CA2221615C - Filled thermoplastic cut-resistant fiber - Google Patents
Filled thermoplastic cut-resistant fiber Download PDFInfo
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- CA2221615C CA2221615C CA002221615A CA2221615A CA2221615C CA 2221615 C CA2221615 C CA 2221615C CA 002221615 A CA002221615 A CA 002221615A CA 2221615 A CA2221615 A CA 2221615A CA 2221615 C CA2221615 C CA 2221615C
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Classifications
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/442—Cut or abrasion resistant yarns or threads
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/24—Resistant to mechanical stress, e.g. pierce-proof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Sealing Material Composition (AREA)
Abstract
A fiber having increased cut resistance is made from an isotropic polymer and a hard filler having an average particle size in the range of about 0.25 to about 10 microns and having a Mohs Hardness Value greater than about 3. The filler is included in an amount of at least about 0.1 % by weight. The preferred isotropic polymer is poly(ethylene terephthalate). The preferred filler is calcined alumina.
Description
FILLED THERMOPLASTIC CUT-RESISTANT FIBER
Field of the Invention This invention relates to fibers made from thermoplastic polymers containing hard fillers that have improved resistance to cutting.
to Background of the invention Improved resistance to cutting with a sharp edge has long been sought. Cut-resistant gloves are beneficially utiVized in the meat-packing industry and in automotive applications. As indicated by U.S.
Patent Nos. 4,004,295, 4,384,449 and 4,470,251, and by EP
is 458,343, gloves providing cut resistance have been made from yarn which includes flexible metal wire or which consists of high tensile strength fibers.
A drawback with gloves made from yarn that includes flexible metal wire is hand fatigue with resultant decreased productivity and Zo increased likelihood of injury. Moreover, with extended wear and flexing, the wire may fatigue and break, causing cuts and abrasions to the hands. In addition, the wire will ect as a heat sink when a laundered glove is dried at elevated temperatures, which may reduce tensile strength of the yarn or fiber, thereby decreasing glove protection and glove life.
Highly oriented fibers having high modulus and high tensile strength have better resistance to cutting than conventional s semicrystalline polymers. Examples of these highly oriented polymers include polyaramides, thermotropic liquid crystalline polymers, and extended chain polyethylene. These also have shortcomings that limit their usefulness, including loss of properties at temperatures encountered in a drier (polyethylene), poor resistance to bleach ~ (polyaramides), poor comfort, and high cost.
Improved flexibility and comfort and uncomplicated laundering are desirable in cut-resistant, protective apparel. Therefore, there is a need for a flexible, cut-resistant fiber that retains its properties when routinely laundered. Such a fiber may be advantageously used in 1s making protective apparel, in particular highly flexible, cut-resistartt gloves.
Thermoplastic polymers mixed with particulate matter have been made into fibers, but not in a way that significantly improves the cut resistance of the fiber, except for thermotropic liquid crystalline 2o polymers. For example, small amounts of particulate titanium dioxide has been used in polyester fiber as a delustrant. Also used in polyester fiber is a small amount of colloidal silicon dioxide, which is used to improve gloss. Magnetic materials have been incorporated into fibers to yield magnetic fibers. Examples include: cobalt/rare 2s earth element intermetallics in thermoplastic fibers, as in published Japanese Patent Application No. 55/098909 (1980); cobalt/rare earth element intermetallics or strontium ferrite in core-sheath fibers, :~ .~
. . ~ ~,1 v . , .. .r~4~
1 ~ . f 1 . , 1 . t ~ ~ 1 J
n. ,~ 1 described in published Japanese Patent application No. 3-130413 (1991 ); and magnetic materials in thermoplastic polymers, described in Polish Patent No. 251,452 and also in K. Turek et al., J. Magn.
Maan. Mater. (1990), 83 (1-3), pp. 279-280.
Summary of the Invention Fibers and yarns made from melt processable isotropic polymers can be made more resistant to cutting with a sharp edge by inck~ding a .hard filler which is preferably distributed uniformly through the fiber.
to The hard filler has a Mohs Hardness Value of greater than 3 and is present in an amount of 0.1 % to 5% by volume. The average particle size is in the range of 0.25 micrometers to 10 micrometers. The fiber has improved resistance to cutting compared with a fiber made with the same polymer without the hard filler. This improvement is at least 20% when measured by the Ashland Cut Protection Performance test.
A new method of making a synthetic fiber or yarn more resistant to cutting with a sharp edge is also disclosed. The method comprises the steps of making a uniform blend of a melt processable isotropic polymer and a hard filler having a Mohs hardness value greater than 3 and then spinning the polymer in the melt phase into fiber or yarn that has its cut performance as measured by the Ashland Cut Protection Performance improved by at least 20%, and preferably by at least 35%.
The fibers and yarns described above can be made into fabrics that have improved resistance to cutting using any of the methods that are currently used for making fibers and yarns into fabrics, .
ENDED SHEET
WO 96/41042 PC'T/US96/08358 including weaving and knitting. The fibers and yarns can also be made into non-woven fabrics that have improved cut-resistance. Both 'the fabrics and the methods of making cut-resistant fabrics and the resulting fabrics are new.
Detailed Description of the Invention As indicated above, a flexible cut-resistant fiber useful for the 'manufacture of protective apparel may be produced when a hard filler is included in the fiber. The fiber is made from an isotropic polymer.
io 'The term "isotropic" means polymers that are not liquid crystalline.
Preferably, the polymer is melt processable: i.e., it melts in a 'temperature range which makes it possible to spin the polymer into 'Fibers in the melt phase without significant decomposition. The preferred method of making the fiber is by melt spinning.
is Preferred isotropic polymers are semi-crystalline. Semi-crystalline polymers that will be highly useful include poly(alkylene terephthalates), poly(alkylene naphthalates), poly(arylene sulfides), aliphatic and aliphatic-aromatic polyamides, polyesters comprising monomer units derived from cyclohexanedimethanol and terephthalic 2o acid, and polyolefins, including polyethylene and polypropylene.
I=xamples of specific semi-crystalline polymers include polyethylene terephthalate), poly(butylene terephthalate), polyethylene naphthaEatel, poly(phenylene sulfide), poly(1,4-cyclohexanedimethanol terephthalate), wherein the 1,4-cyclohexanedimethanol is a mixture of 25 cis and traps isomers, nylon-6, nylon-66, polyethylene and polypropylene. These polymers are all known to be useful for making ..;
". .., " ; ,_ fibers. The preferred semi-crystalline polymer is polyethylene terephthalate).
Polymers that cannot be processed in the melt can also be filled with hard particles, as for example cellulose acetate, which is typically 5 dry spun using acetone as a solvent, or a polyaramide, such as the polymer of terephthalic acid and p-phenylenediamine, which is dry-jet, wet-spun from a concentrated sulfuric acid solution. The hard particles would be incorporated into the spinning processes for these polymers in order to obtain the filled fibers. Amorphous, non-lo crystalline polymers, such as the copolymer of isophthalic acid, terephthalic acid and bisphenol A (polyarylate) may also be filled and utilized in this invention by a melt spinning process.
An important aspect of this invention is the discovery that a flexible cut-resistant fiber may be made from a suitable polymer filled with a hard material that imparts cut resistance. The material may be a metal, such as an elemental metal or metal alloy, or may be nonmetallic. Generally, any filler may be used that has a Mohs Hardness value of 3 or more. Particularly suitable fillers have a Mohs Hardness value greater than 4 and preferably greater than 5. Iron, 2o steel, tungsten and nickel are illustrative of metals and metal alloys, with tungsten, which has a Mohs value ranging from 6.5 to 7.5 being preferred. Non-metallic materials are also useful. These include, but are not limited to, metal oxides, such as aluminum oxide and silicon dioxide, metal carbides, such as silicon carbide and tungsten carbide, metal nitrides, metal sulfides, metal silicates, metal silicides, metal sulfates, metal phosphates, and metal borides. Other ceramic materials may also be used. Aluminum oxide, ANIEIvDE~ BEET
_ ., . _ ' ' ~ .
_ _ . , , , ., ., ", .:, . ; ,..' and especially calcined aluminum oxide, is most preferred. Titanium dioxide in general is less preferred.
