U.S. patent number 3,589,364 [Application Number 04/767,035] was granted by the patent office on 1971-06-29 for bibulous cellulosic fibers.
This patent grant is currently assigned to The Buckeye Cellulose Corporation. Invention is credited to Walter Lee Dean, George Nathan Ferguson.
United States Patent |
3,589,364 |
Dean , et al. |
June 29, 1971 |
BIBULOUS CELLULOSIC FIBERS
Abstract
Bibulous cellulosic fibers for use in fibrous structures having
an inherently absorptive function, for example surgical dressings,
surgical sponges filters, catamenial napkins, tampons and diapers,
which bibulous cellulosic fibers, and fibrous structures containing
said bibulous fibers in effective amounts, are characterized by
greatly improved absorbency for and retention of aqueous solutions,
including physiological solutions. The bibulous cellulosic fibers
are substantially water-insoluble, wet cross-linked fibrous salts
of carboxymethyl cellulose having a sufficiently high degree of
carboxymethyl substitution to insure water solubility in the
absence of cross-linking. The bibulous cellulosic fibers are
produced under conditions which preserve the fibrous form of the
cellulose fiber raw material.
Inventors: |
Dean; Walter Lee (Memphis,
TN), Ferguson; George Nathan (Memphis, TN) |
Assignee: |
The Buckeye Cellulose
Corporation (Cincinnati, OH)
|
Family
ID: |
27108945 |
Appl.
No.: |
04/767,035 |
Filed: |
September 13, 1968 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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713143 |
Apr 14, 1968 |
|
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|
Current U.S.
Class: |
604/368; 162/146;
604/375; 604/381; 604/904; 427/180; 604/376 |
Current CPC
Class: |
A61L
15/28 (20130101); D06M 15/07 (20130101); C08B
11/12 (20130101); C08B 15/10 (20130101); D06M
13/11 (20130101); D06M 13/21 (20130101); C08B
11/04 (20130101); A61L 15/28 (20130101); C08L
1/26 (20130101); Y10S 604/904 (20130101) |
Current International
Class: |
A61L
15/28 (20060101); A61L 15/16 (20060101); C08B
11/00 (20060101); C08B 11/12 (20060101); C08B
15/10 (20060101); C08B 15/00 (20060101); C08B
11/04 (20060101); D06M 15/07 (20060101); D06M
13/21 (20060101); D06M 13/00 (20060101); D06M
13/11 (20060101); D06M 15/01 (20060101); A61f
013/16 () |
Field of
Search: |
;162/146,157
;8/116.2,129 ;128/155--156,284--285,287,290,296 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Rosenbaum; Charles F.
Parent Case Text
This application is a continuation-in-part of copending
application, Ser. No. 713,143, filed Mar. 14, 1968 now abandoned.
Claims
Having thus described the invention, what we claim is:
1. Substantially water-insoluble, wet cross-linked carboxymethyl
cellulose fibers, having a WRV of about 900 to about 3,400 and a
SRV of about 400 to about 1,500 and manifesting their native
cellulosic fiber structure, for use in fibrous structures for the
absorption and retention of aqueous solutions, which substantially
water-insoluble, wet cross-linked fibers of carboxymethyl cellulose
have a degree of substitution of about 0.4 to about 1.6.
2. Substantially water-insoluble, epichlorohydrin wet cross-linked
carboxymethyl cellulose fibers, having a WRV of about 900 to about
3,400 and a SRV of about 400 to about 1,500 and manifesting their
native cellulosic fiber structure, for use in fibrous structures
for the absorption of aqueous solutions, which substantially
water-insoluble, epichlorohydrin wet cross-linked fibers of
carboxymethyl cellulose have a degree of substitution of about 0.4
to about 1.6.
3. An absorbent fibrous structure, comprising a preformed absorbent
pad, containing in effective amount the substantially
water-insoluble carboxymethyl cellulose fibers of claim 2.
4. The absorbent fibrous structure of claim 3 which is a surgical
dressing.
5. The absorbent fibrous structure of claim 3 which is a catamenial
napkin.
6. The absorbent fibrous structure of claim 3 which is a
diaper.
7. The absorbent fibrous structure of claim 3 which is a
tampon.
8. The absorbent fibrous structure of claim 3 which is a filter for
removing undissolved water from substantially immiscible aqueous
systems comprised of water together with at least one
hydrocarbon.
9. Substantially water-insoluble, wet cross-linked sodium
carboxymethyl cellulose fibers, having a WRV of about 1,100 to
about 3,400 and a SRV of about 400 to about 1,500 and manifesting
their native cellulosic fiber structure, for use in fibrous
structures for the absorption of physiological solutions, which
substantially water-insoluble, wet cross-linked fibers of sodium
carboxymethyl cellulose have a degree of substitution of about 0.6
to about 1.2.
10. A tampon, comprising a preformed fibrous body compressed in
cylindrical form, containing in effective amount the substantially
water-insoluble, wet cross-linked sodium carboxymethyl cellulose
fibers of claim 9.
Description
BACKGROUND OF THE INVENTION
This invention relates to the production of bibulous cellulosic
fibers by chemically modifying cellulosic fibers to produce wet
cross-linked and etherified cellulosic fibers which are
substantially water-insoluble and manifest their original fibrous
structure. More particularly, the invention relates to the
provision of substantially water-insoluble, wet cross-linked
fibrous salts of carboxymethyl cellulose which display improved
absorbency and retention characteristics for aqueous solutions,
including physiological solutions, and impart these characteristics
to fibrous structures in which they are included.
Specifically, the invention, in one of its more important
embodiments, consists of wet cross-linked fibrous salts of
carboxymethyl cellulose which display their original cellulosic
fibrous form and have a sufficiently high degree of substitution
(DS) to be normally water-soluble, which fibrous salts of
carboxymethyl cellulose have been wet cross-linked to achieve
substantial water insolubility. Such substantially water-insoluble,
wet cross-linked carboxymethyl cellulose fibers, sometimes referred
to hereinafter as bibulous fibers for conciseness, are particularly
adapted by their unique intrafiber absorbency for and retention of
aqueous solutions for either use or admixture in effective amount
in fibrous structures, including surgical dressing, surgical
sponges, filters, catamenial napkins, tampons and diapers
containing in effective amount the substantially water-insoluble,
wet cross-linked carboxymethyl cellulose fibers of this invention.
