U.S. patent number 3,658,579 [Application Number 05/028,946] was granted by the patent office on 1972-04-25 for flame-retardant, bonded nonwoven fibrous product employing a binder comprising an ethylene/vinyl chloride interpolymer and an ammonium polyphosphate.
This patent grant is currently assigned to Monsanto Company. Invention is credited to Paul R. Graham, Morris V. Merchant, August F. Ottinger.
United States Patent |
3,658,579 |
Ottinger , et al. |
April 25, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
FLAME-RETARDANT, BONDED NONWOVEN FIBROUS PRODUCT EMPLOYING A BINDER
COMPRISING AN ETHYLENE/VINYL CHLORIDE INTERPOLYMER AND AN AMMONIUM
POLYPHOSPHATE
Abstract
Flame-retardant, bonded nonwoven fibrous products employing an
ethylene/vinyl chloride interpolymer bonding agent having
incorporated therein a phosphorus and nitrogen flame retardant.
Inventors: |
Ottinger; August F. (St. Louis,
MO), Merchant; Morris V. (Florissant, MO), Graham; Paul
R. (Ballwin, MO) |
Assignee: |
Monsanto Company (St. Louis,
MO)
|
Family
ID: |
21846387 |
Appl.
No.: |
05/028,946 |
Filed: |
April 15, 1970 |
Current U.S.
Class: |
442/142;
428/476.3; 428/480; 428/537.1; 428/921; 428/475.8; 428/521;
428/704; 524/415 |
Current CPC
Class: |
D06M
11/72 (20130101); C08K 3/32 (20130101); Y10T
428/31931 (20150401); Y10T 428/31743 (20150401); Y10T
428/31989 (20150401); Y10T 428/3175 (20150401); Y10T
442/268 (20150401); Y10S 428/921 (20130101); Y10T
428/31786 (20150401) |
Current International
Class: |
C08K
3/00 (20060101); C08K 3/32 (20060101); D06M
11/72 (20060101); D06M 11/00 (20060101); B32b
005/02 (); B32b 017/04 (); B32b 027/02 () |
Field of
Search: |
;161/170,92,191,256,204,82,140,141
;260/DIG.24,80.6,8.3N,80.73,87,5C,45.7P,29.6TA
;117/14A,161UT,126GB,138.8N,137 ;252/8.1 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Modern Plastics Encyclopedia 1967, Sept. 1966, Vol. 44, No 1A,
McGraw Hill, New York; pp. 451-455.
|
Primary Examiner: Goolkasian; John T.
Assistant Examiner: Fritsch; D. J.
Claims
The embodiments of this invention in which a particular property or
privilege is claimed are defined as follows:
1. Flame retardant, bonded nonwoven fibrous product comprising
nonwoven fibrous material bonded with a bonding agent composition
comprising an ammonium polyphosphate of the formula
H.sub.(n.sub.-m).sub.+2 (NH.sub.4).sub.m P.sub.n O.sub.3n.sub.+1
wherein n is an integer having an average value greater than 10,
m/n has an average value between 0.7 and about 1.1, and m has an
average value equal to n +2 and an interpolymer selected from the
group consisting of (I) an ethylene/vinyl chloride interpolymer
containing from about 5 to about 70 weight percent ethylene, about
30 to about 95 weight percent vinyl chloride, and about 0.1 to
about 10 weight percent of a polar component selected from the
group consisting of
A. acrylamide, and
B. acrylamide in combination with at least one additional polar
monomer selected from the group consisting of acrylonitrile,
methacrylamide, N-(alkyl) acrylamide, N-(hydroxy substituted alkyl)
acrylamide, and N-(alkyl) methacrylamide having from one to three
carbon atoms in each said alkyl group, acrylic acid, methacrylic
acid and alkali metal and ammonium salts of acrylic and methacrylic
acid, maleic and fumaric acids, itaconic and citraconic acids, half
alkyl esters of maleic, fumaric, itaconic, and citraconic acids
having from one to six carbon atoms in said alkyl groups, acrylyl
and methacrylyl esters of hydroxyalkanoic acids having from two to
six carbon atoms in said alkanoic acids, acrylylamide and
methacrylylamides of aminoalkanoic acids having from two to six
carbon atoms in said aminoalkanoic acid, hydroxyethyl and
hydroxypropyl esters of acrylic, methacrylic, maleic, and fumaric
acids, vinyl esters of alkanoic acids having from one to six carbon
atoms and alkyl sulfonic acid having from one to six carbon atoms,
phenylsulfonic acids, and acrylyl and methacrylyl esters of
hydroxyalkylsulfonic acid having from one to six carbon atoms in
said alkyl moieties and hydroxyalkylsulfonamides having from one to
six carbon atoms in said hydroxyalkyl moieties;
and (II) interpolymers of the type described in (I) treated with an
acid or a base having an ionization constant higher than about
10.sup. .sup.-4 in amounts equivalent to up to about 100 percent of
the amide content of said interpolymer.
2. Product of claim 1 wherein the average value of n of said
ammonium polyphosphate is from about 20 to about 400 as determined
by the end group titration method.
3. Product of claim 1 wherein said ammonium polyphosphate is
present in amounts of from about 1 to about 30 weight percent based
upon the fibers.
4. Product of claim 1 wherein said ammonium polyphosphate is
present in amounts of from about 3 to about 15 weight percent based
upon the fibers.
5. Product of claim 1 wherein the nonwoven fibrous material is made
of natural fiber.