The particle size and particle size ~ distribution are important parameters in obtaining good cut resistance while preserving fiber s mechanical properties. In general, the hard filler should be in the form of particles, with a powder form being generally suitable. Flat particles (i.e. platelets) and elongated particles (needles) also work well. The average particle size is generally in the range of 0.25 to a 7 0 micrometers. Preferably the average particle size is in the range of l0 1 to 6 micrometers. The most preferred average particle size is 3 micrometers. ~ For particles that are flat (i.e. platelets) or elongated, the particle size refers to the length along the long axis of the particle (i.e. the long dimension of an elongated particle or the average diameter of the face of a platelet). The particles preferably should 15 exhibit a log normal distribution. For making textile fibers (i.e. fibers having a denier in the range of 1.5. to 15 dpf), the particles should be filtered or sieved in such a way that particles larger than 6 micrometers are excluded.
- A minor percentage of the hard filler is used. The amount is 2o chosen to yield enhanced cut resistance without causing a significant loss of tensile properties. Desirably, the cut resistance of the fiber or fabric made from the fiber will show improvements of at least 20%
using the Ashland Cut Protection Performance Test. Preferably the cut resistance will improve by at least 35%, and most preferably will 2s improve by at least 50% in comparison with a fiber made of the same polymer but without the filler. The tensile properties of the fiber (tenacity and modulus) preferably will not Aid9EiVDED SHEEN
' CA 02221615 1997-11-19 ,~ ..
decrease by more than 50%, and more p. eferably will not decrease by more than 25%. Most preferably, there will not be a significant change in tensile properties (i.e., less than 10% decrease in properties).
On a weight basis, the filler should be present in an amount of at least 0.1 %. The upper limit of filler is determined mainly by the effect on tensile properties, but levels above 20% by weight are generally less desirable. , On a volume basis, the particle level concentration is in the range of 0.1 % to 5% by volume, more to preferably 0.5% to 3% by volume and most preferably 2.1 % by volume. For the preferred embodiment (calcined alumina in PET), these ranges on a weight basis are 0.3% to 14% (preferred), 1.4% to 8.5% (more preferred), and 6% (most preferred).
In accordance with the present invention, filled fibers are 15 prepared from a filled resin. The filled resin is made by any of the standard methods for adding a filler to a resin. For example, for a melt processable isotropic polymer, the filled resin is conveniently prepared in an extruder by mixing the hard filler with molten polymer under conditions sufficient to provide a uniform distribution of the 2o filler in the resin, such as mixing in a twin screw extruder. The filler may also be present during the manufacture of the polymer or may be added as the polymer is fed into the extruder of fiber spinning enuipment, in which case the blending and spinning steps are nearly simultaneous.
25 Since the filler is distributed uniformly in the polymer melt, the filler particles are also typically distributed uniformly throughout the At~thry'?ri s c~G~-r ~ CA 02221615 1997-11-19 ' _ _' , .,. _..
.._ ' , ~ 1 f ~ 1 ~ _ 7 fibers, except that elongated and flat particles are oriented to some extent because of the orientation forces during fiber spinning. Some migration of the particles to the surface of the fiber may also occur.
Thus, while the distribution of particles in the fibers is described as s '°uniform", the word "uniform" should be understood to include non-uniformities that occur during the processing (e.g., melt spinning) of a uniform polymer blend. Such fibers would still fall within the scope of ~' this invention. Any size fiber may be made according to the present invention. In the manufacture of fabrics and yarns, the fiber will io generally have a denier in the range of 1 to 50 dpf, preferably in the range of 1.5 to 15 dpf, and most preferably 4 dpf. Cut-resistant monofilaments may also be made by including a hard filler.
Monofilaments generally have a diameter of 0.05 to 2mm. The fibers are made by conventional fiber spinning processes. As previously 1s stated, the preferred process is melt-spinning, but wet-spinning and dry-spinning may also be used.
The description above is written with respect to fibers. The term fiber includes not only conventional single fibers but also yarns made from a multiplicity of these fibers. In general, yarns are utilized 2o in the manufacture of apparel, fabrics and the like.
Cut-resistant fabric may be made using a filled fiber in accordance with the present invention by using conventional methods, such as knitting or weaving, and conventional equipment.
Non-woven fabrics can also be made. Such fabric will have improved 25 cut resistance in comparison with the same fabric made using fiber manufactured from the same polymer without a filler. The cut AMENDED SHEET
.~' , , " ~.. . __._ _ , .
. ; : ' , . _ resistance of the fabric will be improved by at least 20% when measured using the Ashland Cut Protection Performance test.
Preferably the cut resistance will improve by at least 35%, and most preferably will improve by at least 50%.
s Cut-resistant apparel may then be made from the cut-resistant fabric described above. For example, a cut-resistant safety glove designed for use in the food processing industries may be manufactured from the fabric. Such a glove is highly flexible and readily cleanable, being resistant to chlorine bleach and to the heat of to a drier. Protective medical gloves may also be made using the cut resistant fibers of this invention. Other uses of the fabrics and monofilaments include side curtains and tarpaulins for trucks, softsided luggage, commercial upholstery, inflatables, fuel cells, collapsible packaging, airline cargo curtains, firehose sheaths, cut is resistant aprons for use in metal packing, chaps, etc.
Example 1 Polyethylene terephthalate) fibers incorporating tungsten powder filler are described below. Tungsten has a Mohs Hardness 2o value of about 6.5 to 7.5. Tire yarn grade polyethylene terephthalate) (PET), having an intrinsic viscosity of about 0.95 when measured in o-chlorophenol, was obtained from Hoechst Celanese Corporation, Somerville, New Jersey in the form of pellets. A master batch was made by blending the polymer with 10% tungsten powder 2s on a weight basis in a twin screw extruder. The tungsten had an average particle size of about 1 micrometer. The polymer pellets and tungsten were both dried before blending. The master batch was AMENDED SHEET
blended with additional PET in a twin screw extruder to yield blends having 1 % and 4% tungsten on a weight basis. The samples were melt spun by forcing the molten blend first through a filter pack and then through a spinneret. The yarn was subsequently drawn off a heated feed roll at 90°C, then drawn over a heated shoe, and finally subjected to a 2% relaxation at 225°C. The yarn was plied for testing of properties. The data are summarized in Table 1. One of the 10% tungsten-loaded fibers was also analyzed for tungsten to ensure that the filler was not filtered out. The analysis of the fiber to shows about 8.9% by weight tungsten in the fiber.
Tensile properties. The tenacity, elongation and modulus were measured using ASTM test method D-3822.
Cut resistance. The fiber was first knitted into fabric for the testing of cut resistance. The areal density of yarn in the fabric was is measured in ounces/square yard (OSY in Tables 1 and 2). The cut resistance of the fabric was then measured using the Ashland Cut Performance Protection (°°CPP") test. The test was carried out at 'rRl/Environmental, Inc., 9063 Bee Cave Road, Austin, Texas 78733-6201. In the test, the fabric sample is placed on the convex surface of a mandrel. A series of tests is carried out in which a razor blade loaded with a variable weight is pulled across the fabric until the fabric is cut all the way through. The distance the razor blade travels across the cloth until the blade cuts completely through the cloth is measured. The point at which the razor blade cuts through the fabric '' 2s is the point at which electrical contact is made between the mandrel and razor blade. The distance required to make the curt is plotted on a graph as a function of the load on the razor blade. The data are ' ; _ _ ., ..
measured and plotted for cut distances varying from 0.3 inches(0.7 cm) to 1.8 inches (4.6 cm). The resulting plot is approximately a straight line. An idealized straight line is drawn or calculated through the points on the plot, and the weight required to cut through the cloth after one inch of travel across the cloth is taken from the plot or calculated by regression analysis. The interpolated values of the weight required to make a cut after one inch of blade travel across the cloth are shown in Tables 1 and 2 as "CPP", an abbreviation for Cut Protection Performance. ~ Finally, for purposes of comparing the data to for different area) densities of cloth sample, the CPP value is divided by the areal density of the cloth (OSY) to compensate for variations in areal density. This value is shown as CPP/OSY in Tables 1 and 2.
