U.S. patent number 3,853,462 [Application Number 05/228,722] was granted by the patent office on 1974-12-10 for compaction of polyester fabric materials.
This patent grant is currently assigned to Meadox Medicals, Inc.. Invention is credited to Ray E. Smith.
United States Patent |
3,853,462 |
Smith |
December 10, 1974 |
**Please see images for:
( Certificate of Correction ) ** |
COMPACTION OF POLYESTER FABRIC MATERIALS
Abstract
Knitted flat stock or tubing fabric material of a suitable
polyester material such as polyethylene terephthalate is treated to
reduce its porosity. The resulting product is useful as a synthetic
inter-cardiac (e.g., vascular) prosthesis. Treatment is performed
by immersing the knitted fabric material in a compacting solution
containing a minor amount of an acidic organic component and a
major amount of a halogenated aliphatic hydrocarbon having up to
about 6 carbon atoms for a time sufficient to reduce the porosity
of the knitted fabric material at least about 30 percent in the
wale direction. A mixture containing about 90 to 98 percent by
weight of methylene chloride and about 10 to 2 percent by weight of
hexafluoroisopropanol is an example of a suitable compacting
solution.
Inventors: |
Smith; Ray E. (Homewood,
AL) |
Assignee: |
Meadox Medicals, Inc. (Oakland,
NJ)
|
Family
ID: |
22858339 |
Appl.
No.: |
05/228,722 |
Filed: |
February 23, 1972 |
Current U.S.
Class: |
8/130.1; 66/170;
8/DIG.21; 623/1.1 |
Current CPC
Class: |
A61F
2/06 (20130101); D06M 13/144 (20130101); D06M
13/152 (20130101); D06M 13/08 (20130101); Y10S
8/21 (20130101) |
Current International
Class: |
A61F
2/06 (20060101); D06M 13/152 (20060101); D06M
13/144 (20060101); D06M 13/08 (20060101); D06M
13/00 (20060101); D06m 005/04 (); A61g
001/24 () |
Field of
Search: |
;8/130.1,DIG.4 ;139/387R
;66/170 ;3/DIG.1 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
The Merck Index, Seventh Edition, 1960, pages 243, 245, 294, 428,
676, 795, 1020 and 1058..
|
Primary Examiner: Rosdol; Leon D.
Assistant Examiner: Wolman; H.
Attorney, Agent or Firm: Burns, Doane, Swecker &
Mathis
Claims
I claim:
1. A process for preparing a synthetic vascular prosthesis
comprising the steps of:
a. providing a knitted synthetic linear polyester fabric tubing
material having a uniform porosity, measured on the Wesolowski
scale, above about 7,500 up to about 20,000 and in excess of that
suitable for long-term healing effects without undue hemorrhaging
at implantation;
b. immersing said porous knitted synthetic linear polyester fabric
tubing material in a compacting solution consisting essentially of
from about 2 to about 10 percent by weight of an acidic organic
component selected from the group consisting of
hexafluoroisopropanol, phenol, meta-cresol, hexafluoroacetone
propylene adduct, trichloroacetic acid, parachlorophenol and
hexafluoroacetone sesquihydrate and about 98 to about 90 percent by
weight of a halogenated aliphatic hydrocarbon selected from the
group consisting of methylene chloride, chloroform,
tetrachloroethane and ethylene dichloride until said fabric
material uniformly shrinks at least about 30 percent measured in
the wale direction and the porosity of the said fabric material is,
measured on the Wesolowski scale, from about 30 to about 5,000 and
suitable for long-term healing effects without undue hemorrhaging
at implantation;
c. removing said compacted fabric material from said compacting
solution;
d. washing said compacted fabric material to remove all traces of
said compacting solution; and
e. forming said compacted fabric material into a vascular
prosthesis.
2. The method of claim 1 wherein said acidic organic component is
hexafluoroisopropanol and the said halogenated aliphatic
hydrocarbon is methylene chloride.
3. The process of claim 2 wherein said compacting solution contains
from about 4 to about 8 percent by weight of hexafluoroisopropanol
and about 96 to about 92 percent by weight of methylene
chloride.
4. The method of claim 1 wherein said polyester is polyethylene
terephthalate.
5. The method of claim 1 wherein said compacting includes a
shrinkage of at least about 40 percent in the wale direction.
6. The process of claim 1 wherein said forming of the prosthesis
includes crimping of the compacted tubing.
