|Publication number||US3704198 A|
|Publication date||Nov 28, 1972|
|Filing date||Oct 9, 1969|
|Priority date||Oct 9, 1969|
|Publication number||US 3704198 A, US 3704198A, US-A-3704198, US3704198 A, US3704198A|
|Inventors||Prentice James S|
|Original Assignee||Exxon Research Engineering Co|
|Export Citation||BiBTeX, EndNote, RefMan|
|Referenced by (175), Classifications (6)|
|External Links: USPTO, USPTO Assignment, Espacenet|
1972 J. 5. PRENTICE NONWOVEN POLYPROPYLENE MATS 0F INCREASED STRIP TENSILE STRENGTH Filed 001;. 9, 1969 FIG. I.
JAMES S. PRENTICE,
BY Mfg ATTORNEY.
United States Patent 3,704,198 NONWOVEN POLYPROPYLENE MATS 0F INCREASED STRIP TENSILE STRENGTH James S. Prentice, Baytown, Tex., assignor to Esso Research and Engineering Company Filed Oct. 9, 1969, Ser. No. 865,089 Int. Cl. D0411 3/14 US. Cl. 161148 7 Claims ABSTRACT OF THE DISCLOSURE The strip tensile strength of nonwoven mats of polypropylene fibers having a diameter from about 1 to about microns is increased, for example, to strengths greater than 4000 m., by fuse-bonding, as by calendering or point-bonding, at least a portion of the fibers of the mat at temperatures Within the range from about 250 F. to about 325 F., preferably, from about 280 F. to about 315 F., while the mat is subjected to pressure sufiicient to prevent shrinkage of the fibers in the mat.
BACKGROUND OF THE INVENTION (1) Field of the invention The present invention is directed to nonwoven mats of polypropylene fibers having a diameter from about 1 to about 10 microns and to a method for treating such mats so that they have high strip tensile strength.
(2) Prior art US. Pat. 3,276,944; Wente, Van A., Super-Fine Thermoplastics, Industrial and Engineeirng Chemistry, vol. 48, No. 8 (.1956), pp. 1342-1346.
SUMMARY OF THE INVENTION In this invention, the strip tensile strength of nonwoven mats of polypropylene fibers having diameters from about 1 to about 10 microns is increased by fusebonding, as by point-bonding or by calendering, at least a portion of the fibers of the mat at a temperature within the range from about 250 F. to about 325 F., while maintaining pressure on the nonwoven mats sufiicient to prevent shrinkage of the fibers while they are exposed to the fuse-bonding temperatures. The nonwoven mats so treated have fusion-bonds throughout their thickness, and may have strip tensile strengths greater than 4000 m., preferably, greater than 5000 or even 6000 m.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic perspective view of an overall melt blowing process;
FIG. 2 is a detailed view in longitudinal cross section of a die which may be used in the melt blowing process;
FIG. 3 is a schematic view of a press used to increase the strip tensile strength of a nonwoven mat of polypropylene fibers of diameters from about 1 to about 10 microns; and
FIG. 3A is a schematic view of calender rolls which may be used instead of the press of FIG. 3.
7 3,704,198 Patented Nov. 28, 1972 DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring to FIG. 1 of the drawings, a polypropylene resin is introduced into a pellet hopper 1 of an extruder 2. The resin is forced through the extruder 2 into a die head 3 by a drive 4. The die head 3 may contain heating plates 5 which may control the temperature in the die head 3. The polypropylene resin is then forced out of a row of die openings 6 in the die head 3 into a gas stream which attenuates the resin into fiber 7 which are collected on a moving collecting device 8 such as a drum 9 to form a continuous mat 10. The gas stream which attenuates the polypropylene is supplied through gas jets 11 and 12 respectively, which are seen more clearly in FIG. 2. The gas slots 11 and 12 are supplied with a hot gas, preferably air, by gas lines 13 and 14 respectively.
The process may be further understood by considering the details of the die head 3 which is more fully set forth in FIG. 2. The die head 3 is made up of an upper die plate 15 and a lower die plate 16. The polypropylene resin is introduced in the back of the die plates 15 and 16 through an inlet 17 as it is forced through the extruder 2 into the back of the die head 3. The polypropylene then goes into a chamber 18 between the upper and lower die plates 15 and 16 respectively. The facing of the die plate 16 may have milled grooves 19 which terminate in the die openings 6. It is understood, of course, that the milled grooves may be in the lower die plate 16, in the upper die plate 15, or that grooves may be milled in both plates 15 and 16. Still further. if a single plate is used in place of the upper and lower die plates, the grooves may be drilled to produce the die openings 6. An upper gas cover plate 20 and a lower gas cover plate 21 are connected to the upper die plate and lower die plate 15 and 16 respectively to provide an upper air chamber 22 and a lower air chamber 23 which terminate in the gas slots 11 and 12 respectively. The hot gas is supplied through inlet 24 in upper gas cover plate 20 and inlet 25 in lower gas cover plate 21. Suitable bafliing means (not shown) may be provided in both the upper air chamber 22 and lower air chamber 23 to provide a uniform rflow of air through the gas slots 11 and 12 respectively. The die head 3 may contain heating means 5 for heating both the polypropylene and air in the die head 3.
The characteristics of the nonwoven polypropylene mats produced by the melt blowing process will vary considerably depending upon the particular process conditions used. The characteristics of the nonwoven polypropylene mats are affected in large part by the air flow rates used relative to the rate of resin throughput in the melt blowing process and by the distance of the take-up device from the die openings in the die head. In the melt blowing process, when the air rates are high and the pounds of air to pounds of polypropylene extruded through the die head are high (suitably greater than about 140, desirably 150, and preferably in excess of 200 lbs. air/lbs. of polymer for polypropylene) the polypropylene fibers in the nonwoven mat are such that generally the mat has a high zero span tensile strength. The fibers at the higher air rates appear to be drawn, and are much finer fibers as evidenced by their small diameters, which range from 1 to microns.
