EP1590533A1 - Procede de fabrication d'une structure fibreuse comprenant des fibres de cellulose et synthetiques - Google Patents
Procede de fabrication d'une structure fibreuse comprenant des fibres de cellulose et synthetiquesInfo
- Publication number
- EP1590533A1 EP1590533A1 EP04708251A EP04708251A EP1590533A1 EP 1590533 A1 EP1590533 A1 EP 1590533A1 EP 04708251 A EP04708251 A EP 04708251A EP 04708251 A EP04708251 A EP 04708251A EP 1590533 A1 EP1590533 A1 EP 1590533A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fibers
- fibrous structure
- web
- synthetic fibers
- molding member
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
- D21F11/006—Making patterned paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
- D21F11/14—Making cellulose wadding, filter or blotting paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
- D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
- D21H15/10—Composite fibres
Definitions
- the present invention relates to fibrous structures comprising cellulose fibers and synthetic fibers in combination, and more specifically to fibrous structures having cellulose fibers distributed generally randomly and synthetic fibers distributed in a non-random pattern or having cellulose fibers distributed in a non-random pattern and synthetic fibers disposed generally randomly.
- Fibrous structures such as paper webs
- Typical tissue paper is comprised mostly of cellulosic fibers, often wood-based.
- cellulosic fibers are generally high in dry modulus and relatively large in diameter, which may cause their flexural rigidity to be higher than desired.
- cellulosic fibers can have a relatively high stiffness when dry, which may negatively affect the softness of the product and may have low stiffness when wet, which may cause poor absorbency in the resulting product.
- the fibers in typical disposable paper products are bonded to one another through chemical interaction and often the bonding is limited to the naturally occurring hydrogen bonding between hydroxyl groups on the cellulose molecules. If greater temporary or permanent wet strength is desired, strengthening additives can be used. These additives typically work by either covalently reacting with the cellulose or by forming protective molecular films around the existing hydrogen bonds. However, they can also produce relatively rigid and inelastic bonds, which may detrimentally affect softness and absorption properties of the products.
- Synthetic polymers can be formed into fibers with very different characteristics, including very small fiber diameters. Further, such fibers can be lower in modulus than cellulose. Thus, a fiber can be made with very low flexural rigidity, which facilitates good product softness.
- functional cross-sections of the synthetic fibers can be micro-engineered as desired. Synthetic fibers can also be designed to maintain modulus when wetted, and hence webs made with such fibers resist collapse during absorbency tasks.
- thermally bonded synthetic fibers in tissue products can result in a strong network of highly flexible fibers (good for softness) joined with water-resistant high-stretchjbonds (good for softness and wet strength).
- synthetic fibers can be relatively expensive as compared to cellulose fibers.
- a unitary fibrous structure having a plurality of synthetic fibers disposed in a generally non-random pattern and a plurality of cellulosic fibers disposed generally randomly and a method of making such a structure.
- the method may include the steps of: providing a plurality of synthetic fibers onto a forming member having a pattern of channels such that at least some of the synthetic fibers are disposed in the channels; providing a plurality of cellulosic fibers onto the synthetic fibers such that the cellulosic fibers are disposed adjacent to the synthetic fibers; and forming a unitary fibrous structure including the synthetic fibers and the cellulosic fibers.
- a web having a plurality of cellulosic fibers disposed in a generally non-random pattern and a plurality of synthetic fibers disposed generally randomly is provided.
- the method to make such a web may comprise the steps of: providing a plurality of cellulosic fibers onto a forming member having a pattern of channels such that at least some of the cellulosic fibers are disposed in the channels; providing a plurality of synthetic fibers onto the cellulosic fibers such that the synthetic fibers are disposed adjacent to the cellulosic fibers; and forming the unitary fibrous structure from the synthetic fibers and the cellulosic fibers.
- Figure 1 is a side view of an embodiment of the process of the present invention.
- Figure 2 is a plan view of an embodiment of a forming member having a substantially continuous framework.
- Figure 3 is a representational cross-sectional view of an exemplary forming member.
- Figure 4 is a plan view of an embodiment of a forming member having a substantially semi- continuous framework.
- Figure 5 is a plan view of an embodiment of a forming member having a discrete pattern framework.
- Figure 6 is a representational cross-sectional view of an exemplary forming member.
- Figure 7 is a cross-sectional view showing exemplary synthetic fibers, distributed in the channels formed in the forming member.
- Figure 8 is a cross-sectional view showing a unitary fibrous structure of the present invention, wherein the cellulosic fibers are randomly distributed on the forming member including the synthetic fibers.
- Figure 9 is a cross-sectional view of a unitary fibrous structure of the present invention, wherein the cellulosic fibers are distributed generally randomly and the synthetic fibers are distributed generally non-randomly.
- Figure 9A is a cross-sectional view of a unitary fibrous structure of the present invention, wherein the synthetic fibers are distributed generally randomly and the cellulosic fibers are distributed generally non-randomly.
- Figure 10 is a plan view of an embodiment of the unitary fibrous structure of the present invention.
- Figure 11 is a cross-sectional view of a unitary fibrous structure of the present invention between a pressing surface and a molding member.
- Figure 12 is a cross-sectional view of a bi-component synthetic fiber co-joined with another fiber.
- Figure 13 is a plan view of an embodiment of a molding member having a substantially continuous pattern framework.
- Figure 14 is a cross-sectional view taken along line 14-14 of Figure 13, DETAILED DESCRIPTION OF THE INVENTION
- Unitary fibrous structure is an arrangement comprising a plurality of fibers that are inter-entangled or otherwise joined to form a sheet product having certain pre-determined microscopic geometric, physical, and aesthetic properties.
- the fibers may be cellulosic and/or synthetic fibers and may be layered or otherwise arranged in the unitary fibrous structure.
- Micro-geometry refers to relatively small (i.e., “microscopical") details of the fibrous structure, such as, for example, surface texture, without regard to the structure's overall configuration, as opposed to its overall (i. e., "macroscopical") geometry.
- the fluid-permeable areas and the fluid-impermeable areas in combination comprise the micro-geometry of the molding member.
