Title of Invention

CHITOSAN COATED ARAMID FIBERS

Abstract A coated aramid fiber is disclosed wherein the coating is a small amount of chitosan and the coated fiber is useful in manufacture of an improved friction paper. An improved friction paper is, also, disclosed wherein chitosan is present throughout the paper as a coating on all components.
Full Text Field of the Invention
This invention relates to the chitosan coated aramid fibers.
This invention also relates to a friction paper, a process for making the chitosan coated aramid fibers and a process for making a friction paper.
This invention particularly relates to pulp, papers made from such pulp, and to methods for making such pulp and such papers. The papers of this invention include aramid pulp with chitosan as an additive and they perform especially well at high temperature and under other extreme conditions.
Description of the Prior Art
Japanese laid-open patent application 90-2303, published January 8, 1990, discloses use of chitosan as a coating on sheets made from natural fibers to increase the strength of the sheets in water. The sheets are biodegradable and are used in agricultural applications for plantings.
European Patent Application 123,312, published October 31, 1984, discloses a friction paper which includes aromatic polyamide fibers, fillers, and other materials, impregnated with a curable, thermosetting resin. The resin is present in the paper at from 15 to 60 weight percent.
SUMMARY OF THE INVENTION
This invention relates to an aramid fiber having a length of 0.15 to 10 millimeters, a surface area of 0.5 to 20 square meters per gram and a coating of chitosan in the amount of 1 to 10 percent, based on the weight of the fiber. The aramid fiber, in the form of pulp or a floe, can be a fiber component of a paper comprising 5 to 95 percent, by weight, aramid fiber, 0 to 20 percent, by weight, binder material, and 10 to 80 percent, by weight, inorganic filler, wherein the aramid fiber has a coating of chitosan in the amount of 1 to 10 percent, based on the weight of the fiber.


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The coated aramid fiber- can be made by dispersing uncoated fiber in an aqueous solution of chitosan and adjusting the pH of the solution to precipitate the chitosan onto the fibers. Coated pulp can, also, be made by refining uncoated floe in a solution of chitosan to yield a dispersion of pulp in the solution; and, then, adjusting the pH to precipitate the chitosan. Coated floe can be made by so-precipitating chitosan onto a dispersion of floe.
Paper can be made by combining the chitosan-coated aramid pulp of this invention with other, usual, components of an aramid paper on a paper making machine; and it can, also, be made by combining all of the components of an aramid paper and adding the chitosan, for example as an aqueous solution, at the paper making machine.
Accordingly, the present invention relates to the chitosan coated aramid fibers comprising aramid fibers having a length of 0.15 to 10 millimeters., a surface area of 0.5 to 20 square meters per gram and a coating of chitosan in the amount of 1 to 10 percent, based on the weight of the fibers.
The presently disclosed fiber is an article and not a chemical substance prepared from a chemical process involving a chemical reaction.
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DETAILED DESCRIPTION
It is generally observed that as the aramid fiber content of a paper increases, the friction coefficient of the paper decreases and the dispersion of fibers in the paper becomes nonuniform. Use of shorter aramid fibers improves uniformity of fiber dispersion but results in a decrease in paper strength leading to processing problems during the paper making. It is desirable to use a shorter aramid fiber with improved paper strength and increased friction coefficient.
The aramid fiber of this invention is made from aromatic polyamide fiber, wherein at least 85% of the amide (-CONH-) linkages are attached directly to two aromatic rings. Additives can be used with the aramid; and it has been found that up to as much as 10 percent by weight of other polymeric material can be blended with the aramid or that copolymers can be used having as much as 10 percent of otner diamine substituted for the diamine of the aramid or as much as 10 percent of other diacid chloride substituted for the diacid
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chloride of the aramid. Para-aramids are the primary polymers in fibers of this invention and poly(p-phenylene terephthalamide)(PPD-T) is the preferred para-aramid. Meta-aramids, also, may find use in the fibers of this invention and poly(m-phenylene isophthalamide)(MPD-I) is the preferred meta-aramid.
The aramid fiber of this invention can be floe or pulp. Aramid floe is made by cutting long aramid fibers, such as those prepared by processes described in U.S. Patent Nos. 3,063,966, 3,133,138, 3,767,756, and 3,869,430.
The aramid pulp is made by refining floe or can be made directly from ingredients as was taught in U.S. Patent No. 5,202,184. By "pulp" is meant particles of aramid material having a stalk and fibrils extending therefrom wherein the stalk is generally columnar and about 10 to 50 microns in diameter and the fibrils are hair-like members only a fraction of a micron or a few microns in diameter attached to the stalk and about 10 to 100 microns long. In paper manufacture, the fibrils on pulp are important to act as hooks or fasteners to hold adjacent particles in the paper and provide integrity to the paper construction.
Paper can also be made using a combination of aramid floe and aramid fibrids wherein the fibrids serve to hold together the floe and other paper components.
Aramid fibrids are sometimes used as binder materials for the purpose of this invention. Fibrids are not fibers. The term "aramid fibrids" refers to non-granular film like particles of aromatic polyamide having a melting point or decomposition point above 320°C. The fibrids have an average length of 0.2 to 1 mm with a length-to-width aspect ratio of 5:1 to 10:1. The thickness dimension is on the order of a fraction of a micron. Such aramid fibrids, before being dried, can be used wet and can be deposited as a binder physically entwined about the aramid floe component of

