PROCESS AND DEVICE FOR THE PREPARATION OF COMPOSITE RETICULAR STRUCTURES

Abstract: Process for the continuous preparation of open-net shaped structures comprising the steps of fibrillating a longitudinally oriented 15-200µ thick polymeric film by passing it over pinned rollers so as to form unfibrillated oblique bands at an angle βo of from 0.3°-50° with the fibrillation direction, superimposing at least two of the thus fibrillated films, transversally stretching the assembly of said fibrillated films until the unfibrillated oblique bands form an angle βε comprised between βo and ± 80° with respect to the fibrillation direction, and thermostabilizing the open-net shaped assembly thus obtained. Expanded and/or superficially abraded films can be used in the fibrillation step, to obtain high-surface open-net structures. A device (Fig. II) is also disclosed for the transversal stretching of fibrillated films or assembly thereof, comprising feeding system (1) for said fibrillated film or assembly, a pair of diverging guides (2), each closing upon itself in a ring, clamps (3) freely sliding on said guides to grip the film or assembly at their edges, devices (4) for feeding the clamps to the guides, pulling devices (6) for engaging the clamps, moving in the feeding direction of the film or assembly, devices (13) for opening the clamps and dragging them to the feeding devices (1) and a winder (11) for the open film or assembly.

Description: The present invention concerns a process and a device fo the preparation of composite reticular structures starting from films of synthetic polymers, as well the structures thus obtained. The fibrillation of the synthetic polymer films is an operation that has been known for quite some time and in general has been used in the manufacture of ropes, strings, textile staples, besides for obtaining flat reticular structures suited for use as reinforcement (stiffening) of laming ed materials such as for instance: paper, cement slabs, non-woven fabrics, etc. Amongst the various methods for preparing the above men tioned structures, the most important of them consist in em bossing or slitting mono-oriented films by means of heated points or blades, and by then stretching the film thus obtai ned crosswise (transversally) thereby imparting to it a netlike structure. Such methods will be found to be described in U.S. Pat. nO 3,137,746 and in British patents nos. 1,083,847 and 1,481,520. According to British Pat. nO 1,337,442 to this crosswise stretching operation is made to follow the superimposition or overlapping of the single nets at a certain angle to each other, in its turn followed by a lamination of the assembly of superimposed nets in order to obtain one single composite net-shaped structure. Since the crosswise stretching of the fibrilred film is a difficult and delicate operation, the continuous preparation of suc composite structures requires at least two distinct operations: the first being the stretching and the second being a superimposition, carried out with lines of machines in an angled position to each other. The extreme lightness and delicacy of the material, the phenomenon of longitudinal shrinkage of the film during the stretching, as well as the poor resistance of the fibrils to longitudinal slip stesses are all elements that make the stretch-reticulation operation quite critical and thus hinde in this case the use of the conventional stretching or opening systems used in the textile field, such as clamps or pins supporting chains or other rigid retractor elements of this kind. On the other hand, the fibrilled film opening systems already suggested by the Prior Art, and which consist for in stance, according to French Patent nO 1,331,095, in compressing the film between elastical bands while these latter are forced to expand transversally, find limits and difficulties with regard to the achievement of micro-fibrilled structures as well as with regard to the application of the method -to the continuous preparation of composite structures with a plurality of mutually angulated layers of nets. One of the objects of this invention is thus to provide a process for the preparation in a continuous way of open composite reticulated structures consisting of at least two superimposed or overlapping fibrilled films. A further object of this invention is that of providing a device suited for the transversal opening or stretching (with respect to the direction of the slitting or fibrillin of a fibrilled film or of a combination of at least two superimposed fibrilled films, which allows to operate excluding the above described difficulties. The process according to this invention consists in the following operational phases, in the given order: (1) preparation of a film formed by at least one synthetic polymer, and having a thickness comprised between 35 and 1.200/A; (2) longitudinal or prevailingly longitudinal orientation of the film by means of known mono-axial stretching me thods, with longitudinal drawing ratios comprised bet ween 3 and 15, and with the formation of an oriented film with a thickness comprised between 15 and 200 ? . (3) fibrilling of the film thus oriented, by passing said film over surfaces fitted with pins, blades or other such like agents suited for producing slits, and the consequential formation of oblique unfibrilled bands, as more closely defined further on, forming an angle with the direction of the slits of the film compris ed between about 0.300 and about 500; (4) superimposing of at least two films thus fibrilled with the oblique bands of each film intersecting the obli que bands of the other at any desired angle and any al ternance; (5) transversal stretching of the assembly or pack of su perimposed films, thereby achieving a rotation on the plane of the oblique unfibrilled bands of each film, until these form with the original direction of the slits a new angle pg with the values comprised between and +800C with respect to the direction of the slits; (6) thermostabilization of the assembly of the stretched and superimposed films. The preparation of the starting film may be carried out according to any one of the known film-making methods for synthetic polymers, such as for instance: by extrusion, casting, etc.