The disclosed bibulous fibers also exhibit a particular and unique
absorbent affinity for dilute aqueous solutions of salts and other
physiological solutions. In addition, the disclosed bibulous fibers
exhibit the capability of absorbing and retaining virtually all of
the undissolved water from substantially immiscible aqueous systems
comprised of water together with at least one hydrocarbon such as
chloroform, gasoline, benzene, toluene, kerosene, xylene, pentane,
hexane, cyclohexane, and longer chain length saturated and
unsaturated hydrocarbons of this type.
Several papermaking techniques and fiber selections intended to
result in absorbent fibers, fibrous structures, waddings, nonwovens
and papers have been developed and used heretofore. For example,
the commercial grades of absorbent papers designated as blotting
papers, filter papers, paper towelings and sanitary tissues are, in
general, characterized by being produced in a soft, loosely felted
condition to maximize absorbency. Such absorbent papers are
generally unsized and are also often accorded a creping or other
mechanical treatment after drying to further enhance and increase
subjective softness and absorbency. The individual fibers from
which such absorbent papers are produced are carefully selected for
their contribution to the absorbency characteristics of such
papers. Such individual fibers can be and are selected from rag
fibers, high alpha wood and cotton linter fibers, ground wood
fibers and mixtures thereof, and minor amounts of other fibers, for
example crimped staple rayon fibers, can be incorporated to enhance
structure. Further, such selected fibers in a furnish for producing
absorbent papers are usually beaten lightly, if at all, to maximize
the absorbency characteristics of the resulting papers, wadding and
felted products.
Papermaking fibers, specifically cotton linter fibers and woodpulp
fibers, have further been cross-linked without etherification prior
to their inclusion in papermaking furnishes according to the
teaching of U.S. Pat. No. 3,069,311, issued to John A. Harpham and
Harry W. Turner on Dec. 18, 1962. Also, U.S. Pat. No. 3,241,553,
issued to Fred H. Steiger on Mar. 22, 1966, discloses the
cross-linking of cellulosic fibers, including cotton, wood pulp,
cotton linter and regenerated cellulosic fibers, while they are in
a wet swollen condition, to improve the fluid absorbency and fluid
retention characteristics of fibrous structures from such fibers
for body fluids. Cotton fabrics and fabrics woven of other
cellulosic fibers, for example rayon and cellulose acetate, have
also been accorded a measure of crease resistance by treatments
with both a polyfunctional agent for cross-linking, for example
epichlorohydrin and formaldehyde, and a monofunctional agent for
either of etherification or esterification, for example
monochloroacetic acid as disclosed in U.S. Pat. No. 2,971,815,
issued to Austin L. Bullock and John D. Guthrie on Feb. 14,
1961.
Applicants have found, however, that the absorbency and retention
characteristics of cellulosic fibers for aqueous solutions,
including physiological solutions, can be greatly improved, i.e.,
about three times to in excess of about 20 times improved, over
such characteristics of fibers produced according to teachings and
suggestions previously available in the art. Such large scale
improvements are generally realized, according to applicants'
present disclosure, by converting cellulosic fibers into fibrous
salts of carboxymethyl cellulose having a degree of substitution
(DS) sufficient to insure water solubility in the absence of
cross-linking. The carboxymethylation is accomplished either in an
organic liquid media slurry process or in a so-called "dough"
process which preserves the original fibrous form of the cellulose.
The resulting carboxymethylated cellulosic fibers are then wet
cross-linked to insure substantial water insolubility and retention
of fibrous form in use. Applicants point out, however, that the
order of performance of the carboxymethylation and wet
cross-linking steps, whereby the bibulous fibers are produced, is
not critical, and initial wet cross-linking followed by
carboxymethylation or simultaneous performance of the two steps of
carboxymethylation and wet cross-lining is within the purview of
the present invention.
SUMMARY OF THE INVENTION
Inasmuch as fibers having increased absorbency and retention
capacities for aqueous solutions, including physiological
solutions, were desired for use in various types of fibrous
structures, applicants further investigated their discovery that
certain wet cross-linked cellulose derivative fibers exhibited the
stated bibulous characteristics to an astonishingly high degree.
Applicants' investigation revealed that the unusually absorbent and
retentive fibers can be prepared by carboxymethylating native and
regenerated cellulosic fibers to a DS which normally assures water
solubility while preserving their initial fibrous form. The
resulting fibrous sodium carboxymethyl cellulose is then wet
cross-linked to produce the instant bibulous fibers. Wet
cross-linking in the present instance comprises the step of
treating fibrous salts of carboxymethyl cellulose, swollen with at
least minor amounts of water, with a reagent polyfunctional with
respect to cellulose, for example epichlorohydrin.
Although the wet cross-linking of unmodified cellulose fiber is
known to result in about a two-fold improvement in the absorbency
of fibrous structures, applicants were surprised to discover that
the present bibulous fibers having a DS of about 0.4 to about 1.6,
preferably about 0.6 to about 1.2, exhibited a manyfold increase in
intrafiber absorbency and retention. Applicants were further
surprised to discover that as minimum values increased over the
minimum required DS to insure water solubility in a cellulosic
fiber without wet cross-linking according to the instant invention,
there existed a range of substantially water-insoluble wet
cross-linked fibrous carboxymethyl products, at a DS of about 0.6
to about 1.6, which exhibited a particularly effective absorbency
and retention of water, dilute salt and other physiological
solutions.
It is, accordingly, a principal object of this invention to provide
wet cross-linked fibrous salts of carboxymethyl cellulose which
exhibit superior absorbency and retention characteristics with
respect to water and aqueous solutions, including physiological
solutions.
