 90 C. is used instead of xylene. The product obtained has a character different from that of paper and is suitable for clothing purposes, the pentyl acetate treatment resulting in about 95% of the admixed copolymer being dissolved. In the dried state of the product it is extremely soft and relatively bulky, the surfaces of the fibres being relatively hydrophilic and of hairy appearance. To obtain a fabric with sufficient strength in all directions the web is cut into short lengths which are placed on top of each other in a cross-wise arrangement and stitched or glued together. The material, either in a single layer or laminated, is suitable as padding for fabrics, e.g. underwear, robes, sport-shirts and light curtains. In Example 4 a non-woven fabric of a structure similar to that of Example 3 is made from polycaprolactam using 35% of polyoxyethylene as the B-phase. The film forming process is in general similar to that of Example 1. Drawing is replaced by lateral rolling by cutting the film into sheets and by passing through a calender, and the resulting fibre product has the character of a paper without any bulk effect. A product of a bulky structure, similar to that of Example 3 is obtained by rolling to produce a stretching ratio of 5: 1 before washing out the B-phase. Corresponding results can be obtained, using a polyester as the A material instead of the polyamide. In Example 5, polyethylene terephthalate is used as the A-phase (70%) and 30% of the copolymer of caprolactam and hexamethylene diamine adipamide in a ratio of 60: 40 is admixed as the B-phase. The polymers are admixed and extruded and stretched longitudinally to a thickness of 50Á. Subsequently the B-phase is strongly swollen at 50 C. and the sheet stretched transversely by rolling. The fibres produced by the splitting have a relatively hydrophilic cover of the copolymer. In Example 6, a block copolymer having segments of polyethylene terephthalate alternating with segments of macroglycol is split by admixing polyethylene as the B-phase. The ratio between macroglycol and polyester in the copolymer is 40: 60 and 35% of polyoxyethylene is admixed, the m