-Polymers usable for the purposes of this invention are olefinic polymers such as polyethylene and polypropylene, the polyamides, the vinylpolymers such as polyvinyl chloride, polyester resins, as well as the mixtures of said polymers. The fibrillation of the oriented film is achieved by passing the film over rollers or, in general, on surfaces provided with either blades or pins or projections having an orderly and predetermined geometrical arrangement, such as to be reproduceable on the film in the form of slits. Fibrillation methods of this type are described, for instance, in English Patent nO 1,073,741. - In figure I, (A) represents, in the way of an example, an orderly pattern of slits in the film, while (B) shows the arrangement on the plane of the slitting elements (6), such as for instance the points of needles of a fibrilling roller. Moreover: (a) = the distance between 2 needles arranged on a generat ing line of the cylindrical roller, (c) = distance between 2 needles arranged on adjacent cir cumferences of needles and also to the distance bet ween 2 adjacent slits. (d) = the distance between adjacent generating lines of needles, (e) = the length of a slit, (f) = the unslitted stretch between two successive slits; (g) = the stagger between the slits, that is, the distance between the starting or end points of two adjacent slits; (h) = the width of the oblique unfibrilled band, consisting ideally of the oblique succession of the stretches of unslitted film; (p0) = the obliquity of such band, that is, the angle which said band displays in the not transversally stretched fibrilled film, with respect to the direction of the fibrillation of the film. Such an angle will have a clockwise or counter clock wise direction and, thus, a positive or negative sign, with respect to the direction of the slitting of the film, depending on the respectively right-handed or left-handed arrangement of the needles. The angle P o (c) (g) distance between two adjacent slits - stagger between slits wherein the value (g) of the stagger between the slits may be pre-arranged, in the case of the use of fibril ling rollers, on tve basis of the ratio K advancement speed of the film peripheral speed of the pins on fibrilling roller taking into account the relationship: (g) = Times the distance between adjacent generating lines of needles (d). Thus, angle P of the oblique unfibrilled bands is easi ly pre-determined at will within the above indicated limits, with a suitable pattern of the fibrilling system, for instan ce on a needle roller, and with respect to the fibrilling procedures. As already said, this invention envisages to fibrillate in such a way as to obtain angular values of g comprised in the range of from about 0.300 to about 500C. Typical values for the parameters previously defined are, for instance: (c) = 0.1 mm (c) = 1.6 mm (d) = 25 mm (d) = 2.5 mm K = 0.70 K = 0.54 Po 0.330 = about 500 The fibrillation may be carried out with one or more superimposed films on the same fibrilling device or on the single separate films, each of which is fibrilled on a fibrilling device having a different needle distribution partern, so as to obtain from the same fibrillation line the production of films with different /3 angles, necessary for the manufacture of a reticulated and multi-oriented end product. The superimposition of the fibrilled films is preferably carried out in such a way as to get the oblique unfibrilled bands of each film not to coincide with each other but in such a way that said bands will form varied angles, in order to obtain a reticulated assembly endowed with cha racteristics that be as much as possible isothrope. The altern;nce with which the films are superimposed may be anyone wished, especially in the case of films which, although having different fibrilling patterns, show in the course of the successive stretchings out to a net, longitudinal shrinkages of the same order of magnitude, at equal transversal stretching. Preferably, the pack obtained by the superimposition of the single fibrilled films, is welded at the edges so as to facilitate the successive operations. The welding operation may also be carried out on the pack of stretched out and superimposed nets, successively trimming the molten edges. The transversal stretching out of the assembly of super imposed films may be preceded by an impregnation phase of the assembly with sizing and/or glueing products such as polyvinylacetate or an aqueous carboxymethylcellulose solution in order to render the product more solid and handable and, at the same time, to favour its adhering to the products to be reinforced. That impregnation may be achieved, for instance, by diE ping, spraying or by passing the products between rollers, according to known methods. Said impregnation may also be carried out, instead of on films before stretching out, cn already stretched out nets, with the above indicated methods. The transversal stretching out of the pack of fibrilled films must be such as to produce a rotation of the oblique bands on the plane until they form with the direction of the film slitting a new angle h with a value comprised bet ween o and 80 with respect to the direction of the slit ting. Theoretical considerations and experimental measurements show that between the transversal stretch values and the difference