It is, accordingly, a principal object of this invention to provide
wet cross-linked fibrous salts of carboxymethyl cellulose which
exhibit superior absorbency and retention characteristics with
respect to water and aqueous solutions, including physiological
solutions.
It is a further object of the present invention to provide bibulous
fibers for inclusion in papermaking furnishes, air-laid and
water-laid nonwoven fabrics and in other fibrous pads and bandages
whether they be of paper, woven or nonwoven origin.
It is yet another object of the present invention to provide wet
cross-linked substantially water-insoluble fibers of carboxymethyl
cellulose, having a DS sufficiently high to insure water solubility
in the absence of wet cross-linking, for inclusion in the fibrous
structure of a catamenial tampon having a substantially higher
in-use absorptive capacity than that of prior art devices, which
catamenial tampon provides increased protection and wearing
time.
It is also an object of this invention to provide catamenial
tampons, surgical dressings and other absorbent pads and fibrous
structures either prepared from bibulous fibers or containing
bibulous fibers in admixture with other fibers.
BRIEF DESCRIPTION OF THE DRAWINGS
Other objects and advantageous features of the present invention
will become apparent as the following description of the instant
bibulous fiber product, together with methods for its production
and examples of its advantageous inclusion in useful fibrous
structures, proceeds apace in this specification, as illustrated in
part by the accompanying drawings wherein:
FIG. 1 is a graph which relates the DS of examples of the present
wet cross-linked fibrous carboxymethyl cellulose fibers to their
intrafiber absorbency as measured by Water Retention Value
(WRV);
FIG. 2 is a graph which relates the DS of examples of the present
wet cross-linked fibrous carboxymethyl cellulose fibers to their
intrafiber absorbency as measured by Salt Water Retention Value
(SRV).
The pertinent values of comparative fibers are also plotted on
FIGS. 1 and 2 in order to illustrate the high degree of absorbency
exhibited by the present bibulous fibers in comparison with other
fibers.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In general, applicants have found that the foregoing objectives can
be met, as before stated, by preparing a water-soluble salt of
carboxymethyl cellulose having a DS of about 0.4 to about 1.6,
preferably about 0.6 to about 1.2, which retains the fibrous form
of the original cellulose raw material with prior, concommitant or
subsequent introduction of sufficient intrafiber cross-links into
the wet or swollen form of said fibrous water-soluble salt of
carboxymethyl cellulose to insure substantial water insolubility.
Such substantially water-insoluble, wet cross-linked carboxymethyl
cellulose fibers exhibit a WRV of about 900 to about 3,400 and a
SRV of about 400 to about 1,500 in the stated DS range of about 0.4
to about 1.6. In the preferred DS range WRV's of about 1,100 to
about 3,400 and SRV's of about 400 to about 1,500 are achieved.
Fibrous salts of water-soluble carboxymethyl cellulose having DS's
in excess of about 1.6 can be used, although, as a practical
matter, the increased absorbency gained through the use of such
high DS material is difficult to justify versus the increased
chemical costs for etherification and cross-linking. Potassium
sodium and lithium salts of fibrous water-soluble carboxymethyl
cellulose are suitable for wet cross-linking in practicing the
present invention; and, although the invention will hereinafter be
illustrated in terms of fibrous water-soluble salts of sodium
carboxymethyl cellulose (NaCMC), it will be appreciated and
understood that other fibrous water-soluble salts of carboxymethyl
cellulose, for example ammonium salts of fibrous water-soluble
carboxymethyl cellulose, can be employed. The necessary wet
cross-links can be introduced into water swollen fibrous NaCMC by
treatment with a suitable cellulosic cross-linking reagent,
selected from the group enumerated hereinbelow, but preferably
epichlorohydrin. Suitable cellulosic fibers for carboxymethylation
and wet cross-linking to form the present bibulous fibers are
cotton, wood pulp and rayon fibers, although lesser used cellulosic
fibers, for example cellulosic fibers attained from straw, esparto
grass, bagasse and other cellulosic fibers will be found to
increase in absorbency.
The minimum degree of substitution of about 0.4 required to assure
water solubility in the fibrous NaCMC prior to wet cross-linking to
achieve substantial water insolubility is obtainable by operation
of the semidry processes disclosed in such patents as U.S. Pat. No.
2,510,355, issued to William F. Waldeck on June 6, 1950 and U.S.
Pat. No. 2,553,725, issued to Linwood N. Rogers, William A. Mueller
and Ernest E. Hembree on May 22, 1951, but preparation of the
fibrous NaCMC of the herein disclosed DS for cross-linking is
readily accomplished by operation of any of these so-called slurry
processes for the manufacture of NaCMC, for example the slurry
process taught in U.S. Pat. No. 3,345,855, issued to Russell Nelson
on Oct. 17, 1967. Such slurry processes have the advantage, in the
preparation of the instant bibulous fibers, that they can be easily
controlled and operated to produce NaCMC having a DS in the range
of about 0.4 to about 1.6 and in the preferred range of about 0.6
to about 1.2 in the fibrous form of the original cellulose raw
material as required for production of the fibrous wet cross-linked
NaCMC product of the present invention. The production of NaCMC
fibers having DS's of less than about 0.8 can be accomplished in
one etherification stage, but the achievement of DS's in excess of
about 0.8 is more easily accomplished and controlled by the use of
at least two etherification stages.
The fibrous water-soluble NaCMC with DS of about 0.4 to about 1.6
is then treated in the wet or swollen state with a suitable
cellulosic cross-linking agent to introduce, engender or cause
sufficient intrafiber cross-links to be formed so that the fibrous
NaCMC becomes substantially insoluble in water. It is also possible
to reduce the water solubility of bibulous fibers for particular
applications by extracting crude bibulous fiber products with water
prior to their use as fibers or admixture fibers in fibrous
products. Suitable cross-linking reagents for use in producing the
water-insoluble intrafiber cross-linked NaCMC product are, for
example, epichlorohydrin and formaldehyde, and the type and amount
of intrafiber cross-linking is derived from an amount of
cross-linking agent sufficient to provide about one cross-link per
about six to about 19 anhydroglucose units, with the cross-links
having been introduced into the cellulose or cellulose derivative
while it is in the wet state. In the practice of the invention with
epichlorohydrin, for example, the required cross-linking is
accomplished by reaction with about 3 percent to about 10 percent
preferably about 3 percent to about 7 percent, by weight of
epichlorohydrin based on the dry weight of the original cellulose
fiber.