7. The process of claim 1 wherein said fabric material is immersed
in the said compacting solution for a time of from about 15 seconds
to 30 minutes.
8. A process for preparing a synthetic vascular prosthesis which
comprises the steps of:
a. providing a uniformly porous, knitted polyethylene terephthalate
tubing having a wall thickness between about 0.1 and 0.3 mm. and a
porosity, measured on the Wesolowski scale, above about 7,500 up to
about 20,000;
b. immersing said porous, knitted polyethylene terephthalate tubing
in a compacting solution consisting essentially of from about 4 to
about 8 percent by weight hexafluoroisopropanol and from about 96
to about 92 percent by weight of methylene chloride for from about
5 to about 15 minutes to uniformly compact the tubing, said
compacted tubing having a porosity, measured on the Wesolowski
scale, of from about 30 to about 5,000;
c. removing said compacted tubing from the compacting solution;
d. washing and drying said compacted tubing to remove all traces of
the compacting solution and wash liquid; and
e. crimping said dried compacted tubing.
9. A process for reducing the porosity of a uniformly porous
knitted synthetic linear polyester fabric material which comprises
contacting said fabric with a compacting solution containing a
minor proportion of a solvent for the polyester and a major
proportion of a shrinking agent for the polyester for a time
sufficient to uniformly compact said fabric at least about 30
percent measured in the wale direction of the fabric, said solvent
being selected from the group consisting of hexafluoroisopropanol,
phenol, meta-cresol, hexafluoroacetone propylene adduct,
trichloroacetic acid, parachlorophenol and hexafluoroacetone
sesquihydrate, and said shrinking agent being selected from the
group consisting of methylene chloride and chloroform, said
solution having a solubility parameter approximately that of the
polyester, said solubility parameter of the solution being defined
in accordance with the following:
S.sub.s = V.sub.1 S.sub.1 + V.sub.2 S.sub.2
where S.sub.s is the solubility parameter of the solution, V.sub.1
is the volume fraction of the solvent component, S.sub.1 is the
solubility parameter of the solvent component, V.sub.2 is the
volume fraction of the shrinking agent component and S.sub.2 is the
solubility parameter of the shrinking agent component; and removing
all traces of said compacting solution from said compacted
fabric.
10. The process of claim 9 wherein said compacting solution
contains from about 2 to about 10 percent by weight of the solution
of the solvent for the polymer and from about 98 to about 90
percent by weight of the shrinking agent for the polymer.
11. The process of claim 10 wherein said compacting solution
contains from about 4 to about 8 percent by weight of the solution
of the solvent for the polymer and from about 96 to about 92
percent by weight of the shrinking agent for the polymer.
12. The process of claim 9 wherein said polyester is polyethylene
terephthalate.
13. A process for reducing the porosity of a uniformly porous,
relatively smooth-surfaced knitted synthetic linear polyester
tubing which comprises immersing said tubing in a compacting
solution for a time sufficient to uniformly compact said tubing at
least about 30 percent measured in the wale direction of the tubing
without appreciable distortion of the smooth surface of the tubing,
said compacting solution containing a mixture of from about 2 to
about 10 percent by weight of hexafluoroisopropanol and from about
90 to about 98 percent by weight of methylene chloride; and
removing all traces of said compacting solution from said compacted
fabric.
14. The process of claim 13 wherein said tubing is immersed in the
said compacting solution for from about 30 seconds to about 30
minutes.
15. The process of claim 14 wherein said tubing is immersed in the
said compacting solution for from about 5 to about 15 minutes.
16. The process of claim 13 wherein said solution contains from
about 4 to about 8 percent by weight of hexafluoroisopropanol and
from about 96 to about 92 percent by weight of methylene
chloride.
17. The process of claim 13 wherein the polyester is polyethylene
terephthalate.
18. The process of claim 13 wherein the yarn in said tubing has a
denier of 40.
19. The process of claim 13 wherein the yarn in the tubing has a
denier of 70.
