U.S. patent number 3,739,782 [Application Number 05/194,748] was granted by the patent office on 1973-06-19 for absorbent fibers of phosphorylated cellulose with ion exchange properties and catamenial tampons made therefrom.
This patent grant is currently assigned to Kimberly-Clark Corporation. Invention is credited to Leo J. Bernardin.
United States Patent |
3,739,782 |
Bernardin |
June 19, 1973 |
ABSORBENT FIBERS OF PHOSPHORYLATED CELLULOSE WITH ION EXCHANGE
PROPERTIES AND CATAMENIAL TAMPONS MADE THEREFROM
Abstract
Absorbent dressings, such as tampons, made from highly absorbent
cellulose fibers with ion exchange properties. These fibers are
obtained by phosphorylating cellulose fibers, hydrolyzing the fiber
walls with acid, converting the phosphorylated fibers to the sodium
salt form, mechanically refining these fibers to rupture the
primary fiber wall and permit subsequent swelling or ballooning,
acidifying the refined fibers to reconvert the phosphorylated
cellulose into the acid form, and drying the fibers in a manner to
substantially avoid appreciable hydrogen bonding.
Inventors: |
Bernardin; Leo J. (Appleton,
WI) |
Assignee: |
Kimberly-Clark Corporation
(Neenah, WI)
|
Family
ID: |
26711513 |
Appl.
No.: |
05/194,748 |
Filed: |
November 1, 1971 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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34878 |
May 5, 1970 |
3691154 |
|
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Current U.S.
Class: |
604/375; 536/62;
8/195; 604/904 |
Current CPC
Class: |
A61F
13/2051 (20130101); Y10S 604/904 (20130101) |
Current International
Class: |
A61F
13/20 (20060101); A61f 013/20 () |
Field of
Search: |
;128/284,285,290,296
;260/212,219 ;8/116 ;162/157 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Rosenbaum; Charles F.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a division of copending application Ser. No.
34,878 filed May 5, 1970 and now U.S. Pat. No. 3,691,154. A related
application is copending application of Leo J. Bernardin, Ser. No.
30,811, filed April 22, 1970 and now U.S. Pat. No. 3,658,790.
Claims
What is claimed is:
1. An improved absorbent dressing for absorbing and simultaneously
acidifying body fluids in contact therewith, comprising a fibrous
mat of phosphorylated cellulose fibers in acid form, said fibers
being characterized by a structure in which a major portion of the
primary wall of each of said fibers is broken away leaving the main
internal body of each of said fibers substantially unconfined by
said primary wall, said internal body structure being in a swelled
and ballooned condition, whereby said fiber mat provides improved
capacity for absorbing aqueous fluids.
2. The dressing of claim 1 in which said mat is in the form of a
tampon suitable for internal deployment in body cavities.
3. The dressing of claim 1 in which said mat has other absorbent
fibers admixed therewith.
Description
BACKGROUND OF THE INVENTION
It is well know that the normal healthy vagina is acidic, having a
pH in the neighborhood of about 3.8 to 4.5. At that pH, numerous
species of micro-organisms are present which play a beneficial role
in providing protection and resistance to infection. During
menstruation, however, a slightly alkaline pH is frequently
established. Under such conditions growth of favorable microflora
is inhibited while undesirable types thrive. This causes the vagina
to be more susceptible to infection and inflammation during
menses.
Various attempts have been made to control this condition by
providing catamenial devices which act to lower the alkaline pH
during menstruation to the desired pH of 4.5 or less while
simultaneously absorbing discharged menstrual fluids. One of these
may be found in U.S. Pat. No. 3,091,241 to Kellett which employs
glyceryl triacetate in an absorbent tampon as a physiological
biostat or automatic pH controller.
In another U.S. Pat. No. 3,187,747 to Burgeni et al., catamenial
tampons are made from multicomponent alloy fibers in which one of
the components is absorbent, such as regenerated cellulose, while
the other is an acidifying polymer, such as carboxymethyl cellulose
in hydrogen form.
In each of the above patents, the tampon structure required at
least two components, one performing the necessary absorbency
function, while the other acts as the pH controller.
The present invention is directed to a cellulose fiber product
which combines the pH control and the absorbency function in one
fiber, without requiring chemical adjuvants or alloys.
In the copending Bernardin application, referenced above,
phosphorylated cellulose fibers in sodium salt form were found to
have a markedly increased absorbency over unmodified cellulose. The
product was obtained by chemically substituting phosphate groups
for hydroxyls on the cellulose, hydrolyzing the fiber walls with
acid, then converting the substituted and hydrolyzed fibers to the
salt form by ion exchange, and solvent drying or otherwise drying
the fibers in a manner to substantially avoid appreciable hydrogen
bonding. It was found that the phosphorylated fibers in their acid
form, before conversion to salt form, and whether solvent dried or
not, showed no improvement in absorbency over unmodified cellulose,
while the salt form was found to be up to 5 times as absorbent.