Although the general preparation of the bibulous cross-linked
carboxymethyl cellulose fibers of the present invention has been
described above in terms of preparing NaCMC of the prescribed DS
and then introducing sufficient wet cross-links to insure
substantial water insolubility, it is to be understood that the wet
cross-linking and the one or more etherification steps can be
carried out in any order or concomitantly. Applicants have found
that cross-linking wet cellulose fibers to form wet cross-linked
cellulose prior to one or more stages of etherification to obtain a
desired DS has some materials handling advantages, although
simultaneous etherification and wet cross-linking offers some
economies in equipment and chemical usage.
As stated before, the bibulous fibers of the present invention are
substantially water-insoluble. In practice, applicants have found
that bibulous fibers having water solubilities of less than about
30 percent do not inhibit the penetration of liquid into fibrous
structures in which they are present and do not interfere with the
increased total absorbency of such structures. Actually, the
present bibulous fibers would be found almost totally insoluble if
the etherification and wet cross-linking reactions were homogeneous
in nature. In practice, however, cellulosic fibers having varying
degrees of polymerization enter into the wet cross-linking and
etherification reactions, so that a degree of heterogeneity
together with some solubility results in the resulting bibulous
fibers. In applications of the bibulous fibers where essentially
water-insoluble fibers are desired, it is possible to remove
water-soluble fractions from the bibulous fibers by extraction with
water prior to use.
Referring now to FIG. 1 of the accompanying drawings, which
graphically relates to the carboxymethyl DS of fibrous NaCMC wet
cross-linked to substantial water insolubility with epichlorohydrin
to fiber absorbency in terms of the Water Retention Value/100
(WRV/100) as defined below, applicants have discovered that the
ability of wet cross-linked NaCMC fibers to retain water is greatly
improved as the DS of the cross-linked NaCMC exceeds about 0.4. The
graph points are identified as bibulous fibers in the following
examples. Higher DS's up to about 1.6 are also shown to be related
to desirable and increased WRV values. Applicants further prefer to
produce the present bibulous fibers by wet cross-linking NaCMC
fibers having a DS of about 0.6 to about 1.2 because they have
found, as illustrated by the graphed values of FIG. 1, that
bibulous fibers in this DS range achieve the most advantage in
increased absorbency versus production difficulties and chemical
economies.
The graph points for illustrations 1, 2 and 3 are respectively the
absorbency results for wood pulp fibers with no carboxymethylation
(DS=0), wet cross-linked wood pulp fibers with no
carboxymethylation, and wet cross-linked NaCMC fibers with a DS of
0.14. The inclusion of these illustrations in FIG. 1 serves to
illustrate the large increase in absorbency achieved in the present
bibulous fibers over previous absorbent fibers. In FIG. 1 the upper
solid line represents the curve for bibulous fiber examples having
a lower epichlorohydrin treatment of about 3 percent while the
lower dotted line represents the curve for bibulous fiber examples
having an epichlorohydrin treatment of about 5 percent. The area
between the two lines encompasses advantageous bibulous fiber
products, and increased amounts of epichlorohydrin treatment, as
stated before, will result in only a slight downward displacement
of the dotted line.
In a manner similar to the graphical illustration of FIG. 1, FIG. 2
graphically relates the carboxymethyl DS of fibrous NaCMC wet
cross-linked to substantial water insolubility with epichlorohydrin
to its fiber absorbency in terms of the Salt Water Retention
Value/100 (SRV/100), as defined below. Illustrations 1, 2 and 3 are
included for comparison as in FIG. 1, and it is noted that an
aqueous solution containing 1 percent by weight of salt displays
absorbent properties similar to physiological solutions such as
urine, menstrual blood and blood.
As previously stated, the necessary wet cross-linking of the NaCMC
fibers in the disclosed range of DS is accomplished by treatment of
the fibrous NaCMC with a cross-linking reagent. Suitable
cross-linking reagents for use in preparing the present fibers are,
for example, bis-epoxypropyl ether, dichloroethane, divinyl
sulfone, epichlorohydrin, ethylene glycol-bis-epoxypropyl ether,
formaldehyde, vinyl cyclohexene dioxide, 1,3-dichloro-2-propanol,
1,3-di(.beta.-hydroxy-.GAMMA.-chloropropoxy)-2-propanol,
1,2-di(.beta.-hydroxy-.GAMMA.-chloropropoxy)ethane,
1,2:3,4-diepoxybutane, 1,2:5,6-diepoxyhexane,
2,3-dibromo-1-propanol, 2,3-dichloro-1-propanol and
2,2'-dichloroethyl ether, although other reagents polyfunctional
with respect to cellulose can be employed. All of the cross-linking
reagents listed above, with the exception of formaldehyde which
requires acidic conditions, will cross-link carboxymethyl cellulose
under alkaline conditions and result in cross-links containing at
least one carbon atom.
Applicants prefer epichlorohydrin for wet cross-linking in forming
the present bibulous fibers because both the wet cross-linking and
etherification can be simultaneously accomplished in a single
alkaline medium. The wet cross-linking necessary to result in
substantial water insolubility can result from the treatment of
NaCMC fibers, slurried in inert organic diluent and swollen in the
presence of minor but swelling amounts of water, with about 3
percent to about 10 percent, preferably about 3 percent to about 7
percent, based on the weight of the original cellulose in the NaCMC
of epichlorohydrin under alkaline conditions for about 24 hours at
a temperature of about 25.degree. C. Formaldehyde cross-linking can
e accomplished by treating swollen fibrous NaCMC fibers under
acidic conditions with a dilute aqueous solution of
formaldehyde.