20. A process for preparing a synthetic inter-cardiac prosthesis
comprising the steps of:
a. providing a knitted synthetic linear polyester fabric material
having a uniform porosity, measured on the Wesolowski scale, above
about 7,500 up to about 20,000 and in excess of that suitable for
long-term healing effects without undue hemorrhaging at
implantation;
b. immersing said porous knitted synthetic linear polyester fabric
material in a compacting solution consisting essentially of from
about 2 to about 10 percent by weight of an acidic organic
component selected from the group consisting of
hexafluoroisopropanol, phenol, meta-cresol, hexafluoroacetone
propylene adduct, trichloroacetic acid, parachlorophenol and
hexafluoroacetone sesquihydrate and about 98 to about 90 percent by
weight of a halogenated aliphatic hydrocarbon selected from the
group consisting of methylene chloride, chloroform,
tetrachloroethane and ethylene dichloride until said fabric
material uniformly shrinks at least about 30 percent measured in
the wale direction and the porosity of the said fabric material is,
measured on the Wesolowski scale, from about 30 to about 5,000 and
suitable for long-term healing effects without undue hemorrhaging
at implantation;
c. removing said compacted fabric material from said compacting
solution; and
d. washing said compacted fabric material to remove all traces of
said compacting solution.
Description
BACKGROUND OF THE INVENTION
It is often desirable for synthetic textile materials to have a
stable, controlled porosity structure. A particularly demanding end
use for such compact synthetic textile structures is as flat stock
or tubing material adapted to replace human arteries or to be used
as patches in repairing hernias or the like. Materials of these
types are otherwise known as synthetic inter-cardiac grafts or
prostheses. Synthetic vascular prostheses, an important type of
inter-cardiac prostheses, for use in the repair and replacement of
vessels and tracts in human and animal bodies are shown, for
example, in U.S. Pat. Nos. 2,978,787 and 3,096,560.
There are certain necessary characteristics essential to the
successful performance of a synthetic inter-cardiac or vascular
prosthesis in an animal or human body. These characteristics
include a porosity sufficient to promote optimum healing while
preventing undue hemorrhaging at implantation, a relatively thin
thickness of the fabric material (e.g., about 0.1 mm. to 0.3 mm.,
wall thickness of the tubing, about the same wall thickness as the
average wall of a natural blood vessel of about the same diameter),
flexibility, strength and resilience sufficient to withstand body
stresses, compatibility with human tissues and sterilization
capability.
Synthetic vascular prostheses have been made from tubing materials
such as extruded plastic tubing, seamless braided and knitted
tubing, cut and Jacquard-woven tubing, as well as seamless woven
tubing. Each of these has been found lacking in one or more of
these essential characteristics. Extruded plastic tubing has lacked
porosity and attempts to deliberately perforate the tubing have
proved unsuccessful. Woven tubing made with a Jacquard-woven seam
has a selvage edge which makes a suture between natural and
synthetic materials. Seamless woven tubing, while better in some
respects, has proved to be unsatisfactory in all areas where good
tissue ingrowth is necessary. Also, woven tubing is subject to
unraveling. Knitted seamless tubing, while sufficiently flexible,
has been found to have undue leakage at the necessary thin wall
thicknesses. Also, the porosity of knitted seamless tubing often is
not constant along its length.
Similar disadvantages have occurred with the manufacture and use of
flat stock material for use as an inter-cardiac prosthesis. e.g.,
as a hernia patch or ligature or in general surgical or
orthodontical use.
The porosity of the prosthesis precursor is a function both of the
size and multifilament nature of the yarn, as well as the close
proximity of the yarns as laid in the knitting step.
As known in the art, the body heals by fibrosis. That is, the body
will react to the implantation of a synthetic graft such as a
vascular graft by encapsulating the graft with fibers or scar
tissue forming both an outer layer and an inner layer of fibrous
tissue. The healing process begins very shortly after implantation
with the deposit of a fibrous layer on the inside of the graft in
contact with the blood stream. Eventually, a mature layer of scar
tissue will be formed. The inner fibrous layer is, however,
believed to originate by migration of fibroblasts from the outer
capsule through the mesh or interstices of the vascular prosthesis.
Thus, an important factor in the determination of the ease of
formation of the fibrous layers and the biological fate of the
synthetic prosthesis is the porosity of the prosthesis
material.
It is also known, however, that implantation of a synthetic
prosthesis having a high porosity generally more suitable for
long-term healing effects may result in undesirable hemorrhaging as
the blood stream is allowed to pass through the graft following the
initial implantation. The porosity of the synthetic prosthesis thus
should be balanced between that necessary to provide good long-term
healing characteristics and that preventing undue hemorrhaging at
implantation.
