KR19990008402A - Abrasion resistant composite sheet - Google Patents

Abstract

Composite sheets with a surface layer 17 of vertical fibers 10 on a resin impregnated ply provide a sheet with a generally high abrasion resistance. The surface layer 17 has various properties including an effective pile density of 0.1 to 0.5 g / cm ³ , a total density of 0.4 g / cm ³ or more, a resin content of 25 to 90 wt%, and a file parameter of 0.3 g / cm ³ or more Respectively. Preferably, the pile fibers 10 contained in the surface layer 17 are derived from a special shrink knitted fabric or a shrunk 2-barstock stitching fabric 20.

Description

Abrasion resistant composite sheet

Various woven fabrics or nonwoven fabrics are laminated on a resin layer to form a composite sheet for thermoforming and molding processes. For example, such composite sheets are disclosed in U.S. Patent No. 4,298,643 to Miyagawa et al., U.S. Patent No. 5,075,142 to Zafiroglu, and Japanese Patent Publications No. 63-111050 and No. 63-162238 have. Composite composites have been used in many fields. However, such composites need to be improved when they are intended for use in articles that are subject to strong wear, such as sneakers, padding surface layers, protective work clothes, and sturdy bags.

Pile fabrics or pile fabrics such as velvet, velours, terry fabrics, moquette, and tufted-pile fabrics have surface layers in which the fibers are generally perpendicular to the surface of the fabric. In addition, U.S. Patent Nos. 4,773,238 and 4,876,128 to Zapiroglu disclose certain stitch bonded fabrics that allow the use of elastic yarns to shrink the fiber layer to form a pile fabric group. Generally, such fabric is not disclosed for incorporation into a resin-impregnated composite sheet. However, Japanese Patent Laid-Open Nos. 64-85614 and 64-85615 disclose a floor mat comprising a tuft-pile fabric with a rubber resin added thereto. The file height of this tufted-file was 8 mm and the file fiber density was 0.08 g / cm ³ . The combination of pile fiber and resin is 62% by weight pile fiber and 38% by weight resin. The average total density of this combination is 0.13 g / cm < ^{3 &} gt ;. The file parameter P of this mat (as defined below) was only 0.1 g / cm < ^{3 &} gt ;. The present invention does not (a) provide a high abrasion resistance to the mat when such low file fiber concentration and so low total layer density and low file parameters are superimposed, and (b) there is a dense resin layer at the outermost end of such a relatively high file (E.g., all of the resin is within 1 mm of the top of the pile), such a resin / pile layer is stretched and torn by strong abrasive forces. If the wear resistance of such a floor mat increases, its utility will be improved.

U.S. Patent No. 4,808,458 to Watt et al. Discloses a method for producing a suede effect by placing the foamed resin mainly in 75% pile bottom, preferably 50% bottom so that the flocked ) Pile fabrics are disclosed. Such products are ineffective in enduring severe surface wear.

International Patent Publication No. 94/19523 of Zapiroglue discloses a wear resistant resin impregnated nonwoven fabric. This fabric is produced by shrinking the nonwoven fiber layer so that the fiber group is bent out of the layer surface to form an inverted U-shaped loop projecting generally perpendicularly from the layer, and then impregnating the shrunk layer with resin. Typically, the fibers lie in any direction within the nonwoven fibrous layer. The individual fibers in the loop of the warped fiber layer are therefore not laid out in a direction generally perpendicular to the contraction but rather in any direction within the loop of the warped, nonwoven fabric layer. Even if the fiber group forms a vertical U-shaped loop, the majority of the fibers in the loop are still not perpendicular to the layer surface. The resin impregnation of the shrunk fiber layer provides a composite sheet with superior abrasion resistance over a resin impregnated flat (shrink or non-warp) nonwoven layer, but further improvement in durability is desired.

It is an object of the present invention to provide a composite sheet having very high resistance to severe abrasion.

SUMMARY OF THE INVENTION

The present invention provides a wear resistant composite sheet. The sheet has an upper surface and a lower surface and contains a resin, a pile group of fibers and a flat fibrous web. The fibrous web is placed between, and substantially parallel to, the top and bottom surfaces of the composite sheet. The pile fabric group lies between the upper and lower surfaces and is mechanically connected to the planar fibrous web and protrudes generally vertically therefrom. The elongation of the composite sheet does not exceed 25% in any direction. The pile fabric group has an effective pile density c _eff in the range of 0.10 g / cm ³ or more, preferably 0.15 to 0.4 g / cm ³ , and is fixed in a generally vertical posture surrounded by the resin. Typically, the resin accounts for 30 to 90%, preferably 50% or more of the total weight of the composite sheet. The pile fabric and the planar fibrous web are made of textile decitex (i.e., 0.7 to 20 dtex) fibers. Further, the pile fiber / resin layer has a thickness of 0.5 to 3 mm, preferably 1 to 3 mm, a total density d of 0.4 g / cm ³ or more, preferably 0.5 to 1.2 g / cm ³ , ( _Cff ) (d)] ^1/2, where the elongation is 25% or less, preferably 10% or less, and the vertical compression ratio is 25% or less, preferably 10% P is 0.3 g / cm ³ or more, preferably at least 0.35. Typically, the unit weight of the pile fiber / resin layer is in the range of 500 to 2,500 g / m ² . The surface of the composite sheet is abrasion resistant and wears less than 50 microns per 1000 cycles of the 40-grit by Wyzenbeek abrasion test.

The present invention also relates to

(a) a fabric that forms or forms a pile of fibers on a surface layer of 0.5 mm to 3 mm thickness, said pile fabric group being generally perpendicular to the surface of the fabric, Providing a fabric that is mechanically attached to one of the generally horizontal fibrous webs or protruding therefrom,

(b) shrink the area of the fabric to at least 2 times, usually up to 15 times, preferably 3 to 12 times, such that the groups of fibers on the surface are deflected and oriented vertically and the concentration of the generally vertical pile fibers is 0.10 g / cm ³ or more, preferably increasing to about 0.15 to about 0.4 g / cm ³ range,

(c) and contains a resin in the surface layer-resin layer accounted for 30 to 90% of the total weight - by providing 0.4 g / cm full density and 0.3 g / cm ³ or more files, the parameter P ³ or more in the layer file the group of fibers In a generally vertical posture, and

(d) optionally stabilizing the dimensions of the composite by attaching the inelastic element to the composite sheet,

And a method of producing a wear resistant sheet.

The present invention also provides a shaped article and article, wherein said wear resistant composite sheet is attached to at least a portion of the article surface. The composite sheet provides a surface layer capable of withstanding a Vichenbach 40-grit abrasion test (described below) with a thickness reduction of 50 microns / 1000 cycles or less.

The present invention relates to a wear-resistant composite sheet and a method for producing the same. More particularly, the present invention relates to such a composite sheet wherein the pile-like fibers are secured in a generally normal posture to the surface of the sheet by means of a resin.

Figure 1 is a schematic diagram showing an ideal enlarged section of the wear resistant surface layer of the present invention, in which the pile fabric group is in the form of an inverted U-shaped loop 10 which is generally perpendicular to the height H and the base B, And is fixed in the resin 15 between the upper surface 17 and the lower surface 18 of the resin-impregnated fiber layer. The loop 10 is generally perpendicular to the upper surface 17 of the layer and the retracted element 20 is generally parallel to the surfaces 17 and 18. The surface 17 is the surface to which the abrasion conditions are to be exposed. Figure 2 is a section 11 of a yarn or fiber bundle in a nonwoven fibrous layer prior to curl or shrinkage of the yarn or layer, which section is between needlepoints 12 or 13 spaced by a distance S, Lt; / RTI > Figs. 3 and 4 show shapes in which a piece or fabric layer in which the piece 11 is placed is shrunk by 2 times (Fig. 2) or 3 times (Fig. 3) in the longitudinal direction of the piece. It should be noted that when the shrinkage is large, the vertical tendency of the fiber bundle or yarn is also greater.

The following description of the preferred embodiments is included for illustrative purposes and is not intended to limit the scope of the invention, the scope of which is defined by the appended claims.

As used herein, the term filamentous fiber group or filamentous fiber includes bent yarns, inverted-U loops formed from a curved nonwoven layer of textile fibers, tuft yarns, and the like. The fibers in each of these pile fabric groups, as well as the fibers of the nonwoven fabric layer, have a typical textile fiber decitex, say 0.7 to 20 decitex.