Cross-linking of the cellulose raw material in its original fibrous
and unmodified form can be accomplished by the foregoing treatment
with epichlorohydrin or formaldehyde, and this treatment can be
followed by etherification to result in the present bibulous
fibers. Alternately, simultaneous cross-linking and etherification
is, in general and for example, carried out by treating
water-swollen cellulose fibers with epichlorohydrin and with
monochloroacetic acid in the presence of a slight excess of sodium
hydroxide in an inert organic diluent or slurry medium. Other
carboxymethylating agents known in the art can be used to effect
the required etherification.
In describing the characteristics of the bibulous fibers which are
the subject of the present application, applicants have used
several testing procedures. Included in these testing procedures
are the determination of the Degree of Substitution (DS), the
determination of the Water Retention Value (WRV), the determination
of the Salt Water Retention Value (SRV), and the determination of
the solubility in 1 percent NaCl. Determinations of these
characteristics of bibulous and comparative fibers as reported
herein were made according to the following procedural methods.
The DS of carboxymethyl cellulose is the number of carboxymethyl
groups per anhydroglucose unit of cellulose. The analytical method
employed herein was authored by Karin Wilson and published in
Svensk Papperstidning, 63, pp. 714--15 (1960). This method has been
accepted as giving correct results for grades of carboxymethyl
cellulose varying widely in DS and purity. In this analytical
method NaCMC is given an initial treatment with 1 N HC1 in order to
destroy any carbonates present, and if the sample is other than
NaCMC, it must be converted to NaCMC or the procedure must be
modified. The 1 N HC1 treatment is followed by neutralization of
the remaining HC1 with a 1 N aqueous solution of sodium hydroxide.
The purified NaCMC, or wet cross-linked carboxymethyl cellulose
fibrous material, in the sample is then isolated quantitatively by
adding ethyl alcohol to result in a final alcohol concentration of
80 percent by volume. The carboxymethyl cellulose, precipitated
from the 80 percent by volume ethyl alcohol solution, is then
washed free of NaCl, first with 80 percent by volume ethyl alcohol
and then with 95 percent by volume ethyl alcohol. The remaining
precipitate sample, consisting of purified carboxymethyl cellulose,
is subsequently dried, weighed and ashed at 575.degree. C. The
sodium carbonate thus obtained is titrated to a methyl red end
point with standard sulfuric acid. The DS is the calculated as
follows:
The WRV's reported herein were determined by a procedure in which
samples of bibulous fibers weighing from about 0.05 grams to about
0.30 grams are soaked in 100 milliliters of water in a covered
container for at least 16 hours at room temperature. In this
procedure for the determination of absorbency, subsequent to the
soaking period, the soaked bibulous fibers are collected on a
filter, lightly squeezed and then transferred to 80-mesh screen
baskets which are supported one-half inch above the bottom of metal
centrifuge tubes. The tubes are covered with plastic covers, and
the samples are centrifuged at a relative centrifugal force of
1,500 to 1,700 gravities for 20 minutes. The centrifuged samples
are removed rapidly from the screens by means of tweezers to tared
weighing bottles and weighed. The weighed samples are then dried to
constant weight at 110.degree. C. and reweighed. The WRV is
calculated as follows:
Where
W = sample wet weight
D = sample dry weight
W-D = weight of absorbed water
The procedure used for the determination of the SRV's reported
herein was the same as the method described above for use in the
determination of WRV's, with the exceptions that aqueous sodium
chloride solution containing 1 percent by weight of sodium chloride
was used in the procedure instead of water, and the calculation,
given below, corrects for the sodium chloride remaining on the
dried fibers. The calculation is as follows:
The procedure used for determining the solubility in 1 percent NaCl
employs a 0.2--0.3 gram sample of the bibulous fibers to be tested.
The sample is washed with 80 percent by volume methanol and with
100 percent by volume methanol prior to drying the sample at
110.degree. C. and weighing it in a tared weighing bottle. The
weighed sample is then washed into a beaker and soaked for an
extended period (overnight) in 100 milliliters of aqueous solution
containing 1 percent by weight of sodium chloride. The soaked
fibers are then collected on a tared sintered glass filter, weighed
while wet, dried at 110.degree. C. and weighed again. The
calculation used to obtain the solubility in 1 percent NaCl is as
follows:
Where
B = Initial dry weight
W = Wet weight of extracted sample
E = Extracted dry weight
W-E = Water evaporated from wet sample
(W-E)/99 = Weight salt deposited on sample
The following examples will serve to illustrate in detail the
manner in which the bibulous fibers of this invention can be
prepared and incorporated in useful fibrous structures. It will be
understood, however, that the invention is not confined to the
specific limitations or methods set forth in the individual
examples, but rather to the scope of the appended claims.
EXAMPLE I
Eighteen hundred and sixty-five grams of sheeted purified wood pulp
were steeped in a steeping press in 25 liters of aqueous sodium
hydroxide solution containing 8 percent by weight of sodium
hydroxide at room temperature for a period of 45 minutes. The
steeped sheets were then pressed to a press weight ratio of alkali
cellulose weight to weight of air dry cellulose (PWR) of 2.5, and
the pressed sheets were shredded in a Baker-Perkins sigma blade
shredder at room temperature for a period of 45 minutes. After
shredding the alkali cellulose in the Baker-Perkins sigma blade
shredder, 56.5 grams of epichlorohydrin were added to the shredded
alkali cellulose in the shredder, and shredding was continued for
an additional 45 minutes. The fibrous alkali cellulose, with
epichlorohydrin thoroughly dispersed throughout, was then sealed in
a plastic bag and remained therein for 18 hours at 25.degree. C.
The resulting wet cross-linked cellulose fibers were then dispersed
in water, neutralized with acetic acid, washed with water and
centrifuged. The wet cross-linked cellulose fibers were then dried
and found to be essentially insoluble in cadoxen and other solvents
for cellulose. A sample of these wet cross-linked cellulose fibers
was taken as illustration 2.