- Terms containing "macroscopical” or “macroscopically” refer to a "macro- geometry," or an overall geometry, of a structure or a portion thereof, under consideration when it is placed in a two-dimensional configuration, such as the X-Y plane.
- a fibrous structure when disposed on a flat surface, comprises a flat sheet.
- the fibrous structure may comprise a plurality of micro- regions that form differential elevations, such as, for example, a network region having a first elevation, and a plurality of fibrous "pillows" dispersed throughout and outwardly extending from the framework region to form a second elevation.
- Basis weight is the weight (measured in grams) of a unit area (typically measured in square meters) of the fibrous structure, which unit area is taken in the plane of the fibrous structure. The size and shape of the unit area from which the basis weight is measured is dependent upon the relative and absolute sizes and shapes of the regions having differential basis weights. Basis weight is measured as described in the test method section, below,
- Caliper is the macroscopic thickness of a sample. Caliper should be distinguished from the elevation of differential regions, which is a microscopical characteristic of the regions. Most typically, a caliper is measured under a uniformly applied load of 95 grams per square centimeter (g/cm 2 ). Caliper is measured as described in the test method section, below.
- Density is the ratio of the basis weight to a thickness (taken normal to the plane of the fibrous structure) of a region. Apparent density is the basis weight of the sample divided by the caliper with appropriate unit conversions incorporated therein. Apparent density used herein has the units of grams per cubic centimeter (g/cm 3 ).
- Machine direction (or “MD") is the direction parallel to the flow of the fibrous structure being made through the manufacturing equipment.
- Cross-machine direction or “CD" is the direction perpendicular to the machine direction.
- X,” “Y,” and “Z” designate a conventional system of Cartesian coordinates, wherein mutually perpendicular coordinates "X” and “Y” define a reference X-Y plane, and "Z” defines an orthogonal to the X-Y plane.
- X-Y plane When an element, such as, for example, a molding member curves or otherwise deplanes, the X-Y plane follows the configuration of the element.
- substantially continuous region refers to an area within which one can connect any two points by an uninterrupted line running entirely within that area throughout the line's length. That is, a substantially continuous region or pattern has a substantial "continuity" in all directions parallel to the X-Y plane and is terminated only at edges of that region.
- substantially in conjunction with “continuous” is intended to indicate that while an absolute continuity is contemplated, minor deviations from the absolute continuity may be tolerable as long as those deviations do not appreciably affect the performance of the fibrous structure or a molding member as designed and intended.
- Substantially semi-continuous region refers to an area which may have “continuity” in all, but at least one, directions parallel to the X-Y plane, and in which area one cannot connect every set of two points by an uninterrupted line running entirely within that area throughout the line's length. Of course, minor deviations from such continuity may be tolerable as long as those deviations do not appreciably affect the performance of the structure or the molding member.
- Discontinuous regions refer to discrete, and separated from one another areas that are discontinuous in all directions parallel to the X-Y plane.
- “Redistribution” means at least some of the plurality of fibers comprised in the unitary fibrous structure of the present invention at least partially melt, move, shrink, and/or otherwise change their initial position, condition, and/or shape in the web.
- Co-joined fibers means two or more fibers that have been fused or adhered to one another by melting, gluing, wrapping around, chemical or mechanical bonds, or otherwise joined together while at least partially retaining their respective individual fiber characteristics.
- the process of the present invention for making a unitary fibrous structure will be described in terms of forming a web having a plurality of synthetic fibers 101 disposed in a generally non-random pattern and a plurality of cellulosic fibers 102 disposed generally randomly (e.g. as shown in Figures 9 and 10).
- the method and apparatus of the present invention are also suitable for forming a web having a plurality of cellulosic fibers 102 disposed in a generally non-random pattern and a plurality of synthetic fibers 101 disposed generally randomly (e.g.
- the method may include the steps of: providing a plurality of synthetic fibers 101 onto a forming member such that the synthetic fibers 101 are located at least in predetermined regions or channels; providing a plurality of cellulosic fibers 102 generally randomly on the forming member containing the synthetic fibers 101; and forming a unitary fibrous structure including the randomly disposed cellulosic fibers 102 and the non-randomly disposed synthetic fibers 101.
- the method may include the steps of: providing a plurality of cellulosic fibers 102 onto a forming member such that the cellulosic fibers 102 are located at least in predetermined regions or channels; providing a plurality of synthetic fibers 101 generally randomly on the forming member containing the cellulosic fibers 102; and forming a unitary fibrous structure including the randomly disposed synthetic fibers 101 and the non-randomly disposed cellulosic fibers 102.
- Figure 1 shows one exemplary embodiment of a continuous process of the present invention in which an aqueous mixture, or aqueous slurry 1 1 of cellulosic and synthetic fibers, from a headbox 12 is deposited on a forming member 13 to form an embryonic web 10.
- the forming member 13 is supported by and continuously traveling around rolls 13a, 13b, and 13c in a direction of the arrow A.
- a web will be formed having at least some synthetic fibers 101 disposed non-randomly.
- the synthetic fibers 101 may be deposited prior to the deposition of the cellulosic fibers 102 and directly onto the forming member 13.
- more than one headbox 12 can be employed and/or the synthetic fibers 101 may be deposited onto a forming member 13 and then transferred to a different forming member where the cellulosic fibers 102 are then deposited.
- the synthetic fibers 101 could be one of several layers that are deposited onto the forming member 13 at about the same time as other types of fibers.
- the synthetic fibers 101 should be deposited in such a way that at least some of the synthetic fibers 101 are directed into predetermined regions, such as channels 53 present in forming member 13 (e.g. as shown in Figures 7-8). If a web is desired having at least some of the cellulosic fibers disposed non-randomly, any of the above-noted techniques may be used.