Knitted tubing offers many advantages of strength, flexibility adn
ease of handling. In addition, knitted tubing is relatively
inexpensive to produce at the desired wall thickness. The knitted
structure locks the yarns in a very stable manner. Knitting also
provides a fabric material with more numerous interstices per unit
of material and larger numbers of interstices may be advantageous
for certain conditions of use. However, as noted before, such
knitted flat stock or tubing is produced at a porosity in excess of
that which is suitable for the effective utilization of the tubing
as an inter-cardiac prosthesis. Even the finest knitted fabric
material has this excessive porosity.
It is an object of this invention to provide a process for the
production of knitted flat stock or tubing of synthetic material
suitable for use as synthetic inter-cardiac prostheses.
It is a further object of this invention to provide a relatively
rapid and inexpensive process for the production of knitted flat
stock or tubing of fine filamentary polymeric materials which
tubing has porosity characteristics to allow for good healing.
It is also an object of this invention to provide a process for the
production of knitted fabric material having a constant porosity
throughout the length of the material.
It is another object of this invention to provide a process for
producing a synthetic inter-cardiac prosthesis having excellent
physical and handling characteristics.
It is another object of this invention to provide a process for
producing knitted tubing of fine filamentary polyester materials
which are suitable for use as synthetic vascular prostheses.
It is another object of this invention to provide a process for
producing synthetic knitted polyester patches for use as synthetic
intercardiac prostheses.
It is another object of this invention to provide a compacting
solution suitable for use in a process for the production of
knitted polyester fabric material having uniform, fine porosity
throughout the material.
It is another object of this invention to provide a compacting
solution suitable for use in a process for the production of
knitted polyester inter-cardiac prostheses.
It is still another object of this invention to provide a
compacting solution suitable for use in a process producing a
synthetic intercardiac prosthesis having good long-term healing
characteristics while preventing undue hemorrhaging at
implantation.
SUMMARY OF THE INVENTION
These and other objects of the invention are achieved in one aspect
by a process for preparing a synthetic inter-cardiac prosthesis
comprising the steps of: (a) providing a knitted polyester fabric
material having a porosity in excess of that suitable for long-term
healing without undue hemorrhaging at implantation; (b) immersing
said porous knitted polyester fabric material in a compacting
solution consisting essentially of from about 2 to about 10 percent
by weight of an acidic organic component and about 98 to about 90
percent by weight of a halogenated aliphatic hydrocarbon having up
to about 6 carbon atoms until said fabric material shrinks at least
about 30 percent measured in the wale direction and the porosity of
the said fabric material is reduced to that suitable for long-term
healing effects without undue hemorrhaging at implantation; (c)
removing said compacted fabric material from said compacting
solution; and (d) forming said compacted fabric material into a
vascular prosthesis.
In another aspect, the objects of this invention are achieved by a
solution for compacting a knitted polyester fabric material at
least about 30 percent measured in the wale direction of the fabric
consisting essentially of from about 2 to about 10 percent by
weight of an acidic organic component and from about 98 to about 90
percent by weight of a halogenated aliphatic hydrocarbon having up
to about 6 carbon atoms.
DETAILED DESCRIPTION OF THE INVENTION
The knitted fabric material useful as a starting point in the
preparation of a synthetic inter-cardiac prosthesis by the process
of the present invention may be made from fine-denier synthetic
yarns of materials selected for desired inter-cardiac implant
properties such as discussed before. The yarn material found most
satisfactory to date is a terephthalic acid-ethylene glycol
polyester such as that which is commercially produced by E. I.
duPont de Nemours Co. under the trademark "Dacron." Such polyester
yarn is compatible with human tissue and wettable by blood so as to
promote the starting of clotting and attendant growth of a layer of
collagen on the wall of the prosthesis after implantation. In
addition, the yarn has suitable strength, flexibility and
resiliency properties accompanied by appropriate water-absorptivity
and capacity to withstand sterilization. The yarn may have any
denier which will result in the desired thin thickness of flat
stock or tubing wall. The yarn can have a denier of from about 20
to about 250, preferably from about 30 to about 150. It has been
found that multi-filament yarns give superior results in
implantation use as compared with solid or monofilament yarn.
Preferred for use in the formation of the knitted material herein
is a multi-filament Dacron polyester yarn of a denier of from about
40 to about 70 denier.
