A method of making dual modulus oriented elastomeric filaments

Abstract: An oriented elastomeric filament spun from a thermoplastic elastomeric material which is a block copolymer selected from either a block copolymer of polybutylene terephthalate and polytetramethylene glycol; a block copolymer of polybutylene terephthalate/polybutylene isophthalate and polyethylene glycol/polypropylene glycol; a block copolymer of polybutylene terephthalate/polyhexene terephthalate and polytetramethylene glycol; or a block copolymer of polyurethane and polytetramethylene glycol, the mole fraction of said polybutylene terephthalate, polybutylene terephthalate/polybutylene isophthalate and polybutylene terephthalate/polyhexene terephthalate in the respective block copolymer being less than 0.5: and said elastomeric filament being further oriented after said spinning by stretching said elastomeric filament at temperatures between 20 o C to 120 o C in a draw ratio producing between 500 to 700 percent elongation of said elastomeric filament so that said oriented elastomeric filament exhibits a two-stage low tensile modulus and high tensile modulus behaviour, when tested in accordance with ASTM D-638 tensile test procedures, such that the high tensile modulus of said oriented elastomeric filament is at least 2 times greater than the low tensile modulus thereof.

Description: Field of the invention This invention generally relates to an oriented elastomeric filament, for example as disclosed in U.S. patent 4,545,614. More particularly, this invention concerns a method of making oriented elastomeric filaments which exhibit a dual modulus or a two-stage low tensile modulus and high tensile modulus type of mechanical behavior when tested in a standard ASTM D-638 tensile test. Background of the invention A feature of the present invention is to provide dual modulus-oriented elastomeric filaments to be used in a seat suspension element in a vehicle seat assembly formed from a block copolymer material capable of being oriented to provide a two-stage modulus in the direction of the suspension span for providing a high comfort index under static load-support conditions and an increasing load-support characteristic for absorbing road impacts. Traditionally, moulded foam cushioning elements of the type set forth in U.S. patent 3,161,436 have been used in automobile and vehicular applications to provide a vehicle seating assembly with both static and dynamic load-supporting characteristics for passenger comfort. In such applications, the element is supported by a rigid backing member forming part of the seat assembly frame for attachment to the vehicle body. The modulus of elasticity of the foam cushioning element and the thickness of the element is selected to provide a static deformation which conforms to and comfortably supports the weight and shape of the different passengers. The cushioning elements have an elastic modulus and are dimensioned to absorb dynamic impacts which are transferred through the vehicle suspension system into the seat assembly. In such cases, the elastic modulus and dimensions of the seating element are selected to absorb the impact loading without causing the foam element to fully compress and "bottom-out" (i.e., flatten against the rigid backing member. Such objectives can only be combined by use of foam elements having a thickness that will produce impact load absorption in a material of an elastic modulus that has a comfortable feel under static load conditions. Such a thickness of the foam element increases the weight of the vehicle seat assembly. U.S. patents 2,251,318 and 4,545,614 disclose vehicle seat assemblies in which elastomeric webbing strips are stretched between vehicle seat frame components to form a suspension for a seat cover. In the case of U.S. patent 2,251,318 the strips are covered by a layer of foam material like sponge material which will impart static comfort to the assembly. The strap components are configured to yield to accommodate impact loads. The straps are reinforced by fabric to control against excessive deflection of natural rubber material of the straps. The U.S. patent 4,545,614 uses strips or fibres of a material having a tensile modulus at high deformation which is a multiple of the tensile modulus of natural rubber to control " bottoming-out" of the suspension system. The material disclosed is a block copolymer of poly(tetramethylene terephthalate) and poly(tetramethylene ether) which is formed by spinning and stretching into filaments having a dual modulus property. The use of strips, filaments or straps requires a cover to impart a smooth seating surface. Such covers can set or distort into the shape of the underlying strip array following periods of use because the filaments are too soft because their elongation is too high. Orientation of various polymeric materials is performed to achieve improved properties, such as tensile strength, creep resistance, abrasion, and permeability resistance. These various