- the synthetic fibers 101 are provided so as to be predominantly disposed in the channels 53 of the forming member 13. That is, more than half of the synthetic fibers 101 are disposed in the channels 53 when the web 10 is being formed. In other embodiments, it may be desired that at least about 60%, about 75%, about 80%) or substantially all of the synthetic fibers 101 are disposed in the channels 53 when the web 10 is being formed. In addition, it may be desirable that the resulting web 100 include a certain percentage of synthetic fibers 101 disposed in one or more layers. For example, it may be desirable that the layer formed by fibers deposited first or closest to the forming member 13 have a concentration of greater than about 55%, greater than about 60% or greater than about 75% synthetic fibers 101.
- the cellulosic fibers 102 be provided so as to be disposed predominantly in at least one layer adjacent the layer formed by the synthetic fibers 101. In other embodiments, it may be desired that at least a certain percentage of the cellulosic fibers 102 are disposed in at least one layer of the web 100, such as for example, greater than about 55%, greater than about 60% or greater than about 75%o. At least one layer of the cellulosic fibers 102 may be disposed generally randomly.
- the resulting web 100 can be provided with a non-random pattern of synthetic fibers 101 joined to one or more layers of generally randomly distributed cellulosic fibers 102 (e.g. Figures 9 and 10). Further, a fibrous structure can be formed that has micro-regions of different basis weight.
- the cellulosic fibers 102 may be provided so as to be predominantly disposed in the channels 53 of the forming member 13. That is, more than half of the cellulosic fibers 102 are disposed in the channels 53 when the web 10 is being formed. In other embodiments, it may be desired that at least about 60%, about 75%, about 80%o or substantially all of the cellulose fibers 102 are disposed in the channels 53 when the web 10 is being formed. In addition, it may be desirable that the resulting web 100 include a certain percentage of cellulose fibers 102 disposed in one or more layers.
- the layer formed by fibers deposited first or closest to the forming member 13 have a concentration of greater than about 55%, greater than about 60% or greater than about 75% cellulose fibers 102.
- the synthetic fibers 101 be provided so as to be disposed predominantly in at least one layer adjacent the layer formed by the cellulosic fibers 102.
- at least a certain percentage of the synthetic fibers 101 are disposed in at least one layer of the web 100, such as for example, greater than about 55%, greater than about 60% or greater than about 75%.
- At least one layer of the synthetic fibers 101 may be disposed generally randomly.
- the resulting web 100 can be provided with a non-random pattern of cellulosic fibers 102 joined to one or more layers of generally randomly distributed synthetic fibers 101 (e.g. Figure 9A). Further, as stated above, a fibrous structure can be formed that has micro-regions of different basis weight.
- the forming member 13 may be any suitable structure and is typically at least partially fluid-permeable.
- the forming member 13 may comprise a plurality of fluid- permeable areas 54 and a plurality of fluid-impermeable areas 55, as shown, for example in Figures 2-6.
- the fluid-permeable areas or apertures 54 may extend through a thickness H of the forming member 13, from the web-side 51 to the backside 52.
- some of the fluid-permeable areas 54 comprising apertures may be "blind,” or "closed", as described in U.S. Patent 5,972,813, issued to Polat et al. on Oct. 26, 1999.
- the fluid permeable areas 54 whether open, blind or closed form channels 53 into which fibers can be directed.
- At least one of the plurality of fluid-permeable areas 54 and the plurality of fluid-impermeable areas 55 typically forms a pattern throughout the molding member 50.
- a pattern can comprise a random pattern or a non-random pattern and can be substantially continuous (e.g. Figure 2), substantially semi-continuous (e.g. Figure 4), discrete (e.g. Figure 5) or any combination thereof.
- the forming member 13 may have any suitable thickness H and, in fact, the thickness H can be made to vary throughout the forming member 13, as desired.
- the channels 53 may be any shape or combination of different shapes and may have any depth D, which can vary throughout the forming member 13. Also, the channels 53 can have any desired volume. The depth D and volume of the channels 53 can be varied, as desired, to help ensure the desired concentration of synthetic fibers 101 or cellulosic fibers 102 are disposed in the channels 53. In certain embodiments, it may be desirable for the depth D of the channels 53 to be less than about 254 micrometers or less than about 127 micrometers.
- the amount of synthetic fibers 101 or cellulosic fibers 102 deposited onto the forming member 13 can be varied so as to ensure the desired ratio or percentage of synthetic fibers 101 and/or cellulosic fibers 102 are disposed in the channels 53 of a particular depth D or volume.
- Some exemplary forming members 13 may comprise structures as shown in Figures 2-8 including a fluid-permeable reinforcing element 70 and a pattern or framework 60 extending there from to form a plurality of channels 53.
- the forming member 13 may comprise a plurality of discrete protuberances 61 joined to or integral with a reinforcing element 70.
- the reinforcing element 70 generally serves to provide or facilitate integrity, stability, and durability.
- the reinforcing element 70 can be fluid-permeable or partially fluid-permeable, may have a variety of embodiments and weave patterns, and may comprise a variety of materials, such as, for example, a plurality of interwoven yarns (including Jacquard- type and the like woven patterns), a felt, a plastic or other synthetic material, a net, a plate having a plurality of holes, or any combination thereof.
- suitable reinforcing elements 70 are described in U.S. Patents 5,496,624, issued March 5, 1996 to Stelljes, et al tension 5,500,277 issued Mar. 19, 1996 to Trokhan et al., and 5,566,724 issued Oct. 22, 1996 to Trokhan et al.
- a reinforcing element 70 comprising a Jacquard-type weave, or the like, can be utilized.
- Illustrative belts can be found in U.S. Patents 5,429,686 issued July 4, 1995 to Chiu, et al.; 5,672,248 issued Sept. 30, 1997 to Wendt, et al.; 5,746,887 issued May 5, 1998 to Wendt, et al,; and 6,017,417 issued January 25, 2000 to Wendt, et al.
- various designs of the Jacquard-weave pattern may be utilized as a forming member 13.