The yarn may be knitted into flat stock or tubing by any suitable
technique. A preferred method of forming knitted tubing is
disclosed in copending U.S. Pat. application Ser. No. 865,326,
filed Oct. 10, 1969 now abandoned, assigned to the same assignee as
the present invention and herein incorporated by reference. As
disclosed therein, the tubing may be produced on a fine (56) gauge
double needle bar Raschel machine in which the yarn is warp-knitted
with a tricot or lock stitch. The resulting knitted product has a
smooth, hard surface and a standard, uniform porosity. Other
suitable knitting techniques known to those skilled in the art
which will provide a similar product may also be utilized. Similar
fine gauge knitting may be utilized to form lengths of knitted flat
stock material. It should be understood that knitted tubing
suitable for use in the present invention includes bifurcated
tubing.
The porosity of such known knitted products are, however, too high
for successful implantation use, that is, the porosity of the
knitted material is in excess of that necessary to provide good
long-term healing characteristics and that preventing undue
hemorrhaging at implantation. Porosity of the knitted material is
measured on the Wesolowski scale and by the procedure of
Wesolowski. In the Wesolowski test, the fabric test piece is
clamped flatwise and subjected to a column of water at a constant
pressure head of 120 mm. of mercury. Readings are obtained which
express the number of milliliters of water permeating per minute
through each square centimeter of fabric. The meter scale reads in
units expressive of such water porosity ranging from absolute
impermeability of zero upwardly through the range of 1,000, 2,000,
etc., to a value of 20,000 as equivalent to free flow.
It has been found that the porosity of the synthetic inter-cardiac
graft should be from about 30 to about 5,000, preferably from about
2,000 to about 4,000, on the Wesolowski scale. Knitted fabric
material (e.g., tubing or flat stock), even that knitted on the
finest gauge double needle bar Raschel machine commercially
available, however, generally has a porosity of above about 7,500,
often above about 8,500, on the Wesolowski scale.
The knitted fabric material therefore must be compacted or shrunk,
generally at least about 30 and preferably at least about 40
percent in the wale direction, in order to provide a synthetic
inter-cardiac prosthesis having the requisite characteristics.
The knitted polyester fabric material is thus immersed in a
compacting solution for a time sufficient to compact the fabric
material at least about 30, preferably at least about 40 percent
measured in the wale direction. The compacting solution can be any
solution, liquid, mixture or single solvent which will compact or
shrink the knitted fabric material the amount necessary to provide
the product having the desired characteristics. Generally, the
compacting solution is a mixture of two or more components which
yield, in combination, a suitable solution.
The compacting solution may consist essentially of a minor
proportion, e.g., 2 to 10 percent, of an acidic organic component
and a major proportion, e.g., 98 to 90 percent, of a liquid
halogenated aliphatic hydrocarbon having up to 6 carbon atoms.
Preferably, the compacting solution contains a mixture of from
about 4 to about 8 percent by weight of the total solution of the
solvent and from about 96 to about 92 of the shrinking agent. The
mixed solution should preferably have a solubility parameter about
that of the polyester tubing material.
The solubility parameter is a measure of the cohesive energy of a
substance. Solubility parameters for liquids can be calculated from
the heats of vaporization and molar volumes of the liquids in a
manner known to those skilled in the art. Solubility parameters of
many liquids have been published or may be derived from the known
physical characteristics of these liquids. Solubility parameters
for synthetic polymeric materials such as polyesters are usually
determined experimentally by measuring the swelling of the polymer
in various solvents of known solubility parameters. The solubility
parameter of polyethylene terephthalate (Dacron) has been
determined to be 10.7. The compacting solution should have a
solubility parameter of from about 9.1 to about 11.0 in order to
shrink the polyethylene terephthalate fabric material at least
about 30 percent in the wale direction.
The acidic organic component may be any liquid or solid organic
material having acidic (i.e., ester-forming) properties, which is
soluble in the liquid halogenated aliphatic hydrocarbon material
and which will function in solution to compact the polyester fabric
material the necessary amount. Often the acidic organic component
is a liquid which is a solvent for the polyester fabric material.
Typical acidic organic components useful in a polyethylene
terephthalate-compacting solution include organic acids such as
benzoic acid and trichloroacetic acid, phenolic compounds such as
phenol meta-cresol, parachlorophenol, halogenated lower alkanols
such as hexafluoroisopropanol and also compounds such as
hexafluoroacetone propylene adduct and hexafluoroacetone
sesquihydrate.
