Ceramic fiber blanket production line

Improved wet laid bonded fibrous web containing bicomponent fibers including LLDPE EP 0465203 A1 Abstract A thermally bonded fibrous wet laid web containing a bicomponent fiber including a polyester or polyamide fiber component and a component consisting of a linear low density polyethylene having a density in the range of 0.88 to 0.945 g/cc. A grafted HDPE can be added to the LLPDE to improve adhesion of the bicomponent fiber. The bonded fibrous wet laid web may further include a matrix fiber selected from the group consisting of cellulose paper making fibers, cellulose acetate fibers, glass fibers, polyester fibers, ceramic fibers, mineral wool fibers, polyamide fibers, and other naturally occurring fibers. It has been found that a thermally nonwoven fibrous web made using the foregoing ingredients has improved and unexpected strength, lower web variability and is softer.

Claims 1. A thermally bonded fibrous wet laid web consisting essentially of a bicomponent fiber comprising a component of polyester or polyamide; and a second

component consisting essentially of a linear low density polyethylene (LLDPE) having a density in the range of 0.88 to 0.945 g/cc. 2. A thermally bonded fibrous wet laid web of claim 1 wherein the first component is polyester. 3. A thermally bonded fibrous wet laid web of claim 1 wherein the LLDPE has a density of 0.90 g/cc to about 0.940 g/cc and has a C - C alkene comonomer content of about 1% to about 20% by weight of the LLDPE. 4. A thermally bonded fibrous wet laid web of claim 3 wherein the alkene comonomer comprises 1-octene. 5. A thermally bonded fibrous wet laid web consisting essentially of a bicomponent fiber comprising a first component of polyester or polyamide, and a second component consisting essentially of a linear low density polyethylene copolymer having a density in the range of 0.88 to 0.945 g/cc, and grafted high density polyethylene, HDPE, having initially a density in the range of 0.94 to 0.965 g/cc, which has been grafted with maleic acid or maleic anhydride, thereby providing succinic acid or succinic anhydride groups grafted along the HDPE polymer. 6. The thermally bonded fibrous wet laid web of claim 5 wherein the ungrafted LLDPE has a density in the range of about 0.90 g/cc to about 0.940 g/cc and has a C - C alkene comonomer content of about 1% to about 20% by weight of the LLDPE. 7. The thermally bonded fibrous wet laid web of claim 6 wherein the alkene comonomer comprises 1-octene. 8. The thermally bonded fibrous wet laid web of claim 5 wherein LLDPE copolymer is one having a density in the range of about 0.88 g/cc to about 0.945 g/cc containing about 0.5% to about 35% by weight of a C - C alkene comonomer. 9. The thermally bonded fibrous wet laid web of claim 8 wherein the ungrafted LLDPE copolymer contains about 2% to about 15% by weight of 1-octene comonomer. 10. A thermally bonded fibrous wet laid web consisting essentially of a bicomponent fiber comprising a first component of polyester or polyamide and a second component consisting of linear low density polyethylene having a density in the range of 0.88 to 0.945 g/cc and a matrix fiber selected from the group consisting essentially of cellulose paper making fibers, cellulose acetate fiber, glass fibers, polyester fibers, metal fibers, mineral wool fibers, polyamide fibers and other naturally occurring fibers. 11. A thermally bonded fibrous wet laid web of claim 10 wherein said first component is polyester. 12. A thermally bonded fibrous wet laid web of claim 10 wherein the LLDPE has a density of 0.90 g/cc to about 0.935 g/cc and has a C - C alkene comonomer content of about 1% to about 20% by weight of LLDPE. 13. A thermally bonded fibrous wet laid web of claim 12 wherein the alkene comonomer comprises 1-octene. 14. A thermally bonded fibrous wet laid web of claim 10 wherein the bicomponent fiber has a length to diameter ratio between about 100 and about 2000. 15. A thermally bonded fibrous wet laid web consisting essentially of a bicomponent fiber comprising a first component of polyester or polyamide; and a second

component consisting essentially of linear low density polyethylene copolymer having a density in the range of 0.88 to 0.945 g/cc and grafted high density polyethylene, HDPE, having initially a density in the range of 0.94 to 0.965 g/cc, which has been grafted with maleic acid or maleic anhydride, thereby providing succinic acid or succinic anhydride groups grafted along the HDPE polymer claim; and a matrix fiber selected from the group consisting essentially of cellulose paper making fibers, cellulose acetate fibers, glass fibers, polyester fibers, metal fibers, mineral wool fibers, polyamide fibers and other naturally occurring fibers. 16. The thermally bonded fibrous wet laid web of claim 15 wherein the LLDPE has a density in the range of about 0.90 g/cc to about 0.940 g/cc and has a C - C alkene comonomer content of about 1% to about 20% by weight of the LLDPE. 17. The thermally bonded fibrous wet laid web of claim 16 wherein the alkene comonomer comprises 1-octene. 18. The thermally bonded fibrous wet laid web of claim 15 wherein LLDPE copolymer is one having a density in the range of about 0.88 g/cc to about 0.945 g/cc containing about 0.5% to about 35% by weight of a C - C alkene comonomer. 19. The thermally bonded fibrous wet laid web of claim 15 wherein the LLDPE copolymer contains abut 2% to about 15% by weight of 1-octene comonomer. 20. A thermally bonded fibrous wet laid web comprising a bicomponent fiber comprising a core of a polyester or polyamide; and a sheath consisting of linear low density polyethylene copolymer having a density in the range of 0.88 g/cc to 0.945 g/cc and grafted high density polyethylene, HDPE, having initially a density in the range of 0.94 to 0.965 g/cc, which has been grafted with maleic acid or maleic anhydride thereby providing succinic acid or succinic anhydride groups grafted along the HDPE polymer chain wherein the bicomponent fiber has a length to diameter ratio between about 100 and about 2,000; and a matrix fiber selected from the group consisting essentially of cellulose acetate fibers, glass fibers, polyester fibers, ceramic fibers, wool fibers, polyamide fibers, and other naturally occurring fibers. 21. A method of forming a thermally bonded fibrous wet laid web by wet laying fibers on paper making equipment or wet lay nonwoven equipment, the web comprising bicomponent fibers comprising a first component consisting of polyester or polyamide; and a second component consisting essentially of linear low density polyethylene having a density in the range of 0.88 g/cc to 0.945 g/cc; wherein the steps of forming a fiber furnish by dispersion of said bicomponent fibers in a carrier medim consisting essentially of water, thickener and dispersant and supplying the fiber furnish at a consistency in the range of 0.01 to 0.5 weight percent fibers to the wire of a machine forming a fibrous web followed by heating the web to cause the second component of the bicomponent fiber melt to provide the thermally bonded fibrous web. 22. A method of forming a thermally bonded fibrous wet laid web by wet laying fibers on paper making equipment or wet lay nonwoven equipment, the web comprising bicomponent fibers comprising a first component of polyester or polyamide, and a second component consisting essentially of linear low density polyethylene copolymer having a density in the range of 0.88 to 0.945 g/cc and grafted high

density polyethylene, HDPE, having initially a density in the range of 0.94 to 0.965 g/cc, which has been grafted with maleic acid or maleic anhydride, thereby providing succinic acid or succinic anhydride groups grafted along the HDPE polymer; and matrix fibers wherein the steps of forming a fiber furnish by dispersion of said bicomponent fibers and matrix fibers in a carrier medium consisting essentially of water and a dispersant and a thickener, and supplying the fiber furnish at a consistency in the range of 0.01 to 0.5 weight percent fibers to the wire of a machine forming a fibrous web an then heating the fibrous web to melt the second component and thermally bond the fibrous web. Description Background of the Invention 1. Field of the Invention

[0001] The present invention relates to a thermally bonded fibrous wet laid web containing a specific bicomponent fiber. This thermally bonded fibrous wet laid web not only has increased web strength, but also is found to provide greater web uniformity. Furthermore, the web is found to be much softer than a regular paper web. In particular, the bicomponent fiber consists essentially of a first component consisting of polyester or polyamide and a second component consisting of linear low density polyethylene. The thermally bonded fibrous wet laid web may further include a matrix fiber selected from a group consisting of cellulose paper making fibers, cellulose acetate fibers, glass fibers, polyester fibers, ceramic fibers, metal fibers, mineral wool fibers, polyamide fibers, and other naturally occurring fibers. 2. Prior Art

[0002] In the prior art processes of making wet laid webs or paper from fibers of whatever source, it is customary to suspend previously beaten fibers, or what is generally known as pulp, in an aqueous medium for delivery to a sheet-forming device, such as a Fourdrinier wire. This fiber containing aqueous dispersion is commonly referred to in the art as a furnish. One troublesome problem at this stage of making wet laid fibrous webs, is the tendency for the fibers to clump, coagulate or settle in the aqueous vehicle. This condition is generally referred to as flocculation, and greatly impedes the attainment of uniform web formation. That is, flocculation causes a nonuniform distribution of fibers in the paper product produced therefrom and manifests not only a mottled, uneven appearance, but is also defective in such important physical properties as tear, burst, and tensile strength. Another problem in making wet laid fibrous webs is a tendency of the fibers to float to the surface of the furnish.

[0003]

For the manufacture of fibrous wet laid webs from conventionally used fibers such as cellulose, methods are known for attaining uniform dispersion of the fibers and reducing and even preventing the occurrence of flocculation. One of the more effective means has been to add a small amount of karaya gum to the fiber furnish. However, this has proved unsuccessful in various applications but other agents such as carboxymethyl cellulose or polyacrylamide have been used to attain the desired result of the cellulose in the furnish.

[0004] Fibrous wet laid webs may also be made from other natural or synthetic fibers in addition to the wood cellulose paper-making fibers. A water furnish of the fibers is generally made up with an associative thickener and a dispersant. The cellulose pulp is dispersed in water prior to adding the dispersant, followed by the addition of the associative thickener in an amount in the range up to 150 pounds per ton of dry fiber making up the water furnish and then the addition and dispersion of the natural and/or synthetic fibers. Finally, the dispersion of mixed fibers in a water carrier is diluted to the desired headbox consistency and dispensed onto the forming wire of a conventional paper-making machine. An anti-foam agent may be added to the dispersion to prevent foaming, if necessary, and a wetting agent may be employed to assist in wetting the fibers if desired. A bonded fibrous web may be formed from the fiber furnish on a high speed conventional Fourdrinier paper making machine to produce a strong, thermally bonded fibrous wet laid web.

[0005] In prior art processes for wet lay wherein the textile staple fibers are polyester fibers, water-based binders are generally added to the process to insure adhesion between the cellulose fibers and the polyester fibers. Generally, from about 4% to about 35% binder material is employed. One of the problems encountered using a water based binder is the binder leaches out of the resultant web in such applications as filters. Addition of binders increases cost and results in environmental problems. Furthermore, latex binders have a short shelf life and require special storage conditions. Also, the latex binders may be sensitive to the condition of the diluent water employed.

[0006] It is well known to blend bicomponent fibers with natural and synthetic fibers in dry processes of making nonwoven fabrics. For example, in European Patent Application No. 0 070 164 to Fekete et al there is disclosed a low density, high absorbent thermobonded, nonwoven fabric comprising a staple length polyester/polyethylene bicomponent fiber and short length natural cellulose fibers. The U. S. Patent No. 4,160,159 to Samejima discloses an absorbent fabric containing wood pulp combined with short-length, heat fusible fibers.

Although these patents disclose the use of the combination of bicomponent fibers and cellulose fibers, the disclosure is not directed to a wet lay application. Many problems arise in attempting to incorporate a heat fusible fiber such as a bicomponent fiber into a wet lay fibrous web.

[0007] Such nonwoven textile fabrics are normally manufactured by laying down one or more fibrous layers or webs of textile length fibers by dry textile carding techniques which normally align the majority of the individual fibers more or less generally in the machine direction. The individual textile length fibers of these carded fibrous webs are then bonded by conventional bonding (heating) techniques, such as, for example by point pattern bonding, whereby a unitary, self-sustaining nonwoven textile fabric is obtained.

[0008] Such manufacturing techniques, however, are relatively slow and it has been desired that manufacturing processes having greater production rates be devised. Additionally, it is to be noted that such dry textile carding and bonding techniques are normally applicable only to fibers having a textile cardable length of at least about 1/2 inch and preferably longer and are not applicable to short fibers such as wood pulp fibers which have very short lengths of from about 1/6 inch down to about 1/25 inch or less.

[0009] More recently, the manufacture of nonwoven textile fabrics has been done by wet forming technique on conventional or modified paper making or similar machines. Such manufacturing techniques advantageously have much higher production rates and are also applicable to very short fibers such as wood pulp fiber. Unfortunately, difficulties are often encountered in the use of textile length fibers in such wet forming manufacturing techniques.

[0010] Problems encountered in attempting to incorporate a heat fusible fiber such as a bicomponent fiber into a wet lay process is attaining uniform dispersion of the bicomponent fiber as well as attaining a thermally bonded web with sufficient strength such that the thermally bonded web is usable. It has been found in the past that bicomponent fibers containing a sheath of high density polyethylene (HDPE) and a core of polyester are difficult to uniformly disperse in wet lay solutions. When dispersion of fibers has been attained, fibrous webs produced therefrom have been found to have lacked the desired strength.