O ) between and P OX expressed in radians, there exists a relationship: # = C x (E - 1) final width of the film wherein E = extent of stretch = starting width of the film and where C is a constant that depends on the distribution o layout of the slits in the fibrilled film, and that may also be determined experimentally on any type of such a film. Thus, by properly chosing the values of p and of the characteristical dimensions or sizes of the fibrilled film indicated in figure I with (c), (e), (f) and (g), it is pos sible to obtain with the same extrusion E, a series of different values of pt for each type of fibrillation of the films, consequently obtaining a composite net of different layers, each having its own, predetermined angle of the non -fibrilled oblique bands. Since, moreover, the rotation of the oblique non-fibril led bands occurs always in the polar direction of the start ing angle o, the stretching out of films having starting angles + o and - o, will lead in the stretched out net, to final angles +Pe and - , and, thus, to crossed angles. The combined reticular product thus obtained is, therefore, formed of layers of nets, which will display oblique unfibrilled bands arranged according to angles different in value and sign with respect to the direction of extrusion of the original film, and arranged (laid out) in any sort of alternating order or succession. Once the transversal or cross stretching of the fibrilled film has been accomplished, the opened composite net thus obtained is stabilized dimensionally by thermal treatment that may consist in an inhibited (impeded) shrinkage passage through an oven or on a calender with heated pressu re rolls at a temperature below that of softening of the polymer or polymers constituting the film. The net thus stabilized may be gathered in rolls or on reels ready for use. The composite reticulated structures thus obtained are easy to handle, and the various layers or fibrilled films forming said structures may be welded to each other for use in lamination with other materials, or they may be loose for impregnation with liquid or pasty substances such as hydraulic binders, bituminous, waxy or pasty substances. The process for their preparation, as described above, is simple and may be carried out without interruptions or discontinuities, from the polymer up to the finished product: at industrially convenient operations speeds, and allows to obtain a wide range of products as for weight, size, orien tation and dimensions of the fibrils, and for the number of layers of fibrilled films. Thus, the process can be used for the manufacture of composite open-net shaped structures endowed with unusually high surface area values, such as higher than 12 m2/g by starting from films containing blowing or expanding agents which are caused to expand before the subjecting the films to longitudinal orientation (2). In this case the expansion operation is carried out following the conventional techniques of the prior art, depending on the type of expanding agent used. The quantity, granulometry, the type of expanding agent as well as the expansion conditions, should at any rate be chosen in such a way that the bubbles that form inside the film shall have a mean diameter not exceeding 50%, but preferably not exceed ing 20% of the thickness of the film. The expansion of the film may also be obtained by allowing liquids having boiling temperatures below the temperature of the molten polymer, to expand in the molten polymer in the presence of nucleating agents acting as expansion starters and regulators. Techniques of this kind are describ ed, for instance, in Italian Pat. nO 841,148. When the film is prepared by extrusion, at a temperature corresponding to or greater than the temperature at which the expanding agent becomes active, or if it is prepar ed according to procedures requiring the attainment of such a temperature, the expansion operation may be carried out contemporaneously with the film-preparation operation, provided that it is operated under strictly controlled conditions, such as to give place to the formation of microsized bubbles, uniformly distributed throughout the film, without compromising the integrity of this latter and, on the contra ry, allowing its monoaxial stretching without rupteres. According to another method, which may be used either alone or in combination with the one described above, composite open-net structures having such high surface area values can be obtained by subjecting the longitudinally orient ed film obtained from operation (2), before the fibrillating step (3), to a superficial abrasion operation. The abrasion operation may be achieved by rubbing the film between emery cloths, abrasive papers or grinding wheels, or also by sandblasting, rubbing between brushes, or by other such like methods. The abrasion shall not, however, lead to the proper fis suring or slitting of the film. Once they have been obtained, the fibrillated or net -structured films of this invention may be made wettable by means of oxidative superficial treatments such as the known flame treatments or by high frequency electric discharges. The net-opening device for fibrilled films that forms one of the objects of this invention, allows to obviate the difficulties so far met in this type of operation, and 'more particularly the drawbacks due to the phenomenon of lon gitudinal shrinkage of the fibrilled film, which occurs dur ing its opening to form a net, and which leads easily to the rupture of the film when one tries -to achieve openings of a certain amplitude, or to the distorsion of the unfi brilled bands when the opening is very limited. The device that forms one of the objects of this invention, allows to overcome such drawbacks and may be used either for the ope ning of