One of the other process variables in the melt blowing process which materially affects the characteristics of the nonwoven polypropylene mat is the distance of the take-up device from the die openings and the die head. When the collecting device is between 1 and 6 inches from the die openings, there is evidence of considerable self-bonding of the fibers as they are laid down in the nonwoven mat. At distances greater than 6 inches between the die openings and collector device, some self-bonding still occurs but the amount of self-bonding decreases with distance. The term self bonding herein means thermal bonding of one fiber to another in the melt blowing process as the nonwoven thermoplastic polymer mats are formed. The strip tensile strength of the polypropylene mats as produced by the melt blowing process is greatest in those mats having the highest degree of self-bonding; but as the self-bonding decreases, the mat is comprised essentially of entangled fibers and the strip tensile strength materially decreases.
Another factor in the strip tensile strength of the melt blown mat is the tensile strength of the fiber itself. The tensile strength of the fibers in the melt blown nonwoven mat are found by measuring the zero span tensile strengths of the mats, a measurement which utilizes the same general procedure employed to obtain the strip tensile strength of the mats. The procedure for obtaining strip tensile strength and zero span tensile strength are those in ASTM procedure D-828-60, with the exception that to measure the strip tensile strength the clamps are set apart at a distance of two inches, using an elongation rate of 250% /min., but to measure the zero span tensile strength, the clamps are not separated by any distance. In both instances, the results are reported in meters, the unit resulting when the force necessary to break the mat, measured in grams, is divided by the width of the sample, measured in meters, all of which is divided by the basis weight of the sample in terms of gm./m. The process variables used in the melt blowing process to obtain mats of high zero span tensile strength result in low tear resistances in those mats, as measured by a standard Elmendorf tear strength tester in accordance with ASTM procedure D-689-62.
The strip tensile strength of melt blown nonwoven mats of polypropylene fibers are generally lower than desirable for load bearing applications, even though the zero span tensile strengths of the mats may be quite high. The principal object of the present invention is to make the strip tensile strength of a nonwoven mat approach, and even more desirably, attain or exceed the zero span tensile strength of that mat.
in accordance with this invention, the strip tensile strength of nonwoven mats of polypropylene fibers having diameters between about 1-10 microns is increased by fuse bonding the nonwoven mat at temperatures within the range from about 250 F. to about 325 F., preferably from about 280 F. to about 315 F., while compressing the mat sufiiciently to prevent shrinkage of the fibers in the mat.
The fuse-bonding process may be accomplished by applying a spaced pattern of heat to the mat to melt discrete portions of the mat and to fuse a portion of the fibers in the mat. Herein, this is termed "point-bonding. Alternatively, the fuse-bonding may be effected by a general fusion of the fibers by applying an unbroken pattern of heat to the mat, such as by calendering. In the fuse-bonding process, application of sufficient pressure to the nonwoven mat to prevent shrinkage of the fibers in the mat is indicated by a lack of difference in the size of the mat before and after fuse-bonding and by a lack of decrease in the zero span tensile strength of the nonwoven mat.
Referring to FIG. 3, a heated press 30 may be used in the fuse-bonding process to increase the strip tensile strengths of the melt blown nonwoven mats. The press 30 comprises a plate 31 and a plate 32. The plate 31 has a plurality of spaced apart projections 33 which terminate in flat lands 34 that are spaced in a design or pattern. The spacing of the projections 33, the total surface of the flat lands 34 and the pattern of the projections 33 of the plate 31 will partially determine the degree to which the fibers of the nonwoven mats are point-bonded. The spacing of the projections 33 and the pattern may vary greatly although suitable patterns are rectilinear or diagonal grids. Suitable spacing for the projections 33 is between about inch and inch. The depth to which the projections 33 will penetrate the nonwoven sheet may be controlled by the use of spacers or shims placed between plate 31 and plate 32. The plate 32 may have a flat surface which would come in contact with the lands 34 of the projections 33 of plate 31 or the plate 32 may also have projections which are aligned with the projections of plate 31 so that the lands of the projections of plate 32 would contact the lands 34 of the projections of plate 31. To obtain higher increases in the strip tensile strengths of the nonwoven mats, the deeper penetration of the projections 33 into the nonwoven mats is desired. Each of the plates 31 and 32 may be heated independently so that the temperatures of the plates are not necessarily the same.
In the fuse-bonding process of the nonwoven mats, it is convenient to use spacer sheets between the nonwoven mats and the plates 31 and 32 of the press to prevent the nonwoven mat from sticking to the plates either during or subsequent to the fuse-bonding operation. Suitable spacer sheet material which may be employed include insulating materials such as tissue paper, ordinary paper and the like or heat conducting materials such as aluminum foil and the like. The conducting spacer sheets are preferred since the additional heat increases the fusing of the fibers in the fuse-bonding process.
For the continuous production of the nonwoven mats of improved higher strip tensile strengths, it is advantagcous to carry out the fuse-bonding process by calendering the nonwoven mats under heating conditions which effect fiber-to-fiber fusion under pressure suflicient to prevent shrinkage of the fibers of the nonwoven mat. Referring to FIG. 3A, calender rolls 40 and 41 are shown which may be employed instead of the press 30. The calender roll 40 may have projections which terminate in flat lands which may be patterned in a wide variety of forms, such as a diagonal grid (not shown). In the calen dering operation to carry out the fuse-bonding, spacer sheets may also be used to prevent the nonwoven mats from sticking to the calender rolls.