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a paper. The fibrids in paper of this invention can be prepared using a fibridating apparatus of the type disclosed in U.S. Patent No. 3,018,091 where a polymer solution is precipitated and sheared in a single step.
Although the length of pulp particles is a direct consequence of the length of the starting floe, pulp and floe generally have a length of about 0.15 to 10 millimeters. Surface area is an important characteristic of pulp to be used in this invention because the surface area is a measure of the degree of fibrillation and influences the porosity of the paper and the effective area available for interfiber bonding. The surface area of pulp used herein is 0.5 to 20 square meters per gram, and the surface area for floe is 0.08 to 0.6 square meters per gram. Because floe lacks the fibrillation of pulp, paper made with floe often, also, has a binder such as fibrids, among the paper components.
The Canadian Standard Freeness of the pulp as measured per TAPPI test T 227 om-92, which is a measure of its drainage characteristics, varies from 100 ml to 800 ml. Also, the % retained on the 14 mesh screen of a Clark Classifier as per TAPPI test T 233 cm-82, is used as a measure of length for fibers. That amount is to 0 to 15% for pulp used in this invention.
Chitosan is an aminopolysaccharide usually prepared by deacetylation of chitin (poly-beta(1,4)-N-acetyl-D-glucosamine) obtained from marine organisms (shrimp, crabs, lobsters, squid, and the like). The degree of deacetylation is generally reported as a percentage of the amine groups that are deacetylated and is generally greater than 50 percent. The molecular weight of chitosan is a function of its source and processing history. A measure of the molecular weight is obtained through measurement of intrinsic viscosity in 0.3 M acetic acid with 0.2 M sodium acetate or by measuring the viscosity of a one percent solution of chitosan in 1 percent acetic acid