Example 2 1s In these experiments, PET fiber samples were filled with alumina powder, which was sold commercially under the trademark MICROPOLISH~ II as a polishing abrasive. Two different alumina powders were used having average particle sizes of about 0.05 micrometers and about 1 .0 micrometers. Both were obtained as 2o deagglomerated powders from Buehler, Ltd., Waukegan Road, Lake Bluff, Illinois 60044. The 0.05 micrometer alumina was gamma alumiha with a cubic crystal structure and a Mohs Hardness Value of 8. The 1.0 micrometer material was alpha alumina having a hexagonal crystal structure and a Mohs Hardness Value of 9. The 2s two alumina powders were blended with PET using the same method as in Example 4 to yield filled PET samples containing alumina at levels of about 0.21 %, 0.86%, 1.9% and 2.1 % by weight.
Measurements of fiber properties ~~~ t~~~- cr:_~
~;~~._,°t. . .
~ CA 02221615 1997-11-19 ..
.. ~ >.~ >,._ ~ " .' . '."
' ; ; , , ... .,. . ..
and cut resistance were made using the same methods as in Example 1 . The data are presented in Table 2.
The data in Tables 1 and 2 show that there is an improvement in cut resistance of at least about 10-20% at all levels of filler used in these experiments. Both sets of data incorporate filler in the fiber at levels of about 0.07% to about 0.7% on a volume basis. The fiber properties do not appear to significantly degrade with these amounts and sizes of particles.
Example 3 A series of experiments was run using tungsten particles of several different particle sizes (0.6 - 1 .6 micrometers) as fillers in PET
at concentrations of 0.4 - 1.2 volume %. The tungsten-filled PET was spun into yarn, which was subsequently knitted into fabric for testing.
Cut resistance was again measured by the Ashland Cut Protection Performance Test, using the modified procedure described below.
The CPP values were divided by the areal densities of the cloth to correct for the fact that the tests were carried out on different ° densities of cloth. The data are presented in Table 3.
' Cut Protection Performance (CPP) The Ashland CPP Test was run as described at the end of Experiment 1, but a calibration against a standard with a known CPP
value was used to correct the results. The calibration standard was 2s 0.062 inch (0.157 cm) neoprene, style NS-5550, obtained from FAIRPRENE, 85 Mill Plain Road, Fairfield. CT 06430, which has a CPP
value of 400 gms. The CPP value was measured for this standard at the beginning AMENDED SHEET
f ~ 1 9 Z 9 ~ ~ f 1 9vf 7 as and end of a series of tests, and an average normalization factor was calculated that would bring the measured CPP value of the standard to 400 gms. The normalization factor was then used to correct the measured data for that series of tests. Also, in caculating the CPP
value, a plot of the logarithm of the distance required to cut the fabric vs. the load on the razor blade was utilized, as it was more linear.
Example 4 A series of experiments was run using calcined aluminum oxide to as the filler for the fiber. The experiments were run using the same procedure as used in Examples 1-3, but with a broader range of particle sizes (0.5 - 3 micrometers) and a wider range of concentrations (0.8 - 3.2 volume %) than in Example 2.
The calcined aluminum oxide used in the experiments was obtained from Agsco Corporation, 621 Route 46, Hasbrouck, N.J.
07604, and is in the form of platelets, referred to as Alumina #1.
The CPP values were measured using the procedure described at the end of Example 3. The CPP/OSY values were then calculated as described above. These data are presented in Table 4.
~ It can be seen from the data in the tables that the CPP/OSY
values are affected by all of the variables listed (i.e., particle size, particle concentration, areal density, and the fiber dpf). At the high areal densities (OSY), the CPP/OSY values fall off significantly. Thus comparisons are preferably made for tests in fabrics having similar 2s areal densities.
Nevertheless, it can be seen from the data in Table 4 that at a level of 2.4 volume % (6.8 weight%), with a particle size of 2 AMENDED SNEFT
_"' _ ~.. ,._.
.' . '..; .' .,. .... .., : .,' micrometers, the CPP/OSY values for fabrics made from textile fibers (2.8 dpf) and having areal densities of less than about 10 ounces per square yard were greater than about 100. (Sample Nos. 22-24 and 30). This is much more than a 50% increase over the average s CPP/OSY value of about 53 that was measured for unfilled PET fiber of comparable fiber size and areal density (the three Controls in Table 1 ). The average CPP/OSY values for all the tungsten filled PET
samples of Table 3 !70) and all the aluminum oxide filled PET samples of Table 4 (75) are also significantly higher than the average of the 1o controls.
AIViEIVD~D Si-~E~T
., .,: '. _' -1~
Table 1 . Cut Resistance of PET Filled with Tungsten Particle Size Tungsten (micrometers) No. Wt. Volume ,d~f T/E/M~ CPPZ OSY3 CPP/OSY
Control -- -- -- 3.1 6.8/6.7/124421 7.1 59 Control2-- -- -- 5.0 -- 384 6.8 56 Control3-- -- -- 5.0 -- 589 13.0 45 1-1 l9fo 0.07961 micrometer6.0 6.3/9.0/128540 9.1 59 1-2 196 0.07961 micrometer5.6 565 7.3 77 1-3 496 0.29101 micrometer6.0 7.2/11.6/109643 7.0 92 1-4 496 0.29961 micrometer5.9 7.0112.5/100620 7.3 85 1-5 1096 0.72961 micrometer11.6 6.3/10.0/123697 7.5 93 I
~i 1-6 1096 0.72961 micrometer7.4 4.1122.9/75759 8.5 90 1-7 1096 0.72%1 micrometer6.0 -- 670 7.6 89 . 'Tenacity (gpd), Elongation (°Y~), Modulus (gpd), measured using ASTM
test method D-3822.
ZCut Protection Performance, measured using the Ashland CPP test.
30unces per Square Yard.
AMENDED SH~~'~
'CA 02221615 1997-11-19 "°~ , - ... . ~ ~ . , ~ s r ~ , s ry s -~.~ i~w ,. . vs o Table2. Cut Resistance of PET Filled with Alumina 96 Particle Alumina Size No. Wt. Volume(micrometers)d~f T/ElM' CPPz OSY' CPP/OSY
2-1 0.2196.0796 1 micrometer11.4 6.7!10.31112547 7.2 76 2-2 0.2196.0796 1 micrometer5.6 7.4/12.4/104463 7.5 62 2-3 0.86960.30960.05 5.6 7.4/14.0/110501 7.3 69 micrometer 2-4 0.86960.30960.05 5.7 6.9/12.8/110497 6.7 73 micrometer 2-5 1.9960.67961 micrometer11.8 5.8/12.0/108683 8.2 83 2-6 1.9960.67961 micrometer5.6 7.4/10.9/108478 6.7 71 2-7 2.1960.74960.05 5.4 6.6/11.6/117496 6.7 74 micrometer 2-8 2.1960.74960.05 5.9 5.4/12.8/100431 6.2 69 micrometer 'Tenacity (gpd), Elongation (9b), Modulus (gpd), measured using ASTM test method O-3822.
ZCut Protection Performance, measured using the Ashland CPP test.
30unces per Square Yard.
AMENDED SHEET
~' . . ' ' ..., .. ___.
~' -; ~ ~'~ , . ; .
,' , '.~"
' ' ' ' ~ ~ , .. _ , " " , TABLE 3. Cut Resistance of PET Filled with Tungsten SAMPLE PARTSIZE CONC DPFTENACITYELON MODULUSOSY CPP CPP/OSY
# G
micrometervol% d % d ozl d2 1 0.6 0.4 10 7.3 9 112 8 562 70 2 0.8 1.2 10 5.5 13 102 9.5 557 59 3 1.4 0.4 10 6 14 96 8.2 714 87 4 1.6 1.2 10 5.9 11 100 8.2 821 100 1 0.8 10 8 708 89 6 0.8 0.8 10 5.7 8 109 7 724 103 7 0.6 0:8 10 5.9 13 118 6.8 621 91 8 0.8 0.8 10 5.7 8 109 7 596 85 9 0.6 0.8 10 6.3 13 103 7.9 703* 89 1.5 0.8 12 6.7 9 102 7.6 644 85 11 0.6 0.8 2.4 13.6 656 48 12 1 0.8 7.2 8 108 7.5 503 67 13 0.6 0.8 2.4 28 1226 44 14 0.6 0.8 2.4 19 964 51 0.6 0.8 2.4 26 1225 47 16 0.6 0.8 10 20 900 45 17 0.6 0.8 2.4 12 628 52 18 0.6 0.8 1.4 16 685 43 0:6[ --~.8~ r 7 580 80 1.4 5 PARTSIZE is Particle size, measured in micrometers.