polymers include crystalline thermoplastics, non-crystalline thermoplastics, thermoplastic elastomers, and conventional cross-linkable elastomers. However, none of these commercially available materials in a filament form can be used in a seat suspension application. Some commercial filaments are highly elastic and are excellent for comfort but provide poor support due to their low tensile modulus values. Other filaments have very high tensile modulus values and provide excellent support but are poor on comfort. It is therefore an object of the present invention to provide a fairly flexible elastomeric filament to provide comfort in a seat suspension and allow an appreciable reduction in thickness of the foam material currently used in seat suspensions. It is another object of the present invention to provide an oriented elastomeric filament for seat suspension applications that has a good balance of physical properties of elastic behavior and high tensile modulus. It is yet another object of the present invention to provide an oriented elastomeric filament that is tensioned during extrusion to orient the molecular structure of the material and then annealed to fix the material orientation for establishing a two-stage modulus characteristic in the filament. It is still another object of the present invention to provide an oriented elastomeric filament for absorbing vehicular vibrations and to provide increased support in response to increased load. Summary of the invention The present invention can be carried out by first selecting a suitable material that after orientation possesses a two-stage modulus behavior such that it can be suitably used in a seat suspension application. The applicants have discovered that such a suitable material can be selected from thermoplastic elastomers such as a block copolymer of polybutylene terephthalate and polytetramethylene glycol or a block copolymer of polybutylene terephthalate and polyethylene glycol/polypropylene glycol. The filament is first spun by using a small diameter extruder equipped with a suitable metering screw. After the extruder, the spun filament is stretched in at least one draw step to a temperature or temperatures in the range of 20°C to 120°C to a draw ratio greater than 5.0, and then annealed at a temperature in the range of 120°C to 140°C. Preferably, the filament is predrawn to a ratio of 1.4 at a temperature of 27°C, followed by a second stage of drawing in which the filament is drawn to a ratio greater than 5.0 at a temperature of 50°C and then annealed in a hot air oven at 120° to 140°C. The filament is allowed to shrink to a ratio of e.g. 0.84 during the annealing process. The overall draw ratio of the filament is in the range of 5 to 7. The novel orientation process of the present invention produces a tensile strength of the oriented filament at least five times greater than that for the unoriented filament. Most significantly, whereas the oriented filament and the unoriented filament have a similar stress/strain behavior at low strain values, i.e., up to ten percent strain, the stress levels off at higher strain values in the case of the unoriented filament but climbs very fast in the case of the oriented filament. This is what the applicants have called a two-stage modulus behavior. Therefore, the two filaments both feel soft and comfortable when used in a seat suspension application at low elongation, but in the case of an increase in load, the unoriented filament provides little support whereas the oriented filament provides the needed support to prevent the passenger from contacting the seat frame due to the "bottoming-out" of the seat suspension. Description of the drawings Figure 1 is a schematic diagram showing a melt-spinning and orientation operation for the production of an elastomeric filament, according to the present invention. Figure 2 shows stress/strain curves of an unoriented elastomeric filament and an oriented elastomeric filament. Figure 3 shows stress/strain curves of oriented elastomeric filaments, curve A being for an elastomeric filament oriented at a draw ratio of 5 and curve B being for an elastomeric filament oriented at a draw ratio of 6. Figure 4 shows stress/strain curves of oriented elastomeric filaments, curve A being for an elastomeric filament oriented at a draw ratio of 5 and curve D being for an elastomeric filament at a draw ratio of 3.5. Detailed description of the preferred embodiment Referring initially to Figure 1, where a schematic diagram of a melt-spinning and orientation operation for the production of an elastomeric filament, according to the present invention, is shown. The filament 10 is first spun using a 25.4 mm diameter extruder 12 equipped with a 20 to 1 length/diameter metering screw. For a block copolymer of polybutylene terephthalate and polytetramethylene glycol, the extrusion is conducted at 260°C. The die capillary diameter (not shown) is 2 mm. The spun filament 10 first enters a water cooling bath 14 with cooling water