the single fibrilled films as well as for the openings of a combination superimposed fibrilled films, and for their continuous transformation into open reticulated compo site structures. Substantially, the device according to this invention is characterized in that said device consists of: (A) a feeding system for the fibrilled film or for an as sembly of superimposed fibrilled films; (B) a pair of diverging guides, each closed upon itself to form a ring,which guides, near the feeding system, at the startJare spaced from each other by a length that is equal to the initial width of the film and are then diverging from each other up to a mutual distance equal to the desired width of the extruded film. (C) a series of clamps sliding freely on said guides, so arranged as to allow them to grip the film or assembly of fibrilled films at its edges; (D) a pair of devices for feeding above said clamps to the guides; (E) a series of two pulling devices designed to rigidly en gage the above said clamps, said devices being endowed with a positive drawing or pulling motion in the direc tion of the feeding of the film or assembly of superim posed films; (F) a device suited for opening the clamps and for convey ing them along the guides to the feeding couple (D); (G) a gathering device for the film or assembly of opened films. In figure II are respectively illustrated: a side view (A) and a plan view (B) of a particular embodiment of the device according to this invention. In said figure are shown: the feeding device (1) for the fibrilled film or for the pack of superimposed fibrilled films, which device may consist of a pair or a series of driving rollers; a pair of guides (2) which in this specific case, at the start are parallel and distant from each other by a length Lo, and which then become diverging from each other up to a distance between them L1; the clamps (3), pro vided with teeth (9) designed to mesh with the links of the conveyor chain (6); the feeders (4), which in this specific case consist of wheels with cavities which pick up the clamps and insert them on the guides, at a mutual distance p a device (8) which opens the clamps so that they may grip the film; a set of two stud chains (6) which act as driving or drawing means (E) which engage the teeth of the clamps at the engaging point (10), and which are driven by motor (7) in the direction of the feeding of the film; a 'device (13) which opens the clamps so that these will release the film or pack of stretched films, and which, by the upper part of chains (6), will then carry them back to the feeding device (4);the winding up device (11) for gathering the film or pack of extruded films. From the aforesaid it thus results that the film or pack of fibrilled films enter guides (2), is then grasped by the sliding clamps (3) initially distanced from each other by a distance pO, is thereupon forced to expand in the widening stretch of the guides (2) up to a width L1, necessary to bring the value of the angle of the unfibrilled bands to the desired value. Since the fibrilled film is dragged by the clamps only beginning from the insertion (10) of the chains (6) onward, the film will be free to shrink longitudinally along the whole stretch in which it is subjected to a transversal stretching, thereby drawing closer to each other the clamps (3) themselves. The pair of guides (2) may diverge from each other at equal or different angles with respect to the longitudinal axis of the device. The relationship L1 between their maximum and minimum L o distance consistutes the stretch ratio of the film. The clamps, free to slide along the guides, are operated by a spring and, in the device illustrated in fig. II, are always in the closed position; they only open upon command, through devices (8) and (13) which may be, for instance, especially shaped cams according to techniques well known to the skilled in the Art. If one wishes or it becomes necessary to stabilize dimensionally the reticular shape of the stretched film or pack of films before their winding up, a heating appara tus (5), for instance operating on either hot air or by radiating energy, may be inserted into the device of this invention, between the engaging point (10) and the clamp opening device (13). A regulating device (12) for the longitudinal tension of the film is preferably inserted between the feeding device (1) and the insertion of the film between the guides (2). Said device serves to maintain constant and at the lowest possible values the longitudinal tension of the film at the inlet of guides (2), so as to allow the successive shrin kage due to the transversal extension or stretching. At the outlet of the opening and thermo-stabilizing devices, before the clamp opening device (13), there may be arranged in series equipment for the welding of the edges of the nets as well as devices for the hot compression and cohering of the packs of stretched out nets. More particularly, the hot compressing (or calendering) operation of the pack of stretched out nets may be necessary because the extension or stretching causes a distortion of the shorter fibrils of the net, which then leave the pla nar arrangement (stick out of the planar disposition). This sticking out is partly a favourable element since it acts as a natural link between the layers of nets which are thereby bonded to each other, but at the same time it inure ses the apparent volume of the nets, a fact that may be a disadvantage in impregnation processes of the nets with liquid or pasty products. The compression operation, even if not always necessary, and not indicated in fig. II, has the purpose of reducing the apparent volume and at the same time to impart greater cohesion to the layers to each other, by fixing in a permanent way mutual interlinkages amongst