The highly abrasion-resistant composite material of the present invention has a surface layer in which the pile-like fiber groups are held together by the resin while the pile groups of fibers are flocked to each other in the surface layer. The pile fibers also protrude generally vertically from the fibrous webs located in the surface layer, for example, at the center plane or the bottom of the layer. The fibrous web may be a nonwoven fibrous layer, a woven fabric, a woven fabric, or the like. Typically, as shown in FIG. 1, the fibrous web 20 is located within 3 mm of the outer surface 17 of the layer to be exposed to wear. The resin 15 and the fibrous net 20 prevent the pile fiber 10 from moving sideways or sinking into the floor when the surface of the composite is subjected to lateral and vertical forces during repeated wear or friction cycles do. The elongation percentage of the composite material and the compressibility (measured as described below) of the resin / pile-fiber layer are 25% or less, preferably 10% or less, respectively. Elongation and compressibility are a measure of how far the fiber can move when the composite is subjected to severe abrasion conditions and how the fiber can fall from its vertical posture.

According to the present invention, the surface layer of the wear-resistant composite has a thickness in the range of 0.5 to 3 mm. Thicknesses greater than 3 mm are avoided because the surface to be worn is more than 3 mm away from the horizontal fibrous web, as it is difficult to stabilize and stabilize the pile layer. The effective concentration c _eff of the substantially normal pile-like fibers in the surface layer is in the range of 0.1 to 0.5 g / cm ³ , preferably 0.15 to 0.4 g / cm ³ . In the surface layer of the composite, the resin constitutes 30 to 90%, preferably 50% or more, and most preferably 70% or more of the total weight of the layer. The total density d of the surface layer is 0.4 g / cm < ³ > or more. For high resistance to abrasion and wear, the surface layer of the composite has a file parameter P of at least 0.3 g / cm < ^{3 &} gt ;. The file parameter P, as defined herein, is the square root of the product of the fiber density on the pile and the total density of the surface layer. The file parameter is expressed by the equation P = [(c) (d)] ^1/2 .

Generally, the surface layer of the composite sheet of the present invention is not completely filled with resin and fiber. This layer may contain many small pores. Because the density of most fibers and resins suitable for use in the present invention is greater than or equal to 1.0 g / cm ³ , the overall density of the surface layer, which is greater than 0.4 g / cm ³ , and generally less than about 0.9 g / cm ^3, More than 10%, and more than 65% of the voids in the surface layer. However, a total density as high as 1.2 g / cm ³ , and thus a resin density greater than 1.0 g / cm ^3, is also contemplated for use in the present invention. A surface layer void volume of 25 to 75% is preferred for a lighter, more flexible composite sheet. A large amount of resin is usually used for a composite material having a low vertical fiber concentration in the surface layer. For example, a layer containing 70 to 90% of the resin is preferable for the composite sheet of the present invention, which has a low effective fiber density of 0.1 g / cm < ³ > For relatively high effective pile fiber concentrations, a low percentage of the resin may be used (e.g., 30-50%).

Various types of resins are suitable for fixing fibers or fiber bundles in a generally vertical posture. Particularly useful polymer resins include polyurethanes, epoxides, synthetic rubbers, polyesters, polyacrylates, polyethers, polyether esters, polyamides, copolymers and mixtures thereof, and the like. The resin may be thermoplastic or thermoset. Very soft resins, such as highly foamed soft rubber latexes or resins, are generally not suitable for use in the present invention. Resins suitable for use in the present invention adhere well to the fibers and are usually distributed evenly throughout the pile-fiber layer. However, if the resin is not wholly uniformly distributed throughout the pile-fiber layer, the resin is preferably concentrated on the side closer to the surface to be worn than the end mechanically attached to the horizontal fibrous web.

The resin may be applied to the pile-fiber layer by any one of several conventional means, for example by immersion, spraying, calendering, application with a doctor knife, or other such technique. The resin can be applied as a solution, dispersion or slurry, or by melting the resin layer and pushing it into the vertical fiber layer. The resin may also be inserted into adhesive particles or binder fibers activated by heat or chemicals. Conventional solidification and / or foaming techniques can also be used to apply the resin. In most cases, the resin or binder can be introduced into the fiber layer before, during, or after the shrinkage step required by the method of the present invention to obtain the desired vertical fiber density in the surface layer. However, when forming a surface layer and containing a resin, care should be taken to avoid escaping the fiber from its vertical posture and to avoid pinning the fiber before it assumes a vertical posture. After incorporation into the pile fiber layer, the resin is dried and / or cured by conventional methods. When the thickness of the pile fiber layer is compressed to about 25% when the resin is applied, the pile fiber is often significantly deviated from the vertical direction, and as a result, the abrasion resistance of the composite sheet can be reduced.

The surface layer of the composite sheet of the present invention is much more abrasive than a 100% resin layer that does not contain any vertical fibers or a resin / fiber surface layer where the fibers are not in a vertical posture. For example, a composite of the present invention in which the vertical fibers are wrapped in a relatively soft polyurethane resin layer can resist 50 to 150 times more wear than a layer made of 100% of the same resin. If a resin that is harder and has a relatively higher abrasion resistance is used, the advantages of the fiber / resin layer of the present invention over a 100% same resin layer are not so large. However, the surface layer of the composite material of the present invention is still much more abrasion resistant compared to a surface layer that does not contain fibers at all or contains mainly horizontal fibers.

In the method of the present invention, the first step is to provide a fabric having or capable of forming a fibrous layer on a pile. As used herein, the term on-the-pile fibrous layer refers to the surface layer of the fabric in which the fibers are generally perpendicular to the surface of the fabric.

According to some embodiments of the method of the present invention, this generally perpendicular fiber layer originates from a substantially non-adhesive fibrous nonwoven layer, wherein the nonwoven fibrous or fibrous group of fibers is deflected on the flat side of the fibrous nonwoven, It takes a shrinking step to make it form. The fibers which are generally perpendicular to the pile upper layer are depicted in Fig. 1 and often appear as inverted U-shaped loops of height H and base B. Such loops typically have an average spacing (i.e., base B) in the range of 0.1 to 2 mm and a height-to-base ratio of at least 0.5 when formed from a non-adhesive fibrous nonwoven fabric. If the layer is highly shrunk (e.g., 10 to 15 times) and additional elements capable of forming fibers on a pile or pile are included in the tissue (e.g., other inelastic yarns in the pinched pattern), loop spacing as small as 0.1 mm and 15 A high-to-low ratio can be obtained. A practical method of measuring the H and B dimensions of the loop is described in the section on Test Methods below.

A typical nonwoven fibrous layer for use in embodiments of the method of the present invention is a thin, flexible, substantially non-bonded web of staple fibers or continuous filaments of textile fiber decitex. These fibrous materials are collectively referred to herein as fibers. The fibers are natural fibers or formed from synthetic organic polymers. Fibers that are thinner than 5 dtex and longer than 5 mm are preferred. The preferred fibrous layer can be warped into relatively short intervals (e.g., as small as 1 mm) and is usually in the range of 15 to 100 g / m ² , preferably less than 60 g / m ² . Suitable materials for the starting nonwoven fibrous layer include carded webs, dry-formed webs, wet-formed webs, spunlaced fabrics, spunbonded sheets, and the like. In general, thick and bulged webs, felt, adhesives or thermally bonded webs and the like are not suitable, and such materials are usually difficult to bend at short intervals.

The shrinkage and warpage of the fibrous layer can be accomplished in any of several ways. For example, shrinkable elements, or shrinkable element rows, can be intermittently attached to the fiber layer. The spacing between attachment points is typically at least 1 mm to allow effective bending. This element or urea column then shrinks so that the area of the fiber layer is significantly reduced and the fiber group is bent out of the layer plane. Prior to attachment of the shrinkable element, additional wrinkles or shrinkage may be imparted to the fibrous starting layer by overfilling the fibrous starting layer with a device used to attach the shrinkable element.

Many types of shrinkage elements are suitable for use in the present invention. For example, a nonwoven fabric layer can be stitch bonded to an elastic yarn under tension. Textured stretch yarn, cloth or exposed spandex yarn are suitable yarns for shrinkable element stitching. After stitching, the tension can be released to shrink or warp the desired fiber layer. Elongated elastic elements in the form of weft yarns, cross weft yarns, films, etc. may be intermittently attached to the fibrous layer by hydroentanglement instead of stitching, adhesives, or hot spot bonding. The tension on the elongated element can then be released to cause shrinkage and warpage of the layer.