at 20°C for sufficient cooling before it enters a first set of calendar rolls 16. After leaving the calendar rolls 16, the elastomeric filament enters a predraw oven 18 set at 27°C before being drawn into a second set of calendar rolls 20. The predrawing of the filament is accomplished at an L/Lo ratio of 1.14 where L is the final length of the filament after predrawing and Lo is the starting length. The final drawing of the filament to an L/Lo ratio of greater than 5.0 is carried out at 50°C through draw oven 22 and a third set of calendar rolls 24. The applicants have tried other drawing temperatures up to 120°C, which produce equally satisfactory results. After the final drawing, the oriented elastomeric filament is annealed in a hot air oven 26 at 120° to 140°C before being picked up by a pickup spool 28. During the annealing process, the elastomeric filament is allowed to shrink to an L/Lo ratio of 0.84. The overall draw ratio of the filament is greater than 5.0. One of the thermoplastic elastomers the applicants have used is a block copolymer consisting of 0.31 mole fraction of crystalline polybutylene terephthalate and 0.69 mole fraction of amorphous polytetramethylene glycol. This thermoplastic elastomer is commercially available as Hytrel (R.T.M.) 4056 from the E.I. Dupont Company U.S.A.. The physical properties of this thermoplastic elastomer are shown in Table I. Physical Properties of Hytrel (R.T.M.) 4056 Melting Point (°C) 148°C Hardness, Durometer D 40 Tensile Strength (MPa) 23 Ultimate Elongation (%) 900 Stress at 10% Elongation (MPa) 2.8 Stress at 30% Elongation (MPa) 6.9 Stress at 50% Elongation (MPa) 7.4 The tensile properties shown in Table I were determined in a standard ASTM D-638 tensile test procedure, using a 1.6 mm thick extruded sheet tested using an Instron machine at room temperature and at a cross-head speed of 508 mm/min. The stress/strain curve of this unoriented material is shown in Figure 2 as curve C. As seen from Figure 2, the elastomeric material is highly elastic and has a very high value of ultimate elongation and a tensile strength of 23 MPa. The material, as is, is not suitable as a seat suspension material because it does not provide sufficient support. Even assuming that enough of this material may be used to provide good support under static conditions, the seat suspension will highly elongate and "bottom-out" when a sudden load is applied to it, such as happens when a car goes over a pot-hole in the road. After the orientation process, the tensile strength of the copolymer of polybutylene terephthalate and polytetramethylene glycol drastically increased to approximately 140 MPa for the oriented filament. This is shown in Figure 2 as curve A. It is to be noted that in Figures 2, 3 and 4, the horizontal axis indicates the percent elongation while the vertical axis indicates the stress in units of mega-Pascals. Most significantly, whereas the two filaments have a similar stress/strain behavior at low strain values (up to 10% strain), the stress levels off at higher strain values in the case of the unoriented sample (curve C) but climbs very fast in the case of the oriented sample (curve A). A two-stage low tensile modulus and high tensile modulus behavior is seen in curve A, where the high tensile modulus is at least twice as large as the low tensile modulus. Therefore, the two filaments both feel soft and comfortable in a seat suspension application at low elongation, but in case of increased load the unoriented filament provides little support whereas the oriented filament provides the needed support in preventing the passenger from contacting the seat frame. With the block copolymer of polybutylene terephthalate and polytetramethylene glycol, the applicants have discovered that orientation of the elastomeric filament at a draw ratio higher than 5 will result in a stronger filament. At the same time, the desirable characteristics of the stress/strain curve are maintained at the higher draw ratio. This is shown in Figure 3 as curve B. The draw ratio for curve B was 6. The applicants have also used a draw ratio of 7 on some filaments producing equally satisfactory results. More importantly, the applicants have discovered that orienting this block copolymer at a lower draw ratio of 3.5 not only gives a lower strength filament, but also a filament which does not have the desired stress/strain curve. This is shown in Figure 4 as curve D. It is seen that the oriented filament produced at the lower draw ratio of 3.5 does not stiffen at higher strains. The applicants have also studied the effect of the annealing temperature on the orientation of this block copolymer. For instance, by raising the annealing temperature after the orientation process from 120°C to 140°C, the uniformity of the physical properties is greatly improved. This is shown in Table II. The average load at break and the mean ultimate strain of the filaments annealed at the two different temperatures are similar. However, the scatter in the