[0011]

European Patent Application 0 311 860 discloses a bicomponent fiber having a polyester or polyamide core and a sheath component consisting of a copolymer straight-chain low density polyethylene; and the bicomponent fiber can be formed into a web through the use of known methods of making nonwoven fabrics including wet laying. The copolymer polyethylene is defined as consisting of ethylene and at least one member selected from the class consisting of an unsaturated carboxylic acid, a derivative from said carboxylic acid and a carboxylic acid and a carboxylic acid anhydride. The application fails to provide any details regarding the copolymer polyethylene into a wet lay process or the resulting properties of the web produced therefrom.

[0012] There remains a need to develop a thermally bonded wet lay fibrous web including a suitable heat fusible bicomponent filament which will not only increase the strength of the web, but also avoid problems associated with adding binders. SUMMARY OF THE INVENTION

[0013] The present invention is directed to a thermally bonded fibrous wet laid web including a specific bicomponent fibers so as to yield a thermally bonded web not only having increased strength, but also greater web uniformity and softer than a regular paper web. In particular, the thermally bonded fibrous wet laid web of the present invention consists essentially of a bicomponent fiber comprising a first fiber component of polyester or polyamide, and a second component consisting essentially of a linear low density polyethylene (LLDPE) having a density in the range of 0.88 g/cc to 0.945 g/cc.

[0014] Furthermore, the present invention includes a thermally bonded fibrous wet laid web comprising a bicomponent fiber consisting essentially of a first component of polyester or polyamide, and a second component consisting essentially of a linear low density polyethylene having a density in the range of 0.88 g/cc to 0.945 g/cc; and a matrix fiber selected from the group consisting essentially of cellulose paper making fibers, cellulose acetate fibers, glass fibers, polyester fibers, ceramic fibers, mineral wool fibers, polyamide fibers and other naturally occurring fibers. Brief Description of the Drawings

[0015]

Figure 1 shows a graph illustrating the relationship of tensile strength to various levels of bicomponent fibers in a thermally bonded web as described in Example 2.

[0016] Figure 2 shows a graph illustrating the relationship of elongation to various levels of bicomponent fibers in a thermally bonded web as described in Example 2.

[0017] Figure 3 shows a graph illustrating the relationship of the Elmendorf tear tests to various levels of bicomponent fibers in a thermally bonded web as described in Example 2.

[0018] Figure 4 shows a graph illustrating the relationship of the Mullen Burst test to various levels of bicomponent fibers in a thermally bonded web as described in Example 2. Description of the Preferred Embodiments

[0019] A thermally bonded fibrous wet laid web of the present invention is prepared from a specific bicomponent fiber and optionally a matrix fiber. Processes to make such thermally bonded fibrous wet laid web would also use suitable dispersant and thickeners.

[0020] Bicomponent fibers suitable for the present invention include a first component or a backbone polymer of polyester or polyamide or polypropylene. Polyester, polyamides and polypropylene are well known textile materials used in the manufacture of fabrics and other applications. Although polyester and polyamides have been listed, any suitable backbone polymer would include polymers having a higher melting point than the LLDPE. Generally the backbone polymer has a melting point at least 30C higher than that of the second component.

[0021] Also included in the bicomponent fiber is a second component consisting essentially of a linear low density polyethylene. Such polymers are termed "linear" because of the substantial absence of branched chains of polymerized

monomer units pendant from the main polymer "backbone". It is these linear polymers to which the present invention applies. In some, there is a "linear" type ethylene polymer wherein ethylene has been copolymerized along with minor amounts of alpha, beta-ethylenically unsaturated alkenes having from 3 to 12 carbons per alkene molecule, preferably 4 to 8. The amount of the alkene comonomer is generally sufficient to cause the density of the polymer to be substantially in the same density range of LDPE, due to the alkyl sidechains on the polymer molecule, yet the polymer remains in the "linear" classification; they are conveniently referred to as "linear" low density polyethylene.

[0022] The LLDPE polymer may have a density in the range of about 0.88 g/cc to about 0.945 g/cc, preferably about 0.90 g/cc to about 0.940 g/cc. It is evident to practitioners of the relevant arts that the density will depend, in large part, on the particular alkene(s) incorporated into the polymer. The alkenes copolymerized with ethylene to make LLDPE comprises a minor amount of at least one olefinically unsaturated alkene of the form C - C, most preferably from C - C; 1-octene is especially preferred. The amount of said alkene may constitute about 0.5% to about 35% by weight of the copolymer, preferably about 1% to about 20%, most preferably about 1% to about 10%.

[0023] The LLDPE polymer may have a melt flow value (MFV) in the range of about 5 gm/10 min to about 200 gm/10 min as measured in accordance with ASTM D1238(E) at 190C. Preferably the melt flow value is in the range of about 7 gm/10 min to about 120 gm/10 min, most preferably about 10 gm/10 min to about 105 gm/10 min. Practitioners of the relevant arts are aware that the melt flow value is inversely related to the molecular weight of the polymer.

[0024] The second component of the bicomponent fiber may also include a grafted high density polyethylene (HDPE), in a blend with the LLDPE wherein the HDPE has been grafted with maleic acid or maleic anhydride, thereby providing succinic acid of succinic anhydride groups grafted along the HDPE polymer chain. The HDPE for use in the present invention is a normally solid, high molecular weight polymer prepared using a coordination-type catalyst in a process wherein ethylene is homopolymerized. The HDPE which is used in making the grafted HDPE in accordance with the present invention is characterized as having a melt flow value in the range of about 5 g/10 min to about 500 g/10 min according to ASTM D-1238(E) at 190C and a density in the range of about 0.94 g/cc to about 0.965 g/cc, preferably a MFV about 7 gms/10 min to about 150 gms/10 min and a density of about 0.945 g/cc to about 0.960 g/cc. The anhydride or acid groups generally comprise about 0.0001 to about 10 wt. percent, preferably about 0.01

to about 5 wt. percent of the HDPE. The ratio of grafted-HDPE/ungrafted LLDPE of the present blend is in the range of about 2/98 to about 30/70, preferably about 5/95 to about 20/80.

[0025] The maleic acid and maleic anhydride compounds are known in these relevant arts as having their olefin unsaturation sites conjugated to the acid groups, in contradistinction to the fused ring and bicyclo structures of the non-conjugated unsaturated acids of e.g., U. S. Pat. No. 3,873,643 and U. S. Pat. No. 3,882,194 and the like. Fumaric acid, like maleic acid of which it is an isomer, is also conjugated. Fumaric acid, when heated rearranges and gives off water to form maleic anhydride, thus is operable in the present invention. Other alpha, beta unsaturated acids may be used.

[0026] The grafting of the succinic acid or succinic anhydride groups onto ethylene polymer may be done by methods described in the art, which involve reacting maleic acid or maleic anhydride in admixture with heated polymer, generally using a peroxide or other free-radical initiator to expedite the grafting.

[0027] Grafting may be effected in the presence of oxygen, air hydroperoxides, or other free radical initiators, or in the essential absence of these materials when the mixture of monomer and polymer is maintained under high shear in the absence of heat. A convenient method for producing the graft copolymer is the use of extrusion machinery, however, Banbury mixers, roll mills and the like may also be used for forming the graft copolymers.

[0028] Another method is to employ a twin-screw devolatilizing extruder (such as a Werner-Pfleider twin-screw extruder) wherein maleic acid (or maleic anhydride) is mixed and reacted with the LLDPE at molten temperatures, thereby producing and extruding the grafted polymer. The so-produced grafted polymer is then blended, as desired, with LLDPE to produce the blends of this invention.

[0029] Manufacture of bicomponent filaments of either the sheath/core configuration or the side-by-side configuration by the use of spinning packs and spinnerets is well known in the art. A conventional spinning process for manufacturing a fiber with a sheath/core configuration involves feeding the sheath-forming material to the spinneret orifices in a direction perpendicular to the orifices, and injecting the

core-forming material into the sheath-forming material as it flows into the spinneret orifices. Reference is made to U. S. Patent Nos. 4,406,850 and 4,251,200 which discloses bicomponent spinning assemblies and describe the production of bicomponent fibers. These patents are incorporated by reference.

[0030] Bicomponent fibers of the present invention may be either eccentric or concentric. It is understood, however, that the bicomponent fibers having side-byside configurations or multi-segmented bicomponent fibers are also considered to be within the scope of the present invention.

[0031] It has been found that such bicomponent fibers generally have a length to diameter ratio of between about 1:100 and about 1:2000. Such lengths are generally found to be about 1 mm to about 75 mm and preferably about 10 mm to 15 mm long. Diameters of the fibers are from about 0.5 dpf to about 50 dpf. Such bicomponent fibers are generally cut on conventional process machines wall known in the art.

[0032] The second ingredient that may be used in the present invention is the matrix fibers. Such fibers can be generally characterized by the fact that all these fibers provide chemical bonding sites through hydroxyl or amine groups present in the fiber. Included in the class of such matrix fibers are the cellulose paper making fibers, cellulose acetate fibers, glass fibers, polyester fibers, metal fibers, ceramic fibers, mineral wool fibers, polyamide fibers, and other naturally occurring fibers.

[0033] In the process for dispersing the bicomponent fibers and matrix fibers in a furnish, a whitewater system of water, thickener and dispersant is employed. The dispersant acts first to separate fibers and wet out the surface of the fibers. The thickener acts to increase the viscosity of the water carrier medium and also acts as a lubricant for the fibers. Through these actions, the thickener acts to combat flocculation of the fibers.

[0034] Various ingredients may be used as a thickener. One class of nonionic associative thickeners comprise relatively low (10,000 - 200,000) molecular weight ethylene oxide based urethane block copolymers and are disclosed in U. S. Patent Nos. 4,079,028 and 4,155,892, incorporated herein by reference. These associative thickeners are particularly effective when the fiber furnish

contains 10% or more staple length hydrophobic fibers. Commercial formulations of these copolymers are sold by Rohm and Haas, Philadelphia, PA, under the trade names ACRYSOL RM-825 and ACRYSOL RHEOLOGY MODIFIER QR708, QR-735, and QR-1001 which comprise urethane block copolymers into carrier fluids. ACRYSOL RM-825 is 25% solids grade of polymer in a mixture of 25% butyl carbitol (a diethylene glycol monobutylether) and 75% water. ACRYSOL RHEOLOGY MODIFIER QR-708, a 35% solids grade in a mixture of 60% propylene glycol and 40% water can also be used.

[0035] Similar copolymers in this class, including those marketed by Union Carbide Corporation, Danbury, Conn. under the trade names SCT-200 and SCT-275 and by Hi-Tek Polymers under the trade name SCN 11909 are useful in the process of this invention. Other thickeners include modified polyacrylamides available from Nalco Chemical Company.

[0036] Another class of associative thickeners, preferred for making up fiber furnishes containing predominantly cellulose fibers, e.g. rayon fibers or a blend of wood fibers and synthetic cellulosic fibers such as rayon comprises modified nonionic cellulose ethers of the type disclosed in U. S. Patent No. 4,228,277 incorporated herein by reference and sold under the trade name AQUALON by Hercules Inc., Wilmington, Delaware. AQUALON WSP M-1017, a hydroxy ethyl cellulose modified with a C-10 to C-24 side chain alkyl group and having a molecular weight in the range of 50,000 to 400,000 may be used in the whitewater system.

[0037] The dispersing agents that may be used in the present invention are synthetic, long-chain, linear molecules having an extremely high molecular weight, say on the order of at least 1 million and up to about 15 million, or 20 million, or even higher. Such dispersing agents are oxygen-containing and/or nitrogen-containing with the nitrogen present, for example, as an amine. As a result of the presence of the nitrogen, the dispersing agents have excellent hydrogen bonding properties in water. The dispersing agents are water soluble and very hydrophylic.

[0038] It is also believed that these long chain, linear, high molecular weight polymeric dispersing agents are deposited on and coat the fiber surface and make it slippery. This development of excellent slip characteristic also aids in deterring the formation of clumps, tangles and bundles. Examples of such dispersant agents are polyethylene oxide which is a nonionic long chain homopolymer and

has an average molecular weight of from about 1 million to about 7 million or higher; polyacrylamide which is a long straight chain nonionic or slightly anionic homopolymer and has an average molecular weight of form about 1 million up to about 15 million or higher, acrylamide-acrylic acid copolymers which are long, straight chain anionic polyelectrolytes in neutral and alkaline solutions, but nonionic under acid conditions, and possess an average molecular weight in the range of about 2 - 3 million, or higher; polyamines which are long straight chain cationic polyelectrolytes and have a high molecular weight of from about 1 million to about 5 million or higher; etc. A preferred dispersant is an oxyalkylated fatty amine. The concentration of the dispersing agents in the aqueous media may be varied within relatively wide limits and may be as low as 1 ppm and up to as high as about 200 ppm. Higher concentrations up to about 600 ppm may be used but tend to become uneconomical due to the cost of the dispersing agent and may cause low wet web strength. However, if recovering means is provided whereby the aqueous medium and the dispersing agent therein is recycled and reused, then concentrations up to 1,000 ppm or even higher can result.

