U.S. patent number 3,912,581 [Application Number 05/500,258] was granted by the patent office on 1975-10-14 for non-woven web structures and method for making the same.
This patent grant is currently assigned to Rohm GmbH. Invention is credited to Herbert Fink, Manfred Munzer.
United States Patent |
3,912,581 |
Fink , et al. |
October 14, 1975 |
Non-woven web structures and method for making the same
Abstract
Improved method of preparing non-woven web structures which
comprises adding, to an aqueous suspension of fibers, such as
synthetic fibers, particles of a resin binder in the form of an
aqueous suspension of a polymer having a glass transition
temperature below 35.degree.C. (308.degree.K.), and then forming
and drying said web. Non-woven web structures prepared by this
method.
Inventors: |
Fink; Herbert (Bickenbach,
DT), Munzer; Manfred (Bensheim, DT) |
Assignee: |
Rohm GmbH (Darmstadt,
DT)
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Family
ID: |
27183396 |
Appl.
No.: |
05/500,258 |
Filed: |
August 26, 1974 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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247686 |
Apr 26, 1972 |
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Foreign Application Priority Data
Current U.S.
Class: |
162/164.1;
162/164.7; 162/168.2; 162/168.7; 162/169; 162/164.6; 162/168.1;
162/168.3 |
Current CPC
Class: |
D21H
17/34 (20130101); C08F 2/18 (20130101) |
Current International
Class: |
D21H
17/00 (20060101); C08F 2/12 (20060101); C08F
2/18 (20060101); D21H 17/34 (20060101); D21D
003/00 () |
Field of
Search: |
;162/164,168,169
;260/29.6TA,29.6R |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Williamson "An Improved Inst. for Eval. of the Phys. Prop. of High
Pol. Comp.," British Plastics, Sept. 1950, pp. 87-90, 102. .
Billmeyer "Text Book of Pol. Sci., " 2nd ed. pp. 129, 207, 208,
211, 355-361. .
Casey "Pulp & Paper" Vol. II 2nd ed., (1960) pp. 946,
947..
|
Primary Examiner: Bashore; S. Leon
Assistant Examiner: Chin; Peter
Attorney, Agent or Firm: Curtis, Morris & Safford
Parent Case Text
This is a continuation of application Ser. No. 247,686, filed Apr.
26, 1972 now abandoned.
Claims
What is claimed is:
1. In a process for the preparation of non-woven fabric by adding
particles of a resin binder to an aqueous suspension of fibers,
forming a web by depositing said fibers on a sieve, removing water
from said web, and drying said web, the improvement wherein said
particles of resin binder are added as an aqeous suspension of a
suspension polymer in an amount such that the resin solids added
are from 10 - 100 percent by weight of the suspended fibers, said
suspension polymer particles having an average diameter between
about 0.05 mm and 0.5 mm and said polymer having a glass transition
temperature below 35.degree.C. and being a homopolymer or copolymer
comprising a member selected from the group consisting of acrylic
acid esters having 1 - 18 carbon atoms in the alcohol portion
thereof, methacrylic acid esters having from 4 - 18 carbon atoms in
the alcohol portion thereof, butadiene, vinylidene chloride, vinyl
acetate, methyl methacrylate, ethyl methacrylate,
methacrylonitrile, acrylonitrile, acrylamide, methacrylamide, and
sytrene.
2. A process as in claim 1 wherein said suspension polymer
comprises an alkyl acrylate having from 1 - 18 carbon atoms in the
alcohol portion thereof.
3. A process as in claim 1 wherein said web is dried by heating at
a temperature between about 80.degree. and about 180.degree.C.
4. A process as in claim 1 wherein the aqueous phase of said
aqueous suspension of resin binder comprises a thickening agent
increasing the viscosity of the aqueous phase, whereby the
particles of the suspended polymer phase do not float or sink.
5. A process as in claim 1 wherein the aqueous phase of said
aqueous suspension of resin binder comprises water-soluble
additives rendering the density of the aqueous phase substantially
equal to the density of the suspended polymer phase.