Shrinkage when treated with other types of shrinkable elements, such as heat, moisture, chemicals, etc., can intermittently adhere to the fiber layer without adding initial tension or extension to the element. After attachment, the shrinkage of the shrinkable element can be activated by appropriate treatment.

Another method of achieving shrinkage and warpage of the fibrous layer is to intermittently adhere the fibrous layer to the stretchable substrate that is necked-in in a direction transverse to the direction in which the substrate is pulled. For example, some substrates may automatically experience a substantially irreversible contraction (i.e., neck-in) in the transverse direction by an amount two to three times greater than the elongated amount when stretched by 15% in one direction. Thus, by suitably intermittently attaching the fibrous layer to the stretchable substrate before stretching and necking-in operations, and then applying a stretching force to the combined layer and the substrate, the area of the fibrous layer is significantly reduced, It may cause warping.

In another embodiment of the present invention, the pile-in-fiber layer is derived from a conventional yarn in a knitted fabric or woven fabric made of a shrinkable element. When the shrinkable element shrinks, the area of the cloth significantly decreases and the normal thread of the cloth is gathered and bent to protrude vertically from the horizontal plane of the corrugated cloth. In another embodiment, the pile upper layer comprises a fiber loop projecting from a lapping chamber loosely wrapped about the axis of the shrinkable core of the elastic composite yarn. Generally, shrinkable and warp yarns provide a denser pile layer than that provided by shrunk and warped, nonwoven fibrous layers. After application of the resin according to the present invention, the resulting composite sheet made of warped yarn has a higher abrasion resistance than that made of a warped nonwoven fibrous layer.

In another embodiment of the present invention, the pile upper layer may be derived from a shrunk, substantially unbonded fibrous nonwoven fabric, a loose lapping chamber of a shrunk composite yarn and / or a warped inelastic yarn. In embodiments where the pile layer is partially or wholly formed of warped yarns derived from a woven or woven fabric, the fabric or fabric is sufficiently coarse to allow satisfactory yarn warpage. Typically, the bent element has a planar length of at least 1 mm before bending. In another embodiment of the present invention, the tufted pile fabric is shrunk for use in the composite sheet of the present invention to increase the density of the pile tufts.

As used herein, a composite yarn refers to a yarn having a shrinkable core (e.g., provided by an elastic or stretchable yarn) surrounded by a conventional non-shrinkable wrapping yarn or sheath yarn. The wrapping or cladding chamber can be any natural or synthetic fiber. Lapping can be combined with the elastic core by conventional lapping, winding, piling, coating, air jet entangling, mixing, etc., with the elastic core under tension. The core may be a thread or monofilament of any elastic material. A core made of spandex yarn is preferred. When the lapping chamber is tensioned and loosely coupled with the elongated elastic core (e.g., less than 3 revolutions per inch), when the tension is released, the core shrinks and the lapping chamber shrinks and bends perpendicularly to the core. When the composite yarn undergoing the transient tension is knitted, woven or stitch bonded, when the tension is released from the composite yarn, the yarn is shrunk and the lapping yarn is deflected to give the pile fiber to the surface layer. However, if the lapping chamber is wrapped too tightly around the elastic core, the composite yarn can not provide pile-like fibers to the composite sheet.

In the shrinking step of the method of the present invention, the cloth area from which the vertical fibers are derived is shrunk at least twice, preferably 3 to 10 times and sometimes 15 times. The shrinkage step is adopted before or during the application of the resin. After the resin is cured, the fabric can not be shrunk.

As a result of the shrinking step, the concentration of vertical pile fibers in the surface layer of the fabric increases significantly. Next, the fibers are fixed to the surface layer by adding the resin in an amount in the range of 30 to 90% of the total weight of the resin-containing layer (that is, the weight of the resin and the pile fiber). Preferably, the resin accounts for at least 50% and most preferably at least 70% of the total weight of the layer. Typically, the resin is evenly distributed throughout the layer of pile-like fibers. However, if the pile fibers are fixed in a substantially vertical posture, the distribution of the resin may be somewhat uneven and there may be a considerable pore size in the pile. Pores can account for as much as 75% or more of the total volume of the layer. It is unnecessary to remove the void layer to completely fill the layer with resin. In fact, the technology of this purpose is to be avoided because it often makes the fibers excessively squeezed out of the vertical posture. The vertical pile fiber of the resin / fiber layer is essential for the improvement of the abrasion resistance provided by the composite sheet of the present invention.

In addition to the above-described file onto the fabric composite sheet according to the present invention, the file height and file fiber density of the fabric is within the requirements of the present invention that by combining the fabric and the resin may be a file parameter is to prepare a 0.3 g / cm ³ or more layer One other type of pile fabrics, such as cured pile fabrics, velvet, moquette, and velor. Such a starting fabric typically has a pile fiber concentration in the range of 0.05 to 0.15 g / cm < ^{3 &} gt ;. In composite sheets made from such fabrics, the resin typically accounts for more than two-thirds of the total weight of the fiber / resin surface layer on the pile. The overall density of the pile fabric / resin layer is generally greater than or equal to 0.4 g / cm < ³ >, and preferably in the range of from 0.5 to 0.9 g / cm < ^{3 &} gt ;. Higher file densities than lower ones are desirable because dense files are more resistant to compression and file fiber tipping during the resin impregnation step and ultimately lead to a more abrasion resistant layer.

The abrasion resistant surface of the composite sheet of the present invention is resistant to lateral elongation and vertical compression. The extensibility and compressibility of the composite sheet can be controlled in several ways. The elongation of the composite sheet is largely influenced by the horizontal fibrous network in which the filamentous fiber is attached and the filamentous fiber protrudes. An essentially non-elongated fiber net can impart inelasticity to the resin-fiber surface layer when located within about 3 mm of the outer surface of the composite. For low elongation and low compressibility, a harder resin is preferred than a soft one. The lateral stability of the composite sheet in any linear direction can also be obtained by attaching strong, substantially unstretchable strips, films, sheets, webs, cross wefts, etc. to the back surface of the abrasion resistant layer. This attachment can be accomplished by any convenient means, such as gluing, thermal bonding, and the like.

The abrasion resistant composite sheet of the present invention is suitable for use in many various products. The sheet can be molded into various shapes, and can be used as a single layer or multiple layers, and can be attached to the surface or part of the surface of products of various shapes by various means to provide wear resistance to the product. For example, the composite sheet of the present invention is suitable for use in a shoe upper, a work glove, an automobile engine speed adjustment belt, an imitation leather garment, an indoor sports protective pad, a female handbag, a bag, a bag, a saddle, The more abrasion resistant composite sheet of the present invention may be used in products that are subject to more severe wear conditions, such as the front, back, and / or sole of a shoe, the bottom of an industrial bag frequently pulled from the concrete floor, It is especially suitable for bearing surfaces, soccer balls, boots for work, gloves, pads for motorcycle driver clothing.

Test Methods

The following methods and procedures were used to determine various properties of the resin impregnated fabrics of the present invention.

In the composite sheet of the present invention having the vertical pile-shaped fibers formed by the warping of the non-woven fiber layer or by the warping of the short-interval real pieces, inverted U-shaped loops are formed with warped fibers or warped yarns. The height H and base B of the U-shaped loops of this warped fiber group were measured by optical microscope photographs (eg, 15-20 times) of the loop section taken between the loops in a plane perpendicular to the plane of the fiber layer. This data was then used to calculate the H / B ratio. H and B can be measured directly by using a low magnification microscope with strong top and / or back illumination on the sample. Usually the average loop height H is equal to the thickness of the shrunk fiber layer. Alternatively, the average loop height, H, can be measured directly using a touch micrometer with a flat cylindrical probe with a diameter of 0.64 cm (1/4 inch) that applies a load of 10 g to the contacting surface. The digital micrometer, Model APB-1D, manufactured by Mitutoyo, Japan, is easy to measure.

In addition to the methods described above, the pliability of pile-like fibers can be measured by inspection of the enlarged section of the fiber / resin layer. When the loop is knocked or excessively depressed during application of the resin, a relatively long flat portion of the reverse U-shape is visible near the outer surface of the fiber / resin layer. Tilting of straight fibers or yarns from a vertical posture can also be easily observed. This severe tilting of the pile fibers can occur during resin application. A 30% reduction in the pile fiber layer thickness upon application of the resin can reduce the abrasion resistance of the final composite sheet and is particularly so when the pile fiber concentration is near the lower limit of the concentration range suitable for use in the present invention.