CONC is the concentration of hard particles, measured as a volume % in PET.
DPF is the fiber denier in dpf.
TENACITY, ELONG, and MODULUS are the fiber tensile properties, measured by ASTM test method D-3822.
Field of the Invention This invention relates to fibers made from thermoplastic polymers containing hard fillers that have improved resistance to cutting.
to Background of the invention Improved resistance to cutting with a sharp edge has long been sought. Cut-resistant gloves are beneficially utiVized in the meat-packing industry and in automotive applications. As indicated by U.S.
Patent Nos. 4,004,295, 4,384,449 and 4,470,251, and by EP
is 458,343, gloves providing cut resistance have been made from yarn which includes flexible metal wire or which consists of high tensile strength fibers.
A drawback with gloves made from yarn that includes flexible metal wire is hand fatigue with resultant decreased productivity and Zo increased likelihood of injury. Moreover, with extended wear and flexing, the wire may fatigue and break, causing cuts and abrasions to the hands. In addition, the wire will ect as a heat sink when a laundered glove is dried at elevated temperatures, which may reduce tensile strength of the yarn or fiber, thereby decreasing glove protection and glove life.
Highly oriented fibers having high modulus and high tensile strength have better resistance to cutting than conventional s semicrystalline polymers. Examples of these highly oriented polymers include polyaramides, thermotropic liquid crystalline polymers, and extended chain polyethylene. These also have shortcomings that limit their usefulness, including loss of properties at temperatures encountered in a drier (polyethylene), poor resistance to bleach ~ (polyaramides), poor comfort, and high cost.
Improved flexibility and comfort and uncomplicated laundering are desirable in cut-resistant, protective apparel. Therefore, there is a need for a flexible, cut-resistant fiber that retains its properties when routinely laundered. Such a fiber may be advantageously used in 1s making protective apparel, in particular highly flexible, cut-resistartt gloves.
Thermoplastic polymers mixed with particulate matter have been made into fibers, but not in a way that significantly improves the cut resistance of the fiber, except for thermotropic liquid crystalline 2o polymers. For example, small amounts of particulate titanium dioxide has been used in polyester fiber as a delustrant. Also used in polyester fiber is a small amount of colloidal silicon dioxide, which is used to improve gloss. Magnetic materials have been incorporated into fibers to yield magnetic fibers. Examples include: cobalt/rare 2s earth element intermetallics in thermoplastic fibers, as in published Japanese Patent Application No. 55/098909 (1980); cobalt/rare earth element intermetallics or strontium ferrite in core-sheath fibers, :~ .~
. . ~ ~,1 v . , .. .r~4~
1 ~ . f 1 . , 1 . t ~ ~ 1 J
n. ,~ 1 described in published Japanese Patent application No. 3-130413 (1991 ); and magnetic materials in thermoplastic polymers, described in Polish Patent No. 251,452 and also in K. Turek et al., J. Magn.
Maan. Mater. (1990), 83 (1-3), pp. 279-280.
Summary of the Invention Fibers and yarns made from melt processable isotropic polymers can be made more resistant to cutting with a sharp edge by inck~ding a .hard filler which is preferably distributed uniformly through the fiber.
to The hard filler has a Mohs Hardness Value of greater than 3 and is present in an amount of 0.1 % to 5% by volume. The average particle size is in the range of 0.25 micrometers to 10 micrometers. The fiber has improved resistance to cutting compared with a fiber made with the same polymer without the hard filler. This improvement is at least 20% when measured by the Ashland Cut Protection Performance test.
A new method of making a synthetic fiber or yarn more resistant to cutting with a sharp edge is also disclosed. The method comprises the steps of making a uniform blend of a melt processable isotropic polymer and a hard filler having a Mohs hardness value greater than 3 and then spinning the polymer in the melt phase into fiber or yarn that has its cut performance as measured by the Ashland Cut Protection Performance improved by at least 20%, and preferably by at least 35%.
The fibers and yarns described above can be made into fabrics that have improved resistance to cutting using any of the methods that are currently used for making fibers and yarns into fabrics, .
ENDED SHEET
WO 96/41042 PC'T/US96/08358 including weaving and knitting. The fibers and yarns can also be made into non-woven fabrics that have improved cut-resistance. Both 'the fabrics and the methods of making cut-resistant fabrics and the resulting fabrics are new.
Detailed Description of the Invention As indicated above, a flexible cut-resistant fiber useful for the 'manufacture of protective apparel may be produced when a hard filler is included in the fiber. The fiber is made from an isotropic polymer.
io 'The term "isotropic" means polymers that are not liquid crystalline.
Preferably, the polymer is melt processable: i.e., it melts in a 'temperature range which makes it possible to spin the polymer into 'Fibers in the melt phase without significant decomposition. The preferred method of making the fiber is by melt spinning.
is Preferred isotropic polymers are semi-crystalline. Semi-crystalline polymers that will be highly useful include poly(alkylene terephthalates), poly(alkylene naphthalates), poly(arylene sulfides), aliphatic and aliphatic-aromatic polyamides, polyesters comprising monomer units derived from cyclohexanedimethanol and terephthalic 2o acid, and polyolefins, including polyethylene and polypropylene.
I=xamples of specific semi-crystalline polymers include polyethylene terephthalate), poly(butylene terephthalate), polyethylene naphthaEatel, poly(phenylene sulfide), poly(1,4-cyclohexanedimethanol terephthalate), wherein the 1,4-cyclohexanedimethanol is a mixture of 25 cis and traps isomers, nylon-6, nylon-66, polyethylene and polypropylene. These polymers are all known to be useful for making ..;
". .., " ; ,_ fibers. The preferred semi-crystalline polymer is polyethylene terephthalate).
Polymers that cannot be processed in the melt can also be filled with hard particles, as for example cellulose acetate, which is typically 5 dry spun using acetone as a solvent, or a polyaramide, such as the polymer of terephthalic acid and p-phenylenediamine, which is dry-jet, wet-spun from a concentrated sulfuric acid solution. The hard particles would be incorporated into the spinning processes for these polymers in order to obtain the filled fibers. Amorphous, non-lo crystalline polymers, such as the copolymer of isophthalic acid, terephthalic acid and bisphenol A (polyarylate) may also be filled and utilized in this invention by a melt spinning process.
An important aspect of this invention is the discovery that a flexible cut-resistant fiber may be made from a suitable polymer filled with a hard material that imparts cut resistance. The material may be a metal, such as an elemental metal or metal alloy, or may be nonmetallic. Generally, any filler may be used that has a Mohs Hardness value of 3 or more. Particularly suitable fillers have a Mohs Hardness value greater than 4 and preferably greater than 5. Iron, 2o steel, tungsten and nickel are illustrative of metals and metal alloys, with tungsten, which has a Mohs value ranging from 6.5 to 7.5 being preferred. Non-metallic materials are also useful. These include, but are not limited to, metal oxides, such as aluminum oxide and silicon dioxide, metal carbides, such as silicon carbide and tungsten carbide, metal nitrides, metal sulfides, metal silicates, metal silicides, metal sulfates, metal phosphates, and metal borides. Other ceramic materials may also be used. Aluminum oxide, ANIEIvDE~ BEET
_ ., . _ ' ' ~ .
_ _ . , , , ., ., ", .:, . ; ,..' and especially calcined aluminum oxide, is most preferred. Titanium dioxide in general is less preferred.
The particle size and particle size ~ distribution are important parameters in obtaining good cut resistance while preserving fiber s mechanical properties. In general, the hard filler should be in the form of particles, with a powder form being generally suitable. Flat particles (i.e. platelets) and elongated particles (needles) also work well. The average particle size is generally in the range of 0.25 to a 7 0 micrometers. Preferably the average particle size is in the range of l0 1 to 6 micrometers. The most preferred average particle size is 3 micrometers. ~ For particles that are flat (i.e. platelets) or elongated, the particle size refers to the length along the long axis of the particle (i.e. the long dimension of an elongated particle or the average diameter of the face of a platelet). The particles preferably should 15 exhibit a log normal distribution. For making textile fibers (i.e. fibers having a denier in the range of 1.5. to 15 dpf), the particles should be filtered or sieved in such a way that particles larger than 6 micrometers are excluded.