6. A flexible porous planar non-woven fabric consisting essentially
of fibers bound to one another by fused particles of a suspension
polymer, said suspension polymer particles having an average
diameter between about 0.05 mm and 0.5 mm and said polymer having a
glass transition temperature below 35.degree.C. and being a
homopolymer or copolymer comprising a member selected from the
group consisting of acrylic acid esters having 1 - 18 carbon atoms
in the alcohol portion thereof, methacrylic acid esters having from
4 - 18 carbon atoms in the alcohol portion, butadiene, vinylidene
chloride, vinyl acetate, methyl methacrylate, ethyl methacrylate,
methacrylonitrile, acrylonitrile, acrylamide, methacrylamide, and
styrene.
Description
The present invention relates to non-woven web structures and to a
method for making the same. More in particular, the invention
relates to non-woven web structures prepared using an aqueous
polymer suspension as a binding agent for such structures, and to
the method of preparing the structures.
Ever since paper was first prepared in China for the first time
nearly two thousand years ago from an aqueous pulp of fibers
obtained by the crushing of mulberry bast, hemp, and rags, the
process of preparing a planar structure, or web, from an aqueous
suspension of fibers on a sieve, and the strengthening of this
structure by pressing and drying, has taken on great significance
in manifold variations. The preparation of paper in the modern age
has itself undergone the most rapid development, according to which
it is no longer unusual to achieve production rates of more than
1000 meters per minute and to produce paper in widths of several
meters. The same basic process is also used for the preparation of
other web structures, of which the most important are the non-woven
fabrics, although in the preparation of such fabrics longer fibers
must be employed in order to impart a textile-like hand to the
finished structure. According to a proposal of the German Bureau of
Standards, "Non-woven products" -- in accordance with the American
definition -- would be defined as follows: "Non-woven products are
flexible porous planar structures comprising textile fibers which,
before strengthening by mechanical means (for example by stitching
or the auxiliary use of other textile products), are bound to one
another with the aid of a binding agent, by superficial solvation,
by fusion, or by a combination of these processes."
Of the different methods for preparing non-woven fabrics, for
example the mechanical, the pneumatic, the fiberspinning, and the
wet process, the last-mentioned method can be outlined as follows,
with a view to the invention later described herein.
As in the preparation of paper, fibers are suspended in water.
However, the mixture of water and fibers, which is often
characterized as "pulp", must be present in an extraordinarily high
dilution in comparison with a paper pulp in order to avoid the
entanglement of the fibers which arises when long fibers are used.
The fiber concentrations are, for example, between 0.05 and 0.2
percent of the totoal weight of the suspension. The pulp is then
fed to a webforming structure, for example an inclined sieve.
Formation of the fabric follows by deposition of the fibers on the
sieve, withdrawal of the water, ans subsequent strengthening of the
web. Whereas in the preparation of paper the very finely ground
cellulose fibers are brought into intimate contact and, with the
formation of hydrogen bonds, reach a good initial wet strength, the
longer fibers of non-woven fabrics must be additionally bound by
the use of a binder system. The binder is either added to the
aqueous fiber suspension or is applied to the web after web
formation in a supplemental operation.
As raw materials for non-woven fabrics, synthetic fibers are
preferably employed, in part also in admixture with cellulosics,
said fibers having a staple length between 5 and 30 millimeters.
Fibers of mineral or inorganic substances, such as mineral wool or
glass are to be considered as technical equivalents of cellulose or
textile fibers within the scope of the present invention as are
also natural fibers, for example fibers obtained from scrap
leather.
In the preparation of non-woven fabrics according to the wet
method, the following strengthening techniques have heretofore been
used to advantage: the addition of binding fibers which melt; the
addition of binding fibers which swell in water; the addition of
dispersions of synthetic resin which are precipitated in the fiber
suspension; and, finally, the addition of priorly precipitated
resin dispersions.
The strengthening of non-woven fabrics with the aid of binding
agents of the type disclosed in the present invention on the one
hand resembles the two last-mentioned methods to a certain degree.
However, it is distinguished from these, on the other hand, in such
a considerable degree that the materials used in the present
invention must be viewed as forming a new class of binding agents
for the preparation of planar, or web, structures from fibers, the
use of which new agents entails a number of marked advantages.
In order to make these advantages clear, the following comments
must be made concerning the prior art precipitation of resin
dispersions on the fibers in suspension and the addition of
pre-precipitated dispersions of binding agents. Latex particles
cannot be quickly and completely deposited from a dispersion. This
leads to a considerable loss of the binder and also to the
appearance of so-called "vagabond binder", i.e. a balling together
of the dispersion particles which do not adhere to the fibers to
form large lumps. It is clear that the portions of binder which are
not fixed in the structure leaad to water-disposal problems.