(B) a reference length L ₀ on the specimen in parallel with the longitudinal direction, (c) a 1.0 kg weight on the specimen, (D) Suspending for 2 minutes, (d) re-measuring the reference length with additional hanging and referring to the remeasured length as L _f , (e) calculating the formula% S = 100 (L _f -L ₀ ) / L ₀ % Elongation% S by the following formula.

The compressibility, C, is calculated by measuring the change in thickness of the surface pile-fiber / resin layer of the composite sheet under (a) the pressureless state t ₀ , and (b) at a pressure of 351 kPa (51 psi), tf. A thickness gauge was used to apply a load of 1.14 kg (2.5 pounds) onto the pile fiber / resin composite through a cylindrical foot of 1/4 inch (0.64 cm) in diameter. The% compression% C was then calculated as the formula% C = 100 (t ₀ -t _f ) / t ₀ . In order to avoid possible errors in these measurements due to the presence of a compressive horizontal fibrous network in the impregnated layer and to ensure that the measured properties are the characteristics of the pile fiber / resin layer, only the pile / And the horizontal fibrous web was carefully removed.

The unit weight of the fabric or fiber layer was measured according to ASTM Method D 3776-79. The density of the resin impregnated fabric was calculated from the unit weight of the fabric and the measured thickness. The void fraction of the layer can be easily calculated from measurements of the total density of the layer and the weight and density of the fibers in the layer and the resin.

And feed rate, shrinkage ratio, and total crease are parameters described herein as a measure of how shrinkage or creasing occurs as a result of the operation in which the initial fiber layer is applied to the layer. The overfeed ratio, which applies only to embodiments of the present invention using a curved nonwoven fibrous layer, defines the ratio of the initial area of the starting fibrous nonwoven layer to the area of the layer just prior to the first processing step (e.g., stitch bonding step). And feed causes warping, creasing or compression of the nonwoven layer in the direction in which the layer is supplied to the operation. The shrinkage ratio is a measure of the amount of additional shrinkage caused by the nonwoven layer as a result of a particular operation of the nonwoven layer (e.g., stitch bonding and release of tension from the interspersed fibers). The shrinkage ratio is defined as the area of the fibrous layer when the fibrous layer enters a particular operation divided by the area of the fibrous layer as it emerges from a particular operation. Total wrinkles are defined as the product of the supply and shrinkage ratios. The original area fraction is the reciprocal of the total wrinkles and is equal to the ratio of the final area of the fiber layer to the initial area of the starting fiber layer.

The effective pile fiber concentration is calculated from the concentration of fibers in the surface layer of the composite sheet, which is in a normal (or pile) posture relative to the surface to be exposed to wear. In the case of fabrics derived from rigid warp filaments (eg, in the case of shrunken knitted fabrics), the effective filament density is the weight of the hard yarn in one unit of area divided by the thickness of the layer. Likewise, if the pile yarn is provided in a curved yarn that loosely surrounds the stretched elastic yarn which subsequently contracted, then the gross weight of the lapping chamber is included to calculate the pile yarn density but does not include the weight of the elastic core. In the case of a composite sheet in which the filament yarn is formed from a shrunk and warped nonwoven fibrous layer, only 50% of the weight of the nonwoven fibrous layer is included in the calculation of the filament fiber concentration. The inventors have experimentally found that the wear resistance versus file parameter data for the composite of the present invention show a much better correlation when using half the weight rather than the total weight of the warped fibrous layer. This reflects the fact that, for example, pile fibers formed from warped hard yarn and tufted pile fibers are more effective at providing abrasion resistance to composite sheets than pile fibers formed from shrunk and warped nonwoven fibrous layers. Thus, the effective file fiber concentration, c _eff = 10 ^-4 kw / t, where k is 0.5 for pile fibers provided in warped nonwoven fabric layers and 1.0 for warped yarns or tufts, and w is g / m ² , and t is the thickness of the surface layer in cm).

In order to measure the abrasion resistance of the sample, a Vichenbeek precision grinding test system manufactured by J. K. Technologies Inc., Kangakaki, Illinois, USA, and a 40 grit sandbag sandpaper were placed in a vibration drum of a testing machine. A 2.7 kg (6 pounds) load was applied to the drum and oscillated back and forth across the front of the sample at 90 cycles per minute. The test was conducted according to the general procedure of ASTM D 4157-82. Before and after a given number of wear cycles, the thickness of the sample was measured using the thickness gauge described above, and the friability rate was calculated as micron lost per 1000 cycles. In order to provide suitable abrasion resistance for the composite sheet of the present invention, a fogging rate of less than 50 microns / 1000 cycles is considered satisfactory.

In the following examples, the preparation and abrasion resistance of the various composite sheets of the present invention are illustrated and compared with similar composite sheets outside the present invention. The composite sheet of the present invention is much more wear resistant than the comparative composite sheet. The samples of the present invention are indicated by Arabic numerals and the comparative samples are indicated by capital letters. The specific recycled stitch patterns used to make the various knitted or stitch bonded fabrics of the examples were described using conventional lightweight nomenclature. The table is followed in each example and records the wear performance of the sheets as well as the manufacturing details, weight, composition and properties of each composite sheet.

In the examples, the fabrics made of elastic yarn were sequentially taken out from the fabricator, (2) initial shrinkage occurred, (3) soaked in boiling water (100 DEG C) for 1-2 minutes, (4) dried (5) and heat set at 193 ° C (380 ° F) for 1-1.5 minutes in a tenter frame. The specific elongation in the open and closed longitudinal and transverse directions regulates the final shrinkage experienced by the fabric.

Two different polyurethane resins were used to impregnate the pile layer of the composite sample. ZAR, referred to herein as PU-1, was used in the samples of Examples 1 and 3 as a clear polyurethane finish material sold by United Gilsonite Laboratories, Scranton, PA. PU-2, a more ductile polyurethane resin sold by K. J. Quinn Co., Inc., Sibel, New Hampshire, USA, was used for all other samples. PU-2 was blended as a bicomponent formulation, applied to pile fibers and then cured. The samples were resin impregnated with a conventional immersion technique. The applied resin was dried and / or cured in a hot air oven for more than 12 hours with the doctor blade flattened and pile fibers facing downward. The oven temperature was maintained at 65 ° C for fabrics impregnated with PU-1 and 95 ° C for fabrics impregnated with PU-2. The compressibility, density and 40-grit shrinkage (micron / 1000 cycles) of a 5 mm thick layer of each resin without fiber, and Shore A hardness are as follows:

Suzy Shore A hardness % Compressibility Density (g / cm ³⁾ Wear rate PU-1 70 0 1.1 900 PU-2 53 5 1.0 4,500

Example 1

This example compares two resin-impregnated composite sheet samples of the present invention with one sample out of the present invention. In each sample, pile-based fibers were formed from Kevlar (R) aramid fibers (sold by E. I. du Pont de Nemours Co.). In the sample 1, the pile-like fibers are formed by bending the Kevlar (TM) yarn in the knitted fabric. In Sample 2, the pile fabric was formed from a curved Kevlar (R) nonwoven fibrous substrate in a stitch bonded fabric with a curved Kevlar (R) stitch yarn. Due to the low effective fiber density and low file parameters, in comparative sample A devoid of the present invention, the pile-on-fiber group was formed only with a curved Kevlar (TM) fiber nonwoven layer. Samples 1 and 2 of the present invention were found to have abrasion resistance of about 3 to 5 times that of Comparative Sample A.

The starting fabric for the composite sheet of Sample 1 was a 2-needle knitting fabric manufactured from a Liba machine operated at gauge 10 (10 rows per inch or 4 rows per cm) and 22 rows per inch (8.7 per cm). A filament Kevlar (registered trademark) -29 yarn of 400 denier (440 dtex) was interposed in the rear needle bar to form a repeating pattern of 1-0,4-5 stitches. The front needle bar consisted of a 280 denier (320 dtex) Lycra® spandex elastic core and a 70 denier (78 dtex) 34-filament textured polyester yarn wound tightly around it at about 7 revolutions per inch (2.8 / cm) I put in composite yarn. When the knitted fabric was taken out from the LIBA machine, the knitted fabric weight was 159 g / m ² . The knitted fabric was subsequently refined and heat set. As a result, the fabric contracted 2.6 times and the weight increased to 413 g / m ² . The thread of the back needle bar was bent out to form the inverted U-shaped pile fabric group. The tight lapping of the composite yarn on the front needle bar did not contribute to the formation of pile fabric groups. The fabric was then impregnated with polyurethane resin PU-1 and dried and cured in a hot air oven. The properties of the resulting composite sheet sample 1 are reported in Table 1 below.