- A minor percentage of the hard filler is used. The amount is 2o chosen to yield enhanced cut resistance without causing a significant loss of tensile properties. Desirably, the cut resistance of the fiber or fabric made from the fiber will show improvements of at least 20%
using the Ashland Cut Protection Performance Test. Preferably the cut resistance will improve by at least 35%, and most preferably will 2s improve by at least 50% in comparison with a fiber made of the same polymer but without the filler. The tensile properties of the fiber (tenacity and modulus) preferably will not Aid9EiVDED SHEEN
' CA 02221615 1997-11-19 ,~ ..
decrease by more than 50%, and more p. eferably will not decrease by more than 25%. Most preferably, there will not be a significant change in tensile properties (i.e., less than 10% decrease in properties).
On a weight basis, the filler should be present in an amount of at least 0.1 %. The upper limit of filler is determined mainly by the effect on tensile properties, but levels above 20% by weight are generally less desirable. , On a volume basis, the particle level concentration is in the range of 0.1 % to 5% by volume, more to preferably 0.5% to 3% by volume and most preferably 2.1 % by volume. For the preferred embodiment (calcined alumina in PET), these ranges on a weight basis are 0.3% to 14% (preferred), 1.4% to 8.5% (more preferred), and 6% (most preferred).
In accordance with the present invention, filled fibers are 15 prepared from a filled resin. The filled resin is made by any of the standard methods for adding a filler to a resin. For example, for a melt processable isotropic polymer, the filled resin is conveniently prepared in an extruder by mixing the hard filler with molten polymer under conditions sufficient to provide a uniform distribution of the 2o filler in the resin, such as mixing in a twin screw extruder. The filler may also be present during the manufacture of the polymer or may be added as the polymer is fed into the extruder of fiber spinning enuipment, in which case the blending and spinning steps are nearly simultaneous.
25 Since the filler is distributed uniformly in the polymer melt, the filler particles are also typically distributed uniformly throughout the At~thry'?ri s c~G~-r ~ CA 02221615 1997-11-19 ' _ _' , .,. _..
.._ ' , ~ 1 f ~ 1 ~ _ 7 fibers, except that elongated and flat particles are oriented to some extent because of the orientation forces during fiber spinning. Some migration of the particles to the surface of the fiber may also occur.
Thus, while the distribution of particles in the fibers is described as s '°uniform", the word "uniform" should be understood to include non-uniformities that occur during the processing (e.g., melt spinning) of a uniform polymer blend. Such fibers would still fall within the scope of ~' this invention. Any size fiber may be made according to the present invention. In the manufacture of fabrics and yarns, the fiber will io generally have a denier in the range of 1 to 50 dpf, preferably in the range of 1.5 to 15 dpf, and most preferably 4 dpf. Cut-resistant monofilaments may also be made by including a hard filler.
Monofilaments generally have a diameter of 0.05 to 2mm. The fibers are made by conventional fiber spinning processes. As previously 1s stated, the preferred process is melt-spinning, but wet-spinning and dry-spinning may also be used.
The description above is written with respect to fibers. The term fiber includes not only conventional single fibers but also yarns made from a multiplicity of these fibers. In general, yarns are utilized 2o in the manufacture of apparel, fabrics and the like.
Cut-resistant fabric may be made using a filled fiber in accordance with the present invention by using conventional methods, such as knitting or weaving, and conventional equipment.
Non-woven fabrics can also be made. Such fabric will have improved 25 cut resistance in comparison with the same fabric made using fiber manufactured from the same polymer without a filler. The cut AMENDED SHEET
.~' , , " ~.. . __._ _ , .
. ; : ' , . _ resistance of the fabric will be improved by at least 20% when measured using the Ashland Cut Protection Performance test.
Preferably the cut resistance will improve by at least 35%, and most preferably will improve by at least 50%.
s Cut-resistant apparel may then be made from the cut-resistant fabric described above. For example, a cut-resistant safety glove designed for use in the food processing industries may be manufactured from the fabric. Such a glove is highly flexible and readily cleanable, being resistant to chlorine bleach and to the heat of to a drier. Protective medical gloves may also be made using the cut resistant fibers of this invention. Other uses of the fabrics and monofilaments include side curtains and tarpaulins for trucks, softsided luggage, commercial upholstery, inflatables, fuel cells, collapsible packaging, airline cargo curtains, firehose sheaths, cut is resistant aprons for use in metal packing, chaps, etc.
Example 1 Polyethylene terephthalate) fibers incorporating tungsten powder filler are described below. Tungsten has a Mohs Hardness 2o value of about 6.5 to 7.5. Tire yarn grade polyethylene terephthalate) (PET), having an intrinsic viscosity of about 0.95 when measured in o-chlorophenol, was obtained from Hoechst Celanese Corporation, Somerville, New Jersey in the form of pellets. A master batch was made by blending the polymer with 10% tungsten powder 2s on a weight basis in a twin screw extruder. The tungsten had an average particle size of about 1 micrometer. The polymer pellets and tungsten were both dried before blending. The master batch was AMENDED SHEET
blended with additional PET in a twin screw extruder to yield blends having 1 % and 4% tungsten on a weight basis. The samples were melt spun by forcing the molten blend first through a filter pack and then through a spinneret. The yarn was subsequently drawn off a heated feed roll at 90°C, then drawn over a heated shoe, and finally subjected to a 2% relaxation at 225°C. The yarn was plied for testing of properties. The data are summarized in Table 1. One of the 10% tungsten-loaded fibers was also analyzed for tungsten to ensure that the filler was not filtered out. The analysis of the fiber to shows about 8.9% by weight tungsten in the fiber.
Tensile properties. The tenacity, elongation and modulus were measured using ASTM test method D-3822.
Cut resistance. The fiber was first knitted into fabric for the testing of cut resistance. The areal density of yarn in the fabric was is measured in ounces/square yard (OSY in Tables 1 and 2). The cut resistance of the fabric was then measured using the Ashland Cut Performance Protection (°°CPP") test. The test was carried out at 'rRl/Environmental, Inc., 9063 Bee Cave Road, Austin, Texas 78733-6201. In the test, the fabric sample is placed on the convex surface of a mandrel. A series of tests is carried out in which a razor blade loaded with a variable weight is pulled across the fabric until the fabric is cut all the way through. The distance the razor blade travels across the cloth until the blade cuts completely through the cloth is measured. The point at which the razor blade cuts through the fabric '' 2s is the point at which electrical contact is made between the mandrel and razor blade. The distance required to make the curt is plotted on a graph as a function of the load on the razor blade. The data are ' ; _ _ ., ..
measured and plotted for cut distances varying from 0.3 inches(0.7 cm) to 1.8 inches (4.6 cm). The resulting plot is approximately a straight line. An idealized straight line is drawn or calculated through the points on the plot, and the weight required to cut through the cloth after one inch of travel across the cloth is taken from the plot or calculated by regression analysis. The interpolated values of the weight required to make a cut after one inch of blade travel across the cloth are shown in Tables 1 and 2 as "CPP", an abbreviation for Cut Protection Performance. ~ Finally, for purposes of comparing the data to for different area) densities of cloth sample, the CPP value is divided by the areal density of the cloth (OSY) to compensate for variations in areal density. This value is shown as CPP/OSY in Tables 1 and 2.
Example 2 1s In these experiments, PET fiber samples were filled with alumina powder, which was sold commercially under the trademark MICROPOLISH~ II as a polishing abrasive. Two different alumina powders were used having average particle sizes of about 0.05 micrometers and about 1 .0 micrometers. Both were obtained as 2o deagglomerated powders from Buehler, Ltd., Waukegan Road, Lake Bluff, Illinois 60044. The 0.05 micrometer alumina was gamma alumiha with a cubic crystal structure and a Mohs Hardness Value of 8. The 1.0 micrometer material was alpha alumina having a hexagonal crystal structure and a Mohs Hardness Value of 9. The 2s two alumina powders were blended with PET using the same method as in Example 4 to yield filled PET samples containing alumina at levels of about 0.21 %, 0.86%, 1.9% and 2.1 % by weight.
Measurements of fiber properties ~~~ t~~~- cr:_~
~;~~._,°t. . .
~ CA 02221615 1997-11-19 ..
.. ~ >.~ >,._ ~ " .' . '."
' ; ; , , ... .,. . ..
and cut resistance were made using the same methods as in Example 1 . The data are presented in Table 2.