6. Product of claim 5 wherein the fibers are cellulosic fibers or
glass fibers.
7. Product of claim 1 wherein the nonwoven fibrous material is made
of synthetic fiber.
8. Product of claim 7 wherein the fibers are polyester fibers or
polyamide fibers.
9. Product of claim 1 wherein the nonwoven fibrous material is a
combination of natural fiber and synthetic fiber.
10. Product of claim 1 wherein the nonwoven fibrous material is in
the form of a two-dimensional web.
11. Product of claim 1 wherein the ethylene/vinyl chloride
interpolymer contains from about 15 to about 70 percent ethylene
from about 30 to about 85 percent vinyl chloride and from about 0.1
to about 10 percent acrylamide.
12. Product of claim 1 wherein the ethylene/vinyl chloride
interpolymer contains from about 19 to about 23 percent ethylene,
from about 74 to about 78 percent vinyl chloride, and from about 2
to about 4 percent acrylamide.
13. Product of claim 1 wherein the bonding agent is (II).
14. Product of claim 1 wherein the polar component of the
interpolymer is a combination of acrylamide and an additional polar
monomer.
15. Product of claim 1 wherein the ethylene/vinyl chloride
interpolymer is a quaternary polymer containing from about 15 to
about 70 percent ethylene, from about 30 to about 85 weight percent
vinyl chloride, from about 1 percent to about 5 percent acrylamide,
and from about 0.1 to about 3 percent by weight of bishydroxypropyl
fumarate.
16. Product of claim 1 wherein the nonwoven fibrous material is a
combination of natural and synthetic fibers and the ethylene/vinyl
chloride interpolymer contains from about 15 to about 70 percent
ethylene, from about 30 to about 85 percent vinyl chloride and from
about 0.1 to about 10 percent acrylamide.
17. Product of claim 16 wherein the natural fibers are cellulosic
fibers.
18. Product of claim 17 wherein the cellulosic fibers are wood
fibers.
19. Product of claim 16 wherein the synthetic fibers are polyamides
or polyesters.
20. Product of claim 16 wherein the natural fibers are cellulosic
fibers and the synthetic fibers are polyamides or polyesters.
21. Product of claim 16 wherein the combination of fibers comprises
at least 50 percent by weight of fibers selected from the group
consisting of cellulosic fibers, polyamide fibers, vinyl acetate
fibers, fibers of polymers and copolymers of acrylonitrile,
poly-(ethylene glycol-terephthalate) fibers and mixtures
thereof.
22. Product of claim 1 wherein the nonwoven fibrous material is
composed of wood fibers and the ethylene/vinyl chloride
interpolymer contains from about 15 to about 70 percent ethylene,
from about 30 to about 85 percent vinyl chloride, and from about
0.1 to about 10 percent acrylamide.
23. Product of claim 1 wherein the nonwoven fibrous material is a
combination of polyamide fibers and wood fibers and the
ethylene/vinyl chloride interpolymer contains from about 19 to
about 23 percent ethylene, from about 74 to about 78 percent vinyl
chloride, and from about 2 to about 4 percent acylamide.
24. Method for the preparation of a flame retardant, bonded
nonwoven fibrous product which comprises consolidating a mass of
fibers into a nonwoven fibrous material, dispersing a bonding agent
composition within the material, and heating the resultant material
at a temperature sufficient to effect coalescence and fusion of the
bonding agent within said material, wherein the bonding agent
composition is as defined in claim 1.
25. Method of claim 24 wherein the bonding agent is dispersed in
the material by contacting the material with an aqueous dispersion
of the bonding agent composition.
26. Method of claim 24 wherein the nonwoven fibrous material is in
the form of a two-dimensional sheet.
27. Method of claim 24 wherein the material is contacted with the
bonding agent in a settling chamber.
28. Method of claim 24 wherein the nonwoven fibrous material is a
combination of natural and synthetic fibers and the ethylene/vinyl
chloride interpolymer contains from about 15 to about 70 percent
ethylene, from about 30 to about 85 percent vinyl chloride, and
from about 0.1 to about 10 percent acrylamide.
Description
This invention relates to flame retardant, bonded nonwoven fibrous
products employing a bonding agent composition comprising an
ethylene/vinyl chloride interpolymer and an ammonium
polyphosphate.
The term "nonwoven fibrous material" as used herein means a
consolidated mass of fibers laid down by mechanical, chemical,
pneumatic, electrical or vacuum means, or otherwise deposited, into
the desired shape, either flat (webs, mats or sheets) or
three-dimensional.
Nonwoven fibrous material can be formed by both a wet process and a
dry process. In the wet process, the fibers are slurried in water
or similar inert liquid. The slurry is spread on a flat surface,
the inert liquid drained off, and the web dried under pressure to
form the loosely consolidated mass of randomly distributed fibers.
In the dry process the fibers in the dry state are laid on a solid,
flat surface, for example, a conveyor, by mechanical means or
pneumatic means, for example, a carding machine or an air-lay
machine. The dry process can be used to lay down the fibers in
either a random distribution or an oriented distribution. A
thorough discussion of the formation of nonwoven fabrics is
presented in "Non Woven Fabrics" by F. N Buresh-Reinhold Publishing
Company, New York, New York, (1962).