[0039] The fiber concentration in the fiber slurry may also be varied within relatively wide limits. Concentrations as low as about 0.1% to 6.0% by weight of the furnish are suitable. Lighter or heavier ranges may be employed for special products intended for special purposes.

[0040] It has been found that the bicomponent and matrix fibers may be equally dispersed through an aqueous medium by adding a suitable dispersing agent and thickener to the resulting fiber slurry stirring and agitation of the slurry. The dispersing agent is added to the aqueous medium first and then the bicomponent fibers followed by the thickener and the matrix fibers are subsequently added thereto. The individual bicomponent fibers and matrix fiber are dispersed in the furnish uniformly through stirring with a minimum amount of fiber flocculation and clumping.

[0041] It is believed that by so doing the fibers enter a favorable aqueous environment containing the dispersing agent which is immediately conducive to their maintaining their individuality with respect to each other whereby there is substantially no tendency to flocculate or form clumps, tangles or bundles. This, of course, is to be contrasted to the prior situation wherein when bicomponent fibers are initially placed in an unfavorable aqueous environment not containing any high molecular weight, linear polymeric, water soluble, hydrophilic dispersing agent, which environment is conducive to the loss of fiber individuality whereby

the fibers flocculate and form clumps, tangles, and bundles and tend to migrate either to the top or the bottom of the furnish.

[0042] It has been found that specific types of dispersing agents are required in dispersing the bicomponent fibers of the present invention to arrive at the conditions of nonflocculation.

[0043] After the wet laid web has been formed, execess water is removed from the web by passing the web over a suction slot. Then the web is dried and thermally bonded by passing the web through a drying machine raised to sufficient temperature to melt the second component of the bicomponent fiber which then acts as an adhesive to bond the bicomponent fiber to other bicomponent fibers and matrix fibers upon cooling. One such machine is a Honeycomb System Through-air Dryer. The heating temperature may be from 140C to 220C, preferably 145C to 200C. The thermally bonded web is then cooled with the adhesive bonds forming at below the resolidification of the second component.

[0044] The invention will be described in greater detail in the following examples wherein there are disclosed various embodiments of the present invention for purposes of illustration, but not for purposes of limitation of the broader aspects of the present inventive concept. Experimental Procedure A. Bicomponent Fibers

[0045] Bicomponent fibers were made having a substantially concentric sheath/core configuration. The core was made from a standard 0.64 IV semi-dull polyethylene terephthalate. The sheath was made from a polymer described for the specific bicomponent fiber.

[0046] Bicomponent fiber A was made having a sheath of linear low density polyethylene containing from 1 - 7% 1-octene wherein the polymer had a density of 0.930 g/cc, a melt flow value of 18 gm/10 min at 190C according to ASTM D1236(E). Such a LLDPE is commercially available from Dow Chemical Company or Aspun Resin 6813.

[0047]

Bicomponent fiber B was made having a sheath made from a blend of LLDPE and grafted HDPE wherein the blend had a density of .932 g/cc and a melt flow value of 16 gm/10 min at 190C. The HDPE was grafted with maleic anhydride to contain 1 wt.% succinic anhydride groups. This sheath material is described in U. S. Patent No. 4,684,576. The ratio of grafted HDPE/LLDPE was 10/90.

[0048] Each type of the bicomponent fibers were made by coextruding the core and sheath polymers, and drawing the resulting filaments by processes well known to those skilled in the art, to obtain the desired denier and sheath/core ratio. The bicomponent fibers were cut to have a length of about 0.5 inch. B. Wet Lay Process

[0049] A batch fiber-water furnish was made with 500 liters of water at an ambient temperature in a mix tank equipped with an agitator rotating at 500 rpm. To the furnish was added in the following order:
o o o

a) 20 ml of the dispersing agent Milese T which is commercially available from ICI Americas, Wilmington, Delaware; b) 250 grams of the selected bicomponent fibers; c) 1 liter of 1% solution having a solids content of 35% of the viscosity modifier Nalco 061 commercially available from Nalco Chemical Company, Napierville, Illinois; d) 15 ml of a dispersant for a matrix fiber such as glass fibers Katapol VP532SPB commercially available from GAF Corporation located in New York, New York; and e) 250 grams of a matrix fiber pursuant to the experiment.

[0050] Prepared in a separate tank with an agitator was a white water solution containing 1100 liters of water, 40 ml of Milese T, and 2 liter of 1% solution Nalco 061. The furnish and the white water solution were both pumped to the headbox of a wireformer. Pump rates were 24 l/min of the furnish and 30 l/min of the white water to give a .044% consistency, i.e. grams of fiber to water.

[0051] Once the web was formed, it is then dried and thermally bonded thereafter to produce a thermally bonded fibrous web. The bonded web was then tested for such properties including tensile strength, tear strength, elongation and Mullen Burst and the strength tests were done in the machine direction (MD) and the cross direction (CD). The tensile strength test is used to show the strength of a

specimen when subjected to tension wherein a 1 inch wide sample by 7 inches long was pulled at 12 inch/min with a 5 inch jaw space. Elongation is the deformation in the direction of the load caused by tensile force and the reading is taken at the breaking load during the tensile test. The tear tester used was an Elmendorf Tear Tester which is a tester designed to determine the strength of the thermally bonded wet laid fabric. The Mullen Burst Test is an instrumental test method that measure the ability of a fabric to resist rupture by pressure exerted by an inflated diaphragm. Example 1

[0052] Wet laid webs were made up of bicomponent fibers and glass fibers and thermally bonded at 204C into a thermally bonded web. The thermally bonded web was tested to demonstrate the present invention and compare it to a wet laid web made using a commercially available HDPE/PET bicomponent fiber.

[0053] The glass fibers are made from silica base, having a thickness of 15 microns and a length of 0.5 inch. Such fibers are commercially available from Grupo Protexa, Mexico. The ratio of bicomponent fibers to glass fibers was 50/50. The bicomponent fibers and glass fibers were added to the water furnish as described in the wet lay process.

[0054] In Experiment 1 (the control), a bicomponent fiber was used having a PET core and a HDPE sheath, wherein the sheath/core ratio was 50/50 and the fiber has a denier of 2 dpf and a cut length of 3/8 inches. Such bicomponent fibers are commercially available as K-56 fiber type from Hoechst Celanese Corporation.

[0055] Experiment 2 was similar to Experiment 1, but the bicomponent fiber was replaced with bicomponent fiber A having sheath/core ratio of 50/50, a denier of 2 dpf, and a cut length of 0.5 inches.

[0056] Experiment 3 was similar to Experiment 1 and 2, but the bicomponent fiber used was bicomponent fiber B having a denier of 3 dpf, a cut length of 0.5 inches and a sheath core ratio of 50/50.

[0057]

The webs were tested for the tensila strength and tear strength in both the machine direction and cross direction. Also, the webs were tested for the Mullen Burst test. The results of the example are set forth in Table 1.

[0058] Thermally bonded wet laid web produced in Experiment 1 was the control using a prior art bicomponent fiber of a HDPE sheath and PET core. It's tensile strength was 2.09 lbs./in. in the machine direction, 2.15 lbs./in in the cross direction; the tear strength was 217.3 grams in the machine direction and 213.3 grams in the cross direction; and the Mullen Burst test value of 7.3 PSI.

[0059] Experiment 2 demonstrates that by replacement of the prior art HDPE/PET bicomponent fiber with bicomponent fiber A in the wet laid web of the present invention, the tensile strength and tear strength in both the machine and cross directions significantly increase as does the Mullen Burst Test value which indicates improved adhesion of the bicomponent fiber to the glass fiber in this case. In fact, the strength increase is about 50% over the control.

[0060] Experiment 3 demonstrates that employing a bicomponent fiber having a PET core and a sheath made from a blend of granted HDPE and LLDPE in the wet laid web of the present invention again significantly increases the tensile strength value 200% of the values for the control while maintaining high tear strength and Mullen Burst value. The slightly lower tear strength when compared to Experiment 2 is a further indication of superior bonding between the glass fibers and this bicomponent fiber.

Example 2

[0061] Thermally bonded wet laid webs were made up of varying amounts of bicomponent fibers and varying amounts of PET fibers used as matrix fibers. The webs were thermally bonded at 160C. The thermally bonded webs were tested for strength, elongation and Mullen Burst. These values were compared to a wet laid web made up with a commercially available PET/HDPE bicomponent fiber (K-56) and varying amounts of PET matrix fiber.

[0062] In Experiments 1 A-D (the controls) a bicomponent fiber having a PET core and HDPE sheath as described in Example 1, Experiment 1, was used. The PET matrix fibers had a denier of 1.5 dpf and a cut length of 0.5 inches.

[0063] Experiments 2 (A-D) were similar to Experiment 1, but the bicomponent fiber was replaced with bicomponent fiber B having a sheath core ratio of 40:60, a denier of 3 dpf, and a cut length of 0.5 inches.

[0064] Experiments 3 (A-C) were similar to Experiment 2 except the bicomponent fiber B had a sheath core ratio of 30:70.

[0065] Experiments 4 A-D were similar to Experiment 2, except the bicomponent fiber B had a sheath core ratio of 20:80.

[0066] The webs were tested for tensile strength, elongation Elmendorf tear strength and Mullen Burst values. The results of the Example are set forth in Table 2.

The results as shown in Table 2 are included in the graphs shown in Figures 1-4.

[0067]

Experiments 1 A-D were the controls using a commercially available bicomponent fiber of a HDPE sheath and PET core. When only PET fiber is used in the wet lay, the web has no strength. At 60% bicomponent fiber, 40% PET matrix fiber, the web has only 2.6 lbs. of strength and a Mullen Burst value of 16.6.

[0068] Experiments 2 A-D demonstrates that by replacement of the HDPE/PET bicomponent fiber with bicomponent fiber B having a 40% sheath of the present invention, the strength of the web increases significantly as do the values for the Mullen Burst test.

[0069] Experiments 3 A-C demonstrates that by using the bicomponent fiber B having a 30% sheath, that 100% bicomponent fiber B web has a strength of 11.2 lbs., which is significantly higher than the Experiment 1-D.

[0070] Experiments 4 A-D demonstrates that using the bicomponent fiber B having only 20% sheath still results in a strength superior to that of the Experiment 1-C at 60% bicomponent: 40% PET fiber mix. Example 3

[0071] Thermally bonded wet laid webs were made up of varying amounts of bicomponent fibers and PET fibers such that the total of the two fibers is 100%. The webs were thermally bonded at 370F and were tested for tensile, elongation, Mullen Burst and tear.

[0072] Experiments 1, 2 and 3 were similar in that each contained 100% bicomponent fiber and no matrix fiber. Experiment 1 (control) contained a bicomponent fiber as described in Example 1, Experiment 1. Experiment 2 contained bicomponent fiber A and Experiment 3 contained bicomponent fiber B.

[0073] Experiments 4, 5 and 7 were similar in that each contained 75% bicomponent fiber and 25% PET fiber of 1.5 dpf and cut length of 0.5 inches. Experiment 4

(control) contained the PET/HDPE bicomponent fiber; Experiment 5 contained bicomponent fiber A and Experiment 6 contained bicomponent fiber B.

[0074] Experiments 7, 8 and 9 each contained 50% bicomponent fiber and 50% PET fiber. Experiment 7 (control) contained the PET/HDPE bicomponent fiber; Experiment 8 contained bicomponent fiber A and Experiment 9 contained bicomponent fiber B.

[0075] Experiments 10, 11 and 12 each contained 25% bicomponent fiber and 75% PET fiber. Experiment 10 (control) contained the PET/HDPE bicomponent fiber; Experiment 11 contained bicomponent fiber A and Experiment 12 contained bicomponent fiber B.

[0076] The thermally bonded webs were tested for tensile strength, elongation, Elmendorf tear and Mullen Burst. The results of the test are set forth in Table 3.

The control Experiments 1, 4, 7 and 10 each containing the PET/HDPE bicomponent fiber, have lower strengths as demonstrated by the lower tensile and Mullen Burst values when compared to similar thermally bonded webs containing the bicomponent fibers of the present invention.

[0077] It is apparent that there has been provided in accordance with the invention, that the thermally bonded fibrous wet laid web and a method of preparing such a web incorporating a specific bicomponent fiber, fully satisfies the objects, aims and advantages as set forth above. While the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the

art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications and variations that fall within the sphere and the scope of the invention.