The data in Tables 1 and 2 show that there is an improvement in cut resistance of at least about 10-20% at all levels of filler used in these experiments. Both sets of data incorporate filler in the fiber at levels of about 0.07% to about 0.7% on a volume basis. The fiber properties do not appear to significantly degrade with these amounts and sizes of particles.
Example 3 A series of experiments was run using tungsten particles of several different particle sizes (0.6 - 1 .6 micrometers) as fillers in PET
at concentrations of 0.4 - 1.2 volume %. The tungsten-filled PET was spun into yarn, which was subsequently knitted into fabric for testing.
Cut resistance was again measured by the Ashland Cut Protection Performance Test, using the modified procedure described below.
The CPP values were divided by the areal densities of the cloth to correct for the fact that the tests were carried out on different ° densities of cloth. The data are presented in Table 3.
' Cut Protection Performance (CPP) The Ashland CPP Test was run as described at the end of Experiment 1, but a calibration against a standard with a known CPP
value was used to correct the results. The calibration standard was 2s 0.062 inch (0.157 cm) neoprene, style NS-5550, obtained from FAIRPRENE, 85 Mill Plain Road, Fairfield. CT 06430, which has a CPP
value of 400 gms. The CPP value was measured for this standard at the beginning AMENDED SHEET
f ~ 1 9 Z 9 ~ ~ f 1 9vf 7 as and end of a series of tests, and an average normalization factor was calculated that would bring the measured CPP value of the standard to 400 gms. The normalization factor was then used to correct the measured data for that series of tests. Also, in caculating the CPP
value, a plot of the logarithm of the distance required to cut the fabric vs. the load on the razor blade was utilized, as it was more linear.
Example 4 A series of experiments was run using calcined aluminum oxide to as the filler for the fiber. The experiments were run using the same procedure as used in Examples 1-3, but with a broader range of particle sizes (0.5 - 3 micrometers) and a wider range of concentrations (0.8 - 3.2 volume %) than in Example 2.
The calcined aluminum oxide used in the experiments was obtained from Agsco Corporation, 621 Route 46, Hasbrouck, N.J.
07604, and is in the form of platelets, referred to as Alumina #1.
The CPP values were measured using the procedure described at the end of Example 3. The CPP/OSY values were then calculated as described above. These data are presented in Table 4.
~ It can be seen from the data in the tables that the CPP/OSY
values are affected by all of the variables listed (i.e., particle size, particle concentration, areal density, and the fiber dpf). At the high areal densities (OSY), the CPP/OSY values fall off significantly. Thus comparisons are preferably made for tests in fabrics having similar 2s areal densities.
Nevertheless, it can be seen from the data in Table 4 that at a level of 2.4 volume % (6.8 weight%), with a particle size of 2 AMENDED SNEFT
_"' _ ~.. ,._.
.' . '..; .' .,. .... .., : .,' micrometers, the CPP/OSY values for fabrics made from textile fibers (2.8 dpf) and having areal densities of less than about 10 ounces per square yard were greater than about 100. (Sample Nos. 22-24 and 30). This is much more than a 50% increase over the average s CPP/OSY value of about 53 that was measured for unfilled PET fiber of comparable fiber size and areal density (the three Controls in Table 1 ). The average CPP/OSY values for all the tungsten filled PET
samples of Table 3 !70) and all the aluminum oxide filled PET samples of Table 4 (75) are also significantly higher than the average of the 1o controls.
AIViEIVD~D Si-~E~T
., .,: '. _' -1~
Table 1 . Cut Resistance of PET Filled with Tungsten Particle Size Tungsten (micrometers) No. Wt. Volume ,d~f T/E/M~ CPPZ OSY3 CPP/OSY
Control -- -- -- 3.1 6.8/6.7/124421 7.1 59 Control2-- -- -- 5.0 -- 384 6.8 56 Control3-- -- -- 5.0 -- 589 13.0 45 1-1 l9fo 0.07961 micrometer6.0 6.3/9.0/128540 9.1 59 1-2 196 0.07961 micrometer5.6 565 7.3 77 1-3 496 0.29101 micrometer6.0 7.2/11.6/109643 7.0 92 1-4 496 0.29961 micrometer5.9 7.0112.5/100620 7.3 85 1-5 1096 0.72961 micrometer11.6 6.3/10.0/123697 7.5 93 I
~i 1-6 1096 0.72961 micrometer7.4 4.1122.9/75759 8.5 90 1-7 1096 0.72%1 micrometer6.0 -- 670 7.6 89 . 'Tenacity (gpd), Elongation (°Y~), Modulus (gpd), measured using ASTM
test method D-3822.
ZCut Protection Performance, measured using the Ashland CPP test.
30unces per Square Yard.
AMENDED SH~~'~
'CA 02221615 1997-11-19 "°~ , - ... . ~ ~ . , ~ s r ~ , s ry s -~.~ i~w ,. . vs o Table2. Cut Resistance of PET Filled with Alumina 96 Particle Alumina Size No. Wt. Volume(micrometers)d~f T/ElM' CPPz OSY' CPP/OSY
2-1 0.2196.0796 1 micrometer11.4 6.7!10.31112547 7.2 76 2-2 0.2196.0796 1 micrometer5.6 7.4/12.4/104463 7.5 62 2-3 0.86960.30960.05 5.6 7.4/14.0/110501 7.3 69 micrometer 2-4 0.86960.30960.05 5.7 6.9/12.8/110497 6.7 73 micrometer 2-5 1.9960.67961 micrometer11.8 5.8/12.0/108683 8.2 83 2-6 1.9960.67961 micrometer5.6 7.4/10.9/108478 6.7 71 2-7 2.1960.74960.05 5.4 6.6/11.6/117496 6.7 74 micrometer 2-8 2.1960.74960.05 5.9 5.4/12.8/100431 6.2 69 micrometer 'Tenacity (gpd), Elongation (9b), Modulus (gpd), measured using ASTM test method O-3822.
ZCut Protection Performance, measured using the Ashland CPP test.
30unces per Square Yard.
AMENDED SHEET
~' . . ' ' ..., .. ___.
~' -; ~ ~'~ , . ; .
,' , '.~"
' ' ' ' ~ ~ , .. _ , " " , TABLE 3. Cut Resistance of PET Filled with Tungsten SAMPLE PARTSIZE CONC DPFTENACITYELON MODULUSOSY CPP CPP/OSY
# G
micrometervol% d % d ozl d2 1 0.6 0.4 10 7.3 9 112 8 562 70 2 0.8 1.2 10 5.5 13 102 9.5 557 59 3 1.4 0.4 10 6 14 96 8.2 714 87 4 1.6 1.2 10 5.9 11 100 8.2 821 100 1 0.8 10 8 708 89 6 0.8 0.8 10 5.7 8 109 7 724 103 7 0.6 0:8 10 5.9 13 118 6.8 621 91 8 0.8 0.8 10 5.7 8 109 7 596 85 9 0.6 0.8 10 6.3 13 103 7.9 703* 89 1.5 0.8 12 6.7 9 102 7.6 644 85 11 0.6 0.8 2.4 13.6 656 48 12 1 0.8 7.2 8 108 7.5 503 67 13 0.6 0.8 2.4 28 1226 44 14 0.6 0.8 2.4 19 964 51 0.6 0.8 2.4 26 1225 47 16 0.6 0.8 10 20 900 45 17 0.6 0.8 2.4 12 628 52 18 0.6 0.8 1.4 16 685 43 0:6[ --~.8~ r 7 580 80 1.4 5 PARTSIZE is Particle size, measured in micrometers.
CONC is the concentration of hard particles, measured as a volume % in PET.
DPF is the fiber denier in dpf.
TENACITY, ELONG, and MODULUS are the fiber tensile properties, measured by ASTM test method D-3822.
10 OSY is the areal density of the knitted fabrics, measured in ounces per square yard.
CPP is the CPP value measured by the Ashland CPP test.
CPP/OSY is the ratio of the CPP value to the areal density (OSY).
* - measured by the method described in Example 1.
AMEI'JDED S~>~~T
.. ~r~.
s ~.. ..