Regardless of the method employed to form the nonwoven fibrous
material, the material is at this point only a flimsy structure
having virtually no tensile strength and is unable to remain as a
unitary piece without support. In order that the nonwoven fibrous
material possess the necessary tensile strength and cohesion
required for practical applications, it is necessary that the
fibers be bonded and interlocked in some fashion. The usual and
most economical means of accomplishing the bonding and interlocking
of the fibers is to impregnate or saturate the nonwoven fibrous
material with a bonding agent followed by heating or other means of
activation in order to coalesce and fuse the bonding agent, and
bond and interlock the fibers.
In many applications, it is essential that bonded nonwoven products
exhibit good elongation, resistance to oils and solvents, good
drape and hand characteristics, good flame resistance, and
non-discoloration, as well as high tensile strength.
Various general purpose synthetic polymers and copolymers have been
used as bonding agents for nonwoven fibrous products. Some of the
prior art polymers produce undesirably stiff products which are
unsuitable for textile use because of poor draping qualities and
harsh feel or hand. Other prior art polymers result in
discoloration and loss of strength upon exposure to bleach during
washing. Still other prior art polymers result in bonded nonwoven
fibrous products which exhibit acceptable tensile strength and
elongation but which lack acceptable flame retardancy. In general,
the bonding agents employed heretofore have not been entirely
satisfactory.
In accordance with this invention, it has been found that flame
retardant, bonded nonwoven fibrous products which exhibit good
flame retardancy and the desirable combination of high tensile
strength and elongation, as well as good hand and drape
characteristics, are obtained by using a bonding agent composition
comprising an ethylene/vinyl chloride interpolymer and an ammonium
polyphosphate flame retardant for the nonwoven fibrous
material.
The flame retardants useful in the preparation of the flame
retardant, bonded nonwoven fibrous products of this invention are
the substantially water-insoluble ammonium polyphosphates of the
general formula
H.sub.(n.sub.-m).sub.+2 (NH.sub.4).sub.m P.sub.n
O.sub.3n.sub.+1
wherein n is an integer having an average value greater than 10,
m/n has an average value between 0.7 and about 1.1 and m has an
average value equal to n+b 2. These polymeric polyphosphates have
P-O-P type linkages and the average value of n being greater than
10 is evidenced by the paper chromatography method [Karl-Kroupa,
Anal. Chem., 28, 1091 (1956)], and the polymeric P-O-P type linkage
is evidenced by n.m.r. spectra which indicates substantially no
ammonium polyphosphates type linkages and no ortho, pyro or short
chain P-O-P type groups and by infra-red spectra which indicates
P-O-P type linkages but does not indicate substantially any P-N
type linkages.
These polymeric ammonium polyphosphates can be either straight
chain structures or branched chain structures. It should be noted
that substantially all of the nitrogen in these ammonium
polyphosphates is present as the ammoniacal nitrogen and there is
substantially no nuclear nitrogen present in the polyphosphates.
Although theoretically the ammoniacal nitrogen to phosphorus molar
ratio for the polyphosphates of the instant invention approaches
about 1, when the polyphosphates are completely ammoniated, in some
cases the molar ratio of ammoniacal nitrogen to phosphorus is less
than 1 and it is intended that this invention include only those
polymeric ammonium polyphosphates having a molar ratio of not less
than about 0.7 In addition, when the polyphosphates of the instant
invention are characterized herein as being substantially
water-insoluble it is intended to mean that the solubility of a
slurry of 10 grams of solids/100 cc of water after 60 minutes at
25.degree. C is about 5 grams/100 cc of water or less.
Specifically, for purposes of the present invention an ammonium
polyphosphate having a solubility of a specified value refers to
the solubility value in grams per 100 cc of water when 10 grams of
said polyphosphate is slurried in 100 cc of water for 60 minutes at
25.degree. C.
The degree of polymerization of the substantially water-insoluble
ammonium polyphosphates is difficult to determine since known
methods for determining such are "so-called" solution methods, that
is, they employ solution techniques for polymerization
measurements. For example, as determined by the end group titration
method [Van Wazer, Griffith and McCullough, Anal. Chem., 26, 1755
(1954)] after converting the ammonium polyphosphate to the acid
form by ion exchange resins [Van Wazer and Holst, J. Am. Chem.
Soc., 72, 639 (1950)], the average numerical value of n is from
about 20 to about 400, preferred from about 40 to about 400;
whereas, as determined by the method of light scattering or
viscosity correlations obtained from light scattering [Strauss and
Wineman, J. Am. Chem. Soc., 80, 2366 (1958)] modified by use of the
Zimm plot method [Stacey, "Light-Scattering in Physical Chemistry,"
Butterworths, London (1956)] the average weight value of n is above
about 500 and preferred from about 500 to about 100,000 with from
about 1,000 to about 30,000 being especially preferred.
The term "ammoniacal nitrogen" refers to that nitrogen which is
present in the form of ammonium ions and is capable of being
removed by the hydrogen form of a strong cation exchange resin,
i.e., the hydrogen form of a sulfonate polystyrene resin. The term
"non-ammoniacal nitrogen" or "nuclear nitrogen" refers to nitrogen
incapable of being removed in the manner of true ammonium
nitrogen.
The ammonium polyphosphates can be prepared exhibiting many
different crystalline forms as evidenced by their X-ray diffraction
patterns and, in general, any of such forms can be used (although
Forms 1 and 2, infra, are preferred), as well as the
non-crystalline of amorphous form. Crystalline forms illustrative
of ammonium polyphosphates suitable for use include the
following:
X-Ray Diffraction Data .sup.(a)
Form 1Td Form 2 Form 3 Form 4 Line.sup.(b) d,A. Line.sup.(b) d,A.