- Exemplary suitable framework elements 60 and methods for applying the framework 60 to the reinforcing element 70 are taught, for example, by U.S. Patents 4,514,345 issued April 30, 1985 to Johnson; 4,528,239 issued July 9, 1985 to Trokhan; 4,529,480 issued July 16, 1985 to Trokhan; 4,637,859 issued January 20, 1987 to Trokhan; 5,334,289 issued August 2, 1994 to Trokhan; 5,500,277 issued March 19, 1996 to Trokhan et al.; 5,514,523 issued May 7, 1996 to Trokhan et al.; 5,628,876 issued May 13, 1997 to Ayers et al.; 5,804,036 issued September 8, 1998 to Phan et al; 5,906,710 issued May 25, 1999 to Trokhan; 6,039,839 issued March 21, 2000 to Trokhan et al.; 6,110,324 issued August 29, 2000 to Trokhan et al.; 6,117,270 issued September 12, 2000 to Trokhan; 6,171,447 Bl issued January 9,
- framework 60 may include one or apertures or holes 58 extending through the framework element 60.
- Such holes 58 are different from the channels 53 and may be used to help dewater the slurry or web and/or aid in keeping fibers deposited on the framework 60 from moving completely into the channels 53.
- the forming member 13 may include any other structure suitable for receiving fibers and including some pattern of channels 53 into which the synthetic fibers 101 may be directed, including, but not limited to, wires, composite belts and/or felts.
- the pattern may be discrete, as noted above, or substantially discrete, may be continuous or substantially continuous or may be semi-continuous or substantially semi-continuous.
- Certain exemplary forming members 13 generally suitable for use with the method of the present invention include the forming members described in U.S. Patents 5,245,025; 5,277,761 ; 5,443,691; 5,503,715; 5,527,428; 5,534,326; 5,614,061 and 5,654,076.
- the forming member 13 includes a press felt, it may be made according to the teachings of U.S. Patents 5,580,423, issued Dec. 3, 1996 to Ampulski et al.; 5,609,725, issued Mar. 1 1 , 1997 to Phan; 5,629,052 issued May 13, 1997 to Trokhan et al.; 5,637,194, issued June 10, 1997 to Ampulski et al.; 5,674,663, issued Oct. 7, 1997 to McFarland et al.; 5,693, 187 issued Dec. 2,
- the forming member 13 may be executed as a press felt according to the teachings of U.S. Patent 5,569,358 issued Oct. 29, 1996 to Cameron or any other suitable structure. Other structures suitable for use as forming members 13 are hereinafter described with respect to the optional molding member 50.
- a vacuum apparatus such as vacuum apparatus 14 located under the forming member 13 may be used to apply fluid pressure differential to the slurry disposed on the forming member 13 to facilitate at least partial dewatering of the embryonic web 10.
- This fluid pressure differential can also help direct the desired fibers, e.g. the synthetic fibers 101 into the channels 53 of the forming member 13.
- Other known methods may be used in addition to or as an alternative to the vacuum apparatus 14 to dewater the web 10 and/or to help direct the fibers into the channels 53 of the forming member 13.
- the embryonic web 10, formed on the forming member 13, can be transferred from the forming member 13, to a felt or other structure such as a molding member.
- a molding member is a structural element that can be used as a support for the an embryonic web, as well as a forming unit to form, or "mold," a desired microscopical geometry of the fibrous structure.
- the molding member may comprise any element that has the ability to impart a microscopical three- dimensional pattern to the structure being produced thereon, and includes, without limitation, single-layer and multi-layer structures comprising a stationary plate, a belt, a woven fabric (including Jacquard-type and the like woven patterns), a band, and a roll.
- the molding member 50 is fluid permeable and vacuum shoe 15 applies vacuum pressure that is sufficient to cause the embryonic web 10 disposed on the forming member 13 to separate there from and adhere to the molding member 50.
- the molding member 50 of Figure 1 comprises a belt supported by and traveling around rolls 50a, 50b, 50c, and 50d in the direction of the arrow B.
- the molding member 50 has a web-contacting side 151 and a backside 152 opposite to the web-contacting side 151.
- the molding member 50 can take on any suitable form and can be made of any suitable materials.
- the molding member 50 may include any structure and be made by any of the methods described herein with respect to the forming member 13, although the molding member 50 is not limited to such structures or methods.
- the molding member 50 comprises a resinous framework 160 joined to a reinforcing element 170, as shown, for example in Figures 13-14.
- various designs of Jacquard- weave patterns may be utilized as the molding member 50, and/or a pressing surface 210.
- the molding member 50 may be or include a press felt. Suitable press felts for use with the present invention include, but are not limited to those described herein with respect to the forming member 13
- the molding member 50 may comprise a plurality of fluid- permeable areas 154 and a plurality of fluid-impermeable areas 155, as shown, for example in Figures 13 and 14.
- the fluid-permeable areas or apertures 154 extend through a thickness HI of the molding member 50, from the web-side 151 to the backside 152.
- the thickness HI of the molding member can be any desired thickness
- the depth Dl and volume of the channels 153 can vary, as desired.
- one or more of the fluid-permeable areas 154 comprising apertures may be "blind," or "closed", as described above with respect to the forming member 13.
- At least one of the plurality of fluid-permeable areas 154 and the plurality of fluid-impermeable areas 155 typically forms a pattern throughout the molding member 50.
- a pattern can comprise a random pattern or a non-random pattern and can be substantially continuous, substantially semi-continuous, discrete or any combination thereof.
- the portions of the reinforcing element 170 registered with apertures 154 in the molding member 50 may provide support for fibers that are deflected into the fluid-permeable areas of the molding member 50 during the process of making the unitary fibrous structure 100.
- the reinforcing element can help prevent the fibers of the web being made from passing through the molding member 50, thereby reducing occurrences of pinholes in the resulting structure 100.
- the molding member 50 may comprise a plurality of suspended portions extending from a plurality of base portions, as is taught by U.S. Patent 6,576,090 issued June 10, 2003 to Trokhan et al.
- the suspended portions may be elevated from the reinforcing element 170 to form void spaces between the suspended portions and the reinforcing element 170, into which spaces the fibers of the embryonic web 10 can be deflected to form cantilever portions of the fibrous structure 100.
- the molding member 50 having suspended portions may comprise a multi-layer structure formed by at ( least two layers and joined together in a face-to-face relationship.
- the joined layers may be positioned such that the apertures of one layer are superimposed (in the direction perpendicular to the general plane of the molding member 50) with a portion of the framework of the other layer, which portion forms the suspended portion described above.