Three hundred and one grams (dry basis) of the dried cross-linked
cellulose prepared above were thereafter slurried in 13.4 liters of
2-propanol and 1,602 milliliters of water in a 22-liter
round-bottomed flask equipped with a mechanical stirrer. The
resulting slurry was stirred and heated until the temperature
reached 40.degree. C. When the slurry temperature reached
40.degree. C., 104.5 grams of sodium hydroxide dissolved in 204
grams of water were added to the mixture in the 22-liter flask
during a period of 10 minutes. The heating and stirring were
continued for 30 minutes while the temperature of the mixture was
increased to 60.degree. C. At this time a solution of 112.5 grams
of monochloroacetic acid in 600 milliliters of 2-propanol was added
to the 22-liter flask, and the resulting final reaction mixture was
stirred at 70.degree. C. for a period of 4 hours.
The reaction mixture was then cooled and neutralized with acetic
acid, and the fibrous product was collected by deposition on a
screen. The wet cross-linked carboxymethyl cellulose fibers,
collected on the screen as bibulous fibers, were washed with 76
percent by weight (80/20 vol/vol) aqueous methanol. The washed wet
cross-linked carboxymethyl cellulose fibers were then transferred
to 100 percent methanol and dried therefrom. The resulting bibulous
fibers were tested according to the methods and determinations
detailed above, and were determined to have a DS of 0.47, an SRV of
590, a WRV of 1,650 and a solubility (1 percent NaCl) of 5.7
percent. The essentially water-insoluble cross-linked carboxymethyl
cellulose fiber product was found to be highly absorbent and was
judged suitable for inclusion in the fibrous structure of absorbent
surgical dressings, catamenial napkins, tampons and bandage
pads.
Additional examples of essentially water-insoluble cross-linked
modified cellulosic fibers were prepared by using the cross-linking
and single stage etherification procedure of example I with the
exception that the amounts of etherifying and cross-linking agent
were varied to result in higher and lower DS and cross-linking;
these samples had the characteristics given in table I below. Table
I also indicates the level of cross-linking by the amount of
epichlorohydrin added. The fibers of Illustration 1 are wood pulp
fibers without either etherification or wet cross-linking, while
the fibers of illustration 3 are wet cross-linked, low DS wood pulp
fibers. ##SPC1##
The bibulous fibers of examples I--VIII were highly absorbent with
respect to aqueous solutions, including physiological solutions and
blood, and were judged highly suitable for inclusion in fibrous
structure of absorbent surgical dressings, catamenial napkins,
tampons and bandage pads.
EXAMPLE IX
Eighteen hundred and sixty-five grams of sheeted purified wood pulp
were steeped in a steeping press in 25 liters of 8 percent by
weight sodium hydroxide at room temperature for 45 minutes. The
steeped sheets were then pressed to a press weight ratio of alkali
cellulose weight to weight of air dry wood pulp sheets (PWR) of
2.5, and the pressed sheets were shredded in a Baker-Perkins sigma
blade shredder at room temperature for a period of 45 minutes.
After shredding the alkali cellulose in the Baker-Perkins sigma
blade shredder, 56.5 grams of epichlorohydrin (3 percent
epichlorohydrin on cellulose) were added to the shredded alkali
cellulose remaining in the shredded, and shredding was continued
for an additional 45 minutes. The fibrous alkali cellulose, with
epichlorohydrin thoroughly dispersed throughout, was then sealed in
a plastic bag and remained therein for 18 hours at 25.degree. C.
The resulting wet cross-linked cellulose fibers were then dispersed
in water, neutralized with acetic acid, washed with water and
centrifuged. The wet cross-linked cellulose fibers were then dried
and found to be essentially insoluble in cadoxen and other solvents
for cellulose.
Three hundred and nine grams (dry basis) of the dried cross-linked
cellulose prepared above were thereafter slurried in 13,515
milliliters of 2-propanol and 1,654 milliliters of water in a
22-liter round-bottomed flask equipped with a mechanical stirrer.
The resulting slurry was stirred and heated until the temperature
reached 40.degree. C. When the slurry temperature reached
40.degree. C., 144 grams of sodium hydroxide in 169 grams of water
were added to the heated slurry during a period of 10 minutes. The
heating and stirring were continued for 30 minutes while the
temperature of the mixture was increased to 65.degree. C. At this
time a solution of 155 grams of monochloroacetic acid in 485
milliliters of 2-propanol was then added to the heated mixture in
the 22 liter flask, and the temperature of the heated mixture was
increased to 72.degree. C. for 1 hour. The slurry was thereafter
allowed to cool to 56.degree. C. over a period of 2 hours.
At the end of the 2 hour cooling period an additional 65.6 grams of
sodium hydroxide in 81 grams of water was added to the stirred and
cooled mixture, and stirring was continued at 56.degree. C. for 30
minutes. At this time 77.5 grams of monochloroacetic acid in 245
milliliters of 2-propanol was added to the stirred mixture, and
stirring was continued with additional heating to increase the
temperature of the slurry to 69.degree.--72.degree. C. during a
period of 3 hours.
The slurry was then brought to a neutral pH by the addition of
acetic acid, and the resulting wet cross-linked carboxymethyl
cellulose fibers were then collected on a screen. The collected
bibulous fibers were washed with 76 percent by weight aqueous
methanol (80/20 alcohol/water, vol/vol) solution. The washed
bibulous fibers were then transferred to 100 percent methanol and
dried therefrom.
The dried cross-linked bibulous fibers were tested according to the
method detailed above, and were determined to have a DS of 0.90, an
SRV of 1,460, a WRV of 3030 and a solubility (1 percent NaCl) of
16.1 percent. The bibulous fibers of example IX, judged on the
basis of the above test procedures, were highly suitable for
inclusion into fiber mixtures intended for use in tampons, surgical
dressings and absorbent pads.