Line.sup.(b) d,A. Line.sup.(b) d,A. 1 6.06 1 5.70 1 6.65 1 5.70 2
5.47 2 6.06 2 5.68 5.60 3 3.83 3 3.08 3 5.40 3 3.42 4 3.50 4 2.93 4
3.52 4 7.00 5 3.24 5 3.37 5 3.80 5 6.10
In general, the ammonium polyphosphates can be used in any size
which permits their admixture with the ethylene/vinyl chloride
interpolymers. In particular, ammonium polyphosphates having a
particle size fine enough to pass through an 80 mesh screen (USSS)
are preferred, with a particle size at least fine enough to pass
through a 200 mesh screen being especially preferred.
The substantially water-insoluble ammonium polyphosphate
flame-retardant component of the bonding agent compositions useful
in the present invention can be prepared by many and various
methods. In general, a phosphate containing material, such as
monoammonium orthophosphate, diammonium orthophosphate, condensed
phosphoric acid, orthophosphoric acid and the like, is thermally
condensed with an ammoniating and condensing agent, such as urea,
ammonium carbonate, biuret, sulfamide, sulfamic acid, ammonium
sulfamate, guanyl urea, methyl urea, formamide amino urea,
1-3-diamino urea, biurea and the like. In particular, for example,
monoammonium orthophosphate and urea can be thermally condensed to
prepare substantially water-insoluble ammonium polyphosphates by
heat treating a melt formed from substantially equimolar quantities
at a temperature of about 250.degree. C for a period of about 3
hours.
The ethylene/vinyl chloride interpolymers useful in the preparation
of the flame retardant, bonded nonwoven fibrous products of this
invention generally contain about 5 to about 70 weight percent
ethylene, about 30 to about 95 weight percent vinyl chloride, and
about 0.1 to about 10 weight percent of an additional polar monomer
component. The additional polar monomer component can be entirely
acrylamide or a portion of the acrylamide can be replaced by one or
more polar monomers selected from the group consisting of
acrylonitrile, methacrylamide, N-(lower alkyl) acrylamide, N-(lower
alkyl) methacrylamide and N-(hydroxy substituted lower alkyl)
acrylamide containing from one to three carbon atoms in the lower
alkyl groups, N-[2-(2-methyl-4-oxopentyl)] acrylamide, acrylic
acid, methacrylic acid, and alkali metal and ammonium salts of
acrylic and methacrylacrylic acids, maleic acid, fumaric acid, half
and complete alkali metal and ammonium salts of maleic and fumaric
acids, aconitic acid, itaconic acid, citraconic acid, and alkali
metal and ammonium salts thereof, acrylyl and methacrylyl esters of
hydroxyalkanoic acids having from two to about six carbon atoms in
the alkanoic acid moieties, acrylylamides and methacrylylamides of
aminoalkanoic acids having from two to about six carbons in the
aminoalkanoic acid, hydroxyethyl and hydroxypropyl esters of
acrylic, methacrylic, maleic, and fumaric acids, vinyl esters of
alkanoic acids having from one to six carbon atoms such as vinyl
acetate, vinyl propionate, and lower alkyl (one to six carbon
atoms) sulfonic acid, vinyl esters of phenylsulfonic acids, and
alkylphenylsulfonic acids and acrylyl and methacrylyl esters of
hydroxyalkylsulfonic acids having from one to six carbon atoms in
said alkyl moieties, and hydroxyalkylsulfonamides having from one
to six carbon atoms in said hydroxyalkyl moieties. The polar
monomer component generally contains at least 50 weight percent
acrylamide and preferably at least 80 percent acrylamide.
Thus the interpolymers are at least terpolymers containing
ethylene, vinyl chloride and acrylamide and may be a quaternary or
higher polymer containing one or more of the above exemplified
additional polar monomers in small quantities. Generally such
additional polar monomers will not be present in the interpolymer
in quantities greater than about 3percent by weight.
It is preferred that the interpolymer contain from about 5 percent
to about 70 percent ethylene, 30 percent to about 95 percent vinyl
chloride, and from about 1 percent to about 5 percent acrylamide. A
specific example of choice is a terpolymer containing from about 19
to about 23 percent ethylene; about 74 to about 78 percent vinyl
chloride, and from about 2 to about 4 percent acrylamide.
The interpolymers used in accordance with this invention are
generally unmodified, but modified interpolymers are also included
for use in this invention. The interpolymers are particularly
amenable to hydrolytic modification by the use of small quantities
of a strongly alkaline material such as an alkali metal hydroxide,
or a quaternary ammonium hydroxide such as tetramethyl ammonium
hydroxide, or by a strong acid such as the mineral acids, e.g.,
hydrochloric, sulfuric; phosphoric, nitric. The base or acid used
preferably has an ionization constant higher than 10.sup. .sup.-4
at 25.degree. C.
The hydrolytic modification is carried out by treating an aqueous
dispersion or polymer latex of the ethylene, vinyl chloride, and
acrylamide with aqueous base or acid in an amount chemically
equivalent to from about 0.1 percent to about 100 percent of the
amide equivalent in the interpolymer.