- Another embodiment of the molding member 50 comprising a plurality of suspended portions can be made by a process involving differential curing of a layer of a photosensitive resin, or other curable material, through a mask comprising transparent regions and opaque regions.
- the opaque regions comprise regions having differential opacity, for example, regions having a relatively high opacity (non-transparent) and regions having a relatively low, partial, opacity (some transparency).
- the web 10 When the embryonic web 10 is disposed on the web-contacting side 151 of the molding member 50, the web 10 at least partially conforms to the three-dimensional pattern of the molding member 50.
- various means can be utilized to cause or encourage the cellulosic and/or synthetic fibers of the embryonic web 10 to conform to the three-dimensional pattern of the molding member 50 and to become a molded web designated as "20" in Figure 1. (It is to be understood, that the referral numerals " 10" and “20” can be used herein interchangeably, as well as the terms “embryonic web” and "molded web”).
- One method includes applying a fluid pressure differential to the plurality of fibers.
- vacuum apparatuses 16 and/or 17 disposed at the backside 152 of the molding member 50 can be arranged to apply a vacuum pressure to the molding member 50 and thus to the plurality of fibers disposed thereon.
- portions of the embryonic web 10 can be deflected into the channels 153 of the molding member 50 and conform to the three- dimensional pattern thereof.
- Regions 168 that are not deflected into the apertures may later be imprinted by impressing the web 20 between a pressing surface 218 and the molding member 50 (e.g. Figure 1 1), such as, for example, in a compression nip fomied between a surface 210 of a drying drum 200 and the roll 50c, shown in Figure 1. If imprinted, the density of the regions 168 may increase even more relative to the density of the pillows 150.
- the micro-regions (high and low density) of the fibrous structure 100 may be thought of as being disposed at two different elevations.
- the elevation of a region refers to its distance from a reference plane (i. e., X-Y plane).
- the reference plane can be visualized as horizontal, wherein the elevational distance from the reference plane is vertical (i.e., Z- directional).
- the elevation of a particular micro-region of the structure 100 may be measured using any non-contacting measurement device suitable for such purpose as is well known in the art.
- the fibrous structure 100 according to the present invention can be placed on the reference plane with the imprinted region 168 in contact with the reference plane.
- the pillows 150 extend vertically away from the reference plane.
- the plurality of pillows 150 may comprise symmetrical pillows, asymmetrical pillows, or a combination thereof.
- Differential elevations of the micro-regions can also be formed by using the molding member 50 having differential depths or elevations of its three-dimensional pattern.
- Such three- dimensional patterns having differential depths/elevations can be made by sanding pre-selected portions of the molding member 50 to reduce their elevation.
- a three-dimensional mask comprising differential depths/elevations of its depressions/protrusions, can be used to form a corresponding framework 160 having differential elevations.
- Other conventional techniques of forming surfaces with differential elevation can also be used for the foregoing purposes. It should be recognized that the techniques described herein for forming the molding member are also applicable to the formation of the forming member 13.
- the backside 152 of the molding member 50 can be "textured" to form microscopical surface irregularities.
- Such surface irregularities can help prevent formation of a vacuum seal between the backside 52 of the molding member 50 and a surface of the papermaking equipment (such as, for example, a surface of the vacuum apparatus), creating "leakage” there between and thus, mitigating certain undesirable consequences of an application of a vacuum pressure in a through- air-drying process.
- a surface of the papermaking equipment such as, for example, a surface of the vacuum apparatus
- Other methods of creating such leakage are disclosed in U.S. Patents 5,718,806; 5,741,402; 5,744,007; 5,776,311 and 5,885,421.
- Leakage can also be created using so-called "differential light transmission techniques" as described in U.S. Patents 5,624,790; 5,554,467; 5,529,664; 5,514,523 and 5,334,289.
- the molding member 50 can be made by applying a coating of photosensitive resin to a reinforcing element that has opaque portions, and then exposing the coating to light of an activating wavelength through a mask having transparent and opaque regions, and also through the reinforcing element.
- Another way of creating backside surface irregularities comprises the use of a textured forming surface, or a textured barrier film, as described in U.S. Patents 5,364,504; 5,260,171 and 5,098,522.
- the molding member 50 may be made by casting a photosensitive resin over and through the reinforcing element while the reinforcing element travels over a textured surface, and then exposing the coating to light of an activating wavelength through a mask, which has transparent and opaque regions. It should be understood that the methods and structures described in this paragraph and the preceding paragraph may also be applicable to the structure and formation of the forming member 13.
- the process of the present invention may also include a step wherein the embryonic web 10 (or molded web 20) is overlaid with a flexible sheet of material comprising an endless band traveling along with the molding member 50 so that the embryonic web 10 is sandwiched, for a certain period of time, between the molding member 50 and the flexible sheet of material.
- the flexible sheet of material can have air-permeability less than that of the molding member 50, and in some embodiments can be air-impermeable.
- An application of a fluid pressure differential to the flexible sheet through the molding member 50 can cause deflection of at least a portion of the flexible sheet towards, and in some instances into, the three-dimensional pattern of the molding member 50, thereby forcing portions of the web 20 disposed on the molding member 50 to closely conform to the three-dimensional pattern of the molding member 50.
- U.S. Patent 5,893,965 describes one arrangement of a process and equipment utilizing the flexible sheet of material.
- mechanical pressure can be used to facilitate formation of a microscopical three-dimensional pattern on the fibrous structure 100 of the present invention.
- a mechanical pressure can be created by any suitable press surface 218, comprising, for example a surface of a roll or a surface of a band.
- the press surface 218 can be smooth or have a three-dimensional pattern of its own. In the latter instance, the press surface 218 can be used as an embossing device, to form a distinctive micro-pattern of protrusions and/or depressions in the fibrous structure 100 being made, in cooperation with or independently from the three-dimensional pattern of the molding member 50.
- the press surface can be used to deposit a variety of additives, such for example, as softeners, and ink, to the fibrous structure being made.