The fusion-bonded nonwoven mat of polypropylene fibers suitably has a thickness within the range of from about 1 to about 25 mils, preferably less than about 10 mils. Basis weight may vary from about 10 gmJm. to 300 or more -gm./m. Depending on the degree and manner in which fusion-bonding is accomplished, the fusionbonds which occur throughout the thickness of the nonwoven mat are discrete points in an essentially spaced pattern along its length and breadth or else occur continuously along its length and breadth in an essentially unbroken pattern. The strip tensile strength of the fusionbonded mat is high, greater than about 4000 m., desirably greater than 5000 m., and preferably in excess of 6000 m. The tear resistance of the fusion-bonded mat is low, generally less than 200 dm. rarely if ever as great as 300 dmF.
The fusion-bonded mats, by virtue of their high strength, which may exceed the zero span tensile strength of the untreated mat, are highly useful as fabrics for load bearing applications, such as tapes, reinforcing liners, carpet backing and the like. A special application involves their use as components in laminates to which they con? tribute high strip tensile strength.
The fusion-bonded nonwoven mats of the present invention and the fusion-bonding process are further illustrated by the specific examples hereinafter following. These examples utilize non-woven mats of melt blown polypropylene fibers produced by the melt blowing process illustrated in FIGS. 1 and 2 of the drawings with the specific 6 temperatures ranging from 200 to 320 F. under a roller pressure of 700 pounds per linear inch at a line speed of 20 feet/minute, using a three-roll calender. The results are tabulated in Table 11.
TABLE IL-EXAMPLE 1 Calender roll temperatures F.):
Upper 70 200 225 250 275 287 300 310 320 Lower 70 147 165 185 205 206 220 230 240 Fuse-bonded mat properties:
Strip tensile (m.) 2,346 2,250 2, 150 2,600 3,100 4,900 5, 600 B, 600
Tear resistance (dm.')---- 44 22 29 Zero span tensile (m.) 5, 490 6, 560 7, 130
operating conditions as set forth in Table I. The specific nonwoven mat characteristics are also set forth in Table I as to basis weight, zero span tensile strength and the 2 degree of uniformity of the mat in terms of the zero span tensile strength by the ratio of the cross direction to machine direction (CD/ MD). The fiber diameter of the mats ranged between about 1 to about microns, usually between about 1 to 5 microns.
TABLE I Met Nos A B C D Melt blowing conditions:
Polypropylene MFR 0.6 0.0 0.0 0.6 30
Extruder temp. F Die temp F.) Polymer rate (gm./mi Apparent viscosity (poises).-
Kolymertrate (gnzJnzi p aren viscosi y polses Air tlow (lbs./min.) 4.32 4.2;: 3. 3.36
As shown by Table II, calender roll temperatures of 250 F. or greater were effective in increasing the strip tensile strength of nonwoven mat A. The lack of decrease, indeed, even an increase, of zero span tensile strength at the highest calender roll temperature as well as at an intermediate temperature shows that sufficient pressure was applied to prevent shrinkage of the fibres of the mat.
That the point-bonding technique is efiective to increase the strip tensile strength of other nonwoven mats produced in the same manner as nonwoven mat A of Example l is illustrated by Examples 2-8.
EXAMPLES 2-8 Nonwoven mats B-H, made under melt blowing conditions which produce fibers that have a diameter between about 1 to 10 microns (see Table I), were point-bonded at elevated temperatures to fuse-bond the fibers of the mat. The fuse-bonding was accomplished utilizing a press wherein the temperatures of the plates of the press are separately controlled. The temperatures of the plates are set-forth in Table II, the upper plate being a smooth surfaced plate and the lower plate having projections arranged in a spaced pattern. The fuse-bonding was carried out for 10 seconds, with the mats being closed to a spacing of 0.005 inch between the smooth-surfaced upper plate and the lands of the projections on the lower plate. Except for Example 6, two sheets of tissue paper were used between the nonwoven mats and the lower plate, and one sheet of foil was used between the nonwoven mats and the upper Lbs. air/lb. polymer--.- 233 21; 2 plate. Example 6 had two sheets of foil between it and 6 the lower plate and two sheets of foil between it and the Basis weight (gm-[1113) 0 6 5 53 upper plate. The point-bonded nonwoven mats, as shown gggg g tensile (111-) 32 ggg 5,69 in Table 111, exhibited high strip tensile strengths. The strip tensile strengths were greatly increased from the strip tensile strength of the untreated mat.
TABLE III Example Nos 2 3 4 5 6 7 8 pper Lower- B C D E F G H Fuse-bonded mat properties:
Strip tensile (m.) Tear resistance (dm!) 108 EXAMPLE 1 Having fully and particularly described the fusion- This example illustrates how the strip tensile strength 7 0 bonded nonwoven sheet and the processes involved in of a nonwoven mat is increased by fuse-bonding the mat.
Samples of nonwoven mat A, made under melt blowing conditions which produce fibers that have a diameter from about lto 10 microns (see Table I), were calendered once by passing them through heated calendering rolls at this invention and having set out the best modes thereof, it will be appreciated that alterations and changes may be made by those skilled in the art which are nevertheless within the spirit and scope of the invention, as defined by the appended claims.
1. A nonwoven mat of polypropylene fibers having diameters from about 1 to about 10 microns, said mat having fusion-bonds throughout its thickness, the strip tensile strength of the mat being greater than about 4000 m. and the tear resistance of the mat being no greater than about 300 dm..
2. The nonwoven mat of claim 1 in which said fusionbonds occur in an essentially spaced pattern in said mat.
3. The nonwoven mat of claim 1 in which said fusionbonds occur continuously in an essentially unbroken pattern in said mat.
4. The nonwoven mat of claim 1 having a thickness within the range of from about 1 to about 25 mils.
5. The nonwoven mat of claim 1 in which the polypropylene fibers have diameters of from about 1 to about 5 microns.
6. The nonwoven mat of claim 1 in which the strip tensile strength exceeds 5000 meters and in which the tear resistance is less than about 200 dm..