Specific examples of polar monomers which can be used, as described
above, to replace part of the acrylamide in the polar monomer
component of the interpolymer useful in this invention include
acrylonitrile, N-methacrylamide, N-ethylacrylamide,
N-propylacrylamide, N-hydroxymethyl acrylamide, methacrylamide,
acrylic, methacrylic, maleic, fumaric, itaconic, aconitic, and
citraconic acids and alkali metal and ammonium salts of such acids,
preferably the sodium potassium or ammonium salts, alkyl esters of
such acids, e.g., methyl acrylate, ethylacrylate, butyl acrylate,
methyl methacrylate, butyl methacrylate, ethyl methacrylate,
monoethyl maleate, dipropyl fumarate, acrylyl 3-hydroxyproprionate,
methacrylyl hexamide, 2-hydroxyethyl and 2-hydroxypropyl esters of
acrylic, methacrylic, maleic, fumaric, itaconic, aconitic, and
citraconic acids, vinyl formate, vinyl acetate, vinyl hexanoate,
vinyl and alkyl esters of propanesulfonic acid, vinyl
phenylsulfonate, acrylyl and methacrylyl esters of
2-hydroxypropylsulfonic acid, and N-acrylyl and N-methacrylyl
2-hydroxypropanamides.
Illustrative of interpolymers which can be used in the bonding
agent compositions for the flame retardant, bonded nonwoven fibrous
products of this invention are ethylene/vinyl chloride/acrylamide,
ethylene/vinyl chloride/hydroxyethylacrylate, ethylene/vinyl
chloride/acrylamide/N-isopropylacrylamide, ethylene/vinyl
chloride/arylamide/N-ethylmethacrylamide, ethylene/vinyl
chloride/acrylamide/diammonium itaconate, ethylene/vinyl
chloride/acrylamide/monobutyl acid maleate, ethylene/vinyl
chloride/acrylamide/N-methacrylyl propionamide, ethylene/vinyl
chloride/acrylamide/sodium acrylate and ethylene/vinyl
chloride/acrylamide/sodium methacrylate.
The flame retardant, bonded nonwoven fibrous products of this
invention can be formed of either natural or synthetic fibers or
any combination thereof with the selection of the fiber merely
depending upon the specific end use intended for the bonded
nonwoven fibrous product. Among the fibers that can be used in
accordance with this invention are natural fibers, for example,
wood, jute, sisal, hemp, cotton, cotton linters, silk, mohair,
cashmere, asbestos, wool and glass, and synthetic fibers, for
example, rayon cellulose esters such as cellulose acetate,
polyvinyl chloride, polyvinyl acetate, polyacrylonitrile and
copolymers thereof, polyethylene, polypropylene and the like,
polyesters such as ethylene glycol-terephthalate polymers, and
polyamides of the nylon type.
In many applications, the flame retardant, bonded nonwoven fibrous
products of this invention are prepared from a plurality of natural
fibers, or a plurality of synthetic fibers, or a combination of
natural and synthetic fibers. Combinations of wood fiber and cotton
fiber can be advantageously employed in end products such as shoe
liners and the like. In general, the wood fiber comprises the major
amount of the fiber content of such bonded nonwoven fibrous
products. Combinations of glass fiber and asbestos fiber are
generally employed in insulating applications. Combinations of
glass fiber and wood fiber are also useful in certain drapery
applications. The weight ratio of glass fiber to cellulosic fiber
in such bonded nonwoven fibrous products is usually from about 1:10
to about 10:1.
In wearing apparel applications, a combination of wood fibers and
nylon fibers or a combination of wood fibers and rayon fibers can
be advantageously employed. Combinations of wood fiber and nylon
fiber as well as combinations of wood fiber and polyester fiber are
also widely employed in various applications where reinforced
sheeting is required. In such combinations of natural and synthetic
fibers, the weight ratio of natural fiber to synthetic fiber is
generally from about 1:20 to about 20:1 and preferably from about
1:1 to about 3:1.
The nonwoven fibrous materials useful in the preparation of the
flame retardant, bonded nonwoven fibrous products of this invention
can be prepared by any method known to the art. Thus, the nonwoven
fibrous material can be made of fibers deposited in a random manner
as well as fibers oriented or aligned along a particular axis.
Nonwoven fibrous materials in the form of two-dimensional webs can
be prepared by the following methods. Oriented webs are produced
using conventional web-style machines, such as openers, pickers,
cards, or garnetts. Cross-laid webs are made in a manner similar to
oriented webs, except that the fibers are carefully placed at right
angles to the machine direction to improve cross-wise strength.
Random webs are produced in air-lay machines, and the nonwoven
fibrous material has equal strength in all directions. In the
air-lay method, continuous filaments are fed through a cutter or
breaker which discharges the fibers into the discharge side of a
blower. Suitable conduits are provided to guide the fibers to a
collecting screen or air-pervious structure for collecting the
fibers in the form desired. The screen may be in the form of an
endless traveling belt passing through the lower portion of a tower
into the upper portion of which the blown fibers are introduced by
the conduit. A suction box may be placed beneath the traveling
screen to assist in the deposition of the fibers thereon. Instead
of using a traveling flat screen, a stationary formed screen may be
used. For example, the screen may take the form of a hat shaped
cone, such as that used in the felt hat-making industry.
Alternatively it may have any other form which is suitable to
produce the desired shape of the bonded nonwoven fibrous product
such as a rectangular tray. As is the case with the endless
traveling belt, suction may also be applied beneath the stationary
screen to assist deposition of the fibers thereon.