- additives such for example, as softeners, and ink
- Various other conventional techniques such as, for example, ink roll, or spraying device, or shower, may be used to directly or indirectly deposit a variety of additives to the fibrous structure being made.
- the molding member 50 may be configured to have a linear velocity that is less that that of the forming member 13.
- the use of such a velocity differential at the transfer point from the forming member 13 to the molding member 50 can be used to achieve "microcontraction".
- U.S. Patent 4,440,597 describes in detail one example of wet-microcontraction. Such wet-mi crocontracti on may involve transferring the web having a low fiber-consistency from any first member (such as, for example, a foraminous forming member) to any second member (such as, for example, an open-weave fabric) moving slower than the first member.
- the difference in velocity between the first member and the second member can vary depending on the desired end characteristics of the fibrous structure 100.
- Other patents that describe methods for achieving microcontraction include, for example, U.S. Patents 5,830,321; 6,361,654 and 6,171,442.
- the fibrous structure 100 may additionally or alternatively be foreshortened after it has been formed and/or substantially dried.
- foreshortening can be accomplished by creping the structure 100 from a rigid surface, such as, for example, a surface 210 of a drying drum 200, as shown in Figure 1.
- This and other forms of creping are known in the art.
- U.S. Patent 4,919,756, issued April 24, 1992 to Sawdai describes one suitable method for creping a web.
- fibrous structures 100 that are not creped (e.g. uncreped) and/or otherwise foreshortened are contemplated to be within the scope of the present invention as are fibrous structures 100 that are not creped, but are otherwise foreshortened.
- the synthetic fibers 101 may be desirable to at least partially melt or soften at least some of the synthetic fibers 101.
- the synthetic fibers 101 may become capable of co-joining with adjacent fibers, whether cellulosic fibers 102 or other synthetic fibers 101.
- Co-joining of fibers can comprise mechanical co-joining and chemical co- joining. Chemical co-joining occurs when at least two adjacent fibers join together on a molecular level such that the identity of the individual co-joined fibers is substantially lost in the co-joined area. Mechanical co-joining of fibers takes place when one fiber merely conforms to the shape of the adjacent fiber, and there is no chemical reaction between the co-joined fibers.
- Figure 12 shows one embodiment of mechanical co-joining, wherein a fiber 1 1 1 is physically entrapped by an adjacent synthetic fiber 112.
- the fiber 111 can be a synthetic fiber or a cellulosic fiber.
- the synthetic fiber 112 has a bi-component structure, comprising a core 112a and a sheath, or shell, 112b, wherein the melting temperature of the core 112a is greater than the melting temperature of the sheath 112b, so that when heated, only the sheath 112b melts, while the core 112a retains its integrity.
- different types of bi-component fibers and/or multi-component fibers comprising more than two components can be used in the present invention, as can single component fibers.
- a heating apparatus 90, the drying surface 210 and/or a drying drum's hood can be used to heat the web 100 after it is formed to redistribute at least some of the synthetic fibers 101.
- a heating apparatus 90, the drying surface 210 and/or a drying drum's hood such as, for example, a Yankee's drying hood 80
- the synthetic fibers 101 can move after application of a sufficiently high temperature, under the influence of at least one of two phenomena.
- the resulting liquid polymer will tend to minimize its surface area/mass, due to surface tension forces, and form a sphere-like shape at the end of the portion of fiber that is less affected thermally.
- the temperature is below the melting point, fibers with high residual stresses will soften to the point where the stress is relieved by shrinking or coiling of the fiber. This is believed to occur because polymer molecules typically prefer to be in a non-linear coiled state. Fibers that have been highly drawn and then cooled during their manufacture are comprised of polymer molecules that have been stretched into a meta-stable configuration. Upon subsequent heating, the fibers attempt to return to the minimum free energy coiled state.
- Redistribution may be accomplished in any number of steps.
- the synthetic fibers 101 can first be redistributed while the fibrous web 100 is disposed on the molding member 50, for example, by blowing hot gas through the pillows of the web 100, so that the synthetic fibers 101 are redistributed according to a first pattern.
- the web 100 can be transferred to another molding member 50 wherein the synthetic fibers 101 can be further redistributed according to a second pattern.
- Heating the synthetic fibers 101 in the web 100 can be accomplished by heating the plurality of micro-regions corresponding to the fluid-permeable areas 154 of the molding member 50.
- a hot gas from the heating apparatus 90 can be forced through the web 100
- Pre-dryers can also be used as the source of heat energy.
- the direction of the flow of hot gas can be reversed relative to that shown in Figure 1, so that the hot gas penetrates the web through the molding member 50, Then, the pillow portions 150 of the web that are disposed in the fluid-permeable areas 154 of the molding member 50 will be primarily affected by the hot gas.
- the rest of the web 100 will be shielded from the hot gas by the molding member 50. Consequently, the synthetic fibers 101 will be softened or melted predominantly in the pillow portions 150 of the web 10. Further, this region is where co-joining of the fibers due to melting or softening of the synthetic fibers 101 is most likely to occur.
- any suitable means for heating the fibers 101 can be implemented.
- hot fluids may be used, as well as microwaves, radio waves, ultrasonic energy, laser or other light energy, heated belts or rolls, hot pins, magnetic energy, or any combination of these or other known means for heating.
- redistribution of the synthetic fibers 101 has generally been referred to as having been affected by heating the fibers 101, redistribution may also take place as a result of cooling a portion of the web 10.
- the synthetic fibers 101 may be redistributed due to a reaction with a redistribution material.
- the synthetic fibers 101 may be targeted with a chemical composition that softens or otherwise manipulates the synthetic fibers 101 so as to affect some change in their shape, orientation or location within the web 10.
- the redistribution can be affected by mechanical and/or other means such as magnetics, static electricity, etc.
- redistribution of the synthetic fibers 101 should not be considered to be limited to just heat redistribution of the synthetic fibers 101 , but should be considered to encompass all known means for redistributing (e.g. altering the shape, orientation or location) of any portion of the synthetic fibers 101 within the web 10.