7. The nonwoven mat of claim 1 having a basis weight from about g./m. to about 300 g./m.
8 References Cited UNITED STATES PATENTS 3,276,944 10/ 1966 Levy 161-450 3,532,800 10/1970 Wyly et a1 161140 X 2,988,469 6/1961 Watson 161150 X 3,341,394 9/ 1967 Kinney 161-150 X 3,510,389 5/1970 Olson 161150 X 3,516,899 6/1970 Saunders 161-148 3,532,589 10/1970 David 161-150 US. Cl. X.R. 16l-150,
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US3787265 *||Mar 24, 1972||Jan 22, 1974||Celanese Corp||Process and apparatus for producing fibrous structures|
|US3839139 *||Jun 26, 1973||Oct 1, 1974||Unitika Ltd||Light-occluding and water-permeable sheet|
|US3847676 *||Dec 21, 1972||Nov 12, 1974||Grace W R & Co||Battery separator manufacturing process|
|US3870567 *||Dec 21, 1972||Mar 11, 1975||Grace W R & Co||Battery separator manufacturing process|
|US3907604 *||Oct 17, 1972||Sep 23, 1975||Exxon Research Engineering Co||Nonwoven mat battery separators|
|US3916447 *||Apr 24, 1972||Nov 4, 1975||Kimberly Clark Co||Low cost, absorbent, clinging, aqueous liquid barrier protective covering|
|US4000967 *||Jul 26, 1973||Jan 4, 1977||Exxon Research And Engineering Company||Wettable non-woven structures and components thereof|
|US4003758 *||Dec 21, 1972||Jan 18, 1977||W. R. Grace & Co.||Battery separator with porous body and fused rib|
|US4041203 *||Oct 4, 1976||Aug 9, 1977||Kimberly-Clark Corporation||Nonwoven thermoplastic fabric|
|US4042740 *||Sep 20, 1974||Aug 16, 1977||Minnesota Mining And Manufacturing Company||Reinforced pillowed microfiber webs|
|US4048364 *||Jan 21, 1976||Sep 13, 1977||Exxon Research And Engineering Company||Post-drawn, melt-blown webs|
|US4713068 *||Oct 31, 1986||Dec 15, 1987||Kimberly-Clark Corporation||Breathable clothlike barrier having controlled structure defensive composite|
|US4713069 *||Oct 31, 1986||Dec 15, 1987||Kimberly-Clark Corporation||Baffle having zoned water vapor permeability|
|US4758239 *||Oct 31, 1986||Jul 19, 1988||Kimberly-Clark Corporation||Breathable barrier|
|US4767825 *||Dec 22, 1986||Aug 30, 1988||Kimberly-Clark Corporation||Superabsorbent thermoplastic compositions and nonwoven webs prepared therefrom|
|US4806598 *||Dec 22, 1986||Feb 21, 1989||Kimberly-Clark Corporation||Thermoplastic polymer blends and nonwoven webs prepared therefrom|
|US4818600 *||Dec 9, 1987||Apr 4, 1989||Kimberly-Clark Corporation||Latex coated breathable barrier|
|US4820577 *||Dec 22, 1986||Apr 11, 1989||Kimberly-Clark Corporation||Meltblown superabsorbent thermoplastic compositions|
|US4847141 *||Feb 26, 1988||Jul 11, 1989||Kimberly-Clark Corporation||Superabsorbent thermoplastic compositions and nonwoven webs prepared therefrom|
|US4857251 *||Apr 14, 1988||Aug 15, 1989||Kimberly-Clark Corporation||Method of forming a nonwoven web from a surface-segregatable thermoplastic composition|
|US4894280 *||Dec 21, 1987||Jan 16, 1990||Kimberly-Clark Corporation||Flexible, tear resistant composite sheet material and a method for producing the same|
|US4940626 *||May 26, 1988||Jul 10, 1990||The James River Corporation||Meltblown wiper incorporating a silicone surfactant|
|US4963638 *||Feb 23, 1989||Oct 16, 1990||Kimberly-Clark Corporation||Superabsorbent thermoplastic compositions and nonwoven webs prepared therefrom|
|US4988560 *||Dec 21, 1987||Jan 29, 1991||Minnesota Mining And Manufacturing Company||Oriented melt-blown fibers, processes for making such fibers, and webs made from such fibers|
|US5021288 *||Jan 4, 1990||Jun 4, 1991||The Dow Chemical Company||Microfibers of syndiotactic vinyl aromatic polymers, nonwoven mats of the microfibers|
|US5085920 *||Apr 30, 1990||Feb 4, 1992||Kimberly-Clark Corporation||Nonwoven wipe having improved grease release|
|US5100435 *||Dec 4, 1990||Mar 31, 1992||Kimberly-Clark Corporation||Meltblown nonwoven webs made from epoxy/pcl blends|
|US5141699 *||Jan 16, 1990||Aug 25, 1992||Minnesota Mining And Manufacturing Company||Process for making oriented melt-blown microfibers|
|US5145727 *||Nov 26, 1990||Sep 8, 1992||Kimberly-Clark Corporation||Multilayer nonwoven composite structure|
|US5149576 *||Nov 26, 1990||Sep 22, 1992||Kimberly-Clark Corporation||Multilayer nonwoven laminiferous structure|
|US5178931 *||Jun 17, 1992||Jan 12, 1993||Kimberly-Clark Corporation||Three-layer nonwoven laminiferous structure|
|US5178932 *||Jun 17, 1992||Jan 12, 1993||Kimberly-Clark Corporation||Three-layer nonwoven composite structure|
|US5240479 *||May 17, 1991||Aug 31, 1993||Donaldson Company, Inc.||Pleated filter media having a continuous bead of adhesive between layers of filtering material|