TABLE 4. Cut Resistance of PET filled with Alumina SAMPLE PARTSIZE CONCDPFTENACITY_ELONGMODULUSOSY CPP CPP/OSY
#
(micrometer)(vol%) (gpd) (%) (gpd) (oz/yd2) 1 0.6 2.4 3 22 1285 58 2 0.6 0.8 10 6.6 15 109 10 990" 99 3 0.6 1.6 10 5.2 17 100 12 912 76 4 0.6 2.4 10 5.8 9 107 10 823 82 0.6 3.2 10 4.8 14 93 10 852 85 6 0.6 2.4 3 19 1074 57 7 0.6 2.4 3 9 487 54 8 3 2.4 3.65 23 16 1234 77 9 3 2.4 3.65 23 11 981 89 0.5 2.4 1.44.9 22 15 810 54 11 0.5 2.4 1.44.9 22 13 623 48 12 3 2:4 3.13.4 19 18 1555 86 13 0.5 2.4 5.5 23 1197 52 14 0.5 2.4 5.5 21 1082 52 0.6 2.4 6.4 23 1242 54 16 0.6 2.4 5.5 19 1505 79 17 0.5 2.4 6.7 8 597 75 18 0.6 2.4 4 13 818 63 19 3 2.4 3.1 15 1370 91 3 2.4 3.1 15 1283 86 21 2 2.4 2.85 15 80 18 1562 87 22 2 2.4 2.85 15 80 9 905 101 23 2 2.4 2.85 15 80 5 611 122 24 2 2.4 2.85 15 80 5 615 123 2 2.4 2.85 15 80 11 785 71 26 2 2.4 2.85 15 80 17 1593 94 27 2 2.4 2.85 15 80 17 1506 89 28 2 2.4 2.85 15 80 36 1022 28 29 2 2.4 2.85 15 80 18 1573 87 2 2.4 2.85 15 80 9 956 106 31 ' 3 1.2 10 23 1414 62 32 0.6 2.4 6.4 18 1084 60 33 0.6 2.4 6.4 21 996 47 34 3 2.4 4.2 14 1079 77 3 2.4 4.2 11 883 80 36 ~ 1 ~ 2.4112.~ 73 943 129 ~
PARTSIZE is Particle size, measured in micrometers.
CONC is the concentration of hard particles, measured as a volume 96 in PET.
DPF is the fiber denier in dpf.
TENACITY, ELONG, and MODULUS are the fiber tensile properties, measured by ASTM test method D-3822.
OSY is the areal density of the knitted fabrics, measured in ounces per square yard.
CPP is the CPP value measured by the Ashland CPP test. , CPP/OSY is the ratio of the CPP value to the areal density (OSY).
10 ' - measured by the method described in Example 1. , AMENDED SHEET
CPP is the CPP value measured by the Ashland CPP test.
CPP/OSY is the ratio of the CPP value to the areal density (OSY).
* - measured by the method described in Example 1.
AMEI'JDED S~>~~T
.. ~r~.
s ~.. ..
TABLE 4. Cut Resistance of PET filled with Alumina SAMPLE PARTSIZE CONCDPFTENACITY_ELONGMODULUSOSY CPP CPP/OSY
#
(micrometer)(vol%) (gpd) (%) (gpd) (oz/yd2) 1 0.6 2.4 3 22 1285 58 2 0.6 0.8 10 6.6 15 109 10 990" 99 3 0.6 1.6 10 5.2 17 100 12 912 76 4 0.6 2.4 10 5.8 9 107 10 823 82 0.6 3.2 10 4.8 14 93 10 852 85 6 0.6 2.4 3 19 1074 57 7 0.6 2.4 3 9 487 54 8 3 2.4 3.65 23 16 1234 77 9 3 2.4 3.65 23 11 981 89 0.5 2.4 1.44.9 22 15 810 54 11 0.5 2.4 1.44.9 22 13 623 48 12 3 2:4 3.13.4 19 18 1555 86 13 0.5 2.4 5.5 23 1197 52 14 0.5 2.4 5.5 21 1082 52 0.6 2.4 6.4 23 1242 54 16 0.6 2.4 5.5 19 1505 79 17 0.5 2.4 6.7 8 597 75 18 0.6 2.4 4 13 818 63 19 3 2.4 3.1 15 1370 91 3 2.4 3.1 15 1283 86 21 2 2.4 2.85 15 80 18 1562 87 22 2 2.4 2.85 15 80 9 905 101 23 2 2.4 2.85 15 80 5 611 122 24 2 2.4 2.85 15 80 5 615 123 2 2.4 2.85 15 80 11 785 71 26 2 2.4 2.85 15 80 17 1593 94 27 2 2.4 2.85 15 80 17 1506 89 28 2 2.4 2.85 15 80 36 1022 28 29 2 2.4 2.85 15 80 18 1573 87 2 2.4 2.85 15 80 9 956 106 31 ' 3 1.2 10 23 1414 62 32 0.6 2.4 6.4 18 1084 60 33 0.6 2.4 6.4 21 996 47 34 3 2.4 4.2 14 1079 77 3 2.4 4.2 11 883 80 36 ~ 1 ~ 2.4112.~ 73 943 129 ~
PARTSIZE is Particle size, measured in micrometers.
CONC is the concentration of hard particles, measured as a volume 96 in PET.
DPF is the fiber denier in dpf.
TENACITY, ELONG, and MODULUS are the fiber tensile properties, measured by ASTM test method D-3822.
OSY is the areal density of the knitted fabrics, measured in ounces per square yard.
CPP is the CPP value measured by the Ashland CPP test. , CPP/OSY is the ratio of the CPP value to the areal density (OSY).
10 ' - measured by the method described in Example 1. , AMENDED SHEET
Claims (28)
1. A cut-resistant fiber comprising an isotropic melt-processable polymer and a hard filler distributed uniformly in the fiber, wherein:
the filler has a Mohs Hardness value greater than 3 and an average particle size in the range of 0.25 micrometers to 10 micrometers and is present in an amount of 0.1% to 5% by volume based on the fiber, and the fiber has a denier in the range of 1 to 50 dpf.
the filler has a Mohs Hardness value greater than 3 and an average particle size in the range of 0.25 micrometers to 10 micrometers and is present in an amount of 0.1% to 5% by volume based on the fiber, and the fiber has a denier in the range of 1 to 50 dpf.
2. The cut-resistant fiber as recited in claim 1, wherein the hard filler has a Mohs Hardness value greater than 5.
3. The cut-resistant fiber as recited in claim 1 or 2, wherein the average particle size of the hard filler is in the range of 1 to 6 micrometers.
4. The cut-resistant fiber as recited in claim 1 or 2, wherein the average particle size of the hard filler is 3 micrometers.
5. The cut-resistant fiber as recited in any one of claims 1 to 4, wherein the hard filler is a non-metal selected from the group consisting of metal oxides, metal carbides, metal nitrides, metal sulfides, metal silicates, metal silicides, metal sulfates, metal phosphates, metal borides, and mixtures thereof, except for titanium dioxide.
6. The cut-resistant fiber as recited in claim 5, wherein the hard filler is aluminum oxide or silicon dioxide.
7. The cut-resistant fiber as recited in claim 5, wherein the hard filler is calcined aluminum oxide.
8. The cut-resistant fiber as recited in any one of claims 5 to 7, wherein the hard filler is contained in an amount of 0.5% to 3% on a volume basis.
9. The cut-resistant fiber as recited in any one of claims 5 to 7, wherein the hard filler is contained in an amount of 2.2% by volume.
10. The cut resistant fiber as recited in any one of claims 1 to 4, wherein the hard filler is a metal or metal alloy.
11. The cut-resistant fiber as recited in claim 10, wherein the hard filler is contained in an amount of 0.5%
to 3% by volume.
to 3% by volume.
12. The cut-resistant fiber as recited in claim 10, wherein the hard filler is contained in an amount of 2.1% by volume.
13. The cut-resistant fiber as recited in any one of claims 10 to 12, wherein the hard filler is selected from the group consisting of iron, steel, nickel, tungsten and mixtures thereof.
14. The cut-resistant fiber as recited in any one of claims 10 to 12, wherein the hard filler is tungsten.
15. The cut-resistant fiber as recited in any one of claims 1 to 14, wherein the isotropic melt-processable polymer is selected from the group consisting of poly(alkylene terephthalates), poly(alkylene naphthalates), poly(arylene sulfides), aliphatic polyamides, aliphatic-aromatic polyamides, polyesters of cyclohexanedimethanol and terephthalic acid, and polyolefins.