the secondary distorted fibrils. The compressing (or calendering) is carried out according to known methods between pairs of heated rollers or bands, at temperatures below those of the softening of the polymer used. Depending on the use to which the nets are destined to, the compression may be carried out at a pressure of between 0.05 and 2 Kg/sq.cm. Lastly, the winding up or gathering device (11) may constist of a series of reels on which the reticulated product is gathered by winding up, or it may consist of a support of paper, film, fabric or of other similar materials. The particular type of machine illustrated in fig. II, may be realized in different variants, provided that there will be satisfied the possibility of a longitudinal shrinkage of the film during its opening, and, moreover, to main tain the stretching (extension) of the film, without interruptions or discontinuities between the stretching and the thermostabilization phases, which would cause the net to lose, in an uncontrollable way, part of the acquired extension or stretch. In the following are given for exemplifying purposes, but without any limiting effects, a few variants of embodiment of this invention: - the clamps may be so built as to remain always closed, like in example of fig. II: in that case, device (8) must open them in order to allow the film to pass through them, or they may be built in such a way as to be always open, wherefore along guides (2), in the opening and in the thermostabilization of the slitted film, there must be provided devices, for instance, suitably profiled cams suited for keeping the clamps closed; - the opening and closing of the clamps may be carried out by means of electromagnetic, hydraulic or pneumatic sy stems instead of mechanical one, following the techni ques known to the skilled in the-Art; - the clamps may be substituted by systems of needles or pins penetrating the fibrous structure; - the pulling devices defined under point (E) may consist, besides of chains, also of electromagnetic, pneumatic or hydraulic pulling systems; - the clamps may also drag the film along by gravity, with out the need of pulling systems giving to the pair of di verging guides either a vertical or oblique arrangement; - the clamps may be connected with one another mechanical ly also in the opening stretch, for instance, by means of a chain, provided, however, that the connecting ele ments, for instance the links of the chain, may gradual ly draw nearer to one another as the film is opening up, for instance by means of a profiled cam. Such a system will, however, require the adaptation of the profile of the cam for each type of fibrilled film depending on the peculiar relationship existing between the stretch ing and the longitudinal shrinkage of the latter; - with reference to fig. II, device (4) for the periodical feeding of the clamps to the guides (2), which in said figure is represented as a toothed driving wheel compri sing, as opening device (8), a fixed cam for the opening by pressure of the clamps, may be realized with known techniques also with other systems such as for instance with electromagnetic impulse-controlled pusher or a hydra ulic or pneumatic, intermittently working system; - with reference to fig. II, devices (8) and (13) for the opening of the clamps, which in said figure consist of a simple fixed cam, may be realized by known techniques in other forms of embodiment, such as for instance elec tromagnetic systems controlled by a microswitch that is in contact with the arriving (incoming) clamps, or by means of hydraulic or pneumatic systems. The following examples are just given for illustrating and not limiting purposes to more clearly illustrate the in ventive idea. EXAMPLE 1: On a tubular film extruder there was produced a polypro pylene film, using a polymer with a M.I. = 6.7 and with a melt temperature of 165 OC. The film was 120 micron thick and was stretched longitu dinally at a temperature of 1500C and with a drawing ratio of 9. The film thus obtained, 40 micron thick and 80 cm wide, after the cutting of the selvedges, was subdivided into 4 films, each 20 cm wide. The 4 films were, thereupon, passed at a feeding rate of 40 mt/min., respectively over 4 fibrilling rollers having, according to the previously indicated symbols, the following arrangement of the needles: (a) (c) -(d) arrang. of rol (in mm) (in mm) (in mm) of ler needles ¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯¯ needles (in mm) First roller 1.0 0.25 4.0 + 81.5 Second roller 1.0 0.25 4.0 - 81.5 Third roller 1.0 0.25 8.5 - - + 108.0 Fourth roller 1.0 0.25 8.5 - 108.0 The first and second rollers revolve at a peripheral velocity of 61.5 mt/min., while the third and fourth rollers revolve at 100 mt/min. The 4 fibrilled films, according to the symbols previously specified, show repsectively the following characteristics: (c) (e) (f) (g) (g > (in mm) (in mm) (in mm) (in mm) ¯¯¯¯¯¯¯¯¯ First film 0.25 8.4 2.0 2.6 + 50,5 Second film 0.25 8.4 2.0 2.6 - 50 0 Third film 0.25 15.0 2.0 4.3 + 30,0 Fourth film 0.25 15.0 2.0 4.3 - 30,3 The fibrilled films were then superimposed on one another to form one single four-layer ribbon by means of known transmission techniques on obliquely oriented or askew-axes, and welded at the edges by means of heated revolving welders, thereby obtaining one single ribbon consisting of 4 superimposed layers. This ribbon was thereupon impregnated by passing it in a vat containing a 5% carboxymethylcellulose solution, and then through squeezing rollers, after which it was sent to the opening and thermostabilizeing operations, using the device illustrated in figure II, fitted with a guide displaying a symmetrical divergence with an l.1/L ratio equal to 5. In that device the ribbon, fed by device (1), was gathered (picked up) by the system of clamp pull of 10 cm, which was stabilized by heat at 1550C by means of a heating element (5), with a dwell time, at this temperature, of about 1.5 seconds. In consequence of the stretching of the films, the net of the four films showed a longitudinal shrinkage of 88-90%, which becomes visible through the reciprocal drawing closer to each other of the clamps at the end of the transversal stretching run, to about 9 cm distance from each other. The examination of the net samples showed the following angular values first film Bf = about + 300 second film ss# = about - 30 third film p g = about + 160 fourth film =.about - 160 The resulting composite net was passed over a calender fitted with heated pressure rollers, heated at a temperature of 1200C, and was then wound up on reels. EXAMPLE 2: On a flat head extruder of 120 cm width, there was produced a polypropylene film, using the polymer of example 1. The film obtained, 106 cm wide, after listing, showed a thickness of 212 microns. It was stretched at 1500C with a stretch ratio = 7, thereby obtaining a film of 80 micron, thickness and 40 cm width, which was subdivided into 2 films each 20 cm wide. The 2 films were then made to pass contemporaneously on two fibrilling rollers similar to the first and second rol lers of the preceding example, thereby obtaining the characteristics already previously indicated, adn more particularly the angles: +sso =+5 .5 -sso =-5 .5 Other 2 films of the same type were allowed to pass over the fibrilling rollers similar to the third and fourth rollers of the preceding example, obtaining in particular the angles: +sso = + 3 .3 -sso = -3 .3 The 4 films were superimposed on each other by pairs, weldede together at their edges so as to form 2 ribbons, each consisting of films respectively with angles sso= 5 ,5 and p = + 30,3, which were then impregnated with carboxymethylcellulose. These two pairs of fibrilled films were separately stret ched transversally 7 times their original width and then thermostabilized with the technique and device described in example 1, whereafter they displayed a longitudinal shrinka ge of respectively 75% and 88%. At the end of the stretching there were obtained nets, each of which was formed of 2 open fibrilled films characte rized by the following values of first net : ss# = 53 second net : ss# = 23 The 2 nets were superimposed on each other by means of known techniques, welded at the edges and compressed at about 1200C on a calender, thereby obtaining a final single net. EXAMPLE 3: On a blowing-head extruder, with a 500 mm spinneret, there was produced a tubular polypropylene film consisting prevailingly of isotactic macromolecules, which had a M.I. equal to 8, admixed with 15 of low-density polyethylene. The film thus obtained, which halved and listed has a width of 102 cm and a thickness of 255 microns, was stretched lon gitudinally at 1550C with a drawing ratio of 6.5, then obtaining 2 films each 40 cm wide and 100 microns thick. The two films were, thereupon, contemporaneously fibril led on 2 fibrilling rollers similar to the first and second rollers of example 1, thereby obtaining fibrilled film having the same characteristics of the first and second films of that example. Further two unfibrilled films, equal to the preceding ones, were fibrilled on two rollers (third and fourth rollers) with a distribution of the needles characterized by the following parameters: (a) (c) (d) Needle Roller (in mm) (in mm) (in mm) distrib. (in mm) third roller : 4.8 0.8 2.5 + 71.5 fourth roller: 4.8 0.8 2.5 - 71.5 The fibrillation obtained showed the following charac teristics: (c) (e) (f) (g) C3 ) (in mm) (in mm) (in mm) (in mm) third film : 0.8 7.5 3.2 1.8 + 240 fourth film : 0.8 7.5 3.2 1.8 - 240 The films were superimposed separately on each other in pairs and then welded together at their edges, thereby ob taining two (2) ribbons, each formed by two films with re spectively P = + 5 .5 and p = + 240. Both ribbons were stretched separately 2.5 times their width by means of the device used in example 1, thereafter they were thermostabilized, thereby obtaining two pairs of nets each 100 cm wide and each one formed of 2 layers. After stretching, the nets showed up as being formed of fibrilled films having the following angles first and second film : g = + 150 third and fourth film : Pf = + 550 The two nets were then superimposed on each other so as to form one single net and were then welded together at their edges by means of rotary welders and on three (3) inside rows spaced from each other at equal distances of 25 cm each, by means of spot welder, with the welding spots spa 'ced from each other on the same row by 2.5 cm. Thereupon the resulting net was compressed at 1250C on a calender and finally wound up on reels. EXAMPLE 4: On a flat-headed extruder there was extruded into a water-filled tank a 210/(thick polypropylene film having a mel index of 16, additioned with 9% of low density polyethylene. The extrusion temperatures were around 1850C at the wormscrew, and around 1650C at the extrusion nozzle, while the distance between water and nozzle amounted to about 5 cm. The film was stretched longitudinally at a temperature of 1500C, with a stretch ratio of 7, thus obtaining an oriented film 80 micron thick and 80 cm wide, which was then subdivided into 4 films, each 20 cm wide. The 4 films were thereupon fibrillated by passing, respectively over 4 fibrilling rollers having the same characteristics as the fibrilling rollers of Example 1, and by using the same fibri ling conditions as described in that Example. The fibrilled films thus obtained showed a surface area of 9.6 sq.mt/g Another set of 4 films was then prepared and fibrilled by the same way and conditions as described above, thus obtain ing