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Patent 2221615 Summary

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(12) Patent: (11) CA 2221615
(54) English Title: FILLED THERMOPLASTIC CUT-RESISTANT FIBER
(54) French Title: FIBRES THERMOPLASTIQUES CHARGEES RESISTANTES A LA COUPURE
Status: Expired and beyond the Period of Reversal
Bibliographic Data
(51) International Patent Classification (IPC):
  • D01F 01/10 (2006.01)
  • A41D 31/24 (2019.01)
  • C08K 03/013 (2018.01)
  • C08K 03/08 (2006.01)
  • C08K 03/22 (2006.01)
  • C08L 67/02 (2006.01)
  • C08L 77/10 (2006.01)
  • D01F 06/60 (2006.01)
  • D01F 06/62 (2006.01)
  • D02G 03/44 (2006.01)
(72) Inventors :
  • SANDOR, ROBERT B. (United States of America)
  • GILLBERG-LAFORCE, GUNILLA E. (United States of America)
  • CLEAR, WILLIAM F. (United States of America)
  • FLINT, JOHN (United States of America)
  • LANIEVE, LESLIE (United States of America)
  • THOMPSON, SCOTT W. (United States of America)
(73) Owners :
  • HOECHST CELANESE CORPORATION
  • HOECHST CELANESE CORPORATION
(71) Applicants :
  • HOECHST CELANESE CORPORATION (United States of America)
  • HOECHST CELANESE CORPORATION (United States of America)
(74) Agent: SMART & BIGGAR LP
(74) Associate agent:
(45) Issued: 2006-08-01
(86) PCT Filing Date: 1996-05-31
(87) Open to Public Inspection: 1996-12-19
Examination requested: 2003-05-16
Availability of licence: N/A
Dedicated to the Public: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/US1996/008358
(87) International Publication Number: US1996008358
(85) National Entry: 1997-11-19

(30) Application Priority Data:
Application No. Country/Territory Date
08/482,207 (United States of America) 1995-06-07

Abstracts

English 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.


French Abstract

On fabrique une fibre dont la résistance à la coupure est augmentée, à partir d'un polymère isotrope et d'une charge dure ayant une granulométrie moyenne de l'ordre d'environ 0,25 à environ 10 microns et une dureté supérieure à environ 3 sur l'échelle Mohs. La charge introduite représente au moins environ 0,1 % en poids. Le polymère isotrope préféré est le poly(éthylène téréphtalate). La charge préférée est l'alumine calcinée.

Claims

Note: Claims are shown in the official language in which they were submitted.


19
CLAIMS:
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.
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.

20
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.
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-

21
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),

22
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.
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.

23
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.

Description

Note: Descriptions are shown in the official language in which they were submitted.


CA 02221615 2005-06-13
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1
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

CA 02221615 1997-11-19
WO 96/41042 PCT/US96/08358
2
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,

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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

CA 02221615 1997-11-19
WO 96/41042 PC'T/US96/08358
4
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

CA 02221615 1997-11-19
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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

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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
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7
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
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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

CA 02221615 1997-11-19
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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

CA 02221615 1997-11-19
WO 96/41042 PCT/US96/08358
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

CA 02221615 1997-11-19
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11
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
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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

CA 02221615 1997-11-19
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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

CA 02221615 1997-11-19
_"' _ ~.. ,._.
.' . '..; .'
.,. .... .., : .,'
14
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

CA 02221615 1997-11-19
., .,: '. _' -
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
1 -
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
16
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

CA 02221615 1997-11-19
~' . . ' ' ..., .. ___.
~' -; ~ ~'~ , . ; .
,' , '.~"
' ' ' ' ~ ~ ,
.. _ , " " ,
17
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

CA 02221615 1997-11-19
.. ~r~.
s ~.. ..
18
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
~
9
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

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Event History

Description Date
Inactive: IPC assigned 2022-12-19
Inactive: IPC assigned 2022-12-19
Inactive: IPC assigned 2022-12-19
Inactive: IPC assigned 2022-12-19
Inactive: IPC assigned 2022-09-02
Inactive: IPC assigned 2022-09-02
Inactive: IPC removed 2022-09-02
Inactive: IPC expired 2019-01-01
Inactive: IPC expired 2012-01-01
Inactive: IPC removed 2011-12-31
Inactive: IPC deactivated 2011-07-29
Time Limit for Reversal Expired 2010-05-31
Letter Sent 2009-06-01
Grant by Issuance 2006-08-01
Inactive: Cover page published 2006-07-31
Pre-grant 2006-05-16
Inactive: Final fee received 2006-05-16
Inactive: IPC from MCD 2006-03-12
Inactive: IPC from MCD 2006-03-12
Inactive: IPC from MCD 2006-03-12
Inactive: IPC from MCD 2006-03-12
Inactive: IPC from MCD 2006-03-12
Inactive: IPC from MCD 2006-03-12
Notice of Allowance is Issued 2006-02-24
Letter Sent 2006-02-24
Notice of Allowance is Issued 2006-02-24
Inactive: Approved for allowance (AFA) 2005-12-20
Amendment Received - Voluntary Amendment 2005-06-13
Amendment Received - Voluntary Amendment 2005-06-06
Inactive: S.30(2) Rules - Examiner requisition 2004-12-06
Amendment Received - Voluntary Amendment 2003-08-14
Letter Sent 2003-06-13
All Requirements for Examination Determined Compliant 2003-05-16
Request for Examination Requirements Determined Compliant 2003-05-16
Request for Examination Received 2003-05-16
Letter Sent 2000-07-28
Reinstatement Requirements Deemed Compliant for All Abandonment Reasons 2000-07-18
Deemed Abandoned - Failure to Respond to Maintenance Fee Notice 2000-05-31
Inactive: IPC assigned 1998-02-25
Inactive: IPC assigned 1998-02-25
Inactive: First IPC assigned 1998-02-25
Classification Modified 1998-02-25
Inactive: Notice - National entry - No RFE 1998-02-11
Letter Sent 1998-02-11
Application Received - PCT 1998-02-10
Application Published (Open to Public Inspection) 1996-12-19

Abandonment History

Abandonment Date Reason Reinstatement Date
2000-05-31

Maintenance Fee

The last payment was received on 2006-03-20

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  • the reinstatement fee;
  • the late payment fee; or
  • additional fee to reverse deemed expiry.

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Please refer to the CIPO Patent Fees web page to see all current fee amounts.

Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
HOECHST CELANESE CORPORATION
HOECHST CELANESE CORPORATION
Past Owners on Record
GUNILLA E. GILLBERG-LAFORCE
JOHN FLINT
LESLIE LANIEVE
ROBERT B. SANDOR
SCOTT W. THOMPSON
WILLIAM F. CLEAR
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Abstract 1997-11-18 1 45
Description 1997-11-18 18 657
Claims 1997-11-18 6 118
Description 2005-06-05 18 660
Claims 2005-06-05 6 173
Description 2005-06-12 18 656
Claims 2005-06-12 5 167
Notice of National Entry 1998-02-10 1 193
Courtesy - Certificate of registration (related document(s)) 1998-02-10 1 118
Courtesy - Abandonment Letter (Maintenance Fee) 2000-06-27 1 184
Notice of Reinstatement 2000-07-27 1 171
Reminder - Request for Examination 2003-03-02 1 120
Acknowledgement of Request for Examination 2003-06-12 1 173
Commissioner's Notice - Application Found Allowable 2006-02-23 1 161
Maintenance Fee Notice 2009-07-12 1 171
PCT 1997-11-18 34 1,141
Correspondence 2006-05-15 1 38