Elastic bicomponent and biconstituent fibers, and methods of making cellulosic structures from the same US 6811871 B2 Abstract The elasticity of elastic, absorbent structures, e.g., diapers, is improved without a significant compromise of the absorbency of the structure by the use of bicomponent and/or biconstituent elastic fiber. The absorbent structures typically comprise a staple fiber, e.g., cellulose fibers, and a bicomponent and/or a biconstituent elastic. The bicomponent fiber typically has a core/sheath construction. The core comprises an elastic thermoplastic elastomer, preferably a TPU, and the sheath comprises a homogeneously branched polyolefin, preferably a homogeneously branched substantially linear ethylene polymer. In various embodiments of the invention, the elasticity is improved by preparation techniques that enhance the ratio of elastic fiber:cellulose fiber versus cellulose fiber:cellulose fiber bonding. These techniques include wet and dry high intensity agitation of the elastic fibers prior to mixing with the cellulose fibers, deactivation of hydrogen bonding between cellulose fibers, and grafting the elastic fiber with a polar group containing compound, e.g. maleic anhydride. Description CROSS-REFERENCE TO RELATED APPLICATIONS This application is a division of U.S. patent application Ser. No. 10/195,279, filed Jul. 15, 2002, which claims benefit of U.S. Provisional Application No. 60/306,003, filed Jul. 17, 2001. FIELD OF THE INVENTION This invention relates to elastic fibers. In one aspect, the invention relates to bicomponent elastic fibers while in another aspect, the invention relates to biconstituent elastic fibers. In another aspect, the invention relates to bicomponent and biconstituent elastic fibers having a core/sheath construction. In yet another aspect, the invention relates to such fibers in which the polymer that forms the sheath has a lower melting point than the polymer that forms the core. In still another embodiment, the invention relates to methods of forming elastic cellulosic structures from a combination of cellulosic fibers and elastic bicomponent and/or biconstituent fibers having a core/sheath construction. BACKGROUND OF THE INVENTION Cellulosic structures are known for their absorbency, and this property makes these structures useful in a wide variety of applications. Typical examples of such applications are diapers, wound dressings, feminine hygiene products, bed pads, bibs, wipes, and the like. The purpose of

these products, of course, is to absorb and retain liquids, and the efficiency of these products in performing these tasks is determined, in large part, by their structure. U.S. Pat. Nos. 4,816,094, 4,880,682, 5,429,856 and 5,797,895 describe various such products, their construction and the materials from which they are made, and each is incorporated herein by reference. Typically, absorbent cellulosic structures are made of materials that do not easily stretch. For example, cellulose fibers are, for all intent and purpose, inelastic and in many cellulosic structures, e.g. a diaper, they are bonded to one another in a relatively inelastic manner, e.g., through the use of a latex. Unfortunately, many of these structures require some degree of elasticity for reasons of comfort and use, e.g., a diaper conforming to the contours of the human body or a wipe having the touch and drape of cloth, and if the structure is not sufficiently elastic, gaps will form within it. Gaps reduce the absorbency of the structure by preventing the migration of the liquid to all parts of the structure. Demand exists for better form-fitting absorbent products. This usually means that not only must the products have improved elasticity, but they must also be thin and light. Elasticity has been chased to date by adding to or replacing some of the cellulose fibers with an elastic fiber. For example, U.S. Pat. No. 5,645,542 to Anjur et al., the disclosure of which is incorporated herein by reference, describes absorbent products made from a wettable staple fiber (e.g., cellulose fiber) and a thermoplastic elastic fiber, e.g., a polyolefin rubber. However, the mere blending of staple fibers with elastic fibers often is not enough to obtain the full benefit of the elastic fiber without compromising the absorbency of the staple fiber. Cellulose fibers (the commonest of the staple fibers) tend to adhere to one another as opposed to adhering with an elastic fiber. As a result, unless a highly uniform mixture of the two fibers is formed during the construction of the absorbent structure, the two types of fibers tend to segregate and the benefit of the elastomeric fibers is reduced or lost. Accordingly, the absorbent product industry has a continuing interest in the design and construction of absorbent products with improved elasticity without a compromise in absorbency. This interest extends to both the nature of the fibers from which the absorbent products are made, and the methods by which these absorbent products are constructed. SUMMARY OF THE INVENTION In one embodiment, the invention is a bicomponent fiber of a core/sheath construction in which the core comprises the thermoplastic elastomer, preferably a thermoplastic polyurethane (TPU), and the sheath comprises the homogeneously branched polyolefin. Preferably, the polymer of the sheath has a lower melting point than the polymer of the core, and more preferably the polymer of the sheath has a gel content of less than 30 percent. In another embodiment, the invention is a biconstituent fiber in which one constituent comprises the thermoplastic elastomer, preferably a TPU, and the other constituent comprises the homogeneously branched polyolefin. Preferably, the constituent that forms the majority of the external surface of the fiber has a lower melting point than the other constituent, and preferably has a gel content of less than 30 percent.

In another embodiment, the invention is a blend of fibers (or simply a fiber blend) comprising (i) an elastic fiber comprising an elastic core and an elastic sheath, and (ii) at least one fiber other than the elastic fiber of (i). The core of the elastic fiber preferably comprises a thermoplastic elastomer, preferably a TPU, and the sheath of the elastic fiber preferably comprises a homogeneously branched polyolefin, more preferably a homogenously branched, substantially linear ethylene polymer. The polymer of the sheath has a melting point below the melting point of the polymer of the core, and preferably the polymer of the sheath has a gel content of less than 30 weight percent. The fiber of (ii) is essentially any fiber other than the fiber of (i), preferably a fiber of cellulose, wool, silk, a thermoplastic polymer, silica or a combination of two or more of these. In another embodiment of the invention, the fibers of (i) are melt bonded to the fibers of (ii), preferably by exposure to a temperature that is at or slightly below the melt temperature of both the fiber of (ii) and the polymer of the core of fiber (i) but above the melt temperature of the polymer of the sheath of fiber (i). In yet another embodiment of this invention, the melt bonded fiber blend is substantially free of any added adhesives, e.g., glue. In another embodiment of this invention, the blends described in the preceding paragraph are used to build elastic, absorbent structures. Such structures include paper with elasticity, e.g., form-fitting labels, and the absorbent padding of a disposable diaper. In another embodiment, the invention is a fabricated article comprising elastic fiber and a nonwoven substrate, the fiber comprising at least two elastic polymers, one polymer preferably a thermoplastic elastomer, more preferably a TPU, and the other polymer a homogeneously branched polyolefin, preferably a homogeneously branched, substantially linear ethylene polymer, in which the fiber is melt bonded to the nonwoven substrate in the absence of an adhesive. Exemplary fabricated structures of this embodiment include the leg cuffs, leg gatherers, waistbands and side panels of a disposable diaper. In another embodiment of the invention, the ratio of nonelastic staple fibers, e.g., cellulose fibers, bonded to elastic fibers versus nonelastic staple fibers bonded to other nonelastic staple fibers, is increased by a method in which the elastic fiber is a hydrophobic fiber grafted with a hydrophilic agent, e.g., a polyethylene fiber grafted with maleic anhydride. In an extension of this embodiment, and in which the hydrophilic agent is an acid or an anhydride, e.g., maleic anhydride, once the agent is grafted to the fiber it is then reacted with an amine. In another embodiment of the invention, for those nonelastic staple fibers that bind to one another due to hydrogen bonding, e.g., cellulose fibers, the ratio of nonelastic staple fibers bonded to elastic fibers versus nonelastic staple fibers bonded to other nonelastic staple fibers is increased by treating the nonelastic staple fibers, prior to or simultaneously with blending these fibers with the elastic fibers, with a debonding agent, e.g., a quaternary ammonium compound containing one or more acid groups. The debonding agent deactivates at least a part of the hydrogen bonding between the nonelastic staple fibers. In another embodiment of the invention, blending of nonelastic staple fibers with elastic fibers is enhanced by blending the fibers in an aqueous media, preferably in the presence of a surfactant and with intense agitation. This procedure enhances the separation of the elastic fibers from one another, and thus makes each fiber more accessible for bonding with a nonelastic staple fiber.

This method can be used alone or in combination with one or more other fiber separation embodiments of this invention. In another embodiment of the invention, high intensity air mixing is used to separate elastic fibers from one another prior to blending with staple fibers. This technique also promotes separation of the elastic fibers from one another, and this, in turn, improves their accessibility for bonding with the staple fibers. This embodiment of the invention can also be used alone or in combination with one or more other embodiments of the invention. The three fiber separation and the grafting embodiments described above are particularly useful in the construction of elastic absorbent structures such as diapers, wound dressings and the like. DESCRIPTION OF THE PREFERRED EMBODIMENTS Elastic Bicomponent and Biconstituent Fibers As here used, fiber or fibrous means a particulate material in which the length to diameter ratio of such material is greater than about 10. Conversely, nonfiber or nonfibrous means a particulate material in which the length to diameter ratio is about 10 or less. As here used, elastic or elastomeric describes a fiber or other structure, e.g., a film, that will recover at least about 50 percent of its stretched length after both the first pull and after the fourth pull to 100 percent strain (doubled the length). Elasticity can also be described by the permanent set of the fiber. Permanent set is measured by stretching a fiber to a certain point and subsequently releasing it to its original position, and then stretching it again. The point at which the fiber begins to pull a load is designated as the percent permanent set. As here used, bicomponent fiber means a fiber comprising at least two components, i.e., of having at least two distinct polymeric regimes. The first component, i.e., component A, serves the purpose of generally retaining the fiber form during the thermal bonding temperatures. The second component, i.e., component B, serves the function of an adhesive. Typically, component A has a higher melting point than component B, preferably component A will melt at a temperature at least about 20 C, preferably at least 40 C, higher than at the temperature at which component B will melt. For simplicity, the structure of the bicomponent fibers is typically referred to as a core/sheath structure. However, the structure of the fiber can have any one of a number of multi-component configurations, e.g., symmetrical core-sheath, asymmetrical core-sheath, side-by-side, pie sections, crescent moon and the like for bicomponent fibers. The essential feature on each of these configurations is that at least part, preferably at least a major part, of the external surface of the fiber comprises the sheath portion of the fiber, i.e., the adhesive, or lower melting point, or less than 30 wt % gel, or component B, of the fiber. FIGS. 1A-1F of U.S. Pat. No. 6,225,243, the disclosure of which is incorporated herein by reference, illustrate various core/sheath constructions.

As here used, biconstituent fiber means a fiber comprising an intimate blend of at least two polymer constituents. The structure of the biconstituent fiber is an islands-in-the-sea construction. The bicomponent fibers used in the practice of this invention are elastic and, each component of the bicomponent fiber is elastic. Elastic bicomponent and biconstituent fibers are known, e.g., U.S. Pat. No. 6,140,442 the disclosure of which is incorporated herein by reference. In this invention, the core (component A) is a thermoplastic elastomeric polymer illustrative of which are diblock, triblock or multiblock elastomeric copolymers such as olefinic copolymers such as styrene-isoprene-styrene, styrene-butadiene-styrene, styrene-ethylene/butylene-styrene or styrene-ethylene/propylene-styrene, such as those available from the Shell Chemical Company under the trade designation Kraton elastomeric resin; polyurethanes, such as those available from The Dow Chemical Company under the trade designation PELLATHANE polyurethanes or spandex available from E.I. Du Pont de Nemours Co. under the trade designation Lycra; polyamides, such as polyether block amides available from Elf AtoChem Company under the trade designation Pebax polyether block amide; and polyesters, such as those available from E.I. Du Pont de Nemours Co. under the trade designation Hytrel polyester. Thermoplastic urethanes (i.e., polyurethanes) are a preferred core polymer, particularly Pellethane polyurethanes. The sheath (the adhesive or component B) is also elastomeric, and it is a homogeneously branched polyolefin, preferably a homogeneously branched ethylene polymer and more preferably a homogeneously branched, substantially linear ethylene polymer. These materials are well known. For example, U.S. Pat. No. 6,140,442 provides an excellent description of the preferred homogeneously branched, substantially linear ethylene polymers, and it includes many references to other patents and nonpatent literature that describe other homogeneously branched polyolefins. The homogenously branched polyolefin has a density (as measured by ASTM/D792) of about 0.91 g/cm3 or less with a melting point at or below 110 C (as measured by DSC). More preferably, the density of the polyolefin is between about 0.85 and about 0.89 g/cm3 with a melting point between about 50 and about 70 C. Preferably, the polyolefin has a viscosity at the melt point that permits easy flow for bonding to the staple fibers or a nonwoven fabric structure. The melt index (MI as measured by ASTM DI238 at 190 C) for the polyolefin is at least about 30, and preferably at least about 100. Additives such as antioxidants (e.g., hindered phenolics (e.g., Irganox.RTM. 1010 made by Ciba-Geigy Corp.), and phosphites (e.g., Irgafos.RTM. 169 made by Ciba-Geigy Corp.)), cling additives (e.g., polyisobutylene (PIB)), antiblock additives, pigments and the like can also be included in the homogeneously branched ethylene polymers used to make the elastic fibers to the extent that they do not interfere with the enhanced fiber and fabric properties characteristic of this invention. The gel content of the polyolefin is less than 30, preferably less than 20 and more preferably less than 10, weight percent. The gel content is a measure of the degree of cross-linking of the polyolefin and because a principal function of the polyolefin is to provide a meltable exterior component to the fiber for easy thermal bonding to staple fibers and/or nonwoven structures,