|US5244525 *||Jul 20, 1992||Sep 14, 1993||Kimberly-Clark Corporation||Methods for bonding, cutting and printing polymeric materials using xerographic printing of IR absorbing material|
|US5244723 *||Jan 3, 1992||Sep 14, 1993||Kimberly-Clark Corporation||Filaments, tow, and webs formed by hydraulic spinning|
|US5244947 *||Dec 31, 1991||Sep 14, 1993||Kimberly-Clark Corporation||Stabilization of polyolefin nonwoven webs against actinic radiation|
|US5283023 *||Jan 3, 1992||Feb 1, 1994||Kimberly-Clark Corporation||Method of imparting delayed wettability to a nonwoven web|
|US5300167 *||Jun 11, 1993||Apr 5, 1994||Kimberly-Clark||Method of preparing a nonwoven web having delayed antimicrobial activity|
|US5342335 *||Dec 22, 1993||Aug 30, 1994||Kimberly-Clark Corporation||Nonwoven web of poly(vinyl alcohol) fibers|
|US5344862 *||Oct 25, 1991||Sep 6, 1994||Kimberly-Clark Corporation||Thermoplastic compositions and nonwoven webs prepared therefrom|
|US5369858 *||Aug 19, 1992||Dec 6, 1994||Fiberweb North America, Inc.||Process for forming apertured nonwoven fabric prepared from melt blown microfibers|
|US5382703 *||Nov 6, 1992||Jan 17, 1995||Kimberly-Clark Corporation||Electron beam-graftable compound and product from its use|
|US5413655 *||Apr 6, 1994||May 9, 1995||Kimberly-Clark Corporation||Thermoplastic compositions and nonwoven webs prepared therefrom|
|US5445785 *||Dec 22, 1993||Aug 29, 1995||Kimberly-Clark Corporation||Method of preparing a nonwoven web of poly(vinyl alcohol) fibers|
|US5455074 *||Dec 29, 1992||Oct 3, 1995||Kimberly-Clark Corporation||Laminating method and products made thereby|
|US5478224 *||Feb 4, 1994||Dec 26, 1995||Illinois Tool Works Inc.||Apparatus for depositing a material on a substrate and an applicator head therefor|
|US5494855 *||Nov 30, 1994||Feb 27, 1996||Kimberly-Clark Corporation||Thermoplastic compositions and nonwoven webs prepared therefrom|
|US5512358 *||Sep 22, 1993||Apr 30, 1996||Kimberly-Clark Corporation||Multi-component polymeric strands including a butene polymer and nonwoven fabric and articles made therewith|
|US5554435 *||Mar 18, 1994||Sep 10, 1996||Hercules Incorporated||Textile structures, and their preparation|
|US5567372 *||May 26, 1994||Oct 22, 1996||Kimberly-Clark Corporation||Method for preparing a nonwoven web containing antimicrobial siloxane quaternary ammonium salts|
|US5569732 *||May 25, 1995||Oct 29, 1996||Kimberly-Clark Corporation||Antimicrobial siloxane quaternary ammonium salts|
|US5578369 *||May 25, 1995||Nov 26, 1996||Kimberly-Clark Corporation||Laminating method and products made thereby|
|US5582632 *||May 11, 1994||Dec 10, 1996||Kimberly-Clark Corporation||Corona-assisted electrostatic filtration apparatus and method|
|US5582907 *||Jul 28, 1994||Dec 10, 1996||Pall Corporation||Melt-blown fibrous web|
|US5586997 *||Feb 16, 1995||Dec 24, 1996||Pall Corporation||Bag filter|
|US5618622 *||Jun 30, 1995||Apr 8, 1997||Kimberly-Clark Corporation||Surface-modified fibrous material as a filtration medium|
|US5641822 *||Apr 14, 1995||Jun 24, 1997||Kimberly-Clark Corporation||Surface-segregatable compositions and nonwoven webs prepared therefrom|
|US5643653 *||May 22, 1995||Jul 1, 1997||Kimberly-Clark Corporation||Shaped nonwoven fabric|
|US5652050 *||Mar 1, 1996||Jul 29, 1997||Pall Corporation||Fibrous web for processing a fluid|
|US5656361 *||Jul 23, 1996||Aug 12, 1997||Kimberly-Clark Worldwide, Inc.||Multiple application meltblown nonwoven wet wipe and method|
|US5667750 *||Feb 14, 1996||Sep 16, 1997||Kimberly-Clark Corporation||Process of making a nonwoven web|
|US5688465 *||May 13, 1996||Nov 18, 1997||Kimberly-Clark Worldwide, Inc.||Method of corona treating a hydrophobic sheet material|
|US5696191 *||May 31, 1995||Dec 9, 1997||Kimberly-Clark Worldwide, Inc.||Surface-segregatable compositions and nonwoven webs prepared therefrom|
|US5698294 *||Oct 11, 1996||Dec 16, 1997||Kimberly-Clark Worldwide, Inc.||Sterilization wrap material|
|US5698481 *||Oct 24, 1996||Dec 16, 1997||Kimberly-Clark Worldwide, Inc.||Sterilization wrap material|
|US5700531 *||Nov 17, 1995||Dec 23, 1997||Kimberly-Clark Worldwide, Inc.||Pull-activated container|
|US5733603 *||Jun 5, 1996||Mar 31, 1998||Kimberly-Clark Corporation||Surface modification of hydrophobic polymer substrate|
|US5738745 *||Nov 27, 1995||Apr 14, 1998||Kimberly-Clark Worldwide, Inc.||Method of improving the photostability of polypropylene compositions|
|US5741564 *||Jun 22, 1995||Apr 21, 1998||Kimberly-Clark Worldwide, Inc.||Stretch-activated container|
|US5744548 *||Oct 30, 1996||Apr 28, 1998||Kimberly-Clark Worldwide, Inc.||Melt-extrudable thermoplastic polypropylene composition and nonwoven web prepared therefrom|