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at 25°C. The viscosity of chitosan used in this invention varies from 10 mPa-sec to 22,000 mPa-sec and the intrinsic viscosity varies from 4 to 20 dl/g. The chitosan can be used as a solution in acids, such as acetic, lactic and citric acids, or can be used in the form of salts with these acids, such as acetate, lactate and citrate.
The process of this invention involves coating aramid fibers with chitosan either in a separate process or as a part of a paper-making process. As a separate process, chitosan is dissolved in water in the form of acetate, citrate, lactate, hydrochloride, and the like at a pH on the acid side preferably 2.5 -4.5 or slightly higher at a concentration of about 1 to 10 weight percent, based on weight of the aramid fibers, are dispersed therein. The pH of the dispersion is. then increased to 6.5 to 11 by addition of a base. The preferred base is sodium hydroxide but any appropriate base can be used. Raising the pH causes the chitosan to precipitate onto the aramid fibers -- thus coating them. If desired, for any reason, the chitosan can be dissolved in water which already has the aramid fibers dispersed therein; -- the order of addition making no difference in preparation of the coated aramid fiber product.
As was previously stated, aramid pulp is aramid floe which has been refined to, produce fibrils. The process of this invention can also be practiced by establishing a dispersion of aramid floe in a chitosan solution; and refining the floe to pulp in that solution before increasing the pH, removing the water, and recovering a chitosan-coated aramid pulp product.
As a part of a paper-making process, a dispersion, or paper furnish, including aramid fibers coated at a concentration of 1 to 10 weight percent chitosan, based on weight of dry aramid fibers, is poured onto a paper-making screen, water of the furnish is removed from the fibers, and the fibers are dried to
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yield a paper. The paper is usually 5 to 95 percent aramid fibers, based on the weight of the paper and the aramid fibers are usually aramid pulp already coated with chitosan. Although not preferred, the invention can be practiced by adding chitosan to a paper furnish which includes aramid fibers, and then coating the fibers with chitosan by increasing the pH of the furnish to 6.5 - 11 to precipitate the chitosan. In this embodiment, chitosan is added in an amount which, on precipitation, will result in a coating, on the aramid fibers, of I to 10 percent, based on the weight of the fibers.
It has been found to be a good practice to increase the pH of the furnish to 6,5 to 11 whether the aramid fibers are coated with chitosan in the furnish or before being added to the furnish.
The coated aramid fibers of this invention find use, among other uses, in friction paper. Friction paper is paper which is used in power transmission clutch facings and transmission bands to provide smoother engagements, better cooling efficiency and overall improvement in transmission performance. Friction papers of this invention generally include reinforcing fibers in the form of pulp or floe, binders, and fillers. The friction papers are usually impregnated with resins, such as phenolic or silicone resins or combinations thereof to make clutch facings. The friction papers generally have about 5 to 95%, by weight, pulp or floe, 15 to 85% filler and 0 to 10% binders, with 0 to 3 0% other components. The pulp or floe is the coated aramid fiber of this invention. The fillers can be inorganic materials such as diatomaceous earth, talc, carbon, and the like. The other components can include other fibers, such as glass fibers, or ceramic fibers, and the like.
The paper of this indention includes 1 to 10 percent, by weight, chitosan. The chitosan increases the friction coefficient of the paper of this invention
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by a surprising amount as compared with similar friction papers having no chitosan; and the chitosan significantly enhances the strength of the paper. It is the chitosan on the fibers and in the paper of this invention which is considered to impart patentability.
TEST METHODS
Friction Testing Procedure
Sheets were tested for sliding friction coefficient using a Kayness friction tester made by Kayness, Inc., Morganstown PA 19543. The usual testing force was increased from 200 grams to 1456 grams by adding additional weight to increase the sensitivity of the measurement. Care was exercised to ensure that the stainless steel table was clean for each measurement and the sample surface and stainless table top were not contaminated. The samples for testing were cut using a 6.3 centimeters by 11.4 centimeters template with a "V" notch as recommended in the Kayness friction testing procedure. Each sample was wrapped around the bottom of the rectangular testing weight and taped securely. The weight was positioned at the same spot on the stainless; table for each test. The force gage was set to zero for each test run and the machine was adjusted to a linear speed 15.2 ± 0.2 centimeters per minute. For each test, the weight was allowed to slide approximately 14 centimeters before the machine was stopped and the frictional force on the gage was noted. For each sheet, four samples were tested unless otherwise noted in the Tables. For each sample, five frictionai force readings were taken. Friction coefficient is the ratio of the frictional force and the normal force. The normal force is equal to the weight. The sliding friction coefficient was calculated by dividing the frictional force by 1456. The twenty coefficients thus obtained were averaged and the standard deviation calculated and reported in the
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Tables. The laboratory temperature during those tests was about 23°C.
Procedure for Determination of Chitosan in Paper
The amount of chitosan left on paper samples was determined by the following procedure. One gram of a dry paper sample was weighed to the nearest 0.0001 g. The sample was then cut into small pieces and placed in a 500 ml beaker with 250 ml of 1% acetic acid. The contents of the beaker were heated while stirring to 55-60°C for 60 minutes. The beaker and its contents were then cooled in an ice bath to less than 3 0°C. The beaker contents were then filtered and the filtrate was evaporated to dryness in a tared container in a vacuum oven at 130°C and the residue was further dried by placing the container in a forced air oven for 30 minutes at 130°C. The container and the residue was placed in a dessicator to cool and was then weighed. As a blank, 250 ml of 1% acetic acid with no paper sample was run using the procedure above. The residue weight was calculated as follows:
Residue Weight = Weight of (Container + Residue) -Weight of Container - Weight of 1% acetic acid blank The percent chitosan was determined as follows:
% Chitosan = (Residue Weight/l.37)/Sample Weight The factor 1.37 was used to account for the difference between chitosan and chitosan acetate and is the ratio of the molecular weight of chitosan acetate to chitosan.
EXAMPLE 1
Papers for friction testing were prepared by the following procedure, using a 20 centimeter by 20 centimeter laboratory handsheet mold. Each handsheet was prepared with 85% by weight of para-aramid floe with a linear density of 2.0 dtex and a length of about