little, if any, cross-linking of the polyolefin is preferred. In addition, usually the less cross-linked a polyolefin, the lower its melting point. Nonwoven structure means a group of fibers connected together in such a fashion such that the group forms a cohesive, integrated structure. Such structures can be formed by techniques known in the art, such as air-laid, spun bonding, staple fiber carding, thermal bonding, and melt blown and spun lacing. Polymers useful for making such fibers include PET, PBT, nylon, polyolefins, silicas, polyurethanes, poly(p-phenylene terephthalamide), Lycra (a polyurethane made from the reaction of polyethylene glycol and toluene-2,4-diisocyanate by E.I. Du Pont de Nemours & Co.), carbon fibers and natural polymers such as cellulose and polyamide. As here used, staple fiber means a natural fiber or a length cut from, for example, a manufactured filament. These fibers act in the absorbent structure of this invention as a temporary reservoir for liquid and also as a conduit for liquid distribution. Staple fibers include natural and synthetic materials. Natural materials include cellulosic fibers and textile fibers such as cotton and rayon. Synthetic materials include nonabsorbent synthetic polymeric fibers, e.g. polyolefins, polyesters, polyacrylics, polyamides and polystyrenes. Nonabsorbent synthetic staple fibers are preferably crimped, i.e., fibers having a continuous wavy, curvy or jagged character along their length. Cellulosic fibers are the preferred staple fibers for reasons of availability, cost and absorbency. In order to promote good mixing of the staple and elastic fibers, the bicomponent fibers are preferably wetted. As here used, wetted or wettable means a fiber which exhibits a liquid in air contact angle of less than 90 degrees. These terms and the measurement of this property are more fully described in U.S. Pat. No. 5,645,542. The wettable staple and elastic fibers are present in the elastomeric absorbent structure of this invention in an amount sufficient to impart the desired absorbent and elastic properties. Typically, the staple fiber is present in an amount from about 20 to about 80 percent by weight, preferably from about 25 to about 75 and more preferably from about 30 to about 70 percent, by weight based on the total weight of the staple fiber and elastic fiber. Although the bicomponent and/or biconstituent fibers are used in the same manner as other elastomeric fibers for the construction of elastic, absorbent structures, preferably these fibers are used in combination with one or more of the embodiments of this invention as described below. In any instance, however, the use of a bicomponent or biconstituent fiber as the elastic fiber component of elastic, absorbent structures provides an elastic, absorbent structure with improved elasticity without compromising the absorbency of the structure. This results in lighter, thinner and/or better form-fitting structures. Graft-modified Elastic Fibers In this embodiment of the invention, adhesion of the elastomeric fibers to the staple fibers is enhanced by grafting to the elastomeric fiber a compound containing a polar group, such as a carbonyl, hydroxyl or acid group. This embodiment of the invention is applicable to both homofil and bicomponent or biconstituent elastomeric fibers. Homofil fibers are fibers

comprising a single component or, in other words, are essentially homogeneous throughout their length. With respect to bicomponent and biconstituent fibers, the polar group containing compound is grafted to the sheath component (i.e., the component that forms at least a part of the exterior surface) of the fiber. The organic compound containing the polar group can be grafted to the elastomeric fiber by any known technique, e.g., those taught in U.S. Pat. Nos. 3,236,917 and 5,194,509 of which the disclosures of both are incorporated herein by reference. For example, in the '917 patent the polymer (i.e., the elastomeric fiber polymer) is introduced into a two-roll mixer and mixed at a temperature of 60 C. An unsaturated, carbonyl-containing organic compound is then added along with a free radical initiator, such as, for example, benzoyl peroxide, and the components are mixed at 30 C until the grafting is completed. In the '509 patent, the procedure is similar except that the reaction temperature is higher, e.g. 210-300 C, and a free radical initiator is not used. An alternative and preferred method of grafting is taught in U.S. Pat. No. 4,950,541 the disclosure of which is also incorporated herein by reference. This procedure uses a twin-screw devolatilizing extruder as the mixing apparatus. The elastomeric fiber, e.g., a polyolefin, and an unsaturated carbonyl-containing compound are mixed and reacted within the extruder at temperatures at which the reactants are molten and in the presence of a free radical initiator. In this procedure, preferably the unsaturated carbonyl-containing organic compound is injected into a zone maintained under pressure within the extruder. The polymer from which the fiber is made is usually grafted with the polar group containing compound prior to the formation of the fiber (by whatever method is used to construct the fiber). The polar group containing organic compounds which are grafted to the elastomeric fiber are unsaturated, i.e., they contain at least one double bond. Representative and preferred unsaturated organic compounds that contain at least one polar group are the ethylenically unsaturated carboxylic acids, anhydrides, esters and their salts, both metallic and non-metallic. Preferably, the organic compound contains ethylenic unsaturation conjugated with a carbonyl group. Representative compounds include maleic, fumaric, acrylic, methacrylic, itaconic, crotonic, alpha-methylcrotonic, cinnamic and the like, acids and their anhydride, ester and salt derivatives, if any. Maleic anhydride is the preferred unsaturated organic compound containing at least one ethylenic unsaturation and at least one carbonyl group. The unsaturated organic compound component of the grafted elastomeric fiber is present in an amount of at least about 0.01 percent, preferably at least about 0.1 and more preferably at least about 0.5 percent, by weight based on the combined weight of the elastomeric fiber and the organic compound. The maximum amount of unsaturated organic compound can vary to convenience, but typically it does not exceed about 10, preferably it does not exceed about 5, and more preferably it does not exceed about 2, weight percent. With respect to bicomponent and biconstituent fibers, the graft can be produced by either graftreacting the polar group containing compound with all of the sheath component (component B1), or by using a graft concentrate or master batch (B2), i.e., the polar group containing compound mixed with the sheath component. If such a blend of components is used, then preferably

component B2 is between about 5 and 50, and more preferably between about 5 and 15, weight percent of the combination of B1 and B2. The preferred concentration of the polar group containing compound in the blend is such that after blending with the sheath component, the final mixture has a final polar group containing concentration of at least 0.01 percent by weight, and preferably at least about 0.1 percent by weight. In those situations in which a graft concentrate is used with respect to a bicomponent fiber, preferably the graft concentrate (B2), is of a lower viscosity than the matrix adhesive material (B1). This will enhance migration of the graft component to the surface of the fiber during passage of the material through a fiber-forming die. The object, of course, is to enhance the adhesion of the bond fiber to the staple fiber by enhancing the concentration of the graft compound to the fiber surface. Preferably, the melt index of component B2 is between 2 and 10 times the melt index of component B1. Deactivation of Cellulose Hydrogen Bonds In another embodiment of the invention (an embodiment in which the staple fibers are cellulose fibers), the elastic performance of the absorbent elastic structure is enhanced through the promotion of more cellulosic-elastic fiber bonds at the expense of cellulosic-cellulosic fiber bonds. In this embodiment, the cellulosic staple fibers are treated either prior to or simultaneously with their mixing with the elstomeric fibers with a debonding agent. These bonds and their disruption were described in a presentation given by Craig Poffenberger entitled Bulk and Performance, But Soft and Safe at the Insight 2000 Non-wovens/Absorbents Conference held in Toronto from Oct. 30 through Nov. 2, 2000. With the decoupling of these hydrogen bonds, more cellulose fiber is available to bond with the elastic fiber and the more celluloseelastic fiber bonds that are formed, the more elastic is the resulting absorbent structure. Compounds that are useful in decoupling inter-fiber hydrogen bonds of cellulose fibers include quaternary ammonium compounds containing one or more acid or anhydride groups. Typical of these compounds are difattydimethyl, imidazolinum, N-alkyldimethylbenzyl and dialkoxylated alkyldimethyl. The debonding agent is used in an amount of about 0.01 to about 10 percent by weight based on the weight of cellulose fiber to be treated. Another compound that is useful in decoupling cellulose-cellulose hydrogen bonding is AROSURF PA-777, a surfactant manufactured by Goldschmidt Corp. This embodiment of the invention can be used alone or in combination with one or more of the other embodiments of the invention. Agitation in a Water Media to Separate Elastic Fibers In this embodiment of the invention, the elastic fibers are separated from one another by agitation in a water media. Elastic fibers, typically fine denier elastic fibers, are difficult to separate from one another and as such, are difficult to blend uniformly with staple fibers during the construction of an elastic absorbent structure. As here used, fine denier elastic fiber means an elastic fiber having a diameter of less than about 15 denier per filament. Fibers are typically classified according to their diameter, and monofilament fiber is generally defined as having an

individual fiber diameter greater than about 15 denier, usually greater than about 30 denier. Microdenier fibers are generally defined as fiber having a diameter of less than about 100 microns. In this embodiment, the elastic fibers are placed in an aqueous media, and then are subjected to vigorous agitation by any conventional means, e.g. mechanical stirrer, jet pump, etc. Surfactants and/or wetting agents can be employed and after the elastic fibers have sufficiently separated from one another, the staple fibers can be added. In a preferred embodiment of this invention, the staple fibers are added in combination with a debonding agent. After a homogeneous blend of the elastic and staple fibers has been formed, the water is removed, typically by filtering followed by exposure to heat, e.g. time in an oven. Once sufficiently dry, the resulting fluff pulp is ready for processing into an elastic absorbent structure. At this point, various additives, e.g. super absorbent powder, can be added to the pulp. During the drawing step, care is required to avoid warming the fibers to a temperature that would prematurely activate/melt the bond fibers. This particular embodiment is also useful with any elastomeric fiber of any composition and structure (including homofil fibers), and it is also useful with any staple fiber. High Intensity Air Mixing In this embodiment of the invention, the elastomeric fibers are separated from one another using a high intensity air mixing technique. This technique is similar to the agitation in a water media technique described above, except it does not employ an aqueous media (or for that matter, any liquid media). The elastomeric fiber, either homofil or bicomponent, is subjected to intense agitation, either mechanically or through pneumatic means, and once sufficiently separated, and in a further embodiment of this invention, blended with the staple fibers. While this technique avoids the need for drying the resulting blend of fibers, it does not lend itself well to use in combination with a debonding agent for the cellulosic fibers, or surfactants and/or wetting agents for use with the elastomeric fibers. Here too, however, this embodiment can be combined with one or more other embodiments of the invention, e.g., use of bicomponent or biconstituent elastomeric fibers, graft-modified elastomeric fibers, and cellulosic fibers of which the hydrogen bonding between fibers has previously been deactivated. Elastic Absorbent Structure Construction The elastic absorbent structure of this invention can be constructed from a blend of staple fibers and bicomponent and/or biconstituent elastic fibers of a core/sheath construction in which the core is a thermoplastic urethane and the sheath is a homogeneously branched polyolefin. According to this embodiment, the blend of staple and elastic fibers is prepared in any conventional manner and/or using any one of the inventive techniques described above and, optionally, is subsequently admixed with one or more super-absorbent polymers. This admixture is also performed using conventional technology but due to the presence of the low melt temperature adhesive component in the bicomponent or biconstituent fiber (i.e., the homogeneously branched polyolefin), the fluff pulp can be bonded together with heat as low as about 70 C to form an elastic absorbent structure, e.g. a diaper. The lower melt point of the adhesive component of the elastic bond fibers allows the use of currently-in-use commercial

equipment but at a lower temperature which, in turn, means the faster production rates are achieved over both monofil elastomeric fibers and bicomponent elastomeric fibers in which the adhesive component has a higher melt temperature. However, the lower melt temperature and/or faster bond rate reduces or alleviates the problems of bond fiber activation in, or in-line with, the structure making machines, e.g., a diaper-making machine. In conventional absorbent cores or structures, the cellulosic fibers are typically bonded to one another using latex. The latex often collects at the cellulosic fiber interfaces and, upon curing, holds the cellulosic fibers together. The use of a bicomponent or biconstituent bond fiber with two distinct regimes, e.g., a core and sheath, make for a better bond system. The core has a melting point above the oven temperature, and the sheath has melt point below the oven temperature. The bicomponent and biconstituent fibers efficiently fuse to the cellulosic fibers wherever they touch. The connections between the cellulosic fibers are thus longer than just the size of the fusion joints. This, in turn, produces a more flexible structure. Homogeneously branched ethylene polymers, particularly homogeneously branched, substantially linear ethylene polymers, make excellent sheath materials because their melting point is lower than many other elastic polymeric materials. Preferably, the sheath material will melt at least about 20 C, more preferably at least about 40 C, below the melt point of the core material. Elastic Paper Construction Bicomponent and biconstituent elastic bond fibers are useful in the production of elastic paper, i.e., paper with some degree of elasticity. As described above, these elastic bond fibers for elastic paper comprise an elastic polyurethane core with an elastic homogeneously branched polyofelin, more preferably a homogeneously branched polyolefin grafted with maleic anhydride or similar compound. If these bicomponent elastic fibers are mixed with cellulose fibers without interrupting the cellulose-cellulose hydrogen bonds, then the addition of these bicomponent or biconstituent elastic fibers will reduce tensil and provide some measure of elasticity, but the paper will tear at five percent strain. In other words, the benefit of the addition of bicomponent and/or biconstituent elastic fiber is minimized if the cellulose-cellulose hydrogen bonds are not interrupted. If, however, the cellulose-cellulose hydrogen bonds are interrupted with bicomponent or biconstituent elastic fiber, then the resulting paper exhibits a marked drop in tensil, significant elastic recovery, and resists tear at five percent strain. The cellulose-cellulose hydrogen bonds can be interrupted as taught above. To maximize the benefit of the disrupted cellulose-cellulose hydrogen bonds, good dispersion of the bicomponent elastic fiber with the cellulosic fiber is desired. Dispersion of the bicomponent elastic fiber within the cellulose fiber matrix is enhanced by separating the elastic fiber bundles prior to mixing with the cellulose fibers. Here too, the separation of fiber bundles is facilitated by either the dry (i.e., high intensity air agitation) or wet separation methods taught above, with the dry separation method preferred over the wet separation method.