These results appeared to confirm the belief, at that time, that in
order for substituted celluloses to have a sufficient increase in
absorbency to warrant commercial use, it was necessary for the
cellulose to be in an alkaline salt form. Prior art developments
involving carboxymethyl cellulose having particular degrees of
substitution also supported this belief.
However, as work continued it was found that even greater
absorbency could be developed in the phosphorylated cellulose in
salt form if the fibers were refined for at least one minute before
drying. Such refining increased absorbent properties almost
threefold over the unrefined fibers. It was then found, rather
unexpectedly, that if these refined fibers were reconverted to the
acid form, they retained much of the increased absorbency developed
by refining and exhibited by the salt form fibers. This finding
seemed to contradict the earlier conclusion that the acid form of
phosphorylated cellulose shows no increase in absorbency over
unmodified pulp. This unexpected result immediately opened up a
number of possibilities for use of the product in areas where
absorbency and ion exchange complement one another.
SUMMARY OF THE INVENTION
Phosphorylated fibers in acid form with improved absorbency
characteristics combined with high ion exchange capacity are
produced by first saturating cellulose pulp sheets in a
phosphorylating bath; drying and reacting the saturated sheets at
elevated temperature; dispersing the reacted sheets in water, which
preferably is deionized, and washing the reactant therefrom;
converting the washed phosphorylated fibers to the acid form by
treatment with acid; converting the acidified fibers to sodium salt
form; mechanically refining the fibers in aqueous dispersion;
reconverting the refined fibers to acid form; and finally drying
the fibers in a manner to substantially avoid appreciable hydrogen
bonding of the fibers to each other during the water removal
process. When formed into mats the resulting fibers exhibit high
ion exchange capacity and much higher capillary suction pressure
and absorbent capacity than unmodified cellulose fibers.
These fibers are markedly superior in absorbent capacity to
phosphorylated fibers in the acid form which have not been refined.
They are also superior in absorbency to fibers which have been
refined while in acid form. Accordingly, in order to obtain this
improved absorbency in the acid-form fibers of this invention, it
is necessary to first refine the fibers in salt form and then
reconvert the refined fibers to acid form.
The preferred method of phosphorylating is the urea phosphate
method, wherein the fibers are reacted at a temperature of from
about 130.degree. to 195.degree.C for about 5 to over 30 minutes in
a solution of urea and phosphoric acid. Other known but less
satisfactory methods of phosphorylation may be used including
treatment with phosphorous oxychloride and pyridine; phosphorous
oxychloride and phosphoric acid; phosphorous oxychloride and
dioxane; phosphorous oxychloride alone, and alkali metal salts of
phosphoric acid.
When converting the washed phosphorylated fibers to acid form
immediately after phosphorylation, cold acid may be used, but it is
preferred to use hot acid because the latter more readily
hydrolyzes the fiber walls which is highly desirable in developing
the improved capillary suction pressures described herein.
In converting the phosphorylated fibers to salt form the alkali
preferably employed is a dilute solution of sodium hydroxide.
However, other solutions of basic salts such as sodium carbonates,
phosphates and the like may be used.
In order to dry the fibers in a manner to avoid hydrogen bonding,
conventional solvents such as acetone, alcohol, alcohol followed by
hexane, and the like may be used.
Freeze drying may also be used since such a drying method also
substantially avoids hydrogen bonding.
It is the primary object of this invention to provide chemically
modified cellulose fibers which in their acid form have markedly
improved fluid absorbency characteristics.
Another object is to provide absorbent pads from fibers which have
high absorbency combined with high ion exchange capacity.
Other features, objects and advantages of the invention will become
apparent by reference to the following specification.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In a preferred embodiment, four sheets of unbeaten, bleached,
northern softwood, kraft pulp weighing about 14 grams each were
immersed for about 30 minutes in a bath consisting of 50 percent
urea, 18 percent orthophosphoric acid, and 32 percent water by
weight. The saturated pulp sheets were drained to a consistency of
1 part fiber to 3 parts by weight of solution. The moist sheets
were dried and reacted or cured in an oven for 20 minutes at
160.degree.C. The cured sheets were dispersed in deionized water
and the resulting slurry washed free of the treating solution by
several rinses with deionized water using a suction filter.
The filtered material which is believed to be comprised of
cellulose monoammonium monohydrogen phosphate was dispersed in a 3
percent solution of hot hydrochloric acid and soaked at a
temperature of between 60.degree. and 70.degree.C for one-half
hour. The acid form of phosphorylated fiber thus obtained was
washed free of excess acid and separated into two portions. One
portion was refined in a conventional PFI laboratory refiner for 2
1/4 minutes at 10 percent consistency and solvent dried from
acetone, the other portion was converted to salt form by soaking in
a 5 percent solution of Na.sub.2 CO.sub.3 for one-half hour. The
fiber was washed again and then refined at 10 percent consistency
in a conventional PFI laboratory refiner for 2 1/4 minutes. The
refined pulp was reconverted to acid form, i.e., a pH of 3, with
hydrochloric acid, washed free of excess acid, and then solvent
dried from acetone.
Absorbency characteristics in terms of capillary suction pressure
of the two kinds of phosphorylated cellulose in acid form obtained
by the above described process were then compared to each other and
to an unmodified cellulose which was also refined for 2 1/4 minutes
and solvent dried.