16. The cut-resistant fiber as recited in any one of claims 1 to 14, wherein the isotropic melt-processable polymer is selected from the group consisting of poly(ethylene terephthalate), poly(butylene terephthalate), poly(ethylene naphthalate), poly(phenylene sulfide), poly(1,4-cyclohexanedimethanol terephthalate), nylon-6, nylon-66, polyethylene, and polypropylene.
17. The cut-resistant fiber as recited in any one of claims 1 to 14, wherein the isotropic melt-processable polymer is polyethylene terephthalate).
18. The cut-resistant fiber as recited in any one of claims 1 to 4, wherein the hard filler is calcined aluminum oxide and the isotropic melt-processable polymer is poly(ethylene terephthalate).
19. The cut-resistant fiber as recited in any one of claims 1 to 4, wherein the hard filler is tungsten and the isotropic melt-processable polymer is poly(ethylene terephthalate).
20. A method of making a fiber or yarn having increased cut resistance, comprising the steps of:
(a) making a uniform blend of 0.1% to 5% by volume of:
(1) a hard filler having a Mohs Hardness value greater than 3 and a particle size in the range of 0.25 micrometers to 10 micrometers, and (2) an isotropic melt-processable polymer selected from the group consisting of poly(ethylene terephthalate), poly(butylene terephthalate), poly(ethylene naphthalate), poly(phenylene sulfide), poly(1,4-cyclohexanedimethanol terephthalate), nylon-6, nylon-66, polyethylene and polypropylene; and (b) spinning the uniform blend into a fiber or yarn, wherein the fiber or the fiber in the yarn has a denier in the range of 1 to 50 dpf.
(a) making a uniform blend of 0.1% to 5% by volume of:
(1) a hard filler having a Mohs Hardness value greater than 3 and a particle size in the range of 0.25 micrometers to 10 micrometers, and (2) an isotropic melt-processable polymer selected from the group consisting of poly(ethylene terephthalate), poly(butylene terephthalate), poly(ethylene naphthalate), poly(phenylene sulfide), poly(1,4-cyclohexanedimethanol terephthalate), nylon-6, nylon-66, polyethylene and polypropylene; and (b) spinning the uniform blend into a fiber or yarn, wherein the fiber or the fiber in the yarn has a denier in the range of 1 to 50 dpf.
21. The method as recited in claim 20, wherein the spinning is a melt spinning of the uniform blend.
22. A method of making a fabric having increased cut resistance, comprising the steps of:
(a) making a fiber or yarn according to the method of claim 20 or 21, and (b) fabricating the fiber or yarn into a fabric.
(a) making a fiber or yarn according to the method of claim 20 or 21, and (b) fabricating the fiber or yarn into a fabric.
23. A cut-resistant fiber comprising a polymer that is non-melt-processable and a hard filler distributed uniformly in the fiber, wherein the filler has a Mohs Hardness value greater than 3 and an average particle size in the range of 0.25 microns to 10 microns and is present in an amount of 0.1% to 5% by volume based on the fiber.
24. The cut-resistant fiber recited in claim 23, wherein the non-melt-processable polymer is a polyaramide.
25. The cut-resistant fiber recited in claim 24, wherein the polyaramide is a polymer of p-phenylenediamine and terephthalic acid.
26. A cut-resistant yarn comprising a multiplicity of the fibers as defined in any one of claims 1 to 19, wherein the fibers have a denier in the range of 1.5 to 15 dpf.
27. A cut-resistant fabric which is woven or nonwoven and is made of the fiber as defined in any one of claims 1 to 19.
28. A cut-resistant fabric which is woven or nonwoven and is made of the fiber as defined in claim 23.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US48220795A | 1995-06-07 | 1995-06-07 | |
| US08/482,207 | 1995-06-07 | ||
| PCT/US1996/008358 WO1996041042A1 (en) | 1995-06-07 | 1996-05-31 | Filled thermoplastic cut-resistant fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2221615A1 CA2221615A1 (en) | 1996-12-19 |
| CA2221615C true CA2221615C (en) | 2006-08-01 |
Family
ID=23915155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002221615A Expired - Fee Related CA2221615C (en) | 1995-06-07 | 1996-05-31 | Filled thermoplastic cut-resistant fiber |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0845056A1 (en) |
| JP (1) | JPH11511209A (en) |
| KR (1) | KR19990022515A (en) |
| CN (1) | CN1092254C (en) |
| AU (1) | AU717702B2 (en) |
| BR (1) | BR9609091A (en) |
| CA (1) | CA2221615C (en) |
| TW (1) | TW307802B (en) |
| WO (1) | WO1996041042A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5851668A (en) * | 1992-11-24 | 1998-12-22 | Hoechst Celanese Corp | Cut-resistant fiber containing a hard filler |
| DE19605511A1 (en) * | 1996-02-15 | 1997-08-21 | Hoechst Trevira Gmbh & Co Kg | Cut-resistant aramid fibers, yarns containing these aramid fibers and their use |
| KR101129067B1 (en) * | 2008-09-18 | 2012-03-23 | 코오롱인더스트리 주식회사 | Aramid Fiber and bulletproof fabric using the same |
| EP2468120A1 (en) * | 2009-08-19 | 2012-06-27 | Showa Glove Co. | Work glove |
| DE102012001623A1 (en) * | 2012-01-30 | 2013-08-01 | Hahl Filaments GmbH | Producing abrasive bristle, comprises melting a plastic material, mixing granules made of abrasive particles, extruding into a filament, processing and cutting filament, where plastic material is a high-temperature-resistant polymer |
| KR20150096412A (en) * | 2012-12-20 | 2015-08-24 | 디에스엠 아이피 어셋츠 비.브이. | Polyolefin yarns and method for manufacturing |
| CN107574519B (en) | 2017-09-29 | 2024-06-11 | 汇鸿(南通)安全用品有限公司 | Cutting-preventing rubber-coated yarn |
| WO2020065842A1 (en) * | 2018-09-27 | 2020-04-02 | 東洋紡株式会社 | Polyethylene fiber and product employing same |
| CN112779623B (en) * | 2020-09-17 | 2022-03-15 | 安丹达工业技术(上海)有限公司 | Composition for cutting-resistant fiber, application and preparation method |
| CN113897696A (en) * | 2021-11-03 | 2022-01-07 | 福建永荣锦江股份有限公司 | Preparation method of anti-cutting polyamide 6 fiber |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4818581A (en) * | 1986-08-27 | 1989-04-04 | Teijin Limited | Biaxially oriented polyester film |
| JP2720465B2 (en) * | 1988-07-28 | 1998-03-04 | 東レ株式会社 | Thermoplastic polyester composition |
| JP3563752B2 (en) * | 1992-11-24 | 2004-09-08 | エイチエヌエイ・ホールディングス・インコーポレーテッド | Filled fiber |
| DE69527956D1 (en) * | 1994-05-16 | 2002-10-02 | Honeywell Int Inc | FILLED CUT RESISTANT FIBER |
-
1996
- 1996-05-28 TW TW085106334A patent/TW307802B/zh active
- 1996-05-31 KR KR1019970708996A patent/KR19990022515A/en not_active Application Discontinuation
- 1996-05-31 WO PCT/US1996/008358 patent/WO1996041042A1/en not_active Application Discontinuation
- 1996-05-31 JP JP9500984A patent/JPH11511209A/en not_active Ceased
- 1996-05-31 BR BR9609091A patent/BR9609091A/en not_active IP Right Cessation
- 1996-05-31 CN CN96195351A patent/CN1092254C/en not_active Expired - Fee Related
- 1996-05-31 AU AU59677/96A patent/AU717702B2/en not_active Ceased
- 1996-05-31 CA CA002221615A patent/CA2221615C/en not_active Expired - Fee Related
- 1996-05-31 EP EP96916969A patent/EP0845056A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| TW307802B (en) | 1997-06-11 |
| AU5967796A (en) | 1996-12-30 |
| WO1996041042A1 (en) | 1996-12-19 |
| CN1190444A (en) | 1998-08-12 |
| AU717702B2 (en) | 2000-03-30 |
| CN1092254C (en) | 2002-10-09 |
| EP0845056A1 (en) | 1998-06-03 |
| KR19990022515A (en) | 1999-03-25 |
| CA2221615A1 (en) | 1996-12-19 |
| JPH11511209A (en) | 1999-09-28 |
| BR9609091A (en) | 1999-02-02 |
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