US 3907604 A
The strip tensile strength of nonwoven mat battery separators of polypropylene fibers having a diameter from about 1 to about 10 microns is increased, for example, to strengths greater than 4,000 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 DEG F to about 325 DEG F, preferably, from about 280 DEG F to about 315 DEG F, while the mat is subjected to pressure sufficient to prevent shrinkage of the fibers in the mat.
Description (OCR text may contain errors)
nited States Patent r191 Prentice 1*Sept. 23, 1975  NONWOVEN MAT BATTERY SEPARATORS 3,276,944 10/1966 Levy 156/306 75 J s P J m 3,354,247 1l/1967 Zehender et a1... 136/148 1 1 0 3,650,866 3/1972 Prentice 156/306 73 Assignee: Exxon Research and Engineering 3,704,198 11/1972 Prentice 161/150 Company, Linden NJ, .715151 2/1973 Prentice 156/306 The portion of the term of this patent subsequent to Nov. 28, 1989, Primary Examiner-Donald L. Walton has been disclaimed. Attorney, Agent, or FirmDavid A. Roth  Oct. 17, 1972  App1.No.: 298,317
 ABSTRACT Related US. Application Data  Continuation-in-part of Ser. Nos. 865,089, Oct. 9 The strip tensile strength of nonwoven mat battery 1969, Pat. No. 3,704,198, and Ser. No. 233.826 separators of polypropylene fibers having a diameter March 10, 1972- from about 1 to about 10 microns is increased, for example, to strengths greater than 4,000 m, by fuse- U.S. Cl. bonding as calendering or poinpbgnding at least a  hit. Cl. H011 3/02 ti f th fib rs of the mat at temperatures within Fleld of Search 5 6 the range from about 250F to about 325F, preferal61/150 bly, from about 280F to about 315F, while the mat is subjected to pressure sufficient to prevent shrinkage 1 References Cited of the fibers in the mat.
UNITED STATES PATENTS 3,121,658 2/1964 Orsino et a1. 136/148 4 Claims, 4 Drawing Figures 1 ill! SH! M s M 3 3 3| f 33 l ll 11 [H], I :11
I SPACER BLOCK ax?- MAT SPACER BLOCK FIG.3A.
NONWOVEN MAT BATTERY SEPARATORS RELATED APPLICATIONS This application is a continuation in part of my copending applications Ser. No. 865,089 filed Oct. 9,
1969 now US. Pat. No. 3,704,198 and its Division Ser.
No. 233,826, filed Mar. 10, 1972.
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is directed to nonwoven mat battery separators of polypropylene fibers having a diameter from about 1 to about microns and to a method for treating such mats so that they have high strip tensile strength.
2. Prior Art US. Pat. No. 3,276,944. Wente, Van A., Super Fine Thermoplastics," Industrial and Engineering C/MHlib'll), Vol. 48, No. 8 (1956), pp. l342l346.
SUMMARY OF THE INVENTION In this invention, the strip tensile strength of nonwoven mat battery separators of polypropylene fibers having diameters from about 1 to about 10 microns is in creased by fuse-bonding, as by point-bonding or by cal endering, at least a portion of the fibers of the mat at a temperature within the range from about 250F to about 325F, while maintaining pressure on the nonwoven mats sufficient 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 4,000 m, preferably, greater than 5,000 or even 6,000 m. The battery separators are assembled in batteries between the positive and negative plates.
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 I 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.
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 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 baffling means (not shown) may be provided in both the upper air chamber 22 and lower air chamber 23 to provide a uniform flow 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 I to l0 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 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 fibers 7 which are collected on a moving collecting device 8 such as head. When the collecting device is between 1 to 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 greaterthan 6 inches between the die openings and collector device, some self-bonding still occurs but the amount of selfbonding decreases with distance. The term selfbonding 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 are produced by the melt blowing process is greatest in those mats having the highest degree of self-bonding; but as the selfbonding 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 /1/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 250F. to about 325F., preferably, from about 280F. to about 3l5F., while compressing the mat sufficiently 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 dis- 1 crete portions of the mat and to fuse a portion of the fibers in the mat. Herein, this is termed pointbonding. 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 fusebonding and by a lack of decrease in the zero span tensil'e strength of the nonwoven mat.
Referring to FIG. 3, a heated press 30 may be used in the fuse-bondingprocess 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.
trate 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. 4
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 advantageous to carry out the fuse-bonding process by calendering the nonwoven mats under heating conditions which effect fiber-to-fiber fusion under pressure sufficient to prevent shrinkage of the fibers of the nonwoven mat. Referring to FIG. 3A, calender rolls 4t) 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 calendering operation to carry out the fusebonding, 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 gm/m to 300 or more gm/m Depending on the degree and manner in which fusion-bonding is accomplished, the fusion-bonds 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 fusion-bonded mat is high, greater than about 4,000 m, desirably greater than 5,000 m, and preferably in excess of 6,000 m. The tear resistance of the fusion-bonded mat is low, generally less than 200 dm rarely if ever as great as 300 dm 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 lami nates to which they contribute high strip tensile strength. Another special application of the fusionbonded mats is as battery separators. The mats are positioned between and separate the positive and negative TABLE I C mfi u d plates in a battery.