Random webs are also produced by the direct spray method from a
solution or molten mass of the fiber material. This is the
conventional procedure for the formation of glass fibers or mineral
wool fibers, as well as those of nylon or thermoplastic materials,
adapted to be dissolved in a suitable solvent or to be melted. The
solution or melt is directed to suitable nozzles or jet-forming
orifices and a high pressure fluid stream, such air, nitrogen or
steam, is directed against the stream or streams of
filament-forming material to disrupt them and coagulate them as
fibers in the vicinity of the orifices. Electrostatic spinning
methods can also be employed for this purpose. As in the case of
the use of blowers, the disrupted and dispersed fibers can be
directed to the top of the settling tower and allowed to settle
with the aid of suction devices upon a suitable traveling or
stationary screen at the bottom of the tower. This procedure is
particularly adapted to the production of fibers of siliceous
materials such as glass or mineral wool, as well as to
thermoplastic resin fibers.
Wet random webs are formed from a slurry of dispersed fiber on
paper making or modified paper making machines. Spun-bonded webs
are made of randomly oriented continuous filament fibers bonded at
the cross-over point. The method includes extrusion of the
continuous filament fibers, drawing to orient the fiber, some fiber
entanglement by liquids or air, and bonding at the cross-over
points.
The flame retardant, bonded nonwoven fibrous products of this
invention are generally prepared by a method which comprises
consolidating the loose fibers into nonwoven fibrous material
having the structural configuration of the desired bonded nonwoven
fibrous product, dispersing the bonding agent composition
comprising an ethylene/vinyl chloride interpolymer and a phosphorus
and nitrogen flame retardant within the nonwoven fibrous material,
and heating the impregnated nonwoven fibrous material to a
temperature sufficient to coalescence and fuse the interpolymer,
and optionally heating to a temperature sufficient to cross-link
the interpolymer if a sulfur cross-slinking agent is employed.
Another method for the preparation of the flame retardant, bonded
nonwoven fibrous products of this invention which is particularly
useful when the nonwoven fibrous material is formed by the air-lay
method in an air-lay machine comprises contacting the fibers with
the bonding agent composition comprising ethylene/vinyl chloride
interpolymer and phosphorus and nitrogen flame retardant in the
form of dispersion of powder as they fall through the settling
chamber to their point of deposition. This is advantageously
carried out by spraying the bonding agent composition dispersion or
powder into the settling chamber at some intermediate point between
the top and the bottom thereof. By spraying the fibers as they
descend to the point of collection, it is possible to effect a
thorough distribution of the bonding agent composition among the
fibers before they are collected into the nonwoven fibrous
material. In the production of certain fibrous products wherein a
hot molten mass of a polymer such as nylon or a fused siliceous
mass or glass is disrupted by jets of heated air or steam, the
bonding agent composition in the form of dispersion or powder can
be sprayed directly on the fibers while still hot so that
immediately after deposition the bonding agent is set and it bonds
and interlocks the fibers in proper relationship.
The bonding agent compositions can be applied to the fibers of the
nonwoven fibrous material by an means known in the art. The bonding
agent compositions are usually applied to the fibers of the
nonwoven fibrous material by application to the surface thereof, or
by submersion of the nonwoven fibrous material in a liquid,
thickened or foamed dispersion so that the bonding agent
composition penetrates into the interior of the nonwoven fibrous
material. Where the nonwoven fibrous material is a two-dimensional
fabric in the form of a fleece or web, the bonding agent
compositions are usually applied in the form of an aqueous
dispersion. In a typical application, the fabric is impregnated
with the bonding agent compositions by dipping or immersing the
fabric in the dispersion to provide sufficient wet pickup of the
bonding agent. The wetted, nonwoven fibrous material in the form of
a fleece or web can be passed between a pair of pressure rolls to
effect substantially uniform impregnation and also to control the
amount of the bonding agent applied. The impregnated nonwoven
fibrous material is dried by conventional means known to the art in
order to remove all or a portion of the water and to effect
coalescence and fusion of the bonding agent composition within the
nonwoven fibrous material. The drying temperature and drying time
are dependent upon the size, shape and cross-section of the
impregnated, nonwoven fibrous material. In general, the drying
temperature is controlled so that no appreciable deterioration or
degradation of the fibers or bonding agent composition occurs.
When the bonding agent compositions are used in the form of a
dispersion, the dispersion generally contains from about 5 percent
to about 90 percent of ethylene/vinyl chloride interpolymer by
weight and from about 0.1 percent to about 300 percent of ammonium
polyphosphate based on the interpolymer. Such dispersions
preferably contain from about 10 percent to about 60 percent by
weight of interpolymer and from about 1 percent to about 30 percent
of ammonium polyphosphate for ease of application by means of
dipping, soaking, spraying and the like.
The amount of ethylene/vinyl chloride interpolymer based on the
weight of the fiber component of the bonded nonwoven fibrous
product can vary widely depending upon the characteristics desired
in the final product and the specific end use. The flame retardant,
bonded nonwoven fibrous products of this invention generally
contain from about 2 percent to about 200 percent of interpolymer
based on the weight of the fibers. For the production of preforms
intended to be converted into shaped articles, it is preferred to
employ from about 2 percent to about 10 percent of the
ethylene/vinyl chloride interpolymer based on the weight of the
fibers. In the production of insulation materials, the amount of
ethylene/vinyl chloride interpolymer employed generally falls in
the lower part of the above range if the bonding agent is applied
primarily adjacent to the surface or surfaces of the product or if
it is applied in conjunction with other binders.