The liquid halogenated aliphatic hydrocarbon component can have up
to 6 carbon atoms. Typical liquid halogenated aliphatic
hydrocarbons useful as components for compacting the polyethylene
terephthalate include methylene chloride, chloroform,
tetrachloroethane and ethylene dichloride.
Often, the liquid halogenated aliphatic hydrocarbon materials are
known shrinking agents for the polyester. None of these materials,
however, is known to shrink the knitted polyester fabric materials
at least about 30 percent in the wale direction.
Preferred compacting solutions for use with knitted polyethylene
terephthalate fabric materials include solutions of from about 4 to
about 8 percent by weight of either hexafluoroisopropanol or
trichloroacetic acid and from about 96 to about 92 percent by
weight of methylene chloride.
Each of the acidic organic components and liquid halogenated
aliphatic hydrocarbon components has its own solubility parameter.
The solubility parameter of the solution is determined by the
volume fraction of each component, that is,
S.sub.s = V.sub.1 S.sub.1 + V.sub.2 S.sub.2
where S.sub.s is the solubility parameter of the mixture, V.sub.1
is the volume fraction of the first component, S.sub.1 is the
solubility parameter of the first component, V.sub.2 is the volume
fraction of the second component and S.sub.2 is the solubility
parameter of the second component.
The knitted tubing is immersed in the compacting solution for a
time sufficient to compact the tubing at least about 30, preferably
at least 40, percent measured in the wale direction. The compacted
knitted tubing has a porosity sufficient to impart good, long-term
healing effects to the prosthesis without substantial hemorrhaging
at time of implantation. Generally, the tubing is immersed in the
compacting solution for from about 15 seconds to about 30 minutes,
preferably from about 1 to about 5 minutes. The compacted knitted
tubing generally will have a porosity, measured on the Wesolowski
scale, of from about 30 to about 5,000, preferably from about 2,000
to about 4,000.
Immersion of the knitted tubing in the compacting solution can
generally be performed at a temperature of from above the freezing
point of the solution up to about the boiling point of the
solution. Preferably, the immersion is performed at a temperature
of from about 0 to about 40, most preferably from about 15 to about
30.degree.C. The tubing may be suitably immersed into the
compacting solution in any suitable bath-type apparatus. Solution
to sample ratios may vary from about 10:1 to about 50:1 or more,
e.g., up to about 100:1 (by weight).
After the knitted tubing has been compacted, the tubing may be
removed from the compacting solution, washed and dried (preferably
at or near ambient temperatures) to remove all traces of the
compacting solution and wash liquid. The tubing may then be
prepared for use as intercardiac implants. For example, the
compacted knitted tubing may then be micro-crimped to improve
flexibility and handling and sterilized. Suitable micro-crimping
procedures are known in the art and are shown, for example, in U.S.
Pat. No. 3,096,560, which patent is assigned to the same assignee
as the present invention and which is herein incorporated by
reference and in U.S. Pat. No. 3,337,673.
Although the invention has been described with reference to knitted
polyester fabric materials (such as "Dacron" polyethylene
terephthalate), it will be apparent to those skilled in the art
that the present invention may also be used to compact knitted
fabric materials of other synthetic polymeric materials such as the
polyamides (e.g., nylon 66) and polyacrylonitriles (some of which
are commercially available as "Orlon" and "Acrilan").
The invention is additionally illustrated in connection with the
following examples which are to be considered as illustrative of
the present invention. It should be understood, however, that the
invention is not limited to the specific details of the
examples.
EXAMPLE I
A large number of solutions are prepared. Samples of 40-denier
knitted polyethylene terephthalate (solubility parameter of 10.7)
bifurcated tubing are immersed in the liquid systems for 10 minutes
at room temperature (i.e., 20.degree.C.) except as indicated. A
20:1 liquid to sample ratio is used.
The treated samples are removed, quenched in a water bath
containing 1 weight percent of a water-soluble surfactant "Triton
X-100", (an ethoxylated octyl phenol) sold by the Rohm and Haas
Co., rinsed in tap water and dried at 100.degree.C. for 5 minutes.
Each of the treated samples is examined to determine the amount of
shrinkage in the wale direction. The systems which cause 20 percent
or greater shrinkage in the wale direction are shown below in Table
I.