Additional examples of bibulous fibers were prepared by the
two-stage etherification procedure of example IX at higher and
lower DS's and cross-linking by regulating the amounts of
cross-linking and etherification agents employed. These samples had
the characteristics given in table II below. ##SPC2##
The wet cross-linked modified cellulosic fibers of examples IX--XVI
have a higher DS than achieved with a single stage of
etherification in examples I--VIII, and it is noted that the SRV
and WRV values for the higher DS wet cross-linked modified
celluloses also tend to be increased. The wet cross-linked modified
cellulosic fibers of examples IX--XVI were found, like the wet
cross-linked modified celluloses of examples I--VIII to be highly
absorbent for aqueous solutions, including physiological solutions
and blood, and were judged to be highly suitable for inclusion in
the fibrous structure of absorbent surgical dressings, catamenial
napkins, tampons, bandage pads and articles of like use. The
substitution of potassium, lithium or ammonium salts of fibrous
carboxymethyl cellulose in the preparation of the bibulous fibers
of examples I--XVI and other bibulous fibers will result in fibers
with similar characteristics.
EXAMPLE XVII
Thirty-two and two-tenths grams of purified wood pulp fibers were
suspended in 1,428 milliliters of 2-propanol and 164 milliliters of
water in a 2-liter round-bottomed flask and stirred together while
the solution temperature was increased to 44.degree. C. Seventeen
and five-tenths grams of sodium hydroxide in 31 milliliters of
water were then added to the stirred mixture over a period of 10
minutes. The resulting fibrous slurry was stirred for 30 minutes
during which time the slurry temperature was gradually raised to
65.degree. C. After the 30-minute stirring period a solution of
18.8 grams of monochloroacetic acid in 67.5 milliliters of
2-propanol was added to the slurry. The temperature of the solution
was then increased to 71.degree.--74.degree. C., and the resulting
slurry reaction mixture was stirred for 3 hours. After the 3-hour
reaction period a small sample of the fibrous CMC was collected by
screening, neutralized with acetic acid and washed with a 76
percent by weight aqueous methanol (80/20 alcohol/water, vol/vol)
solution. At this point the fibrous carboxymethyl cellulose product
was soluble in water and had a DS of 0.68, although it was
maintained in fibrous form in the alcohol solution.
While the fibrous water-soluble carboxymethyl cellulose remained in
slurry suspension, 3.9 grams of epichlorohydrin were added to the
reaction mixture and the fibrous slurry was stirred for an
additional 3.5 hours at 72.degree. C.
The resulting wet cross-linked carboxymethyl cellulose fibers were
collected on a screen, neutralized with acetic acid, washed with 76
percent by weight methanol and thereafter dried from 100 percent
methanol. The bibulous fiber product of this example XVII was
determined to have a DS of 0.69, SRV of 1340, a WRV of 3,550 and a
solubility (1 percent NaCl) of 19.6 percent. The bibulous fibers as
shown by the test results were highly absorbent, with particular
regard to their affinity for physiological solutions, and were
eminently suitable for inclusion in tampons and surgical
dressings.
EXAMPLE XVIII
Thirty-two and two-tenths grams of wood pulp fibers were slurried
in 1,428 milliliters of 2-propanol and 164 milliliters of water
contained in a 2-liter round-bottomed flask equipped with a
mechanical stirrer. The fibrous slurry was stirred while raising
the solution temperature to 44.degree. C. Seventeen and five-tenths
grams of aqueous sodium hydroxide in 31 milliliters of water were
added to the stirred mixture over a 10-minute period. The resulting
mixture was stirred for 30 minutes during which time the solution
temperature was gradually raised to 65.degree. C. After the
30-minute stirring period, a solution of 18.8 grams of
monochloroacetic acid in 67.5 milliliters of 2-propanol was added
to the solution. Five minutes after the addition of the
monochloroacetic acid in the solution, 3.9 grams of epichlorohydrin
were added, and the temperature of the solution was increased to
71.degree.--74.degree. C. while the resulting reaction mixture was
stirred for 3.5 hours.
The resulting cross-linked modified cellulosic fibers were
collected on a screen, neutralized with acetic acid, washed with 76
percent by weight methanol and thereafter dried from 100 percent
methanol. The bibulous fiber product was determined to have a DS of
0.71, an SRV of 1,265 a WRV of 2,950 and a solubility (1 percent
NaCl) of 14.1 percent.
The bibulous fibers of example XVIII were highly absorbent and
hydrophilic in nature and were suitable for fibers for use in
fibrous structures such as surgical dressings, tampons, catamenial
napkins, etc. where absorbency for aqueous and physiological
solutions is a desirable factor.
EXAMPLE XIX
In order to ascertain the effectiveness of the present bibulous
fibers when included in effective amounts in catamenial dressings
of the tampon type, test tampons were made including amounts of the
presently disclosed fibers. The tampons were constructed from rayon
staple fiber mats having a basis weight of about 2.5 ounces per
square yard. The rayon staple fiber mat was in the form of
garnetted, cross-lapped needle-punched matting prepared from
crimped rayon staple fibers having a denier of 3 and a length of
19/16 inches.
The bibulous fibers of the present invention were in individual
fibrous form, having been run through an attrition mill and sifted
through a 14-mesh Rotap screen to break up fiber clumps.
The test tampons were prepared by cutting squares of the rayon mat
to a dimension of 10 inches .times. 10 inches. A rayon mat-bibulous
fiber stack was then developed by laying down a 10 inch .times. 10
inch square of the rayon mat and sifting 1.5 grams of the bibulous
fibers uniformly thereon through a 14-mesh Rotap screen. After
sifting the 1.5 grams of bibulous fibers on the rayon mat, another
10 inch .times. 10 inch square of rayon mat was laid on top of the
sifted bibulous fibers, and another 1.5 grams of bibulous fibers
were sifted onto the new rayon mat.
This procedure was repeated until there were four layers each of
rayon mat and bibulous fibers. At this point the stack was capped
with yet another square of rayon mat to form a pad containing five
layers of rayon mat and four layers of sifted bibulous fibers. The
so-formed pad or stack was calendered to imbed the bibulous fibers
into the rayon matting, thus preventing a subsequent loss of
bibulous fibers in processing.
Having preformed the rayon mat, bibulous fiber pad, individual
rectangular tampon swatches having a dimension of 6 inches by 13/8
inches were cut from the pad. Each so-cut tampon swatches weighed
about 3.25 grams. Each rayon layer in the tampon swatches weighed
about 0.55 grams, and each bibulous fiber layer weighed about 0.125
grams. The percent of wet cross-linked carboxymethyl cellulose
fibers in each cut tampon swatch was approximately 15 percent.