Results were as follows:
WATER CONTENT IN GRAMS OF H.sub.2 O PER GRAM OF FIBER
Phosphorylated Pulp in Acid Form Capillary Unmodified Refined
Refined Suction Pulp in in Pressure Refined Unrefined Acid Salt
Form Form (In Cm of H.sub.2 O) 60 1.1 0.8 2.0 5.9 40 2.1 1.8 2.8
7.1 25 3.5 3.5 3.8 8.7 15 5.8 6.0 7.1 10.4 10 8.5 7.8 8.0 11.5 5
11.0 9.3 10.4 14.0 13.0 11.0 11.7 17.0
absorption of liquid water as a function of capillary suction
pressure on airlaid mats of fiber is measured by means of a known
capillary tension cell apparatus of the type described in an
article from the Textile Research Journal, Vol. 37, No. 5, May,
1967, pp. 356-366, A. A. Burgeni and C. Kapur, "Capillary Sorption
Equilibria in Fiber Masses." Absorption capabilities for a fiber
mass are cited in the number of grams of water per gram of fiber
which a mat of fibers will absorb under the specified capillary
suction head or pressure indicated.
The results indicate that when phosphorylated pulp is merely
converted to acid form and then refined, it shows no measurable
improvement over unmodified pulp.
The results also show very clearly that when the phosphorylated
pulp is refined in its salt form before converting back to acid
form there is a dramatic increase in its absorbent properties.
It became apparent that the refining of the fibers in salt form and
converting to acid form has a different effect on the fibers than
when they are originally refined while in acid form.
Microscopic examination of the fibers, before and after refining,
indicated that, before refining, the fibers of the phosphorylated
pulp in acid form look very much like ordinary wood pulp fibers
when wet with the fiber walls substantially intact, while the walls
of the phosphorylated pulp in salt form showed signs of rupture of
fraying with some ballooning of the internal structure in a number
of places. Refined unmodified pulp and phosphorylated pulp in acid
form also appeared quite similar, showing some fraying of the fiber
wall, but little ballooning or swelling. The refined phosphorylated
fibers in salt form, on the other hand, exhibited considerable
ballooning and swelling, as the internal structure expanded down
the length of the fiber with only a few confining rings appearing
where the primary fiber wall remained unruptured and intact. The
ballooned and swelled form of the main internal body of the fiber
structure was retained when these fibers in salt form were
converted back to acid form.
Refining phosphorylated fibers in the salt form prior to
reconversion to the acid form is therefore considered to be a
necessary step in the preparation of the highly absorbent fibers in
the acid form of this invention. Without such refining the acid
form of phosphorylated fibers show no improvement in absorbency. In
structure therefore, the acid form of phosphorylated fibers must be
substantially stripped or denuded of the primary fiber wall in
order to obtain the demonstrated improvement in absorbency.
In considering this improved acid form of phosphorylated cellulose
fiber for tampon useage it was also determined that ion exchange
capacity is significant. Accordingly, ion exchange capacity was
tested by potentiometric titration with 0.1N sodium hydroxide. As
indicated in the Burgeni et al. U.S. Pat. No. 3,187,747, the
acidifying capacity of a tampon in vivo can be approximated in
terms of the volume of 0.1N sodium hydroxide consumed by the fibers
in an environment of 0.8 percent NaCl solution at pH values up to
about 4.5. It is also indicated that in distilled water, less
sodium hydroxide would be required for equivalent capacity because
NaCl tends to aid in the liberation of hydrogen ions. Accordingly
the ion exchange capacity exhibited under actual use would be
higher than the capacity indicated by titration in distilled
water.
A number of samples of the acid form of phosphorylated cellulose
fibers refined in salt form as described above were titrated in
distilled water with 0.1N NaOH to determine ion exchange
capacities. One gram of fiber was found to consume about 12.5 ml of
0.1N sodium hydroxide in reaching a pH of about 4.5. Accordingly a
normal tampon weight of about 3 grams would have adequate capacity
for maintaining an acid pH in the vagina under even the most severe
conditions of use. Since such a tampon acts to maintain the
menstrual fluids at an acid pH, the surrounding skin surface is
also maintained slightly acid whereby the environment for the
useful microflora stays favorable.
In view of this high ion exchange capacity it is not necessary to
make the entire absorption device of the phosphorylated fibers of
this invention. They may be admixed with ordinary wood pulp fibers,
with phosphorylated fibers in salt form, with other absorptive
fibers, or with resilient fibers as set forth in the prior art to
provide better expansion properties when used in compressed
form.
While the improved pulp fibers are indicated as being of particular
use in catamenial tampons, they may also be employed where the dual
characteristics of high absorbency and high ion exchange capacity
are required.
The invention is particularly applicable to fibers converted from
wood pulp because of their low cost and ready availability.
However, other fibers normal to the papermaking art may also be
employed such as hemp, jute, esparto, cereal straws, flax, bagasse,
bamboo, reeds, cotton linters, kenaf and the like.
* * * * *