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6,4 millimeters and 15% by weight of a refined meta-aramid fibrid binder. The para-aramid floe was a poly(p-phenylene terephthalamide) fiber product sold by E, 1, du Pont de Nemours and Company under the tradename KEVLAR(r)49. The meta-aramid fibrids were made from poly(meta-phenylene isophthalamide) as described in U.S. Patent No. 3,756,908 and had a Kajaani FS100 Numerical Average length of 0.4 9 mm and a freeness of 341 ml. In addition, various amounts of chitosan were added to the paper furnish to generate the papers identified in Tables I and II. Papers in Table I were produced using a high molecular weight chitosan and those in Table II were produced using a low molecular weight chitosan. The high molecular weight chitosan was supplied by DCV Chitin Technologies L.P. under the tradenarae VNS-618 as a one weight percent chitosan in aqueous solution with one weight percent acetic acid and having a one percent solution viscosity at 25°C, of 11,400 mPa-sec, an intrinsic viscosity of about 12.5 d1/g, and an 85.7 percent degree of deacetylation. The low molecular weight chitosan was supplied by DCV Chitin Technologies L.P, under the tradename VNS-589 as three weight percent chitosan in aqueous solution with three weight percent acetic acid and having a one percent viscosity, at 25°C, of 14 mPa-sec and a 78.9 percent degree of deacetylation.
For each sheet, 1000 ml of water was poured into a British Pulp Evaluation Apparatus (BPEA) and 0.4389 gram on dry basis, of the aforementioned polymetaphenylene-isophthalamide (MPDI) fibrids was added as a 0,3% aqueous slurry. 2.4871 grams on dry basis, of about 6mm long, 12 micron diameter, polyparaphenylene terephthalamide floe was added to this mix along with the appropriate amount of chitosan. An additional 1000 ml of water was added to the BPEA. The dispersion was thoroughly agitated for 5 minutes. The handsheet mold was filled with 8000 ml of water and the dispersion was poured into the moid. A vacuum was applied to the mold to remove water and form

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the sheet. Each sheet was taken out of the mold, blotted and dried at 190°C. The sheets were then pressed in a flat press at 446°C and 285 Knewtons for one minute.
Basis weight and thickness measurements were then made on. each sheet and the sheets were used for friction testing as shown below.
TABLE I

%
Chitosan
Added
%
Chitosan
on Paper
Basis Wt.
(g/m2}*
Density (g/cc)
Mean
Friction
Coefficient Stdev.
0
0
67.5
0.305
0.164
0.002
1
0.71
S9.2
0.306
0.165
0.602
2
1.38
68.2
0.286
0.167
0.002
4
2.00
69.2
0.301
0.172
0.002
6
3.01
72.9
0.315
0.178
0.002
TABLE II

%
Chitosan. Added
%
Chitosan
Basis Wt.
(g/m2)
Density (g/cc)
Mean
Friction Coefficient
Stdey.
0*
0
65.1
0.262
0.165
0.002
1
1.21
66.2
0.260
0.174
0-002
2
1.73
66 . 8
0.254
0.172
0.002
4
1.73
66.1
0.266
0.173
0.004
€**
3.52
66.8
0.263
0.173
0.003
* Only ten friction readings were taken with this
paper. ** Only fifteen friction readings were taken with
this paper.
Examples 2, 3 and 4 below show the effect on paper strength of pulp coated with various levels of chitosan to friction papers containing different amounts of pulp.
For each sheet, PPD-T pulp and 0.393 gms of cotton 1 inters {purchased from Alpha Cellulose Corporation) on a dry basis was added to approximately