The starting fabric for the composite sheet of Sample 2 was a 2-needle bar stitch bonded fabric prepared from a 2-needle Liba machine with a width of 3.6 m (140 inches) suitable for stitch bonding of the nonwoven fabric layer. Each needle bar was squeezed into 14 gauge (14 rows / inch or 5.5 / cm) and 9 stitches (3.5 / cm) per inch were inserted into each row. A 34 g / m ² type Z-11 Sontara (R) spun lace fibrous substrate (made by EI du Pont de Nemours Co.) with Kevlar 29 aramid fibers of 1.5 denier (1.7 dtex) and 2.2 cm length per filament ) Was supplied to LIBA with a supply of 47%. The rear needle bar and front needle bar stitch yarn were identical to those used for sample 1, but formed an opposite two-row atlas stitch pattern. When the stitch bonded fabric was removed from LIBA, the fabric area was reduced and the weight increased to 184 g / m ² . The stitch bonded fabric was then refined, heat-settled and resin-impregnated in the same manner as for Sample 1, but the area of Sample 2 shrank 2.9 times in scouring and heat setting, and a total of 4.3 The exception is wrinkles. Details of the composition and characteristics of Sample 2 are listed in Table 1 below.

Comparative Composite Sheet, Sample A, was made from a Kevlar® spunlace starting fabric of the same type and weight as used in Sample 2. One needle bar stitch binder was used in comparative sample A to weave 12 gauge (12 k / in or 4.7 / cm) and insert with 14 stitches / inch (5.5 / cm). The nonwoven fabric layer was fed at 25% and stitched to the same composite yarn as used to make Samples 1 and 2. 1-0, 2-3 repeating stitch patterns. Sample A was resin-impregnated, refined and heat-set in the same manner as Samples 1 and 2. Details of comparative sample A are summarized in Table 1.

The data in Table 1 clearly show the superior abrasion resistance of the composite sheet samples 1 and 2 as compared to the comparative composite sheet of the comparative sample A. The abrasion resistance of samples 1 and 2 was 2.7 and 3.1 times larger than that of comparative sample A, respectively.

sample One 2 A Starting material Weight of non-woven fabric (g / m ² ) 0 34 34 And supply ratio na 1.47 1.25 Tilt weight (g / m ² ) 135 104 0 Shrinkage Component Weight (g / m ² ) 24 30 44 Gross weight (g / m ² ) 159 184 87 Creasing Shrinkage Weight (g / m ² ) 413 537 361 Contraction ratio 2.6 2.9 4.15 Weight of non-woven fabric (g / m ² ) 0 145 176 Tilt weight (g / m ² ) 351 302 0 Total nonwoven pleats na 4.3 5.2 % Of original area 38 35 24 Resin application Resin weight (g / m ² ) 306 566 510 % File height drop 0 0 0 Surface layer characteristic Gross weight (g / m ² ) 657 1013 686 Thickness (mm) 1.1 2.0 1.4 Density (g / cm ³⁾ 0.59 0.51 0.49 File fiber weight (g / m ² ) 351 445 176 File fiber concentration (g / m ³ ) 0.32 0.23 0.13 Effective file density (g / m ³ ) 0.32 0.19 0.065 File parameter P (g / m ³ ) 0.44 0.32 0.18 Ring base B (mm) 0.7 0.5 0.4 Ring H / B ratio 3.6 5.0 3.5 % By weight resin 46 56 74 % Air gap 51 58 59 % Elongation 10 10 10 % Compressibility 10 10 5 40-Grit abrasion resistance Test duration, (10 ³ cycles) 5 5 5 Marson (micron / 10 ³ cycles) 23 36 110 % Conversion ^* 21 33 100 Note: na = not applicable, ^* = converted to Sample A

Example 2

In this Example, comparative samples were prepared with several composite sheet samples of the present invention, similar to those of Example 1, but the polyurethane resin PU-1 of Example 1 was replaced by a softer polyurethane resin PU-2. Each sample and comparative sample has a pile-like fiber group formed of Kevlar (TM) aramid fibers.

Samples 3, 4 and E contain the same fabrics as Samples 1 and 2 of Example 1 and Comparative Sample A, respectively. The composite sheet of Sample 3 includes an elastic composite yarn in one needle bar, and a shrunk fabric knitted in non-elastic yarn in the second needle bar. The composite sheet of Sample 4 includes a shrunk fabric produced by stitch-bonding a fiber layer to a needle bar with an elastic composite yarn and a non-elastic needle bar. Sample E includes a shrunk fiber layer made by stitching a fiber layer to a single needle bar of an elastic composite yarn. Additional Composite Sheet Comparative Samples B and C were made from the same starting fabric as Samples 3 and 4, respectively, but with different amounts of resin applied. Details of the composition, properties and wear performance of the resulting composite sheet samples are summarized in Table 2 below. Table 2 clearly shows the wear resistance benefits of composite sheets made with high numerical file parameters. For example, refer to the results of the wear test for three samples of comparative sample B and four samples of comparative sample C. In addition, the shrinkage results for these samples and sample E versus the corresponding samples of Example 1 indicate that the wear resistance of the composite of the present invention, in view of increasing the resin hardness as long as the resin fixes the fibers and provides low compression and elongation to the layer Lt; / RTI > Increasing the fiber density and file parameters is more effective.

Two composite sheets, Sample 5 and Comparative Sample D were further prepared in addition to the composite sheet containing the fabric with the file-based Kevlar (R) aramid fiber group. The starting fabric for these two samples was a 14 gauge (14 tufting / inch or 5.5 inch) tufted on a 119 g / m2 lightweight glued Reemay (TM) spunbond polyester nonwoven fabric (Reemay, Inc., Old Hickory, lt; / RTI > denier) and 16 tufts / inch (5.1 / cm) of 1100 dtex Kevlar TM. When the tufted fabric is stretched 20%, about 40% of the necking-in is accompanied and the area of the fabric is contracted twice. Details of composite sheet construction and performance are summarized in Table 2.

sample 3 B 4 C 5 D E Starting material Weight of non-woven fabric (g / m ² ) 0 0 34 34 119 119 34 And supply ratio na na 1.47 1.47 na na 1.25 Tilt weight (g / m ² ) 135 135 104 104 205 205 0 Shrinkage Component Weight (g / m ² ) 24 24 30 30 0 0 44 Gross weight (g / m ² ) 159 159 184 184 314 314 87 Creasing Shrinkage Weight (g / m ² ) 413 413 537 537 636 636 361 Contraction ratio 2.6 2.6 2.9 2.9 2.0 2.0 4.15 Weight of non-woven fabric (g / m ² ) 0 0 145 145 0 0 176 Tilt weight (g / m ² ) 351 351 302 302 415 415 na Total nonwoven pleats na na 4.3 4.3 na na 5.2 % Of original area 38 38 35 35 49 49 24 Resin application Resin weight (g / m ² ) 646 102 1263 192 1680 560 1020 % File height drop 0 0 0 0 0 0 0 Surface layer characteristic Gross weight (g / m ² ) 997 453 1710 639 2095 975 1196 Thickness (mm) 1.1 1.1 2.0 2.0 2.6 2.6 1.1 Density (g / cm ³⁾ 0.91 0.41 0.86 0.32 0.81 0.38 1.08 File fiber weight (g / m ² ) 351 351 447 447 415 415 176 File fiber concentration (g / m ³ ) 0.32 0.32 0.22 0.22 0.16 0.16 0.16 Effective file density (g / m ³ ) 0.32 0.32 0.18 0.18 0.16 0.16 0.08 File Parameters (g / m ³ ) 0.54 0.36 0.40 0.24 0.36 0.25 0.29 Ring base B (mm) 0.7 0.7 0.5 0.5 0.8 0.8 0.4 Ring H / B ratio 3.6 3.6 5.0 5.0 3.8 3.8 3.5 % By weight resin 64 22 74 30 80 57 85 % Air gap 24 66 28 72 32 68 10 % Elongation 0 20 0 15 0 0 0 % Compressibility 0 15 0 15 0 0 0 40-Grit abrasion resistance Test duration, (10 ³ cycles) 13 1.5 25 7.9 25 6 13.2 Marson (micron / 10 ³ cycles) 18 80 25 66 30 60 50 % Conversion ^* 36 160 50 132 60 120 100 Note: na = not applicable, ^* = converted to sample E basis

Example 3

This example further illustrates the powerful effect of total wrinkles and the concentration of pile fibers on the abrasion resistance of the composite sheet of the present invention. The composite sheet samples 6, 7 and 8 and the comparative sample F each contain a layer derived from both a fibrous nonwoven layer in which filamentous fibers are bent and a non-elastic stitching chamber in which the filament is bent. The comparative sample G does not have a warped inelastic yarn.