|US5773120 *||Feb 28, 1997||Jun 30, 1998||Kimberly-Clark Worldwide, Inc.||Loop material for hook-and-loop fastening system|
|US5777010 *||Jul 23, 1996||Jul 7, 1998||Kimberly-Clark Worldwide, Inc.||Melt-extrudable compositions containing antimicrobial siloxane quaternary ammonium salts|
|US5780369 *||Jun 30, 1997||Jul 14, 1998||Kimberly-Clark Worldwide, Inc.||Saturated cellulosic substrate|
|US5800866 *||Dec 6, 1996||Sep 1, 1998||Kimberly-Clark Worldwide, Inc.||Method of preparing small particle dispersions|
|US5801106 *||May 10, 1996||Sep 1, 1998||Kimberly-Clark Worldwide, Inc.||Polymeric strands with high surface area or altered surface properties|
|US5803106 *||Dec 21, 1995||Sep 8, 1998||Kimberly-Clark Worldwide, Inc.||Ultrasonic apparatus and method for increasing the flow rate of a liquid through an orifice|
|US5839608 *||Jan 30, 1997||Nov 24, 1998||Kimberly-Clark Worldwide, Inc.||Stretch-activated container|
|US5846438 *||Jan 20, 1995||Dec 8, 1998||Pall Corporation||Fibrous web for processing a fluid|
|US5853641 *||Apr 20, 1998||Dec 29, 1998||Kimberly-Clark Worldwide, Inc.||Method for preparing polyolefin fibers containing antimicrobial siloxane quarternary ammonium salts|
|US5853883 *||Apr 20, 1998||Dec 29, 1998||Kimberly-Clark Worldwide, Inc.||Polyolefin fibers containing antimicrobial siloxane quaternary ammonium salts|
|US5854147 *||Apr 20, 1998||Dec 29, 1998||Kimberly-Clark Worldwide, Inc.||Non-woven web containing antimicrobial siloxane quaternary ammonium salts|
|US5868153 *||Dec 21, 1995||Feb 9, 1999||Kimberly-Clark Worldwide, Inc.||Ultrasonic liquid flow control apparatus and method|
|US5882573 *||Sep 29, 1997||Mar 16, 1999||Illinois Tool Works Inc.||Adhesive dispensing nozzles for producing partial spray patterns and method therefor|
|US5902540 *||Oct 8, 1996||May 11, 1999||Illinois Tool Works Inc.||Meltblowing method and apparatus|
|US5904298 *||Apr 14, 1997||May 18, 1999||Illinois Tool Works Inc.||Meltblowing method and system|
|US5925712 *||Oct 20, 1997||Jul 20, 1999||Kimberly-Clark Worldwide, Inc.||Fusible printable coating for durable images|
|US5932299 *||Apr 22, 1997||Aug 3, 1999||Katoot; Mohammad W.||Method for modifying the surface of an object|
|US5962149 *||Oct 20, 1997||Oct 5, 1999||Kimberly-Clark Worldwide, Inc.||Fusible printable coating for durable images|
|US5993943 *||Jul 15, 1992||Nov 30, 1999||3M Innovative Properties Company||Oriented melt-blown fibers, processes for making such fibers and webs made from such fibers|
|US5998023 *||Jan 9, 1998||Dec 7, 1999||Kimberly-Clark Worldwide, Inc.||Surface modification of hydrophobic polymer substrate|
|US6020277 *||May 10, 1996||Feb 1, 2000||Kimberly-Clark Corporation||Polymeric strands with enhanced tensile strength, nonwoven webs including such strands, and methods for making same|
|US6033739 *||Apr 5, 1999||Mar 7, 2000||Kimberly-Clark Worldwide, Inc.||Fusible printing coating for durable images|
|US6036467 *||Nov 25, 1997||Mar 14, 2000||Kimberly-Clark Worldwide, Inc.||Apparatus for ultrasonically assisted melt extrusion of fibers|
|US6046378 *||Mar 12, 1997||Apr 4, 2000||Kimberly-Clark Worldwide, Inc.||Wettable article|
|US6051180 *||Aug 13, 1998||Apr 18, 2000||Illinois Tool Works Inc.||Extruding nozzle for producing non-wovens and method therefor|
|US6053424 *||Dec 21, 1995||Apr 25, 2000||Kimberly-Clark Worldwide, Inc.||Apparatus and method for ultrasonically producing a spray of liquid|
|US6060410 *||Apr 22, 1998||May 9, 2000||Gillberg-Laforce; Gunilla Elsa||Coating of a hydrophobic polymer substrate with a nonstoichiometric polyelectrolyte complex|
|US6074597 *||Feb 20, 1999||Jun 13, 2000||Illinois Tool Works Inc.||Meltblowing method and apparatus|
|US6074869 *||Jul 27, 1995||Jun 13, 2000||Pall Corporation||Fibrous web for processing a fluid|
|US6120888 *||Jun 30, 1997||Sep 19, 2000||Kimberly-Clark Worldwide, Inc.||Ink jet printable, saturated hydroentangled cellulosic substrate|
|US6162535 *||Dec 6, 1996||Dec 19, 2000||Kimberly-Clark Worldwide, Inc.||Ferroelectric fibers and applications therefor|
|US6197406||Mar 16, 2000||Mar 6, 2001||Illinois Tool Works Inc.||Omega spray pattern|
|US6200635||Aug 31, 1998||Mar 13, 2001||Illinois Tool Works Inc.||Omega spray pattern and method therefor|
|US6242041||Nov 10, 1998||Jun 5, 2001||Mohammad W. Katoot||Method and composition for modifying the surface of an object|
|US6315215||Feb 8, 2000||Nov 13, 2001||Kimberly-Clark Worldwide, Inc.||Apparatus and method for ultrasonically self-cleaning an orifice|