The fusion-bonded nonwoven mats of the present in- MAT NOS F G H vention and the fusion-bonding process are further illustrated by specific examples hereinafter following. 5 These examplesmtilize nonwoven mats of melt blown Mu mmving Cmditkms polypropylene fibers produced by the melt blowing Polypropylene MFR do or 3.5 3.5 process illustrated in FlGS. l and 2 of the drawings with WH TLmP-(QFl Dw Iem .(F 631 632 ou 60: the specific operating conditions as set forth in Table l. The specific nonwoven mat characteristics are also W set forth in Table l as to basis weight, zero span tensile strength and the degree of uniformity of the mat in terms of the Zero span tensile strength by the ratio of pollmur mm min 04 the cross direction to machine direction (CD/MD). The fiber diameter of the mats ranged between about l to about 10 microns, usually between about 1 to 5 mi- Crons Apparent Viscositflpoisc) 97 I54 84 70 Air Flo\\'(lb/min.) 4.32 4.] 3.35 3.36
Lb. air 7 7 '7') Lb. polymer "I7 Screen Distance(in.) (1 l2 4 4 Mat Characteristics TABLE I MAT NOS A B C D Basis weight mg 51 50 I31 70- Melt Blowing Conditions Polypropylene MFR 0.6 06 0.6 0.6 Extruder Temp. (F) 640 (:53 702 720 7) S I o I. pan Tensile(m) 4820 4730 4930 5383 Dlt. Temp. l-) 600 630 643 642 cD/MD (L78 (L82 0470 0'69 pm Polymer Rate 8.2 8.0 8.0 8.0
" min EXAMPLE 1 Apparent Viscosity-(poise) I77 307 251 i Air Flownh/mim 42 H45 178 434 This example illustrates how the strlp tensile strength Lh. air q q a a of a nonwoven mat is increased by fuse-bonding the 0 Lb. polymer J8 J4 40 mat.
scmc 4 6 6 6 Samples of nonwoven mat A, made under melt blow- Mat Characteristics mg condltlons WhlCh produce fibers that have a diameter from about 1 to 10 microns (see Table l), were calendered once by passing them through heated calengm dering rolls at temperatures ranging from 200F. to m 58 58 66 320F. under a roller pressure of 700 pounds per linear l' ed of 20 feet m' ut usin a three-roll Zero Span Tensile(m) 5490 4580 6440 5340 inch ata lne Spe m g CD/MD ']5 57 (mg Q76 calender. The results are tabulated in Table ll.
TABLE ll EXAMPLE 1 Calender Roll Temperatures Upper (F) 200 225 250 275 287 300 3l0 320 Lower (F) 70 147 l65 I 205 206 220 230 240 Fuse-Bonded Mat Properties Strip Tensile (m) 2346 2250 2l50 2600 3100 4900 5600 5600 Tear Resistance (din 44 22 29 Zero Span Tensile (m) 5490 6560 7l30 As shown by Table ll, calender roll temperatures of 250F. 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 upper plate. The pointbonded nonwoven mats, as shown in Table ll], exhibited high strip tensile strengths. The strip tensile strengths were greatly increased from the strip tensile strength of the untreated mat.
as at an intermediate temperature shows that sufficient pressure was applied to prevent shrinkage of the fibers of the mat.
That the point-bonding technique is effective to increase the strip tensile strength of other nonwoven mats produced in the same manner as nonwoven mat A of Example 1 is illustrated by Examples 28.
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 l), were pointbonded 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 ll, 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 inches 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 plate. Example 6 had two sheets of foil between it and the lower plate and two sheets of foil between it and the Having fully and particularly described the fusionbonded nonwoven sheet and the processes involved in 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. In a battery, a positive plate, a negative plate and a nonwoven mat of polypropylene fibers, said nonwoven mat positioned between and separating said positive and said negative plates and said nonwoven mat having polypropylene fibers having diameters from about 1 to about 10 microns, said mat having fusionbonds throughout its thickness, the strip tensile strength of the mat being greater than about 4,000 m and the tear resistance of the mat being no greater than about 3,00Odm 2. The battery of claim 1 wherein said fusion-bonds of said nonwoven mat occur in an essentially spaced pattern in said mat.
3. The battery of claim 2 wherein said fusion-bonds of said nonwoven mat occur continuously in an essentially unbroken pattern in said mat.
4. The battery of claim 3 wherein said mat has a thickness within the range of from about 1 to about 25