TABLE I
__________________________________________________________________________
Shrinkage Percent System Solubility Parameter in Wale Direction
__________________________________________________________________________
Dichloroethane 9.8 21 Dichloromethane 9.7 26-28 Chloroform 9.3
24-26 Dibromomethane 10.4 25 Tetrachloroethane 10.4 21 6%
HFIP-methylene chloride.sup.a 9.62 39-40 6% HFIP-chloroform 9.24 35
6% HFIP-dichloroethane 9.72 26 6% Phenol-methylene chloride 10.05
35 10% m-Cresol-methylene chloride 10.08 38 10% HFAPA-methylene
chloride.sup.b 38 10% HFAPMA-methylene chloride.sup.c 32 6%
Phenol-tetrachloroethane 10.76 34 6% m-Cresol-tetrachloroethane
10.6 34 6% Benzoic acid-tetrachloroethane 10.55 33 6%
Trichloroacetic acid-methylene chloride 9.67 40-41 6%
p-Chlorophenol-methylene chloride 9.83 36 6% Phenol-chloroform 9.73
36 6% Trichloroacetic acid-chloroform 9.29 35 6%
2-Chloroethanol-chloroform 9.51 30 6% m-Cresol-dichloroethane 10.0
26 6% m-Cresol-chloroform 9.59 33 6% p-Bromophenol-methylene
chloride 9.81 33 3% HFA-methylene chloride.sup.d 39 6%
HFIP-methylene chloride at 0.degree.C. 9.62 39 3% Trichloroacetic
acid-methylene chloride 9.68 36 5% Trichloroacetic acid-methylene
chloride 9.67 39
__________________________________________________________________________
a. HFIP - Hexafluoroisopropanol b. HFAPA - Hexafluoroacetone
propylene adduct c. HFAPMA - Hexafluoroacetone propylene monoadduct
d. HFA - Hexafluoroacetone sesquihydrate
As may be seen from the above data, only systems containing
mixtures of methylene chloride (solubility parameter of 9.7) or
chloroform solubility parameter of 9.3) with hexafluoroisopropanol
(solubility parameter of 8.2), phenol, meta-cresol (solubility
parameter of 12.7), hexafluoroacetone propylene adduct (HFAPA),
trichloroacetic acid (solubility parameter of 9.1),
parachlorophenol (solubility parameter of 11.7), or
hexafluoroacetone sesquihydrate, with the acidic organic component
being present in minor proportions, e.g., from about 2 to 10
percent by weight of the mixture, cause shrinkages above about 35
percent.
A number of other common solvents such as benzene (solubility
parameter of 9.15), methanol (solubility parameter of 14.5),
ethanol, dichloroethylene, trichloroethylene and
1,2,4-trichlorobenzene under the same conditions of use cause less
than 20 (some less than 10) percent shrinkage in the wale
direction. Also, liquid systems such as 6% HFIP-Valclene one (a
fluorinated hydrocarbon solvent composed primarily of
trichlorotrifluoroethane, 6% HFIP-methanol (solution solubility
parameter of 14.3) and 6%-HFIP benzene (solution solubility
parameter of 9.12) all cause less than 12 percent shrinkage in the
wale direction. The system of 6% HFIP-tetrachloroethane is not
miscible and 6% HFIP-carbon tetrachloride stiffens the fabric
without shrinking.
EXAMPLE II
The hexafluoroisopropanol-methylene chloride system is studied in
more detail in this Example. Methylene chloride is a known
shrinking agent for polyesters such as polyethylene terephthalate
(see, for example U.S. Pat. No. 2,981,978) and
hexafluoroisopropanol is a known solvent for polyesters such as
polyethylene terephthalate (see, for example, U.S. Pat. No.
3,418,337.
Samples of 40-denier polyethylene terephthalate tubing (wall
thickness of 0.2 mm.) are immersed in methylene chloride solutions
containing 3, 5, 6, 7, 7.5, 8 and 10 percent by weight of the
solution of hexafluoroisopropanol for 1 minute at room temperature
(10:1 liquid to sample ratio). A 40-denier sample of the same
polyethylene terephthalate tubing is immersed in 100 percent
methylene chloride for 20 minutes at room temperature for
comparison purposes.
Samples of 70-denier polyethylene terephthalate tubing (0.3 mm.
wall thickness) are immersed in the 5, 6, 7.5 and 10 percent
hexafluoroisopropanol-containing methylene chloride solutions in
the same manner as the 40-denier samples. The samples are rinsed,
dried and measured as in Example I. The results are shown in Table
II below.