|US6380264||Dec 21, 1995||Apr 30, 2002||Kimberly-Clark Corporation||Apparatus and method for emulsifying a pressurized multi-component liquid|
|US6395216||Jan 10, 2000||May 28, 2002||Kimberly-Clark Worldwide, Inc.||Method and apparatus for ultrasonically assisted melt extrusion of fibers|
|US6403858||Mar 25, 1999||Jun 11, 2002||Kimberly-Clark Worldwide, Inc.||Wettable article|
|US6450417||Sep 18, 2000||Sep 17, 2002||Kimberly-Clark Worldwide Inc.||Ultrasonic liquid fuel injection apparatus and method|
|US6461430||Mar 16, 2000||Oct 8, 2002||Illinois Tool Works Inc.||Omega spray pattern and method therefor|
|US6543700||Jul 26, 2001||Apr 8, 2003||Kimberly-Clark Worldwide, Inc.||Ultrasonic unitized fuel injector with ceramic valve body|
|US6571960 *||Apr 16, 2001||Jun 3, 2003||Kimberly-Clark Worldwide, Inc.||Faucet-mounted water filtration device|
|US6573205||Jan 27, 2000||Jun 3, 2003||Kimberly-Clark Worldwide, Inc.||Stable electret polymeric articles|
|US6578596 *||Apr 18, 2001||Jun 17, 2003||Stratasys, Inc.||Apparatus and method for thermoplastic extrusion|
|US6602554||Jan 14, 2000||Aug 5, 2003||Illinois Tool Works Inc.||Liquid atomization method and system|
|US6659365||Apr 1, 2002||Dec 9, 2003||Kimberly-Clark Worldwide, Inc.||Ultrasonic liquid fuel injection apparatus and method|
|US6663027||Jul 26, 2001||Dec 16, 2003||Kimberly-Clark Worldwide, Inc.||Unitized injector modified for ultrasonically stimulated operation|
|US6680021||Oct 20, 2000||Jan 20, 2004||Illinois Toolworks Inc.||Meltblowing method and system|
|US6759356||Jun 28, 1999||Jul 6, 2004||Kimberly-Clark Worldwide, Inc.||Fibrous electret polymeric articles|
|US6858551||Mar 12, 1999||Feb 22, 2005||Kimberly-Clark Worldwide, Inc.||Ferroelectric fibers and applications therefor|
|US6875315||Dec 19, 2002||Apr 5, 2005||Kimberly-Clark Worldwide, Inc.||Non-woven through air dryer and transfer fabrics for tissue making|
|US6878238||Dec 19, 2002||Apr 12, 2005||Kimberly-Clark Worldwide, Inc.||Non-woven through air dryer and transfer fabrics for tissue making|
|US6880770||Jul 11, 2003||Apr 19, 2005||Kimberly-Clark Worldwide, Inc.||Method of retrofitting an unitized injector for ultrasonically stimulated operation|
|US6890167||Mar 18, 2000||May 10, 2005||Illinois Tool Works Inc.||Meltblowing apparatus|
|US6893990||Apr 8, 2003||May 17, 2005||Kimberly Clark Worldwide, Inc.||Stable electret polymeric articles|
|US6972104||Dec 23, 2003||Dec 6, 2005||Kimberly-Clark Worldwide, Inc.||Meltblown die having a reduced size|
|US7018945||Jul 2, 2002||Mar 28, 2006||Kimberly-Clark Worldwide, Inc.||Composition and method for treating fibers and nonwoven substrates|
|US7141142||Sep 26, 2003||Nov 28, 2006||Kimberly-Clark Worldwide, Inc.||Method of making paper using reformable fabrics|
|US7294238||Feb 4, 2005||Nov 13, 2007||Kimberly-Clark Worldwide, Inc.||Non-woven through air dryer and transfer fabrics for tissue making|
|US7713252||Dec 14, 2005||May 11, 2010||Kimberly-Clark Worldwide, Inc.||Therapeutic article including a personal care composition and methods of making the therapeutic article|
|US7798434||Dec 13, 2006||Sep 21, 2010||Nordson Corporation||Multi-plate nozzle and method for dispensing random pattern of adhesive filaments|
|US8034430||Oct 27, 2005||Oct 11, 2011||Kimberly-Clark Worldwide, Inc.||Nonwoven fabric and fastening system that include an auto-adhesive material|
|US8074902||Apr 14, 2008||Dec 13, 2011||Nordson Corporation||Nozzle and method for dispensing random pattern of adhesive filaments|
|US8236385||Apr 29, 2005||Aug 7, 2012||Kimberly Clark Corporation||Treatment of substrates for improving ink adhesion to the substrates|
|US8420557||Jun 20, 2006||Apr 16, 2013||Fiberweb Corovin Gmbh||Polyethylene-based, soft nonwoven fabric|
|US8435600||Nov 3, 2011||May 7, 2013||Nordson Corporation||Method for dispensing random pattern of adhesive filaments|
|US8562774||Sep 7, 2011||Oct 22, 2013||Kimberly-Clark Worldwide, Inc.||Method of forming a nonwoven fabric and fastening system that include an auto-adhesive material|
|US9168704 *||Mar 15, 2013||Oct 27, 2015||I-Chung Liao||Manufacturing method of an activated-carbon filter element|
|US9303334||May 7, 2014||Apr 5, 2016||Biax-Fiberfilm||Apparatus for forming a non-woven web|
|US9309612||May 7, 2014||Apr 12, 2016||Biax-Fiberfilm||Process for forming a non-woven web|
|US20020030008 *||Mar 28, 2001||Mar 14, 2002||Kimberly-Clark Worldwide, Inc.||Multi-component filter design|
|US20030119410 *||Sep 24, 2002||Jun 26, 2003||Hassan Bodaghi||Method of making media of controlled porosity and product thereof|