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1500 ml of water and mixed in a British Pulp Evaluation Apparatus (BPEA) for 5 minutes. The PPD-T pulp had a Kajaani FS-200 length weighted average length of about 0.61mm, an arithmetic average length of about 0.18 mm, and a weight weighted average length of about 1.48 mm. For purposes of establishing the preferred average length for practice of this invention, the length weighted average length is used. The chitosan coated pulps were prepared, by adding the required amount of chitosan as a 1% solution in a one percent acetic acid in water to the pulp dispersed in water using a BPEA and was then neutralized to a pH above 8.0. The chitosan used here was the same high molecular weight chitosan (VNS618) used in Example 1, The amount of chitosan was calculated based on the weight percent of pulp on a dry basis. The appropriate amount of activated carbon and diatomaceous earth based on weight percent dry basis of paper were added and mixed for 5 minutes. The pH of the mixture at this stage was between 9 and 10 for all papers. 0.098 g of nitrile latex was added to the mixture while it was being stirred and 11 gms of a 6% solution of alum in water were added to precipitate the latex onto the furnish ingredients. The pH of the furnish was between 5 and 6 in all cases. Approximately 10 g of a Bubond 65 cationic retention aid (purchased from Buckman Laboratories) was added as 0.44% solution. The furnish was poured into an approximately 20 x 20 centimeter handsheet mold filled with 8000 ml of water. A vacuum was applied to the mold to remove water and form the sheet. Each sheet was taken out of the moid, blotted and couched with a roller and dried at about 120°C. Basis weight and thickness measurements were made on each sheet and the tensile strength measured in an Instron tensile tester at a gage length of about 5 cm with a strip width of about 2.5 cm.
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EXAMPLE 2
(4 5% pulp papers)
Amount
Ingredient % Dry Basis g Dry Basis
Pulp 45 4.16
Activated Carbon 35 3.435
Diatomaceous Earth 15 1.472
Cotton Linters 4 0.393
Nitrile Latex 1 0.098
% Basis Tensile
Chitosan Weight Thickness Strength T.S./
on Pulp (g/ (m2) (mm) . Density (kg/cm2) Density
0 219 0.778 0.282 6 .75 23.96
2 , 235 0.882 0.266 8.72 32.72
4 218 0.778 0.280 11.74 41.94
6 230 0.896 0.257 9.98 38.92
EXAMPLE 3
{33% Pulp Papers)
Amount
Inaredient % Dry Rasis g Dry Basis
Pulp 33 3.238
Activated Carbon 47 4.612
Diatomaceous Earth 14 1.472
Cotton Linters 4 0.392
Nitrile Latex 1 0.098
% Basis Tensile
Chitosan Weight Thickness Strength T.S./
on Pulp (g/m2) (mm) Density (kg/cm2) Density
0 218 0.746 0.292 4.50 15.39
2 209 0.746 0.279 6.75 24.21
4 219 0.755 0.290 6.82 23.50
6 222 0.819 0.272 6.96 25.60
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EXAMPLE 4

(20% Pulp Papers) Ingredient
% Dry Rasis
Amount a Dry Basis
Pulp
20
1.963
Activated Carbon
60
5.888
Diatomaceous Earth
15
1.472
Cotton Linters
4
0.393
Nitrile Latex
1
0. 098
% Basis Chitosan Weight on Pulp (g/ (m2.)
Thickness (mm) Density
Tensile Strength T.S./ (kg/cm2) Density
0 210
0.636 0.330
3.52 10.64
2 205
0.645 0.318
3.80 11.93
4 188
0.596 0.316
4.92 15.60
6 202
0.641 0.316
5.41 17.15

EXAMPLE 5

For each sheet, PPD-T pulp, as was used in the previous examples, and 0.88 g of cotton linters were added to approximately 1500 ml of water, mixed in a Waring Elendor for 5 minutes, and transferred to a BPEA. Chitosan coated pulps were prepared by adding the required amount of chitosan as a 1% solution in one percent acetic acid in water to the pulp dispersion in a vessel and then neutralizing the dispersion to a pH of about 10 or above. The chitosan used here was the same high molecular weight chitosan (VNS618) used in Example l. The amount of chitosan was calculated based on the weight of pulp on a dry basis. The appropriate amount of activated carbon and diatomaceous earth, based on dry weight basis of paper, were added and mixed for 5 minutes. 0.44 g of nitrile latex was added to the mixture while it was being stirred and 25 g of a 5% solution of alum in water were added to precipitate the latex onto the furnish ingredients. Approximately 25 g of Bubond 65 cationic retention aid was added as a