When the ethylene/vinyl chloride interpolymer is to serve mainly to
bond the fibers together to form a flame retardant bonded nonwoven
fibrous product in which the maximum porosity is retained in
conjunction with a minimum change of fiber hand and drape
characteristics as well as an increase in tensile strength, there
is preferably employed from about 10 percent to about 70 percent
weight of interpolymer solids based on fiber content. The lower
portion of this range generally gives the maximum porosity and
provides a minimum change in the fiber hand and drape
characteristics although in the higher portion of this range
porosity is mainly retained and the fiber hand and drape
characteristics are still evident. The flame retardant, bonded
nonwoven fibrous products thus obtained are advantageously used for
many sanitary purposes, such as table napkins, bibs, tablecloths,
disposable diapers and disposable sheets. When this amount of
interpolymer is used there is relatively little or no "window
paning," i.e., the interstices between fibers are left open leaving
a highly porous bulky product. If desired, the density of the
product can be modified by the application of various amounts of
pressure prior to, or in many cases, after the saturated nonwoven
fibrous material has been heated for bonding.
Flame retardant, bonded nonwoven fibrous products containing from
about 30 percent to about 150 percent by weight of ethylene/vinyl
chloride interpolymer based on the weight of the fiber generally
find use in the garment industry to provide interlining fabrics for
coats, dresses, collars, cuffs, and the like, and to provide outer
wearing apparel fabrics, such as blouses, skirts, shirts, dresses,
and the like. Flame retardant, bonded nonwoven fibrous products
containing the interpolymer in this range are also useful as
curtain and drapery materials. In addition to the general household
and apparel uses mentioned above, the flame retardant, bonded
nonwoven fibrous products of this invention in which 10 to 100
percent by weight of interpolymer based on the weight of fiber is
employed find many light industrial uses as wiping cloths, filters
and lining materials for packaging.
The amount of ammonium polyphosphate based on the weight of the
fiber component of the flame retardant, bonded nonwoven fibrous
product of this invention will vary from about 1 percent to about
30 percent by weight, and preferably from about 3 percent to about
20 percent by weight.
If desired the bonding agent compositions useful in this invention
can also contain a wetting agent or foaming agent. They can contain
a defoamer when the ingredients of the aqueous dispersion have a
tendency to give rise to foaming and when such foaming is
undesirable. The conventional wetting agents such as the sodium
salt of dioctylsuccinic acid can be used and the conventional
foaming and defoaming agents can be employed such as sodium soaps
including sodium oleate for foaming and octyl alcohol or certain
silicone antifoaming agents for defoaming.
In some instances, the properties of the flame retardant, bonded
nonwoven fibrous products are greatly enhanced by a heat cure of
the interpolymer to effect cross-linking. Ethylene/vinyl chloride
interpolymers can be cross-linked with various sulfur containing
compounds as is disclosed in U.S. Pat. No. 3,356,658. The
interpolymers are cross-linked by subjecting the bonded nonwoven
fibrous product, after the drying operation, or as a final portion
of the drying stage itself, to a curing operation as disclosed in
U.S. Pat. No. 3,356,658.
The interpolymers useful in this invention can also contain from
about 1 to about 100 parts by weight per 100 parts by weight of
interpolymer of a phosphate plasticizer, e.g., phosphoric acid
derivates such as triethyl phosphate, tributyl phosphate, trioctyl
phosphate, tri-(2-ethylhexyl) phosphate, tributoxyethyl phosphate,
triphenyl phosphate, tricresyl phosphate, cresyl diphenyl
phosphate, hexyl diphenyl phosphate, 2-ethylbutyl diphenyl
phosphate, octyl diphenyl phosphate, 2-ethylhexyl diphenyl
phosphate, isooctyl diphenyl phosphate, nonyl diphenyl phosphate,
decyl diphenyl phosphate, 2-butyl octyl diphenyl phosphate,
tridecyl diphenyl phosphate, tetradecyl diphenyl phosphate,
octadecyl diphenyl phosphate, 2-ethylbutyl dicresyl phosphate,
n-octyl dicresyl phosphate, isooctyl dicresyl phosphate,
2-ethylhexyl dicresyl phosphate, nonyl dicresyl phosphate, decyl
dicresyl phosphate, 2-n-propylheptyl dicresyl phosphate,
2-butyloctyl dicresyl phosphate, tridecyl dicresyl phosphate,
tetradecyl dicresyl phosphate, octadecyl dicresyl phosphate,
trichloroethyl phosphate and tri-(dimethylphenyl) phosphate;
The flame retardant, bonded nonwoven fibrous products of this
invention are characterized by high tensile strength, good
elongation, softness, good hand and flexibility, good drape and
resistance to many common solvents and detergents. With these
properties, the flame retardant, bonded nonwoven fibrous products
of this invention are suitable for use in a wide variety of end
applications, many of which have been noted above and including,
for example, paperboard, toweling, wrapping, wallpaper, mats,
napkins, tablecloths, heat or sound insulating materials,
electrolytic condensers, luggage skin and interiors, glue coated
tape stocks, pressure sensitive tape stocks, projection screens,
waterproof wrapping paper, drapery headers, draperies, binders,
hospital items such as caps, masks, gowns, jackets, scrub pants,
capes, shoe covers, wash cloths, pillow cases, wipes, cubicle
curtains, filters for food processing, motors, machines, air
systems or liquid systems, electrical insulators, tapes, ribbons,
automobile head and arm rests, upholstery, stuffed pillows,
fiberfills, sleeping bags, slip covers, bed spreads, blankets,
curtains, window shades, carpeting (nonwoven), carpet backing,
wearing apparel, clothing insulation, underwear, diapers,
interfacing and interliners (collars and cuffs), automotive door
panels, film backings and automotive padding.