TABLE II ______________________________________ 40-denier 70-denier
Hexafluoroisopropanol/ tubing, tubing, methylene chloride by
percent shrinkage percent shrinkage weight percent in wale
direction in wale direction ______________________________________
0/100 26.5 -- 3/97 33 -- 5/95 36.5 31 6/94 40 31 7/93 40 --
7.5/92.5 39 33 8/92 41 -- 10/90 40 33
______________________________________
The amount of shrinkage in the wale direction is relatively
constant for both 40- and 70-denier tubing samples for all the
solutions containing hexafluoroisopropanol and methylene chloride.
In addition, measurement of the treated samples show that the wall
thickness of each sample has increased. The wall thickness of the
compacted 40-denier samples is about 0.3 mm. and 70-denier samples
show about 0.4 mm. wall thickness.
EXAMPLE III
The effect of immersion time on the amount of shrinkage of a
particular compacting solution is investigated by immersing 40- and
70-denier polyethylene terephthalate tubing samples of the type
used in Example II in a mixed solution of 6 percent by weight of
hexafluoroisopropanol and 94 percent by weight of methylene
chloride for 1, 5, 15 and 30 minutes at room temperature
(20.degree.C.) and a 10:1 solution:sample ratio. The compacted
samples are rinsed, dried and measured as in Example I. As shown in
Table III below, essentially all of the shrinkage occurs within 5
minutes and further changes essentially do not occur beyond 5
minutes.
TABLE III ______________________________________ Percent Shrinkage
in the Wale Direction Time, minutes 40-denier tubing 70-denier
tubing ______________________________________ 1 40 31 5 40 33 15 40
34 30 40 33 ______________________________________
The porosity of the 40-denier sample prior to the above treatment
is 8800 on the Wesolowski scale (i.e., 8800 cc water/cm.sup.2 min.)
After 5 minutes immersion in the compacting solution as described
above, the porosity is 2500 on the Wesolowski scale.
EXAMPLE IV
The 40-denier, 5-minute immersion sample of Example III is crimped
in accordance with the teachings of U.S. Pat. No. 3,337,673. The
resulting, crimped tubing is cooled, dried and sterilized and is
suitable for use as a vascular prosthesis.
EXAMPLE V
Example II is repeated for the trichloroacetic acid-methylene
chloride system. Optimum results are again obtained with a solution
containing about 6 to about 8 percent by weight of trichloroacetic
acid and from about 94 to about 92 percent by weight of methylene
chloride.
A 6 percent by weight solution of trichloroacetic acid in 94
percent by weight of methylene chloride is used as the compacting
solution and Example III is repeated. It is again found that
essentially all of the shrinkage occurs within 5 minutes.
EXAMPLE VI
Flat stock material samples of knitted polyethylene terephthalate
made from 40- and 70-denier filaments are immersed in compacting
solutions of 6 percent hexafluoroisopropanol-94 percent methylene
chloride and 6 percent trichloroacetic acid-94 percent methylene
chloride at 20.degree.C. for 5 minutes (40:1 solution to sample
ratio). Examination of the treated samples shows that the flat
stock has shrunk essentially the same amount in the wale direction
as comparable knitted samples.
ADVANTAGES OF THE INVENTION
The present invention offers a number of significant advantages.
Knitted flat stock or tubing may be economically manufactured in
the wall thicknesses suitable for use as a vascular prosthesis.
While the smooth-surfaced, uniformly porous knitted material
possesses superior flexibility, handling and resiliency
characteristics, it has a porosity too high to be suitable for
long-term healing effects without undue hemorrhaging at
implantation.
Treatment of the porous, synthetic knitted polyester material with
the compacting solution as defined in the present invention
compacts or shrinks the material to a porosity which provides
suitable long-term healing effects without undue hemorrhaging at
implantation. The compacted knitted material produced by the
present invention remains smooth-surfaced and has small, uniform
interstices. The preclotting efficiency of the compacted material
is high. Preclotting of the compacted material prior to
implantation in a manner known to those skilled in the art
substantially fills these small interstices making the implant
device substantially impervious.
The principles, preferred embodiments and modes of operation of the
present invention have been described in the foregoing
specification. The invention which is intended to be protected
herein, however, is not to be construed as limited to the
particular forms disclosed, since these are to be regarded as
illustrative rather than restrictive. Variations and changes may be
made by those skilled in the art without departing from the spirit
of the present invention.
* * * * *