The tampon swatches were then further formed into finished tampons
by attaching a withdrawal string to the middle of the tampon swatch
and then folding over the cut tampon swatch to a 3-inch length. At
this point in tampon preparation, the test swatches were
conditioned to a moisture content of about 18 percent, and the
final swatch weight before die pressing about 3.5 grams. The
so-formed and folded tampon swatches comprising preformed fibrous
bodies were compressed in a cylindrical die, and the sides of the
tampons were roughened or abraded by rolling the tampons between
two strips of card clothing, spaced 0.5 inches apart. The finished
length of the tampons was approximately 1.80 inches and the
diameter was approximately 0.45 inches. Comparative tampons were
formed in the described manner from rayon alone, i.e., from five
layers of rayon fiber mat, and from rayon and bibulous fibers.
The test tampons were placed for testing within the confines of a
balloonlike rubber membrane fixed inside a glass jacket. The
tampons were positioned so that about one-quarter inch of their
proximal or internal ends were lying on top of a hypodermic needle
which was positioned in the bottom of the rubber membrane and
through which test fluid was emitted to the test sample in the
artificial vagina formed by the rubber membrane. The distal end of
the tampons, or the end with withdrawal string attached, was then
about 2.5 inches from the artificial vagina opening and the
withdrawal string extended outwardly through the opening. The test
fluid had the following composition: ##SPC3##
This fluid is considered equal in average viscosity and solids
content to menstrual and other physiological fluids.
In testing, water was admitted into the glass jacket to a
hydrostatic pressure of 6 inches. The rubber membrane was thus
collapsed and formed into a tight-fitting sheath around the test
tampon. The test fluid was then admitted through the hypodermic
needle at a rate which varied from about 1 milliliter to about 5
milliliters per minute, with the fluid supply regulated so that
puddling during the test did not occur. The test was considered
complete when test fluid formed a pool inside the rubber membrane
at the distal end of the tampon. At this point the total weight of
test fluid absorbed was obtained, and the absorption efficiency
(weight absorbed/dry weight of test tampon) was calculated. In this
manner the bibulous fiber products of example XIV and example VII
above were tested for their effectiveness in tampons and the
following table of data expresses this effectiveness. ##SPC4##
The data of table IV show that the test tampons containing bibulous
fibers in an amount equal to about 15 percent of their weight were
at least 37 percent more effective in total absorbency than the
comparative test tampon not containing bibulous fibers. The
inclusion of additional weight percentages of bibulous fibers will
increase the total absorbency of such test products, but it is
considered that the inclusion of 15 percent by weight bibulous
fibers is sufficient to result in a tampon product which exhibits
substantially more total absorbency than products presently
available on the market and is characterized by a considerably
reduced failure rate. Tampon failure is defined herein as failure
to contain menstrual flow during use.
EXAMPLE XX
In order to ascertain the effectiveness of the present bibulous
fibers when used in surgical dressings, catamenial napkins and
absorbent pads, a 0.5 gram sample of the bibulous fibers of this
invention, choosing specifically the bibulous fibers of example XI,
were formed into an 2 inch .times. 2 inch absorbent pad. The
bibulous fibers in the pad exhibited a DS of 0.79, an SRV of 1370,
a WRV of 3480 and a solubility in 1 percent by weight aqueous NaCl
of 16.6 percent.
The 2 inch .times. 2 inch absorbent pad of bibulous fibers was
completely saturated with whole human blood by adding blood
dropwise until excess blood flowed from the pad. The excess blood
in the saturated pad was pressed out under a pressure of 1 pound
per square inch on the fiber pad during a 3-minute period between
blotters. The blotters were changed, to present fresh blotting
surfaces, as they took up the excess blood in the pad. The weight
of blood retained in the pad per gram of air dry bibulous fiber was
calculated. The pad of this example IX formed of bibulous fibers
retained 9.3 grams of blood per gram of bibulous fiber. Table V
below compares the blood retention of the bibulous fibers of this
example XI with other fibers commonly used in absorbent pads and
tested by the procedure of this example: ##SPC5##
As shown by the blood retention results given in table V above, the
bibulous fibers of example XI exhibited better than three times the
blood retention capacity of the best of the other commonly employed
fibers tested. When other bibulous fibers are prepared according to
the present disclosure and tested for the retention of blood,
menstrual fluids, 1 percent by weight aqueous salt solutions and
other physiological solutions and for the retention of water,
similarly enhanced and improved results will be obtained.
EXAMPLE XXI
In order to ascertain the effectiveness of the present bibulous
fibers in absorbing and retaining undissolved water from
substantially immiscible aqueous systems comprised of water
together with at least one hydrocarbon, 7 grams of the bibulous
fibers of example II were packed into a cylinder having an inside
diameter of 2 inches and a height of 7 inches. Three and one-half
liters of gasoline containing, as entrained fluid, 50 grams of
water per liter of gasoline was passed through the cylinder. The
gasoline passed through the cylinder while the water was absorbed
and remained therein, as evidenced by a water content of 0.01
percent by weight in the gasoline passing though the cylinder.
Similar results are obtained in substantially immiscible aqueous
systems containing chloroform, toluene, benzene, xylene, kerosene,
pentane, hexane and cyclohexane. Also systems containing mixtures
of the aforementioned solvents, for example 1 liter of chloroform
together with 2.5 liters of hexane, and 175 grams of water, are
found to be amenable to water removal according to the procedure of
example XXI. In certain instances flow rates were improved by
combining the bibulous fibers with glass and other inert carrier
fibers according to conventional dispersive practice in the
formation of filter pads.
Since many apparent and widely different embodiments of the
bibulous fibers of this invention can be made in physical form,
chemical composition and use without departure from the spirit and
scope of the invention, it will be understood that the invention is
not limited to the herein disclosed specific embodiments thereof,
except as defined in the appended claims.
* * * * *