|US20030203162 *||Apr 30, 2002||Oct 30, 2003||Kimberly-Clark Worldwide, Inc.||Methods for making nonwoven materials on a surface having surface features and nonwoven materials having surface features|
|US20030203691 *||Apr 30, 2002||Oct 30, 2003||Kimberly-Clark Worldwide, Inc.||Nonwoven materials having surface features|
|US20030207642 *||Apr 8, 2003||Nov 6, 2003||Myers David Lewis||Stable electret polymeric articles|
|US20040009725 *||Jul 2, 2002||Jan 15, 2004||Kimberly-Clark Worldwide, Inc.||Composition and method for treating fibers and nonwoven substrates|
|US20040118546 *||Dec 19, 2002||Jun 24, 2004||Bakken Andrew Peter||Non-woven through air dryer and transfer fabrics for tissue making|
|US20040121680 *||Dec 23, 2002||Jun 24, 2004||Kimberly-Clark Worldwide, Inc.||Compositions and methods for treating lofty nonwoven substrates|
|US20050133971 *||Dec 23, 2003||Jun 23, 2005||Haynes Bryan D.||Meltblown die having a reduced size|
|US20050161214 *||Jan 25, 2005||Jul 28, 2005||Morten Myhre||Rotationally locked wear sleeve for through-tubing drilling and completion|
|US20060003150 *||Jun 30, 2004||Jan 5, 2006||Kimberly-Clark Worldwide, Inc.||Treatment of substrates for improving ink adhesion to substrates|
|US20070099530 *||Oct 27, 2005||May 3, 2007||Kimberly-Clark Worldwide, Inc.||Nonwoven fabric and fastening system that include an auto-adhesive material|
|US20070134478 *||Jun 20, 2006||Jun 14, 2007||Corovin Gmbh||Polyethylene-based, soft nonwoven fabric|
|US20070135777 *||Dec 14, 2005||Jun 14, 2007||Kimberly-Clark Worldwide, Inc.||Therapeutic article including a personal care composition and methods of making the therapeutic article|
|US20090133813 *||Feb 2, 2009||May 28, 2009||Fiberweb Corovin Gmbh||Method for the manufacture of polyethylene-based, soft nonwoven fabric|
|US20090136606 *||Feb 2, 2009||May 28, 2009||Fiberweb Corovin Gmbh||Device for the manufacture of polyethylene-based, soft nonwoven fabric|
|US20120068374 *||Aug 31, 2011||Mar 22, 2012||Saertex France||Method for making a reinforcement provided with at least one adhesive surface capable of being repositioned and resulting reinforcement|
|US20140265019 *||Mar 15, 2013||Sep 18, 2014||I-Chung Liao||Manufacturing method of an activated-carbon Filter Element|
|US20160263591 *||May 29, 2015||Sep 15, 2016||Bum Je WOO||Purge gas injection plate and manufacturing method thereof|
|DE4130006A1 *||Sep 10, 1991||Mar 11, 1993||Silver Plastics Gmbh & Co Kg||General purpose cleaning cloth - comprises bonded fabric contg. mixt. of LLDPE and homo-polypropylene@ microfibres, with cationic surfactant as disinfectant|
|DE10005454B4 *||Feb 8, 2000||Aug 18, 2005||Papierfabrik Schoeller & Hoesch Gmbh & Co. Kg||Einlagiges, beidseitig abrasives Vlies und Verfahren zu dessen Herstellung|
|DE10302079A1 *||Jan 21, 2003||Aug 5, 2004||Corovin Gmbh||Process and assembly to produce a bulk layer of synthetic fleece has a mechanical thread compression unit positioned between thread bundling unit and conical outlet|
|DE10302079B4 *||Jan 21, 2003||Apr 20, 2006||Corovin Gmbh||Vorrichtung und Verfahren zur Herstellung von gekräuselten Spinnvliesfasern oder gekräuselten schmelzgeblasenen Vliesfilamenten aus geschmolzenem thermoplastischen Material|
|DE102008005466A1||Jan 21, 2008||Jul 23, 2009||Fiberweb Berlin Gmbh||Polymermischung|
|EP0701010A1||Oct 11, 1991||Mar 13, 1996||Exxon Chemical Patents Inc.||Meltblowing Die|
|EP1194626A1 *||Jun 14, 2000||Apr 10, 2002||First Quality Nonwovens, Inc.||Improved method of making media of controlled porosity and product thereof|
|EP1194626A4 *||Jun 14, 2000||Dec 4, 2002||First Quality Nonwovens Inc||Improved method of making media of controlled porosity and product thereof|
|EP1259207B2 †||Mar 2, 2001||Jan 12, 2011||Paul Hartmann Aktiengesellschaft||Single-use absorbent sanitary article|
|EP1950343A1||Apr 30, 2003||Jul 30, 2008||Kimberly-Clark Worldwide, Inc.||Non-woven through air dryer and transfer fabrics for tissue making|
|EP2218811A1||Apr 30, 2004||Aug 18, 2010||Fiberweb Corovin GmbH||Polyethylene-based, soft nonwoven fabric|
|EP2341174A1||Apr 30, 2004||Jul 6, 2011||Fiberweb Corovin GmbH||Polyethylene-based, soft nonwoven fabric|
|WO2001046029A2||Dec 5, 2000||Jun 28, 2001||Kimberly-Clark Worldwide, Inc.||Filtering cap for bottled fluids|
|WO2011144752A2||May 20, 2011||Nov 24, 2011||Fiberweb Corovin Gmbh||Extruded polymer product and method for making the same|
|WO2012126605A2||Mar 19, 2012||Sep 27, 2012||Metz Paul-Friedrich||Composite film and fibre of keratins and cellulose|
|WO2015171707A1 *||May 6, 2015||Nov 12, 2015||Biax-Fiberfilm||A non-woven web|
|U.S. Classification||428/198, 264/210.1, 428/334|