The elasticity of the paper is also influenced by the structure of the fibers. Low modulus elastic fibers provide good fabric performance, but are awkward to process. Long bond fibers (i.e., bicomponent and biconstituent elastic fibers) mixed with short matrix fibers (i.e., cellulose fibers) produce a paper with better elasticity (i.e., less intersectional bonding) but the complete dispersion is more difficult because the long flexible elastic fibers twist easily which make them difficult to unbundle. However, if the elastic bond fibers are thick, they make for a better dispersion although they have an adverse impact on the economics. In sum, a preferred balance of elasticity and dispersion results from the use of a mix of low modulus fibers, the bond fibers of which are long and thick and the matrix fibers are short. In addition, the amount of elastic fibers in the paper also has an impact on the paper strength and elasticity. Too few bicomponent or biconstituent elastic bond fibers results in poor bonding of the other fibers into the fabric which results in a paper with poor strength and elasticity. Too many such elastic bond fibers results in too many intersectional bonds and while the paper strength is good, its elasticity is poor. The negative effect of too many bicomponent elastic bond fibers can be reduced, however, by using a higher loft in the paper construction. The following examples are illustrative of certain of the embodiments of this invention described above. All parts and percentages are by weight unless otherwise noted. SPECIFIC EMBODIMENTS EXAMPLE 1 Graft Modification of Polyethylene A substantially linear ethylene/1-octene polymer (MI-73, density-0.87 g/cm3) is grafted with maleic anhydride to produce a material with a MI of 34.6 and a 0.35 weight percent content of units derived from maleic anhydride. The grafting procedure taught in U.S. Pat. No. 4,950,541 is followed. The grafted polyethylene is used as a graft concentrate, and is let down 2:1 with an ethylene/1-octene polyolefin with an MI of 30 and a density of 0.87 g/cm3. The resulting letdown material is used to form the sheath (adhesive component) of the bicomponent elastic fiber used in the following examples. EXAMPLE 2A Fiber Separation Using Intensive Mixing in an Aqueous Medium Bicomponent, 11.2 denier elastic fiber comprising 50 percent Pellathane 2103-80PF (an elastomeric thermoplastic polyurethane manufactured by The Dow Chemical Company) and 50 percent homogeneously branched, substantially linear ethyline/1-octene polyolefin is prepared as described in Example 1 above. The thermoplastic polyurethane forms the core and the MAHgrafted ethylene polymer forms the sheath of the bicomponent fiber. A mixture of 30 percent of this elastomeric bond fiber and 70 percent Hi Bright cellulose fibers (unbeaten, bleached kraft softwood, macerated and soaked overnight at 1.1 percent in water) in 5 liters of water with 5 grams surfactant (Rhodameer, Katapol VP-532) and 110 grams of 0.5 percent solid Magnafloc 1885 anionic polyacrylamide viscosity modifier is added to a Waring blender. The mixture is

stirred to produce a substantially uniform mixture of elastic and cellulose fibers which are subsequently formed into an elastic, absorbent paper. EXAMPLE 2B Fiber Separation Using Intensive Mixing in an Aqueous Medium and Hydrogen Bonding Deactivation Sample Designation Core/Sheath Composition* 1.2 1.3 2.2 3.2 3.3 Denier

TPU/Engage (30 MI) 6.78 TPU/MAH-g-Engage (30 MI) 11.32 TPU/Engage (30 MI) TPU/Engage (18 MI) 6.4 TPU/Engage (18 MI) 11.4

Initially, all of the five fiber systems (tows) listed above are cut to length using a scissors. A 100 g/m2 air laid pad with 12% binder fiber loading needs to incorporate 0.43 g of binder fiber by weight. Sufficient amount of fiber is cut in all cases to produce 3 pads. Following the cutting of the fiber tows (each tow has 72 individual fiber filaments) to length, the next step is to separate individual fibers from the tows so that these can be incorporated into cellulose pulp and air laid into a pad. The sheath polymer(s) in all the cases are quite tacky even at room temperature (0.870 g/cc density) and the individual fibers are completely fused together in all cases over time. To separate the fiber tows into individual filaments, 0.43 g of binder fiber is weighed and added to a Waring blender. To this is added 2.00 g of cellulose pulp (a total of 3.195 g of cellulose pulp is used in a 100 gsm pad). Next, a 25:1 solution of water with AROSURF PA-777 surfactant blend from Goldschmidt Corp. is added to the binder fiber plus cellulose pulp mix. The blender is activated for 2-3 seconds and during this time the binder fiber tows instantaneously open up into individual fiber filaments. The cellulose pulp is added to the above mix to ensure that the binder fiber filaments stay separated during the subsequent drying process. The above procedure not only enables the separation of binder fiber into individual filaments, but it also results in deactivating the hydrogen bonding in pulp. The next step entails drying the binder fiber and pulp mixture. The fibers are first separated from the water/surfactant solution using a sieve. This fiber mixture is then dried overnight in a vacuum oven at 50 C. to ensure that any residual moisture is also removed. The dried fiber mixture is then incorporated into the air-laid chamber (an additional 1.195 gms of deactivated and dried cellulose pulp is also added at this time) and an absorbent pad structure is made using a vacuum assist process. EXAMPLE 3

Elastic Paper Comparison Eight inch by eight inch (88) elastic paper samples are prepared by using the procedure of Example 2. Samples 3.1 and 3.2 both comprise 100 percent Hi Bright cellulose fiber. Examples 3.3 through 3.8 are made from varying percentages of Hi Bright cellulose fiber and the elastic bicomponent fiber described in Example 2 above. Samples 3.9 and 3.10 contain a third fiber component, i.e. nylon fiber. The paper samples are made using a Noble & Wood paper-making machine. Sample 3.4 is prepared by presoaking 0.9 grams of the bicomponent fiber in 50 cc of water plus 5 drops of Katapol surfactant (VP-532), and then it is soaked for another five minutes before the addition of 190 cc of Hi Bright fibers. The rationale for this procedure is to use the thickening effect of the cellulose fibers to break up the clumps of the bicomponent fiber. The Waring blender is run at 1500 rpm. The resulting paper, which is dried on an Emerson apparatus at 250 F, still has visible clumps of bicomponent fibers. However, when the paper is torn, the tear is between bonded elastic fibers. The paper of Sample 3.5 is prepared in essentially the same manner as that of Sample 3.4 except that some of the clumps of the bicomponent fiber are broken up in a dry state within the Waring blender (an example of high intensity air agitation). After these clumps arc broken up, 50 cc of water with five drops of Katapol are added to the blender and the mixture is stirred again at a low setting. Subsequently, 190 cc of Hi Bright cellulose fiber with another 100 cc of water are added to the mixture, and stirred for an additional 5 minutes at 1000 rpm. The paper of this sample has less visible clumps, and the tear occurs between bonded elastic fibers. Sample 3.6 paper is about 70 pound grade made with the same cellulose pulp content of the previous samples, i.e., 190 cc. Two grams of bicomponent fiber are added to and then broken up in a Waring blender on a dry basis (i.e., in the absence of an aqueous media) at a low setting for one and a half minutes (this procedure is repeated three times with a scrape-down of the blender walls between each stirring). One hundred milliliters of water are subsequently added with five drops of Katapol, the resulting mixture is once again stirred at a low setting for one minute, and then it is combined with 190 cc of Hi Bright cellulose, fibers plus enough water to make 600 cc of total mixture. This total mixture is then transferred to a beaker and stirred at 1500 rpm for two minutes. Paper made from this mixture demonstrates some elasticity before tear. Sample 3.7 is a repeat of sample 3.6 except 2.4 grams of bicomponent fiber is used instead of 2.0 grams. Sample 3.8 is a repeat of sample 3.7 except an anti-foam is added with the Katapol (Foammaster VF made by Diamond Shamrock, 3 drops). Sample 3.9 is a repeat of sample 3.8 except 5 grams of 0.080 SD nylon fibers from Microfibers of Pawtucket, R.I. are also added. The nylon is added with 100 cc of water, and it produces a high dispersion with almost no stirring. She nylon-water mixture is added to the bicomponent fiber-Hi Bright mixture and the total mixture of 600 cc is stirred at 1500 rpm for two minutes.

The purpose of the nylon addition is to facilitate the break-up of the bonding between the cellulose fibers. Sample 3.10 is a repeat of Sample 3.9 except 2.4 grams of bicomponent fiber, 20 drops of Katapol, 6 drops of antifoam, 2 grams of nylon fibers and 100 cc of Hi Bright cellulose fibers (about 1.1 grams) are used. The particulars of the samples and the results of their testing on an Instron instrument are reported in the following Table.

SUMMARY OF ELASTIC PAPER DATA @ 5% strain (0.10 inch displ.), Instron (1 wide, 2 jaw space) Lb (Avg of 2 Tests) Grams (and %) per 8 8 Paper Sample Sample Number 3.1 3.2 3.3 Pulp 3 (100%) 2.1 (100%) 2.1 (70%) 0.059 2.1 (70%) 2.1 (70%) 2.1 (51%) 2.1 (47%) 2.1 (47%)

Initial

2nd 2nd Pull steep Pull, @ Bico Nylon Drops

2nd Pull @ 5%

5% displ., initial strain, % of displ, Fiber Fiber Total Katapol Yes/No Tensile strain inch Peak inch Tore, Peak 0 0 0 0 3 2.1 3 0 0 0 Y, Y Y, Y Y, Y 9.00 5.55 4.50 0.00 0 0.00 0 0.15 3 Total rip Total 0.018 rip 0.018 0.018

0.9 0 (30%) 0.9 (30%) 0.9 (30%) 2 (49%) 2.4 (53%) 2.4 (53%) 0 0 0 0 0

3.4 3.5 3.6 3.7 3.8

3 3 4.1 4.5 4.5

5 5 5 5 5+ antifoam

Y, Y Y, Y

2.30 2.65 2.35 2.80 3.45

0.20 9 0.58 22 0.55 23 1.10 39 2.15 62

0.023 0.062 0.022 0.045 0.014 0.044 0.019 0.045 0.023 0.038

3.9

2.1 (42%) 1.1 (20%)

3.10

2.4 0.5 5 (48%) (10%) 2.4 2 5.5 (44%) (36%)

20+ antifoam 20+ antifoam

3.05

0.65 21

0.018

Y, N

0.85

0.50 59

0.023 0.038

Although the invention has been described in detail by the preceding examples, the detail is for the purpose of illustration and is not to be construed as a limitation upon the invention. Many variations can be made upon the preceding examples without departing from the spirit and scope following claims.

Multiple integrated-layer ceramic fiber filter paper and method US 20070044443 A1 Abstract A composition of a multiple-layered ceramic fiber filter paper and method for manufacturing for use in a filter apparatus removes particulate from high temperature gas streams. In this application, ceramic fibers of varying diameters and lengths are combined in such a manner to yield different specific average pore sizes in segregated locations in the filter paper. The fiber combinations are formed into a paper sheet using a method that produces two or three porosity zones with different average pore sizes in each layer or porosity zone. The porosity gradient from large at gas stream entry to fine at gas stream exit increases particle-holding capacity while reducing the filtered gas backpressure experienced in single sized porosity layer media.

Ultrasonic Additive Manufacturing

Automated Dynamics is currently developing an ultrasonic additive manufacturing (UAM) capability. UAM is a process where layers of tape are bonded together using high frequency vibrations to form a structure. What differentiates Automated Dynamics' process from traditional ultrasonic welding methods is that the welding horn rotates to allow for continuous processing. This UAM process has primarily been used for welding metal foils. The process uses an ultrasonic transducer to vibrate the welding horn as it is placing the tape. The horn also acts as a compaction roller, applying a normal (perpendicular) force to the tape. The surface of the horn is textured, which allows it to grip the surface of the tape and transfer the vibrational energy to the substrate. The material is bonded together in the solid state without requiring molten temperatures at the interface.

Figure 1: Ultrasonic Additive Manufacturing welding system [1] Automated Dynamics is using this technology to develop a process for ultrasonic consolidation of metal matrix composite (MMC) prepreg tapes. This ultrasonic system has been integrated into a processing head on a research workcell (see Figure #3 below), with the capability of being transferred to a full-scale workcell. Initial trials have shown the feasibility for processing the MMC tape. The MMC used here is aluminum reinforced with ceramic fibers (Al/Al2O3). The ceramic fibers offer great strength and stiffness advantages over unreinforced metals as illustrated in figure #2 below.

Figure 2 - MMC Specific Strength & Stiffness [2]

Figure 3: Ultrasonic processing head installed on a research workcell at Automated Dynamics. Ultrasonic welding with a stationary horn is widely used for welding plastics. It has also been used for composite structures by tacking the pre-form together, which is subsequently postprocessed in an autoclave to consolidate the part. However, much of the work performed by Automated Dynamics on UAM with MMCs is directly applicable to in-situ consolidation with polymer matrix composites (PMC). This in-situ process would not require any post-consolidation steps, offering a significantly simpler manufacturing process. Air-purifying fiber reinforced cementitious building material. EP 2275391 A1 Abstract The invention relates to a fiber reinforced cementitious building material with air-purification activity and to the use of said fiber reinforced cementitious building material for exterior wall cladding and roofing applications. The invention also provides a process for the manufacturing of said fiber reinforced cementitious building material.