altogether eight fibrilled films, which were successively superimposed on one another to form one single eight-layer ribbon, and then welded at the edges. This ribbon was impregnated with a 5% carboxymethylcellulose solution, as described in Example 1, after which it was sent to the opening and thermostabilizing operations by using the device illustrated in Example 1, except that the L /L ratio (or divergence) was equal to 8 and the thermo 10 stabilization temperature was 1250C. Using aportland cement, there were prepared composite sheets or plates by alternating layers of nets with layers of cement, in a water/cement ratio equal to 30/100, being careful to arrange the nets in such a way as to maintain constant in each layer the reinforcement direction. There was thus obtained a sheet or plate sized 48x48 cm, 7 mm thick, using for the purpose a total of 8 nets for a total of 124 grams, thus reaching a percentage of polypropy lene net, with respect to the cement, of 8.4% by volume. After allowing the sheet or plate to rest for 24 hours, it was aged in water at room temperature for 28 days. Thereupon the sheets or plates were cut up in the reinforcement direction into test pieces or specimen on which were then carried out three-point flexural strength tests according to the UNI 3948 method. The bending occurs along the direction of the reticular reinforcement of the polypropylenic.net. The unitary resistance to bending stresses at break, measur ed as a mean of 3 specimen drawn at different points of the sheet or plate, amounted to 265 Kg/sq.cm. EXAMPLE 5 On a flat-headed extruder there was extruded a polypropylene film with a melt index of 16, additioned with 9% of polyethylene, of the same process and composition as those indicated in example 4. After stretching (at stretch ratio = 7), the 80t thick film was made to pass with both surfaces over rollers of 80 mm diameter, having a peripheral speed of 90 mt/min., and lined with an abrasive cloth of type 0, with the abrasive particles sized between 100 and 150 micron. Thereby were thus obtained, on the whole surface of the film, superficial incisions or cuts at a specific density of 150-200 incisions/sq.mm, with an average depth of about 10t and a diameter of 20-30/ , with the formation of fibrils in a specific quantity of 50-100 fibrils/sq.mm, which protrude from the surface of the film and have widths and thicknesses of between 20 and 30 microns, and lengths of between 20 and 200 microns. Two sets of four films each, obtained from the thus abraded film, were subjected to fibrillation by using the same device and conditions as described in Example 4, thus obtaining eight fibrilled films having a surface area of 18.5 sq.mê/g. . By using these films and operating as in example 4, the re were prepared 8 -layer ribbons which were subjected to the opening and stabilizing operations as described in example 4. Thereupon there were prepared composite net/cement plates, 7 mm thick, similar in composition and preparation to those of example 4, thereby obtaining test pieces for the flexural resistance tests according to the procedu sores indicated in said example 1. The unitary resistance to bending stress at break of the test pieces amounted to 290 Kg/sq.cm. EXAMPLE 6 Following the same procedures as in example 1, a polypropylene film was extruded, having a melt index of 16, and being additioned with 9 of polyethylene and 0.2% of azodi carbonamide (expanding or bulking product). The extrusion temperatures were maintained at 180tC on the extruding screw and at 1600C on the nozzle, while the cooling water/nozzle distance amounted to 3 cm. The film after stretching with a stretch ratio of 7 times, showed a thickness of about 80/4. The film was then abraded on both surfaces, according to the same procedures as those describ ed in example 5, and then was fibrillated under the same conditions as in example 1. Two sets of four films each, obtained from the thus expanded and abraded film, were-subjected to fibrillation by using the device and conditions described in example 4, obtaining eight fibrilled films having a surface area of 48.0 s.mt././4. By superimposing these films, and by operating as in example 4, there were prepared open and thermostabilized 8-layer nets with which, with the same procedures as those described in said example, there were prepared composite cement plates of the same composition. The microscope examinations of the film before the stret ching showed the presence of close bubbles and cavities, 10 to 20 microns wide and 20-400 microns long. On this film, after stretching, the bubbles were found to be elongated by about 7 times while they were only a few microns wide. On the abraded and fibrilled film, the bubbles caused both by the action of the abrasive as well as by the fibrillating pins or needles, gave place to a finely subdivided structure with the appearance of cavities and very fine fibrils7 ex tremely small and very dispersed. The resistance to flexural stresses of the composite pla te specimen, amounted to 340 kg/sq.cm. EXAMPLE 7 Example 6 was repeated, with the difference that the fibrillated films of said example were treated with electrical high frequency discharges, with a power of 3,000 Watts. The measure of the surfactance degree of the films showed a value of 36 dine/cm., measured according to ASTM D 2578 method. By using the same cement and following the same procedures as those of example 6, there were prepared from such films open and thermostabilized 8-layer nets, and with these latter there were formed composite cement plates. Because of the improved wettability of the nets, there may also be inserted into the cement a total volume of about 9.5% by volume of nets. The flexural stress resistance tests indicated a breaking load of 360 Kg/sq.cm.