To prepare the starting fabric for each sample, a fiber layer of 26 g / m ² Sontara (R) 8017 spunlaced fabric of non-adherent polyester fibers was over-fed to a 2-bin Liba stitch binder. The front needle bar of Liba is made of a composite yarn of 280 denier (311 dtex) Lycra (TM) spandex elastic core wound tightly at 9 revolutions / inch (3.5 / cm) with 70 denier (78 dtex) 34-filament polyester yarn 1-0 and 2-3 stitch patterns were formed. Except for the fabric of the comparative sample G without the rear needle bar, the rear needle bar is 210 denier (233 dtex) 34-filament high stiffness type 62 Dacron (R) polyester yarn 3-4, . Lycra (registered trademark) and Dacron (registered trademark) are sold by DuPont, respectively. A 14 gauge (14 Ko / inch or 5.5 / cm) Liba machine was inserted 14 lines per inch (5.5 / cm). A different amount of tension was added to the composite yarn used to make each sample that caused different amounts of shrinkage when the fabric was removed from Liba. The shrinkage of the composites led to the development of layers of fibers on the pile. The pile fabric was formed by shrinkage and warpage of the nonwoven fabric layer and by the bending of the back needle bar inelastic stitching yarn accompanied by the contraction of the composite yarn. After refining, the shrunk fabric was heat treated in a tenter frame to fix the final dimensions of the fabric. Thereafter, the fabric sample was impregnated with a polyurethane resin PU-1, which is the same resin as used in Example 1, to fix the pile fibers. The impregnated sample was then dried to produce a composite sheet sample. The details of the sample and the results of the abrasion test are summarized in Table 3 below.

sample 6 7 8 F G Starting material Weight of non-woven fabric (g / m ² ) 26 26 26 26 26 And supply ratio 1.2 1.2 1.2 1.2 1.3 Slope (g / m ² ) 71 71 71 71 0 Shrinkage Component Weight (g / m ² ) 31 31 31 31 32 Gross weight (g / m ² ) 133 133 133 133 66 Creasing Shrinkage Weight (g / m ² ) 578 785 918 238 544 Contraction ratio 4.4 5.9 6.9 1.8 8.2 Weight of non-woven fabric (g / m ² ) 137 183 215 56 277 Tilt weight (g / m ² ) 312 418 490 128 0 Total nonwoven pleats 5.3 7.1 8.3 2.2 10.7 % Of original area 19 14 15 45 12 Resin application Resin weight (g / m ² ) 1043 884 655 499 986 % File height drop 10 9 15 9 0 Surface layer characteristic Gross weight (g / m ² ) 1489 1485 1360 683 1263 Thickness (mm) 1.8 2.0 1.8 1.4 1.6 Density (g / cm ³⁾ 0.83 0.74 0.75 0.50 0.79 File fiber weight (g / m ² ) 449 601 705 184 277 File fiber concentration (g / m ³ ) 0.25 0.30 0.39 0.13 0.17 Effective file density (g / m ³ ) 0.21 0.25 0.33 0.11 0.085 File Parameters (g / m ³ ) 0.41 0.44 0.49 0.23 0.26 Ring base B (mm) 0.44 0.30 0.25 1.0 0.30 Ring H / B ratio 4.1 6.6 7.2 1.4 5.3 % Suzy 70 60 48 73 78 % Air gap 31 38 38 58 34 % Elongation 5 5 10 5 0 % Compressibility 10 5 10 15 0 40-Grit abrasion resistance Test duration, (10 ³ cycles) 23 31 25 2.3 16 Marson (micron / 10 ³ cycles) 32 13 12 80 92 % Conversion ^* 35 14 13 87 100 Note: ^* = converted to sample G

Example 4

In this example, a composite sheet sample was produced from a shrunk fabric knitted with a single needle bar using an elastic composite yarn with a loosely wound inelastic lapping chamber. The pile fabric is formed from the lapping chamber when the composite yarn shrinks.

Samples 9,10 and 11 and the comparative sample H were each dipped into a 280 denier (311 dtex) Lycra yarn loosely wound at about 1.5 turns per inch (0.6 / cm) with a 70 denier (78 dtex) 34- filament textured polyester yarn. (Registered trademark) spandex elastic core, and knitted with a 1-needle Liba machine to form a repeating pattern of 1-0, 2-3 stitches. Each sample was prepared with Liba operating at 14 lines per inch (5.5 / cm) and needle bar at 20 gauge (ie, 20 k / inch or 7.9 / cm) except for Example 11 made with 10 gauge. The fabrics for each sample were knitted using composite yarns under different tension. When the fabric is taken out of the knitting machine, the tension of the composite yarn is released and the area of the knitted fabric is shrunk by 11.5 to 14 times, accompanied by warping of the loosely wrapped yarn to form a pile layer. The polyurethane resin PU-2 as used in Example 2 was applied to the pile fibers of each sample. Details of sample composition and wear performance are listed in Table 4 below, which includes Sample G of Example 3 for comparison.

The wear test results listed in Table 4 show that high fiber density and high file parameters, and concomitant high abrasion resistance can be achieved in fabrics having a pile fabric group provided only by warped yarns. This result also demonstrates the importance of avoiding excessive elongation in composite sheets. It should be noted that the pile fiber / resin surface layer of the comparative sample H composite sheet having a resin content of only 25 wt% is easily elongated and shows a wear rate 11 to 18 times greater than the composite sheet sample 9-11 of the present invention. If the fiber / resin layer does not contain sufficient resin, the composite sheet still lacks resistance to elongation and abrasion, although other properties of the layer are in accordance with the present invention. The abrasion resistance data and other details of the samples are summarized in Table 4, where the superior abrasion resistance of the composite sheet of the invention is clearly demonstrated compared to the comparative samples. These data again show that a resin-impregnated pile-on-fiber layer that meets the requirements of the present invention provides highly effective abrasion resistance to the composite sheet.

sample 9 10 11 H G Starting material Weight of non-woven fabric (g / m ² ) 0 0 0 0 26 And supply ratio na na na na 1.3 Slope (g / m ² ) 0 0 0 0 0 Weight of envelope (g / m ² ) 24 24 21 24 0 Shrinkage Component Weight (g / m ² ) 22 22 20 22 32 Gross weight (g / m ² ) 46 46 41 46 66 Creasing Shrinkage Weight (g / m ² ) 557 557 476 557 544 Contraction ratio 11.5 11.5 14.0 11.5 8.2 Weight of non-woven fabric (g / m ² ) 0 0 0 0 277 Total nonwoven pleats na na na na 10.7 Weight of envelope (g / m ² ) 276 276 294 276 0 % Of original area 8.7 8.7 7.8 8.7 12 Resin application Resin weight (g / m ² ) 910 1009 987 94 986 % File height drop 17 17 13 17 0 Surface layer characteristic Gross weight (g / m ² ) 1186 1285 1281 370 1263 Thickness (mm) 1.5 1.5 1.4 1.5 1.6 Density (g / cm ³⁾ 0.79 0.86 0.91 0.25 0.79 File fiber weight (g / m ² ) 276 276 294 276 277 File fiber concentration (g / m ³ ) 0.18 0.18 0.21 0.18 0.17 Effective file density (g / m ³ ) 0.18 0.18 0.21 0.18 0.085 File Parameters (g / m ³ ) 0.38 0.38 0.44 0.38 0.26 Ring base B (mm) 0.12 0.12 0.10 0.12 0.30 Ring H / B ratio 12.5 12.5 14.0 12.5 5.3 % Suzy 76 78 77 25 78 % Air gap 35 28 24 79 34 % Elongation 10 5 5 80 0 % Compressibility 10 5 10 15 0 40-Grit abrasion resistance Test duration, (10 ³ cycles) 20 18 23 0.8 16 Marson (micron / 10 ³ cycles) 30 40 43 450 92 % Conversion ^* 33 43 47 489 100 Note: ^* = converted to sample G