experimental values (the difference between the maximum and the minimum values shown in Table II) is very large when the annealing temperature is 120°C. This scattering in the experimental values is greatly reduced for the samples annealed at 140°C. It is to be noted that in each case shown in Table II, ten samples were tested. The applicants have also discovered that increasing the annealing temperature also improves the dimensional stability of the oriented filaments. This is shown in Table II by the low shrinkage value of the 140°C annealed sample, i.e., 21%, as compared to the 120°C annealed samples, i.e., 63%, after exposure to 130°C temperature in an unrestrained condition for 15 minutes. The applicants have also studied the effect of different diameters of the filament on the physical properties of the block copolymer. This is shown in Table III. Effect of Diameter of Oriented Filament on Tensile Properties Measured Using an Instron at a Crosshead Speed of 127 mm/minute Property Diameter of Filament 0.33 mm 0.51 mm Tensile Strength (MPa) 313 195 Ultimate Strain (%) 92 100 For some oriented filament samples, the diameter of the filament has been reduced after spinning and orientation from 0.51 mm to 0.33 mm. The applicants discovered that the thinner filament had about the same ultimate strain as the larger diameter filament, but it was 60% stronger. This is a significant discovery because it could lead to appreciable material savings at comparable strength when the smaller diameter filament is used. The applicants have also studied elastomeric filaments produced from other thermoplastic elastomeric materials. One such material is a block copolymer consisting of 0.25 mole fraction of crystalline polybutylene terephthalate/polybutylene isophthalate and 0.75 mole fraction of amorphous polyethylene glycol/polypropylene glycol. This block copolymer is commercially available as Hytrel (R.T.M.) 4074 from the E.I. DuPont Company, U.S.A.. The hardness of this material is similar to that of the block copolymer of polybutylene terephthalate and polytetramethylene glycol. Other polyesters include block copolymers of polybutylene terephthalate/polyhexene terephthalate crystalline portion and polytetramethylene glycol amorphous portion. The amorphous portion in these polymers is present at concentration greater than 0.5 mole fraction. The applicants have also found that other block copolymers including polyurethane thermoplastic elastomers consisting of a polyurethane crystalline portion and polytetramethylene glycol amorphous portion (more than 0.5 mole fraction) work equally well in the present invention. The applicants have discovered that, in order to have a block copolymer that exhibits the two-stage modulus behavior such that it can be suitably used in a seat suspension element, the amorphous portion of the block copolymer must not be smaller than 0.5 mole fraction of the total copolymer. This is an important requirement in the making of elastomeric filaments from thermoplastic elastomeric materials.

Claims: A method of making an oriented elastomeric filament spun from a thermoplastic elastomeric material which is a block copolymer consisting of a crystalline portion and an amorphous portion, in which the amorphous portion is not less than 0.5 mole fraction of the total copolymer, the block copolymer being either a block copolymer of polybutylene terephthalate and polytetramethylene glycol; a block copolymer of polybutylene terephthalate and polyethylene glycol/polypropylene glycol; a block copolymer of polybutylene terephthalate/polybutylene isophthalate and polyethylene glycol/polypropylene glycol; a block copolymer of polybutylene terephthalate/polyhexene terephthalate and polytetramethylene glycol; or a block copolymer of polyurethane and polytetramethylene glycol, the mole fraction of said polybutylene terephthalate, polybutylene terephthalate/polybutylene isophthalate and polybutylene terephthalate/polyhexene terephthalate in the respective block copolymer being less than 0.5, said elastomeric block copolymer being in the form of an as-spun, unoriented filament having a single stage stress-strain curve (C, Fig.2); said method comprises drawing and permanently deforming the as-spun elastomeric filament in at least one draw step at a temperature or temperatures in the range of 20°C to 120°C in a draw ratio greater than 5.0; and then annealing the drawn filament at a temperature in the range of 120°C to 140°C whilst allowing the drawn filament to shrink by a limited amount such that the net overall draw ratio of the filament is in the range of 5.0 to 7.0, said oriented elastomeric filament exhibiting a two-stage low tensile modulus and high tensile modulus behaviour and an ultimate strain no larger than 140% when tested in accordance with ASTM D-638 tensile test procedures.

Inventors: ABU-ISA ISMAT A, ABU-ISA, ISMAT A
Applicants: MILLER HERMAN INC, HERMAN MILLER, INC.
Application year: 1990
Main classification: D01F6
IPC codes: D01F6, B60N2