Claims: CLAIMS 1) Process for the preparation in a continuous run of com posite open-net shaped structures, consisting of at least two superimposed fibrilled films, this process consisting of the following operations: (I) preparing a film formed of at least one synthetic polymer, having a thickness comprised between 35 and 1.200 microns; (II) longitudinal or prevailingly longitudinal orienta tion of the film by a monoaxial drawing or stret ching, with longitudinal drawing ratios comprised between 3 and 15, and with the formation of an oriented film having a thickness comprised bet ween: 15, and 200/A (III) fibrilling the film thus oriented by passing it on surfaces fitted with either needles, blades or other means suited for producing slits, with the formation of unfibrilled, oblique bands form ing an angle P with the direction of the slits of the film, comprised between about 0.300 and about 500; (IV) Superimposing at least two films thus fibrilled with the crossing of the oblique bands of each film according to any angle desired, or with any wished alternance or sequence; (V) transversal stretching of the composite assembly or pack of superimposed films, thereby obtaining a rotation of each film on the plane of the unfi brilled oblique bands, until said bands will form with the original slitting direction a new angle with a value comprised between P and +800 with respect to the direction of slitting; (VI) thermostabilizing the assembly of stretched and superimposed films. 2) Process according to claim 1, characterized in that the synthetic polymer is an olefinic polymer. 3) Process according to claim 1, characterized in that the film contains an expanding or bulking agent which is caused to expand before orienting the film. 4) Process according to claim 3, characterized in that the expansion of the expanding agent produces in the film bubbles or cavities having a diameter not exceeding 50% of the thickness of the film. 5) Process according to claim 1, characterized in that the film after longitudinal orientation, and before fibrill ing, is subjected to a superficial abrasion operation. 6) Process according to claim 1, characterized in that the film contains an expanding or bulking agent which is caused to expand before orienting the film, and in: that the film, after longitudinal orientation, is subjected to a superficial abrasion operation. 7) Composite structure of an open-net shape, characterized in that said structures consist of at least two superim posed fibrilled films, obtained by the process according to the above preceding claims. 8) Device for carrying out the opening or transversal stret ching of a fibrilled film or of an assembly of at least two superimposed fibrilled films, consisting of: (A) a feeding system for the fibrilled film or for the assembly of superimposed fibrilled films; (B) a pair of diverging guides, each closing upon itself in a ring, said guides near the feeding system being spaced at the start from each other by a length equal to the initial width of the film, then gradual ly diverging to a mutual distance corresponding to the width desired for the stretched film; (C) a series of clamps freely sliding on said guides ar ranged in such a way as to be able to grip the film or assembly of fibrilled films at their edges; (D) a pair of devices for the feeding of above said clamps to the guides; (E) a series of two pulling devices suited for rigidly engaging the clamps and provided with a positive pulling motion in the direction of the feeding of the film or assembly of films; (F) a device for the opening of the clamps and for drag ging the same among the guides up to the feeding pair (D); (G) a winder for the film or for the assembly of open films. 9) Structures in the form of open net, consisting of a fi brilled film or of a plurality of superimposed fibrilled films, obtained by means of the device according to claim 8.

Inventors: CAMPRINCOLI, PIERPAOLO, DR., FURIA, EDOARDO, GRONDONA, ADRIANO, VITTONE, ANDREA, DR.
Applicants: MONTEDISON S.P.A., MOPLEFAN S.P.A.
Application year: 1980
Main classification: B29D31
IPC codes: B32B27, B29D28, B29C55