Example 5

In this example, a shrunk 2-needle-knit woven fabric knitted fabric resin-impregnated composite sheet was produced. The starting fabric for each of Samples 12-15 and Comparative Sample I was an elastic composite yarn with a loosely wrapped inelastic lapping yarn in one needle bar and an inelastic sewing thread in the second needle barrel and knitted in a 2-barrel Liba machine. The front needle bar is a 280 denier (311 dtex) Lycra (TM) spandex with 70 denier (78 dtex) 34-filament textured polyester yarn loosely wrapped around one revolution per inch (0.4 / cm) 0, and 2-3 stitch patterns were formed. The back needle bar was a typical polyester sewing thread of 150 denier (167 dtex) to form a repeating pattern of 3-4, 1-0 stitches. Each sample was made with Liba operating at 14 lines / inch (5.5 / cm), but with sample 22 with 22 g / inch (8.7 / cm) Except for specimen 13 made by threading 10 gauge yarn. The tension applied to the composite yarn used to make the sample is adjusted so that the knitted fabric area is shrunk 1.9 to 7 times when the knitted fabric is taken out of Liba and refined and heat set. The contraction of the fabric is accomplished by shrinking and deflecting the loosely wrapped lapping chamber and deflecting the second needle barrel. Polyurethane PU-2 (same as in Example 2) was applied to each sample.

Details of the composition and wear performance of the samples are summarized in Table 5 below, in which Sample G of Example 3 was included for comparison. The fogging rate results show that Comparative Samples G and I exhibit a fogging rate that is about 2.5 to 20 times greater than the Samples 12-15 of the present invention. The pile fiber of the Sample I fabric was deviated in the vertical direction during resin application, suggesting a 31% loss in surface layer height and insufficient shrinkage ratio.

The results summarized in Table 5 show that in the case of samples 12-15 of the present invention, the shrinkage of the fabric resulted in the formation of pile-like fibers with substantially vertical. The pile fiber originated from both the shrunken lapping chamber and the warped second needle barrel. In contrast, the fabric of comparative sample I did not provide a satisfactory pile layer and was not adequately resin-impregnated and thus exhibited much inferior abrasion resistance. Sample G, despite its very high resin density, did not provide high abrasion resistance due to its low effective pile density and low pile parameters.

sample 12 13 14 15 I G Starting material Weight of non-woven fabric (g / m ² ) 0 0 0 0 0 26 And supply ratio na na na na na 1.3 Slope (g / m ² ) 92 32 32 32 92 0 Weight of envelope (g / m ² ) 33 23 23 23 26 0 Shrinkage Component Weight (g / m ² ) 28 22 22 22 26 32 Gross weight (g / m ² ) 153 77 77 77 154 66 Creasing Shrinkage Weight (g / m ² ) 554 540 870 870 299 544 Contraction ratio 3.6 7.0 11.3 11.3 1.9 8.2 Weight of non-woven fabric (g / m ² ) 0 0 0 0 0 277 Tilt weight (g / m ² ) 331 224 361 361 175 10.7 Weight of envelope (g / m ² ) 118 161 260 260 49 0 Total nonwoven pleats na na na na na 10.7 % Of original area 28 14 9 9 53 12 Resin application Resin weight (g / m ² ) 826 1098 380 920 408 986 % File height drop 16 4 15 0 31 0 Surface layer characteristic Gross weight (g / m ² ) 1275 1483 1001 1541 632 1263 Thickness (mm) 1.6 2.4 1.7 1.9 1.3 1.6 Density (g / cm ³⁾ 0.65 0.74 0.59 0.81 0.49 0.79 File fiber weight (g / m ² ) 449 385 621 621 224 277 File fiber concentration (g / m ³ ) 0.28 0.16 0.37 0.33 0.17 0.17 Effective file density (g / m ³ ) 0.28 0.16 0.37 0.33 0.17 0.085 File Parameters (g / m ³ ) 0.43 0.34 0.47 0.51 0.28 0.26 Ring base B (mm) 0.3 0.3 0.2 0.2 0.3 0.30 Ring H / B ratio 5.3 8.9 8.5 8.5 4.3 5.3 % By weight resin 65 74 38 60 65 78 % Air gap 46 38 51 33 59 34 % Elongation 10 5 10 0 5 0 % Compressibility 10 5 10 0 25 0 40-Grit abrasion resistance Test duration, (10 ³ cycles) 25 25 25 25 4 16 Marson (micron / 10 ³ cycles) 28 40 8 5 100 92 % Conversion ^* 30 40 9 5 109 100 Note: na = not applicable, ^* = converted to sample G

Example 6

In this example, a composite sheet sample having a fiber layer on a resin-impregnated fork-needled pile was prepared.

The starting fabric for Samples J and 16 was laid on a 119 g / m < ² > Reemay (TM) spunbond polyester fabric using a Dilo pork kneader and dipped for 1.5 denier (1.7 dtex), 3 inch ) Length type 54 Dacron (R) polyester fiber (available from EI du Pont de Nemours Co.) in a 272 g / m < ² > The needle roller was a 14 gauge (14 pork needle / inch or 5.5 / cm) machine with about 130 inserts per square inch (20 / cm ² ). A fiber loop was formed on the surface of Reemay (TM) on the opposite side of the needle into the layer. This loop protruded about 2.5 mm above the surface of Reemay (R). Comparative sample J was refined, heat set, impregnated with polyurethane PU-2, and then dried. Sample 16 was tested in the same manner, except that the sample 16 was stretched 30% longitudinally prior to heat setting, resin impregnation and drying and correspondingly reduced to about 37% of its original width, Lt; / RTI > The compositional details, characteristics and abrasion test results of the samples are summarized in Table 6 below. This summary included data for Comparative Sample G of Example 3 for comparison purposes.

Table 6 shows that the composite sheet sample 16 of the present invention containing pile-on-fiber layers produced by fork needling and shrinking has an abrasion resistance 6.5 times higher than a similarly prepared composite sheet having a fork- . In addition, the composite sheet of Sample 16 had an abrasion resistance of 4.5 times as compared with the composite sheet of Comparative Sample G of Example 3. These results underscore that the file parameters of the resin-impregnated pile-fiber layer are very important for providing abrasion resistance to the composite sheet, although this has been revealed in the previous embodiments. Sample 16 of the present invention has a file parameter of 0.37, while comparison samples J and G have file parameters of 0.22 and 0.26, respectively.

sample J 16 G Starting material Weight of non-woven fabric (g / m ² ) 272 272 26 And supply ratio na na 1.3 Shrinkage Component Weight (g / m ² ) 119 119 32 Gross weight (g / m ² ) 391 391 66 Creasing Shrinkage Weight (g / m ² ) 391 821 544 Contraction ratio 1.0 2.1 3.2 Weight of non-woven fabric (g / m ² ) 272 571 277 Total nonwoven pleats 1.0 2.1 10.7 % Of original area 100 48 12 Resin application Resin weight (g / m ² ) 720 930 986 % File height drop 0 0 0 Surface layer characteristic Gross weight (g / m ² ) 992 1501 1263 Thickness (mm) 2.4 2.5 1.6 Density (g / cm ³⁾ 0.41 0.60 0.79 File fiber weight (g / m ² ) 272 571 277 File fiber concentration (g / m ³ ) 0.11 0.23 0.17 Effective file density (g / m ³ ) 0.11 0.23 0.085 File parameter P (g / m ³ ) 0.22 0.37 0.26 Ring base B (mm) 0.8 0.4 0.3 Ring H / B ratio 3.0 6.0 5.3 % By weight resin 73 62 78 % Air gap 65 50 34 % Elongation 10 0 0 % Compressibility 15 0 0 40-Grit abrasion resistance Test duration, (10 ³ cycles) 5 15 16 Marson (micron / 10 ³ cycles) 130 20 92 % Conversion ^* 141 22 100 Note: na = not applicable, ^* = converted to sample G

Example 7

In this example, two composite sheet samples were prepared with a resin impregnated Velor fabric that provided pile fibers to the resin / fiber layer.