Description FIELD OF THE INVENTION

[0001] The present invention relates to a fiber reinforced cementitious building material with airpurification activity and to the use of said fiber reinforced cementitious building material for exterior wall cladding and roofing applications. The present invention also provides a process for the manufacturing of said fiber reinforced cementitious building material. Specifically, the invention is in the field of fiber reinforced cementitious building materials provided with a photocatalytic cementitious layer capable of oxidizing atmospheric pollutants to harmless soluble salts in the presence of sunlight and water. The invention concerns more particularly a fiber reinforced cementitious building material with a photocatalytic action whose effectiveness is constant and long-lasting. PRIOR ART

[0002] Photocatalysts are semiconductors whose electrons can be transferred from the valence to the conduction band by photons in the UV-A range. The thus created electron holes are responsible for the formation of hydroxyl radicals in the presence of water, which act as a strong oxidant and can hence degrade compounds in further reactions. In particular, they bond to nitrogen oxides (NOx) which are converted to nitrates. In case the photocatalyst is incorporated in a alkaline cementitious matrix, these nitrate ions bind with positive

ions,e.g. of calcium and sodium present in the cementitious matrix, and form salts such as calcium nitrate and sodium nitrate which are flushed from the surface by rain. A preferred semiconductor for the activation of the photocatalytic process is titanium dioxide in its anatase crystal form.

[0003] Cement-based building materials provided with a photocatalytic active surface have already been described.

[0004] JP2000-01 7784 describes an atmosphere purifying roof material characterized by a surface layer with a thickness of at least 0,5 mm and comprising titanium dioxide. EP-A187871 concerns a cementitious surface coating with photocatalytic activity comprising fine photocatalytic particles with a specific surface greater than 200 m2/g and large particles having a specific surface below 100 m2/g, and in which the fine photocatalytic particles are prevalently disposed in the outer surface layer, as they are dragged along by water rising to the surface. Upon evaporation of the water, the dissolved ingredients originating from the cementitious matrix form deposits on the surface, a phenomenon which is known as efflorescence. In the case of Portland cement-based materials, particularly calcium and hydroxide ions are dissolved into the water, forming almost insoluble calcium carbonate on the surface by reaction with atmospheric carbon dioxide, which prevents the contact of the photocatalyst with light.

[0005] However, EP-A-1878711 solves the problem of formation of an efflorescence layer only partially, and there is still calcium carbonate present on the surface, which reduces the efficiency of the photocatalytic layer.

[0006] JP2008-007368 addresses the problem of efflorescence with photocatalytic cementitious materials by using alumina cement. Unfortunately, alumina cement is not only an expensive raw material, but its setting is too fast to be used in a Hatschek process, which is the most common method for the manufacturing of fiber reinforced cementitious building materials. JP2006-248793 and JP2000-233134 tackle the problem of reduced photodecomposition performance with time by adding an efflorescence preventing agent such as a water- repellent agent, to the cement composition.

[0007] However, we observed that avoiding efflorescence does not guarantee a durable photocatalytic performance in the case of fiber reinforced cementitious articles. In fact, the nitrates which are the major photo-oxidation reaction products, penetrate at least

partly into the porous fiber reinforced cement matrix, especially in periods of absence of rainfall. These nitrates promote undesirable microbial growth such as algae, particularly under conditions of high relative humidity, and especially after carbonation of the cementitious matrix, when its reduced alkalinity no longer avoids the microbial growth. The micro-organisms shield the photocatalytic layer from light, and hence air purification efficiency decreases after prolonged atmospheric exposure.

[0008] WO2007/106242 concerns a photocatalytic substrate with a biocidal polymeric coating which provides long-term resistance to staining from bio-organisms or from airborne contaminants. However, such photocatalytic substrates do not have an air depollution function. In case the biocidal polymeric coating does not comprise a photocatalytic antimicrobial agent, there is no direct contact of air pollutants with the photocatalytic particles in the adjacent structural layer. In case the biocidal polymeric coating comprises a photocatalytic antimicrobial material, the polymeric coating degrades upon prolonged exposure to UV light, and an underlying efflorescence layer will shield the photocatalytic material from light, resulting in a lower air purification performance. WO2007/106242 does not disclose the necessary simultaneous presence of photocatalyst, efflorescence preventing agent and biocide to obtain a high and durable air depollution efficiency in the top layer of cementitious substrates.

[0009] EP-A-1 1621 82 discloses a cement-based joint body comprising a hydraulic material, a particulate aggregate having a particle diameter of not more than 10 m, and an antimicrobial/fungicidal agent and/or a photocatalytic metal oxide and characterized by a water absorption of not more than 10%. However, EP-A-1162182 does not provide an air-purifying cementitious article. Moreover, the biocide and the photocatalyst are added to the matrix. This is not feasible for fiber reinforced cementitious building materials manufactured according to the Hatschek process, as the biocide and the photocatalyst contaminate the process water which is normally recycled. Also, adding the biocide throughout the matrix is not economical, especially in case of relative thick fiber reinforced cementitious articles used for covering substantial surfaces such as faades and roofs. BRIEF DESCRIPTION OF THE DRAWING

[0010] The invention will be explained in detail below, referring to the accompanying drawing.
o

Figure 1 is a schematic view of a Hatschek process according to the invention, wherein : 1. 1 spray nozzles 2. 2 conveyor felt

3. 4. 5. 6.

3 forming drum 4 vacuum boxes 5 vat 6 sieve

SUMMARY OF THE INVENTION

[0011] The present invention overcomes the abovementioned problems by providing at least a fiber reinforced cementitious air-purifying building material manufactured according to a process comprising a production step on a Hatschek line and based on a calcium silicate cement composition, and comprising a water-repellent photocatalytic active cementitious top layer characterized in that said top layer further comprises a biocidal agent. It solves more particularly the problem of microbial growth by incorporating a biocidal agent into the photocatalytic cementitious top layer.

[0012] Other aspects of the present invention are a process for the manufacturing of said fiber reinforced cementitious air-purifying building material and the use of said fiber reinforced cementitious air-purifying building material in exterior applications, and more specifically in faade cladding and roofing applications such as slates.

[0013] Fiber reinforced cementitious articles of the present invention are manufactured according to a process comprising a production step on a Hatschek line, which is a modified sieve cylinder paper making machine and which consists in forming a sheet comparable to a paper, by filtration using a fluid aqueous suspension obtained by mixing essentially cement, fibers, water, processing aids and additives. Rotating sieves housed within vats are suspended partially within this slurry. These sieves consist of a drum covered with a filter cloth; since the drum rotates in the vat, the hydrostatic pressure forces some of the water to pass through the filter cloth, whereas the solids, that is to say notably the fibres, the cement particles and other additives, build up on the screen of the drum as a thin layer whose thickness increases with the rotation of the drum. The fibers hold to the sieve, forming an additional screen, the mesh cells of which have a size suitable for retaining the particles, even fine particles, of cement or of other binder or additive, together with an important amount of water which contributes to the cohesion of the layer being formed on the screen. The retention on the sieve can be further enhanced by the addition of flocculants. The layer is transferred from the sieve, usually by means of a felt belt and further dewatered by suction through the belt, to a forming roll, on which the material is built up until the desired thickness has been reached. The green sheet is optionally post-compressed to densify and subsequently left to harden under atmospheric conditions (air-curing) or under pressurized steam at a temperature above 100C (autoclaving).

[0014] The fiber reinforced cementitious building material according to the present invention is preferably air-cured. Preferred fiber reinforced cementitious building material according to the present invention have been pressed.

[0015] The hydraulic-setting composition used for the manufacture of the fiber reinforced cementitious material according to the present invention comprises a calcium silicate based cement as hydraulic binder. Suitable calcium silicate based cements are Portland cement, slag cement, and others. The highly alkaline character of these hydraulic binders is well-known. Portland cement is preferred.

[0016] The hydraulic-setting composition used for the manufacture of the fiber reinforced cementitious material according to the present invention possibly comprises reinforcing organic and/or inorganic fibers. Examples of reinforcing inorganic fibers are alkaliresistant glass fibers, ceramic fibers, and the like, and their blends. Examples of organic reinforcing fibers are fibers of cellulose, polyolefins such as polyethylene or polypropylene, polyamide, polyacrylonitrile, polyester, aramid, polyvinylalcohol, carbon, and the like, and their blends. The content of reinforcing fibers is preferably equal to or less than 1 5% by weight with respect to the initial total weight in the dry state of the hydraulic-setting composition.

[0017] The hydraulic-setting composition used for the manufacture of the fiber reinforced cementitious building material according to the present invention can further comprise processing aids, such as processing fibers, flocculants, anti-foam agents. Appropriate processing fibers are cellulose fibers, polyolefin fibrils, and others, and their blends. The amount of processing fibers is preferably equal to or less than 10% by weight with respect to the initial total weight in the dry state of the hydraulic-setting composition.

[0018] The hydraulic-setting composition used for the manufacture of the fiber reinforced cementitious building material according to the present invention may further comprise fillers and/or additives, such as fly ash, amorphous silica, ground quartz, ground rock, clays, blast-furnace slags, carbonates, pozzolanic earth, etc. The total quantity of fillers and/or additives is preferably less than 50% by weight with respect to the initial total weight in the dry state of the hydraulic-setting composition.

[0019]

The fiber reinforced cementitious building material according to the present invention comprises a water-repellent photocatalytic active cementitious top layer. The latter is preferably applied as cementitious slurry on top of the first fiber cement layer before dewatering on the felt of the Hatschek machine, either by spraying or by rotating brushes. The water/cement ratio of this cementitious slurry is preferably about 1. The thickness of the photocatalytic top layer is preferably at least 100 m, more preferably at least 150 m. The photocatalytic active top layer comprises a photocatalyst. Titanium dioxide is preferred. The anatase form is particularly preferred. Aqueous dispersions of anatase are very suitable. Good results were obtained by using aqueous dispersions of anatase with a solids content in the range between 50 and 80 wt %. Appropriate photocatalytic performance is obtained with a photocatalyst concentration of at least 4 wt % with respect to the total dry weight of the composition of the photocatalytic active top layer. Photocatalyst concentrations of at least 6 wt % with respect to the total dry weight of the composition of the photocatalytic active top layer are particularly preferred. Suitable photocatalysts have a specific surface in the range of from 5 to 30 m2/g. Photocatalysts with a specific surface in the range of from 8 to 15 m2/g are particularly preferred. Photocatalysts with a specific surface higher than 30 m2/g do not give a satisfactory level of photocatalytic activity, because a considerable amount of the photocatalyst is lost during filtration on the felt. Air-purification efficiency is low with photocatalyst characterized by a specific surface below 5 m2/g.

[0020] The photocatalytic active top layer is a cementitious layer, but contrary to the base layer which is formed on a Hatschek machine, it does not comprise fibers; consequently its density is higher and the probability to have photocatalytic particles on the surface increases. The photocatalytic active top layer comprises preferably the same calcium silicate based cement as the base layer.

[0021] The photocatalytic active cementitious top layer possibly comprises pigments, such as chromium oxides, carbon black, iron oxides.

[0022] The photocatalytic active top layer comprises a water-repellent agent. The fiber reinforced cement materials according to the present invention are manufactured using a calcium silicate cement, preferably Portland cement, as hydraulic binder. This raw material has the disadvantage of leading to efflorescence problems, as outlined before. However, non-efflorescing cements, such as alumina cements are too expensive to be used for commodity products and have to be used not only in the photocatalytic top layer of the fiber reinforced cementitious article, but also in the base layer in order to avoid efflorescence; moreover, as mentioned above, alumina cement is not suitable to be used on a Hatschek machine due to its rapid setting. The use of a water-repellent agent in the photocatalytic active top layer avoids the appearance of an efflorescence surface layer

which shields the photocatalyst from contact with light. The water- repellent agent is preferably added to the cementitious slurry used for the photocatalytic top layer. Suitable water-repellents which can be added to to the cementitious slurry used for the photocatalytic top layer have to be alkali-resistant and do not affect the cement hardening. Examples of appropriate water-repellents are silanes, silsesquioxanes, siloxanes and silicones, and their blends. Preference is given to aqueous emulsions of the latter. Good results were obtained with an amount of water-repellent agent in the photocatalytic active top layer are in the range of from 0,01 to 3 wt% with respect to the hydraulic binder. A concentration of water-repellent agent below 0,01 wt% does not give a long-lasting air-purification efficiency; a concentration of water-repellent above 3 wt% does not give an enhanced atmosphere-cleaning performance and hence is not economical. Concentrations of water-repellent agent in the photocatalytic active top layer in the range of from 0,08 to 2 wt% with respect to the hydraulic binder are particularly preferred.