- redistribution has been described in terms of synthetic fibers 101, it should be understood that the cellulosic fibers 102 could also or alternatively be redistributed by means known to affect the shape and/or orientation of cellulosic fibers.
- the process for producing the web can be selected such that the random distribution of the cellulosic fibers 102 is not significantly affected by the means used to redistribute the synthetic fibers 101.
- the resulting fibrous structure 100 whether redistributed or not comprises a plurality of cellulosic fibers 102 randomly distributed throughout the fibrous structure and a plurality of synthetic fibers 101 distributed throughout the fibrous structure in a non-random pattern.
- Figure 10 schematically shows one embodiment of the fibrous structure 100 wherein the cellulosic fibers 102 are randomly distributed throughout the structure, and the synthetic fibers 101 are distributed in a non-random repeating pattern.
- the synthetic fibers 101 can be any material, for example, those selected from the group consisting of polyolefins, polyesters, polyamides, polyhydroxyalkanoates, polysaccharides, and any combination thereof. More specifically, the material of the synthetic fibers 101 can be selected from the group consisting of polypropylene, polyethylene, poly(ethylene terephthalate), poly(butylene terephthalate), poly(l,4-cyclohexylenedimethylene terephthalate), isophthalic acid copolymers, ethylene glycol copolymers, polycaprolactone, poly(hydroxy ether ester), poly(hydroxy ether amide), polyesteramide, poly(lactic acid), polyhydroxybutyrate, starch, cellulose, glycogen and any combination thereof.
- the synthetic fibers 101 can be single component (i.e. single synthetic material or mixture makes up entire fiber), bi-component (i.e. fiber is divided into regions, the regions including two different synthetic materials or mixtures thereof) or multi-component fibers (i.e. fiber is divided into regions, the regions including two or more different synthetic materials or mixtures thereof) or any combination thereof.
- any or all of the synthetic fibers 101 may be treated before, during or after the process of the present invention to change any desired property of the fibers. For example, in certain embodiments, it may be desirable to treat the synthetic fibers 101 before or during the papermaking process to make them more hydrophilic, more wettable, etc.
- the method of making the web 100 of the present invention may also include any other desired steps.
- the method may include converting steps such as winding the web onto a roll, calendering the web, embossing the web, perforating the web, printing the web and/or joining the web to one or more other webs or materials to form multi-ply structures.
- Some exemplary patents describing embossing include U.S. Patents 3,414,459; 3,556,907; 5,294,475 and 6,030,690.
- the method may include one or more steps to add or enhance the properties of the web 100 such as adding softening, strengthening and/or other treatments to the surface of the product or as the web is being fomied.
- the web 100 may be provided with latex or the like, for example, as described in U.S. Patent 3,879,257 or other materials or resins to provide beneficial properties to the web.
- the methods and apparatus described herein can also be used to form a web 100 wherein the cellulosic fibers 102 are generally non-randomly distributed and the synthetic fibers 101 are distributed generally randomly throughout at least a portion of the web 100 (e.g. Figure 9A).
- the variations described herein with respect to the method steps and the different equipment used in the method should be understood to also apply to such alternative web embodiments, as should the alternative and optional steps described herein.
- the resultant products may find use in filters for air, oil and water; vacuum cleaner filters; furnace filters; face masks; coffee filters, tea or coffee bags; thermal insulation materials and sound insulation materials; nonwovens for one-time use sanitary products such as diapers, feminine pads, and incontinence articles; textile fabrics for moisture absorption and softness of wear such as micro fiber or breathable fabrics; an electrostatically charged, structured web for collecting and removing dust; reinforcements and webs for hard grades of paper, such as wrapping paper, writing paper, newsprint, corrugated paper board, and webs for tissue grades of paper such as toilet paper, paper towel, napkins and facial tissue; medical uses such as surgical drapes, wound dressing, bandages, and dermal patches.
- the fibrous structure 100 may also include odor absorbents, termite repellents, insecticides, rodenticides, and the like, for specific uses.
- the resultant product may absorb water and oil and may find use in oil or water spill clean-up, or controlled water retention or release for agricultural or horticultural applications.
- Caliper is measured according to the following procedure, without considering the micro- deviations from absolute planarity inherent to the multi-density tissues made according to the aforementioned incorporated patents.
- the tissue paper is preconditioned at 71° to 75°F and 48 to 52 percent relative humidity for at least two hours prior to the caliper measurement. If the caliper of toilet tissue or other rolled products is being measured, 15 to 20 sheets are first removed from the outside of the roll and discarded. If the caliper of facial tissue or other boxed products is being measured, the sample is taken from near the center of the package. The sample is selected and then conditioned for an additional 15 minutes.
- Caliper is measured using a low load Thwing-Albert Progage micrometer, Model 89-2012, available from the Thwing-Albert Instrument Company of Philadelphia, Pennsylvania.
- the micrometer loads the sample with a pressure of 95 grams per square inch using a 2.0 inch diameter presser foot and a 2.5 inch diameter support anvil,
- the micrometer has a measurement capability range of 0 to 0.0400 inches. Decorated regions, perforations, edge effects, etc., of the tissue should be avoided if possible.
- Basis weight is measured according to the following procedure.
- the tissue sample is selected as described above, and conditioned at 71° to 75°F and 48 to 52 percent humidity for a minimum of 2 hours. Twelve finished product sheets are carefully selected, which are clean, free of holes, tears, wrinkles, folds, and other defects. To be clear, finished product sheets should include the number of plies that the particular finished product to be tested has. Thus, one ply product sample sets will contain 12 one ply sheets; two ply product sample sets will contain 12 two ply sheets; and so on. The sample sets are split into two stacks each containing 6 finished product sheets. A stack of six finished product sheets is placed on top of a cutting die.
- the die is square, having dimensions of 3.5 inches by 3.5 inches and may have soft polyurethane rubber within the square to ease removal of the sample from the die after cutting.
- the six finished product sheets are cut using the die, and a suitable pressure plate cutter, such as a Thwing-Albert Alfa Hydraulic Pressure Sample Cutter, Model 240-7 A.
- the second set of six finished product sheets is cut in the same manner.