The starting fabrics of Samples 17 and 18 were prepared in a three-binocular knitting machine with a width of 130 inches (3.3 m), 70 gauge (70 nits / inch or 27.6 / cm) forming 64 lines / inch (25.2 / cm). A KS3P type machine manufactured by Karl Mayer, Frankfurt, Germany was used. The first needle bar was fitted with a flat (i.e., non-textured) 70 denier (77 dtex) 24-filament polyester yarn to form a repeating pattern of 1-0, 1-1 and 2-1 stitches. The second needle bar was sandwiched by a flat 100 denier (110 dtex) 40-filament polyester yarn to form a repeating pattern of 1-0, 0-0, and 1-1 stitches. In the third needle bar, a flat (i.e., non-textured) 70 denier (77 dtex) 24-filament polyester yarn was interposed to form a repeating pattern of 1-0, 0-0 and 1-1 stitches. Velor fabrics made from this machine is a weight of 347 g / m ² the knitted base (i.e., the bottom) layer and the height 1.5 mm, weight 231 g / m ^2, and the valid file fiber density is 0.18 g / cm ³ the loop-forming ≪ / RTI >

Sample 17 was impregnated with polyurethane resin PU-2 under knitting conditions. The file parameter of the sample after resin curing was 0.31 g / cm < ^{3 &} gt ;. Sample 18 was heat set at a temperature of 191 ° C (375 ° F) in a knitted state condition to stabilize the fabric values. A shear force was then applied to the loop of the thermally fixed sample 18 to obtain a file thickness of 1.2 mm. Sample 18 was also impregnated with polyurethane resin PU-2, resulting in a file parameter of 0.31 g / cm ³ after curing.

As shown in Table 7 below, Samples 17 and 18 were composite sheets of the present invention which exhibited considerably better performance in the 40-grit scratch test. Comparative sample G of Example 3 is also included in Table 7 for comparison. Compared to the composite sheets of samples 17 and 18 of the present invention with numerically impregnated Velor fabrics, the composite sheet of comparative sample G with resin-impregnated shrinkage and warped nonwoven fibrous layers exhibits 2.2 to 2.4 times faster wear than yarns 17 and 18 .

sample 17 18 G Starting material Base layer weight (g / m ² ) 347 347 na File weight (g / m ² ) 231 231 na File Height (mm) 1.5 1.5 na After heat curing and shearing ⁺ Base layer weight (g / m ² ) 347 347 na File weight (g / m ² ) 231 210 na File Height (mm) 1.5 1.4 na Resin application Resin weight (g / m ² ) 452 422 986 % File height drop 15 15 0 Surface layer characteristic Gross weight (g / m ² ) 683 682 1263 Thickness (mm) 1.3 1.2 1.6 Density (g / cm ³⁾ 0.53 0.53 0.79 File fiber weight (g / m ² ) 231 210 277 File fiber concentration (g / m ³ ) 0.18 0.18 0.17 Effective file density (g / m ³ ) 0.18 0.18 0.085 File parameter P (g / m ³ ) 0.31 0.31 0.26 Base B (mm) 0.4 0.4 0.3 H / B ratio 3.3 3.0 5.3 % By weight resin 66 67 78 % Air gap 45 44 34 % Elongation 10 0 0 % Compressibility 15 15 0 40-Grit abrasion resistance Test duration, (10 ³ cycles) 16 15 16 Marson (micron / 10 ³ cycles) 41 38 92 % Conversion ^* 45 41 100 Notes: ⁺ = Sample 180,000 shear, na = not applicable, details of the sample G are shown in Table 3 (Example 3), see, in terms of sample G ^* = reference

Claims (19)

There is an upper surface and a lower surface, A planar fibrous net laid substantially parallel thereto between the upper and lower surfaces, A pile-like fibrous group placed between a lower portion of the sheet and an upper surface and connected to the planar fibrous network and projecting substantially perpendicularly therefrom, Wherein the fiber-based fiber group is fixed in a substantially vertical posture and comprises 30 to 90% of the total weight of the resin-impregnated pile layer, The filamentous fiber group and the flat fibrous nets are made of fibers or filaments of textile decitex, The elongation of the sheet is 25% or less in any direction, Wherein the pile-like fiber group is present in the resin-impregnated pile-on-fiber layer at an effective pile fiber concentration c _{eff of} at least 0.1 g / cm ³ , The resin impregnated pile upper layer has a thickness in the range of 0.5 to 3 mm, a total density d of 0.4 g / cm ³ or more, a unit weight in the range of 300 to 2,500 g / m ² , a vertical compression ratio of 25% Wherein the file parameter P calculated by P = [(c _eff ) (d)] ^1/2 is not less than 0.3 g / cm ³ . The method of claim 1, wherein the resin is the resin accounts for more than 50% of the impregnated file onto the fibrous layer total weight, effective file fiber concentration is from 0.15 to 0.5 g / cm ³ range, the thickness of the layer is 1 to 3 mm range, the layer The total density is in the range of 0.5 to 1.2 g / cm < ³ >, the pile parameter is greater than 0.35 g / cm < ³ >, and the layer is a composite of 40 grit v Wyzenbeek shrinkage of less than 50 microns per 1000 cycles bedsheet. The composite sheet according to claim 2, wherein the elongation of the composite sheet and the compressibility of the resin impregnated pile upper layer are respectively 10% or less. 4. The method according to any one of claims 1 to 3, wherein the pile fibers are in the form of an inverted U-shaped loop or a vertical thread with an average spacing of 0.1 to 2 mm and an average loop height to base ratio of at least 0.5, Wherein the flat fibrous web is provided at least in part by a retracted yarn. 5. The composite sheet of claim 4, wherein the planar fibrous web is a knitted fabric consisting of a shrunk core and a composite yarn with warped hard yarn lapping, wherein the warped lapping forms a pile fabric group. 5. The method of claim 4, wherein the planar fibrous web is a knitted fabric formed using two or more needle bars, wherein one needle bar provides a composite yarn with a shrunk core and the second needle bar has a rigid Composite sheet providing yarn. The composite sheet according to claim 4, wherein the flat fiber layer comprises a nonwoven fabric made of fibers of textile fibers or filaments, and the pile fabric group is a tufted yarn. The composite sheet according to claim 4, wherein the flat fiber layer comprises a shrunk knitted fabric, and the pile-like fiber group is tufts. 5. The composite sheet of claim 4, wherein the U-shaped loops are formed from a shrunk nonwoven layer of partially non-bonded fibers of partially textile fiber decitex. The composite sheet according to claim 4, wherein the flat fiber layer is a stitch-bonded fiber layer, and the stitch bonding thread is a composite sheet having a shrinkable core and loosely surrounding hard sagging. The stitch bonding machine according to claim 4, wherein the flat fiber layer and the pile fabric group are both provided in a contracted 2-bar stitch adhesive fiber layer, the stitch bonding thread of one needle bar is complex with the shrinkable core, . A composite sheet according to any one of claims 1 to 3, wherein the pile fibers and the flat fibrous web are provided by Velor fabrics. Wherein the pile fabric fibers are generally perpendicular to the surface of the fabric and are present at an effective pile fiber concentration of at least 0.1 g / cm < ³ >, wherein the pile fabric fibers are attached to a planar fibrous web positioned within or on a surface of the fabric Providing a fabric having a thickness of 0.5 to 3 mm protruding therefrom, and Phase by introducing the resin in an amount that provides a file parameter full density and at least 0.3 g / cm ³ of 0.4 to 1.2 g / cm ³ range in the impregnated and accounts for 30% to 90% of the impregnated fabric total weight fabrics in fabric file fiber And fixing the group in a vertical state. 14. The method of claim 13, wherein the area of the fabric on the pile is increased by shrinking the area of the fabric by more than two times. 15. The method according to claim 14, wherein the fabric is shrunk to a range of 3 to 12 times. 16. The method of claim 14 or 15, wherein the fabric is a knitted fabric that is knitted using a composite yarn under tension, and optionally using hard yarns, the composite yarn having an elastic core coupled with filament- Forming a knit stitch that provides an interval of at least 1 mm, and wherein the tension is released in the retraction phase. 14. The method according to claim 13, wherein the fixing of the pile fiber group and the stabilization of the fabric dimension are simultaneously achieved by introducing the resin. The method according to claim 17, wherein the composite sheet is further stabilized by attaching a low elongation factor to the back surface of the composite sheet. A shaped article, wherein the wear resistant composite sheet according to claim 1 is attached to at least a part of the product surface.