The ethylene/vinyl chloride interpolymers useful in this invention
are readily prepared by various means well known to the art. The
interpolymers can be prepared by first mixing ethylene and vinyl
chloride in an aqueous medium in the presence of any suitable
anionic or nonionic emulsifier and any initiator capable of
generating free radicals in the chemical mixture at the chosen
reaction temperature and pressure. The acrylamide, preferably in
aqueous solution either alone or mixed with the appropriate amounts
of other polar monomers, is added to the polymerizing ethylene and
vinyl chloride mixture gradually throughout the reaction. The
addition of the acrylamide is preferably begun after about 40 to 50
percent of the desired conversion of the ethylene and vinyl
chloride has been reached. A shell-core latex in which the polar
monomer is concentrated in the outer layers is produced.
The ethylene/vinyl chloride/acrylamide interpolymers used in this
invention are preferably prepared by a process which comprises
mixing ethylene and vinyl chloride monomers in the presence of an
alkaline buffered reduction-oxidation (redox) initiator-catalyst
system, water, and from about 1 percent to about 8 percent by
weight based upon the monomer feed, or from about 4 percent to
about 7 percent based upon the polymer product of an anionic or
non-ionic emulsifying agent having a hydrophilic-lipophilic balance
(HLB) value of from about 10 to about 40, and reacting the mixture
at a temperature and pressure and for a time sufficient to cause
polymerization between the ethylene and vinyl chloride, and then to
introduce acrylamide, either alone, or mixed with other monomers in
minor amounts in an appropriate diluent such as water into the
pressurized polymerizing reaction mixture of the ethylene and vinyl
chloride. This process is described in detail in U.S. Pat. No.
3,428,582 and the subject matter thereof is expressly incorporated
herein by reference.
The following examples will illustrate this invention. Parts and
percent are by weight unless otherwise indicated.
EXAMPLE 1
This example illustrates the preparation of a 21/76/3
ethylene/vinyl chloride/acrylamide interpolymer latex.
Reaction Vessel Initial Charge
11.0 g K.sub.2 S.sub.2 O.sub.3 (KPS) 15.0 g NaHCO.sub.3 0.8 g
Fe(NO.sub.3).sub.3 .sup.. 9H.sub.2 O 1.5 g tetrasodium
ethylenediamine tetraacetate (Na.sub.4 EDTA) 1.2 g Na lauryl
sulfate (SLS) H.sub.2 O to make 1700 ml 450 g Vinyl chloride (VCL)
150 g Ethylene (E)
the above ingredients are charged to a suitable reaction vessel and
heated to 30.degree. C with stirring to give a reaction pressure of
850 psig. Polymerization is started by adding a 1 M sodium
formaldehyde sulfoxylate-NaHSO.sub.2.sup. . CH.sub.2 O.sup..
2H.sub.2 (SFS)/1.5 M ammonium hydroxide (NH.sub.4 OH) solution to
the mixture at a rate of 5.2 ml/hr. at the same time 18 ml/hr. of a
25 percent SLS solution is added and the pressure is kept constant
by the addition of pure vinyl chloride as required. After three
hours, a 50 percent solution of acrylamide in water solution is
added at 40 ml/hr. The reaction stops after 5.5 hours and the feed
streams are turned off. A total of 1,330 g of VCl, 95 ml of the 50
percent acrylamide, 27 ml of the 1 M SFS/1.5 M NH.sub.4 OH
solution, and 92 ml of the 25 percent SLS solution are added. The
resulting polymer latex is vented out the bottom of the auto-clave.
A total of about 3,500 g of the ethylene/vinyl chloride/acrylamide
polymer latex is obtained containing 47 percent total solids, and
1.5 percent sodium lauryl sulfate (based on the weight of the
polymer). It has a pH of 7.7. The composition of the terpolymer is
about 21/76/3 ethylene/vinyl chloride/acrylamide.
EXAMPLE 2
Preweighed samples of Hollingsworth and Vose nonwoven fabric
composite comprising 75 weight percent cellulosic fiber and 25
weight percent nylon fiber are immersed in aqueous dispersions of
bonding agent compositions comprising an ethylene/vinyl chloride
interpolymer and an ammonium polyphosphate. The aqueous dispersions
contain 13.5 weight percent interpolymer solids and 5 weight
percent ammonium polyphosphate of crystalline form 1. The
impregnated fabrics are passed through a size press, weighed, dried
for about two minutes at a temperature of about 118.degree. C. and
weighed. The bonded nonwoven fabrics are subjected to calendering
through a single nip for smoothness and tested for flame retardancy
in accordance with TAPPI T461 vertical flammability test. The
ethylene/vinyl chloride/acryl-amide interpolymer contains 76 weight
percent ethylene, 21 weight percent vinyl chloride and 3 weight
percent acrylamide. The nonwoven fabric samples are 2.75 in. by
8.25 in. Results and further details are given in the Table
below.
TABLE
Ammonium polyphosphate(a) After glow, Char length, in test fabric,
percent sec. in.
__________________________________________________________________________
0 (control) entire sheet entire sheet consumed consumed 4.6 none
31/4 7.6 none 21/4 10.4 none 2
__________________________________________________________________________
(a) Based on the weight of the fiber.
* * * * *