- the two stacks of cut finished product sheets are combined into a 12 finished product sheet stack and conditioned for at least 15 additional minutes at 71° to 75°F and 48 to 52 percent humidity.
- the stack of 12 finished product sheets cut as described above is then weighed on a calibrated analytical balance having a resolution of at least 0.0001 grams.
- the balance is maintained in the same room in which the samples were conditioned.
- a suitable balance is made by Sartorius Instrument Company, Model A200S.
- Basis Weight (lb/3,000 ft 2 ) Weight of 12 ply pad (g) x 6.48
- the units of density used here are grams per cubic centimeter (g/cc). With these density units of g/cc, it may be convenient to also express the basis weight in units of grams per square centimeters. The following equation may be used to make this conversion:
Landscapes
- Nonwoven Fabrics (AREA)
- Paper (AREA)
Abstract
Applications Claiming Priority (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US740059 | 1996-10-24 | ||
US740060 | 1996-10-24 | ||
US10/360,021 US7067038B2 (en) | 2003-02-06 | 2003-02-06 | Process for making unitary fibrous structure comprising randomly distributed cellulosic fibers and non-randomly distributed synthetic fibers |
US360021 | 2003-02-06 | ||
US360038 | 2003-02-06 | ||
US10/360,038 US7052580B2 (en) | 2003-02-06 | 2003-02-06 | Unitary fibrous structure comprising cellulosic and synthetic fibers |
US10/740,059 US7045026B2 (en) | 2003-02-06 | 2003-12-18 | Process for making a fibrous structure comprising cellulosic and synthetic fibers |
US10/740,060 US7041196B2 (en) | 2003-02-06 | 2003-12-18 | Process for making a fibrous structure comprising cellulosic and synthetic fibers |
PCT/US2004/003337 WO2004072373A1 (fr) | 2003-02-06 | 2004-02-04 | Procede de fabrication d'une structure fibreuse comprenant des fibres de cellulose et synthetiques |
Publications (1)
Publication Number | Publication Date |
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EP1590533A1 true EP1590533A1 (fr) | 2005-11-02 |
Family
ID=32872958
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04708251A Withdrawn EP1590533A1 (fr) | 2003-02-06 | 2004-02-04 | Procede de fabrication d'une structure fibreuse comprenant des fibres de cellulose et synthetiques |
Country Status (6)
Country | Link |
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EP (1) | EP1590533A1 (fr) |
JP (1) | JP2006514176A (fr) |
AU (1) | AU2004211619B2 (fr) |
CA (1) | CA2514606C (fr) |
MX (1) | MXPA05007932A (fr) |
WO (1) | WO2004072373A1 (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7045026B2 (en) * | 2003-02-06 | 2006-05-16 | The Procter & Gamble Company | Process for making a fibrous structure comprising cellulosic and synthetic fibers |
US7067038B2 (en) * | 2003-02-06 | 2006-06-27 | The Procter & Gamble Company | Process for making unitary fibrous structure comprising randomly distributed cellulosic fibers and non-randomly distributed synthetic fibers |
US20070116928A1 (en) * | 2005-11-22 | 2007-05-24 | Jean-Louis Monnerie | Sheet slitting forming belt for nonwoven products |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3414459A (en) | 1965-02-01 | 1968-12-03 | Procter & Gamble | Compressible laminated paper structure |
US3556907A (en) | 1969-01-23 | 1971-01-19 | Paper Converting Machine Co | Machine for producing laminated embossed webs |
US3879257A (en) | 1973-04-30 | 1975-04-22 | Scott Paper Co | Absorbent unitary laminate-like fibrous webs and method for producing them |
US4741941A (en) * | 1985-11-04 | 1988-05-03 | Kimberly-Clark Corporation | Nonwoven web with projections |
US5178729A (en) | 1991-01-15 | 1993-01-12 | James River Corporation Of Virginia | High purity stratified tissue and method of making same |
US5245025A (en) * | 1991-06-28 | 1993-09-14 | The Procter & Gamble Company | Method and apparatus for making cellulosic fibrous structures by selectively obturated drainage and cellulosic fibrous structures produced thereby |
EP0575601A1 (fr) * | 1992-01-21 | 1993-12-29 | James River Corporation Of Virginia | Papier absorbant renforce |
US5294475A (en) | 1992-06-12 | 1994-03-15 | The Procter & Gamble Company | Dual ply cellulosic fibrous structure laminate |
US5990377A (en) * | 1997-03-21 | 1999-11-23 | Kimberly-Clark Worldwide, Inc. | Dual-zoned absorbent webs |
US6030690A (en) | 1997-04-23 | 2000-02-29 | The Procter & Gamble Company | High pressure embossing and paper produced thereby |
US5972813A (en) | 1997-12-17 | 1999-10-26 | The Procter & Gamble Company | Textured impermeable papermaking belt, process of making, and process of making paper therewith |
AU2059800A (en) * | 1998-12-30 | 2000-07-31 | Kimberly-Clark Worldwide, Inc. | Layered tissue having a long fiber layer with a patterned mass distribution |
-
2004
- 2004-02-04 AU AU2004211619A patent/AU2004211619B2/en not_active Ceased
- 2004-02-04 JP JP2005518379A patent/JP2006514176A/ja active Pending
- 2004-02-04 CA CA002514606A patent/CA2514606C/fr not_active Expired - Fee Related
- 2004-02-04 MX MXPA05007932A patent/MXPA05007932A/es active IP Right Grant
- 2004-02-04 WO PCT/US2004/003337 patent/WO2004072373A1/fr active IP Right Grant
- 2004-02-04 EP EP04708251A patent/EP1590533A1/fr not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
See references of WO2004072373A1 * |
Also Published As
Publication number | Publication date |
---|---|
MXPA05007932A (es) | 2005-09-30 |
CA2514606A1 (fr) | 2004-08-26 |
AU2004211619A1 (en) | 2004-08-26 |
WO2004072373A1 (fr) | 2004-08-26 |
AU2004211619B2 (en) | 2007-05-24 |
CA2514606C (fr) | 2008-09-02 |
JP2006514176A (ja) | 2006-04-27 |
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