[0023] According to another embodiment of the present invention, the water-repellent agent can be applied on the photocatalytic active cementitious top layer of the fiber reinforced cementitious building material instead of adding it to the cementitious slurry used for the photocatalytic top layer. In this case, the water-repellent agent is preferably applied by roller coating or by spraying once the fiber reinforced cementitious building material has left the Hatschek line and has been cured at a temperature preferably in the range of from 35 to 75C during a period which is preferably in the range of from 5 to 10 hours. According to this particular way of execution of the invention, the water-repellent agent is preferably solvent-based. Suitable water-repellent agents which are used for application on the photocatalytic active top layer of the fiber reinforced cementitious building material are silanes.

[0024] The photocatalytic active top layer also comprises a biocidal agent which avoids the formation of algae, lichen and moss. Although photocatalytic coatings are often applied on surfaces for their self-cleaning and antimicrobial effect resulting from the photooxidation of organic material, they do not impart these properties when incorporated into non-smooth and porous fiber reinforced cementitious substrates. As mentioned above, the nitrates resulting from the photocatalytic reaction with NOx air pollutants, penetrate into the porous cementitious substrate, especially under conditions of high relative humidity in the absence of rain, and form a nutrient layer for micro-organisms such as algae, which cover the photocatalytic top layer to a certain extent and reduce its air depolluting efficiency. Suitable biocides are heat, alkali and UV stable without adversely affecting the performance of the fiber reinforced cementitious article and are released slowly. Useful biocides include organic and inorganic biocides. Examples of organic biocides are oxines or pyrithiones. Inorganic biocides are preferred for exterior applications, especially in the presence of a photocatalyst. Preferred inorganic biocides have a low water solubility and include transition metals such as copper and silver and inorganic

transition metal oxides or salts, for example cuprous and cupric oxide, cupric sulfate, silver chloride and zinc oxide. An amount of biocidal agent in the photocatalytic active top layer in the range of 0,1 to 20 wt% with respect to the total dry weight of the composition of the photocatalytic active cementitious top layer is preferred. A concentration of biocidal agent below 0,1 wt% has not a satisfactory antimicrobial action; a concentration of biocidal agent above 20 wt% leads to undesired adhesion on the forming drum. An amount of biocidal agent in the photocatalytic active top layer in the range of 0,2 to 1 5 wt% with respect to the total dry weight of the composition of the photocatalytic active cementitious top layer is particularly preferred. According to a preferred mode of execution, the biocidal agent is added as an aqueous dispersion to the cementitious slurry forming the photocatalytic top layer. In another embodiment of the present invention, the biocidal agent can be applied applied on the photocatalytic active cementitious top layer of the fiber reinforced cementitious building material once the fiber reinforced cementitious building material has left the Hatschek line and has been cured, for example by roller coating or by spraying.

[0025] The invention also provides a first process for manufacturing fiber reinforced cementitious building material with photocatalytic activity comprising the following steps : 1. a) formation of a first layer of the green base sheet by a Hatschek process, 2. b) formation of a top layer by application of an aqueous cementitious slurry comprising a calcium silicate based cement, a photocatalyst and at least one product selected from a biocidal agent and a water-repellent agent, on said first layer of the green sheet obtained in step (a) as the latter moves on the conveyor felt, and over a length corresponding to the circumference of the forming drum, 3. c) dewatering said first layer of the green base sheet obtained in step (a) provided with the photocatalytic active top layer applied on it in step (b), 4. d) winding the dewatered first layer of the green base sheet obtained in step (a) provided with the photocatalytic active top layer applied on it in step (b) on the forming drum, 5. e) forming additional layers of the base sheet until the desired thickness is obtained on the forming drum, 6. f) curing the product obtained in step e), [0026] Step (a) is the formation of a first layer of the green base sheet. This first layer comprises besides a calcium silicate based cement, reinforcing fibers such as polyvinylalcohol and/or polypropylene fibers, processing fibers such as cellulose fibers and additives such as fly ash, amorphous silica, clays, blast-furnace slags, carbonates, etc.

[0027]

Step (b) is the application of a photocatalytic active top layer as an aqueous cementitious slurry comprising a calcium silicate based cement, a photocatalyst and at least one product selected from a biocidal agent and a water-repellent agent, on said first layer of the green sheet obtained in step (a). The photocatalytic active cementitious slurry does not comprise fibers and is applied using preferably spray nozzles or rotating brushes in a discontinuous way, i.e. only over a length corresponding to the circumference of the forming drum. This forming drum is an inversion roller, and hence the photocatalytic layer which was in contact with its surface during formation of the fiber reinforced cement building material is located on top when the latter leaves the Hatschek line.

[0028] The layers obtained in step (a) and (b) are dewatered together on the felt of the Hatschek line; usually, the dewatering is carried out by using several vacuum boxes located on the bottom side of the felt of the Hatschek line. They are then wound together on the forming drum in step (d), whereby the bottom of the base layer which was in direct contact with the felt is the outer face and the photocatalytic top layer contacts the surface of the forming drum. Subsequent layers of the base sheet are formed in step (e) until the desired thickness is obtained. The uncured fiber reinforced cement sheets are then preferably precut followed by stacking. Next they are preferably pressed between metal templates. During this pressing at pressures which are usually in the range of from 20 to 30 MPa, the density and consequently the strength of the fiber reinforced cement sheet increase. Interlaminar bond strength between the layers and freeze-thaw resistance due to lower water absorption, are also improved by the pressing step. A low water absorption is required for exterior applications, such as faade cladding and roofing applications.

[0029] Cement hardening is accelerated in the curing step f) which is preferably performed in an oven at a temperature in the range of from 50C to 90C during 4 to 10 hours. The density of the fiber reinforced building material according to the present invention obtained after step (f) is preferably at least 1,6 g/cm3, more preferably at least 1,7 g/cm3.

[0030] Finally, the fiber reinforced cement sheets are cut to the desired dimensions. Preferably, rotating blades are used for the cutting.

[0031] According to a second process of the present invention, the fiber reinforced cementitious building material is manufactured according to the process as described above, but without the addition of the water-repellent agent and/or the biocidal agent to the aqueous cementitious slurry in step b). In this process, the water-repellent agent and/or the biocidal agent are/is applied on the photocatalytic active top layer of the fiber reinforced cementitious building material in an additional step. According to this second process of

the present invention, the biocidal agent can be added in step b) while the water-repellent agent is applied in step f), or the water-repellent agent can be added in step b) while the biocidal agent is applied in step f) or the biocidal agent and the water-repellent agent can both be applied in step f). DETAILED DESCRIPTION

[0032] It will be obvious for a person skilled in the art that the present invention is not limited to what was disclosed and described particularly above. All new characteristics and each combination of these characteristics belong to the scope of the invention. The numerical references in the claims do not limit the scope of their protection. The use of the verbs "to comprise or to include" and their conjugated forms does not exclude the presence of other elements than those cited in the claims. The use of the article "a or an" in front of an element, does not exclude the presence of a plurality of such elements. The invention is described hereafter in a detailed way using particular examples of embodiment. EXAMPLES Comparative example 1

[0033] The composition of the first series of reference slates is based on the composition of Alterna slates commercialized by Eternit, except that the cementitious top layer further comprises 7 wt% of Kronos 1001 (TiO2 photocatalyst) and 1 wt % of Dow Corning IE6683 (water-repellent) and that no polymeric coating was applied. Example 1

[0034] Test slates have been manufactured according to the first process provided by the invention. These slates are similar to the first series of reference slates described in comparative example 1 except that the cementitious top layer of about 200 m further comprises 4 wt% of Zinc Oxide Neige C (biocidal agent commercialised by Umicore) with respect to the total dry weight of the composition of photocatalytic active cementitious top layer. Comparative example 2

[0035] The compositon of the second series of reference slates is similar to the composition of the first series of reference slates, except that the cementitious top layer does not comprise a water-repellent agent., but that 25,5 g/m2 of Z-6403 Silane (water-repellent

commercialized by Dow Corning) were applied by roller coating on the slates which were previously air-cured at 40C during 8 hours after production. Example 2

[0036] Test slates have been manufactured according to the second process provided by the invention. These slates are similar to second series of reference slates described in comparative example 2 except that the cementitious top layer of about 200 m further comprises 4 wt% of Zinc Oxide Neige C (biocidal agent commercialised by Umicore) with respect to the total dry weight of the composition of photocatalytic active cementitious top layer.

[0037] Ten slates of each of the four series have been submitted to exterior exposure during 25 months (starting mid-October) on Eternit's production site in Kapelle-op-den-Bos in Belgium.

[0038] The photocatalytic activity is measured according to ISO 22197-1, but using a cycle of an irradiation time of 20 minutes, followed by a dark period of 10 minutes.

[0039] The average results of the NO reduction 1 week after production (reference level of 100%) and after 25 months exterior exposure as well as the visual observations of the microbial growth after 25 months exterior exposure are listed in table 1 below. Table 1 Example 1 Example 2 Comparative Comparative example 1 example 2 NO reduction after 1 week (%) NO reduction after 25 months (%) Visual inspection after 25 months 100 52 OK 100 56 OK 100 9 100 11

Green deposit Green deposit

[0040] The results in table 1 show that the photocatalytic slates according to the present invention maintain the initial photocatalytic activity even after 25 months of exterior exposure, while this is not the case for the slates of the comparative example

not comprising a biocidal agent, and that this durable photocatalytic activity or air depolluting efficiency can be correlated with the absence of microbial growth. Claims 1. Fiber reinforced cementitious air-purifying building material manufactured according to a process comprising a production step on a Hatschek line and based on a calcium silicate cement composition, and comprising a water-repellent photocatalytic active cementitious top layer characterized in that said top layer further comprises a biocidal agent.. 2. Fiber reinforced cementitious building material according to claim 1 wherein the photocatalytic active cementitious top layer has been applied by spraying or by roller coating. 3. Fiber reinforced cementitious building material according to claim 1 or claim 2 wherein the photocatalytic active cementitious top layer has a thickness of at least 100 m. 4. Fiber reinforced cementitious building material according to any of the preceding claims wherein the fiber reinforced cement building material is an air-cured product. 5. Fiber reinforced cementitious building material according to any of the preceding claims wherein the fiber reinforced cement building material is a pressed product. 6. Fiber reinforced cementitious building material according to any of the preceding claims wherein the photocatalytic active cementitious top layer comprises titanium dioxide. 7. Fiber reinforced cementitious building material according to claim 5 wherein the titanium dioxide is in its anatase form. 8. Fiber reinforced cementitious building material according to any of the preceding claims wherein the photocatalyst concentration is at least 4 wt% with respect to the total dry weight of the composition of the photocatalytic top layer. 9. Fiber reinforced cementitious building material according to any of the preceding claims wherein the photocatalytic active cementitious top layer comprises a photocatalyst characterized by a specific surface in the range of from 5 to 30 m2/g. 10. Fiber reinforced cementitious building material according to any of the preceding claims wherein the photocatalytic active cementitious top layer comprises an inorganic biocidal agent. 11. Fiber reinforced cementitious building material according to any of the preceding claims wherein the photocatalytic active cementitious top layer comprises a biocidal agent in the range of from 0,1 to 20 wt% with respect to the total dry weight of the composition of the photocatalytic active cementitious top layer. 12. Process for the production of a fiber reinforced cementitious air-purifying building material manufactured according to a process comprising a production step on a Hatschek line and based on a calcium silicate cement composition, and comprising a waterrepellent photocatalytic active cementitious top layer characterized in that said top layer further comprises a biocidal agent according to any of the preceding claims, comprising the following steps : a) formation of a first layer of the green base sheet, b) formation of a top layer by application of an aqueous cementitious slurry comprising a calcium silicate based cement, a photocatalyst and at least one product selected from a

biocidal agent and a water-repellent agent, on said first layer of the green sheet obtained in step (a) as the latter moves on the conveyor felt, and over a length corresponding to the circumference of the forming drum, c) dewatering said first layer of the green base sheet obtained in step (a) provided with the photocatalytic active top layer applied on it in step (b), d) winding the dewatered first layer of the green base sheet obtained in step (a) provided with the photocatalytic active top layer applied on it in step (b) on the forming drum, e) forming additional layers of the base sheet until the desired thickness is obtained on the forming drum, f) curing the product obtained in step e), 13. Process for the production of a fiber reinforced cementitious air-purifying building material manufactured according to a process comprising a production step on a Hatschek line and based on a calcium silicate cement composition, and comprising a waterrepellent photocatalytic active cementitious top layer characterized in that said top layer further comprises a biocidal agent according to any of the preceding claims, comprising the following steps : a) formation of a first layer of the green base sheet by the Hatschek process, b) formation of a top layer by application of an aqueous cementitious slurry comprising a calcium silicate based cement and a photocatalyst, on said first layer of the green sheet obtained in step (a), c) dewatering said first layer of the green base sheet obtained in step (a) provided with the photocatalytic active top layer applied on it in step (b), d) winding the dewatered first layer of the green base sheet obtained in step (a) provided with the photocatalytic active top layer applied on it in step (b) on the forming drum, e) forming additional layers of the base sheet until the desired thickness is obtained on the forming drum, f) application of at least one product selected from a water-repellent agent and a biocidal agent on the photocatalytic active cementitious top layer of the product obtained in step e) which has been cured. 14. Use of a fiber reinforced cementitious building material according to any of the preceding claims for wall cladding and roofing applications. 15. Use of a fiber reinforced cementitious building material according to claim 13 wherein the fiber reinforced cementitious building material is a slate.