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25% solution. The resulting furnish was poured into an approximately 30 x 30 centimeter handsheet mold. The handsheet mold was filled with approximately 34 liters of water and the furnish was poured into the mold. A vacuum was applied to the mold to remove water and form the sheet. Each sheet was taken out of the mold, couched and then pressed and dried at about 120°C. Thickness measurements were made on each sheet and the tensile strength measured in an Instron tensile tester at a gage length of about 12.7 cm with a strip width of about 2.5 cm. A control was run using the same procedure as set out above, but with no chitosan.

Ingredient
% Dry Basis

a Dry Basis
Pulp
33

7.28
Activated Carbon
46

10-14
Diatomaceous Earth Cotton Linters
15 4

3.31
0.88
Nitrile Latex
2

0.44
% Chitosan on Pulp
Thickness (mm)
Tensile Strength (kg/cm2)
T.S./ T.s. at 0%
0%
0.761
3.02
1
0.1
0.696
4.08
1.35
0.5
0.759
7.31
2.42
1.0
0.716
7.45
2.47
5.0
0.756
7.52
2.49

EXAMPLE 6


These papers were made in a fashion similar to that of Example 5 but the pulp used here was longer, had a Canadian Standard Freeness of 629 ml, and a surface area of 4.36 m2/g with a 14 mesh Clark retention of 10.0%. The pulp had a Kajaani FS-200 length weighted average length of about 1.03 mm, an arithmetic average length of about 0.20 mm, and a weight weighted average length of about 2.63 mm.

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33% Pulp Papers)

%
Chitosan
Basis Weight (g/(m2)
Thickness (mm)
Density
Tensile Strength
(kg/cm2)
T.S./
Density
0
201
0.691
0.291
3.52
12.10
0.1
207
0.728
0.285
5.89
20.68
0.5
174
0.627
0.277
6.27
22.60
1.0
193
0.717
0.268
5.23
19.47



EXAMPLE 7


These papers were the same composition as those in Example 5 made with the same pulp but had an additional 0.45% of latex added to the paper; and, in two cases, the chitosan was added directly to the furnish rather than coated on the pulp before adding the pulp to the furnish. These results indicate the chitosan coated on the pulp before the paper-making process is much more effective in improving strength.

Basis % Weight Chitosan (g/ (m2)
Thickness (mm)
Density
Tensile Strength (kg/cm2)
T.S./
Density
0 206
2% of pulp added Co furnish 229
3% of pulp added to furnish 22 6
1.5% on pulp (wet) 225
0.648 0.841
0.742 0.845
0.318 0.272
0.304 0.265
5.76 4.88
8.43 6.76
18.14 17.93
27.69
25.45
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EXAMPLE 8
These papers were prepared similar to Example 5, but with a composition as shown below. Also, the molecular weights of chitosan as indicated by the viscosity of 1% solution in 1% acetic acid were different. The 5700 cps chitosan was obtained from DCV Chitin Technologies L.P. as a lactate solution with a designation of RNS-049 and had an intrinsic viscosity of 9.5 dl/g.

Ingredient
% Dry Rasis

Amount
a Dry Basis

Pulp
Activated Carbon
33 47

3.238 4.612

Diatomacecus Earth
15

1.472

Cotton Linters
4

0.392

Nitrile Latex
1

0.098

Basis % Weight Chitonan (g/ (m2)
Thickness (mm)
Density
Tensile Strength (kg/cm2)
T.S./
Density
None 222 0.752 0.297 4.29 14-44
11,400 cps
(85.7%
DEA) 244 0.838 0.296 6.89 23.28
VNS-618
5700 cps
(83.2% DEA;
RNS-049 240 0.863 0.277 6.05 21.83
5700 cps
(83.2% DEA)
RNS-04 9 244 0.813 0.3 03 6.47 21.35
EXAMPLE 9
This example demonstrates the benefit of using fibers which have been coated with chitosan in accordance with this invention, rather than merely mixed with chitosan. In this example, 7.28 g of PPD-T pulp were dispersed in 1500 ml of water and the required amount of
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chitosan was added thereto as a 1% solution in one percent acetic acid in water. In one case indicated below, the pulp dispersion was neutralized to a pH of about 8 to precipitate the chitosan, and the water was evaporated from the dispersion to yield dry, chitosan-coated pulp.
In the other cases below, the water was evaporated from the dispersion of pulp and unneutralized chitosan to yield a dry mixture of pulp and chitosan.
Papers were made by the procedure of Example 5 using these pulp and chitosan components with results set out in the Table below:

Chitosan % on Pulp
Thickness (mm)
Density
Tensile
Strength
(kg/cm2)
T.S./
Density
2% Neutralized
0.927
0.351
7.49
21.35
to pH 8 and then dried




1% Dried
0. 953
0.335
5.80
17.31
2% Dried
0.940
0.356
5.38
15.11
3% Dried
0.978
0.347
5.86
16.90
19

WE CLAIM :
1. Chitosan coated aramid fibers comprising aramid fibers having a length of 0.15 to 10 millimeters, a surface area of 0.5 to 20 square meters per gram and a coating of chitosan in the amount of 1 to 10 percent, based on the weight of the fibers. 12. The fibers as claimed in claim 1, wherein chitosan has a 1% solution viscosity in 1% acetic acid of 10 to 22,000 mPa-sec.
3. The fibers as claimed in claim 1, wherein the fibers are aramid
floe.
4. The fibers as claimed in claim 1, wherein the fibers are aramid
pulp.
5. Chitosan coated aramid fibers substantially as herein described
with the help of foregoing examples.

[DR. RAMESH KUMAR MEHTA] OF REMFRY & SAGAR ATTORNEY FOR THE APPLICANTS
Dated this 24th day of December, 1997.
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A coated aramid fiber is disclosed wherein the coating is a small amount of chitosan and the coated fiber is useful in manufacture of an improved friction paper. An improved friction paper is, also, disclosed wherein chitosan is present throughout the paper as a coating on all components.


Documents:

02439-cal-1997-abstract.pdf

02439-cal-1997-claims.pdf

02439-cal-1997-correspondence.pdf

02439-cal-1997-description(complete).pdf

02439-cal-1997-form-1.pdf

02439-cal-1997-form-13.pdf

02439-cal-1997-form-2.pdf

02439-cal-1997-form-3.pdf

02439-cal-1997-form-5.pdf

02439-cal-1997-g.p.a.pdf

02439-cal-1997-priority document.pdf

2439-CAL-1997-(27-10-2011)-CORRESPONDENCE.pdf

2439-CAL-1997-(27-10-2011)-PA.pdf

2439-cal-1997-granted-abstract.pdf

2439-cal-1997-granted-claims.pdf

2439-cal-1997-granted-correspondence.pdf

2439-cal-1997-granted-description (complete).pdf

2439-cal-1997-granted-examination report.pdf

2439-cal-1997-granted-form 1.pdf

2439-cal-1997-granted-form 13.pdf

2439-cal-1997-granted-form 2.pdf

2439-cal-1997-granted-form 3.pdf

2439-cal-1997-granted-form 5.pdf

2439-cal-1997-granted-gpa.pdf

2439-cal-1997-granted-letter patent.pdf

2439-cal-1997-granted-others.pdf

2439-cal-1997-granted-reply to examination report.pdf

2439-cal-1997-granted-specification.pdf

2439-cal-1997-granted-translated copy of priority document.pdf


Patent Number 195454
Indian Patent Application Number 2439/CAL/1997
PG Journal Number 30/2009
Publication Date 24-Jul-2009
Grant Date 11-Nov-2005
Date of Filing 24-Dec-1997
Name of Patentee E. I. DU PONT DE NEMOURS AND COMPANY
Applicant Address 1007 MARKET STREET, WILMINGTON, DELAWARE
Inventors:
# Inventor's Name Inventor's Address
1 SESHADRI RAMACHANDRAN 1209 BENBROOKE COURT, N.W. ACWORTH, GEORGIA 30101
PCT International Classification Number D06M 15/07
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 08/781,331 1997-01-10 U.S.A.