It must further be pointed out that the precipitation of a latex
can only be controlled within wide limits with respect to a uniform
size of the precipitated particles. An unavoidable fraction of
small agglomerates do not form adhesive bonds, but only load the
fibers with binder and thus detract from the textile-like hand of
the material.
In order to precoagulate dispersions, particular apparatus
modifications are necessary. However, these do not lead to a
complete precipitation of all the latex particles so that in this
case also a loss of binder and waste-water problems are involved.
It should not unmentioned that the polymers useful as binders can
also be precipitated from organic solutions. However, this process
involves considerable disadvantages.
The advantage of using dispersions as binding agents in the
preparation of non-woven fabrics, namely that by a choice of the
monomers or monomer mixtures employed products which are "hard" or
"soft" can be produced as desired and that corresponding non-woven
fabrics can be prepared therefrom, is also inherent in the use of
suspension polymers according to the present invention, as will be
explained later herein.
The binding agents used according to the present invention are
distinguished from the synthetic resin dispersions heretofore used
in that they are aqueous suspensions, prepared according to a
suspension polymerization process, of those resins which form "soft
beads" or "soft pearls". Either the glass transition temperature,
T.sub.g, of the polymer, or those values obtained with the aid of
the torsion swign test (DIN 53445), can be employed as a measure of
the softness or hardness of the suspension polymers according to
the present invention.
As is known in the art, the glass transition temperature is
obtained dilatometrically. This measuring technique has the
disadvantage of considerably uncertainty in products having very
low glass transition temperatures. However, since the suspension
polymers suitable for use according to the present invention are
characterized by a maximum value of the glass transition
temperature (i.e. all suspension polymers whose glass transition
temperature falls below a specified value are encompassed within
the scope of the invention), the undependability described above in
the method for determining T.sub.g is without practical
significance in the present case. The characterization 10 suitable
polymers by their glass transition temperature was principally
chosen because the glass transition temperatures of numerous
macromolecular compounds have already been determined and
tabulated. For example, the "Polymer Handbook", by Brandrup and
Immergut, Interscience Publishers, a division of John Wiley &
Sons, New York (1966) lists the glass transition temperatures of a
large number of homopolymers and copolymers in Chapter 3 entitled
"Solid State Properties", pages 61-85. As well, the significance
and the techniques for determining these values are explained.
Homopolymers and copolymers of the kind to be employed according to
the present invention can thus be characterized as being prepared
as suspension polymers, as already explained; as being employed in
the form of an aqueous suspension; and finally as showing a glass
transition temperature, T.sub.g, less than 35.degree.C (less than
308.degree.K.).
Data which are obtained from the torsion swing test mentioned
earlier have in the recent past been increasingly used for the
characterization of synthetic resins. Since the suspension polymers
to be used according to the present invention can also be
characterized by these test values, a short description of their
determination follows.
In the torsion swing test, the temperature dependence of the
dynamic shear modulus, G,(T), and of the torsion swing damping,
.OMEGA. (T), are measured by means of free torsion swings.
The shear modulus is the quotient of the shear stress and the shear
deformation. It is, thus, a measure of the stiffness of a polymer
film.
For characterization of the softening region, use is made of a
still further value determinable from the torsion swing test,
namely the T.OMEGA..sub.max value. This value is the temperature at
which the logarithmic decrement of the torsion swing damping goes
through a maximum. The damping decrement is a measure of the inner
friction of the material and is determined from the decrease in
amplitude of a freely-damped torsional vibration.
The T.OMEGA..sub.max value which corresponds to the critical glass
transition temperature, T.sub.g, of 35.degree. is about
60.degree.C. However, it should be repeated that in doubtful cases
the glass transition temperature is to be taken as the decisive
criterion of the suspension polymers in question.
The suspension or bead polymerization of polymerizable monomeric
compounds can, as known in the art, be regarded as a well-cooled
bulk polymerization in which a water-insoluble monomer is dispersed
in the form of fine droplets by stirring in water in the presence
of so-called suspension stabilizers or dispersing agents, for
example gelatin, pectin, watersoluble starch, or synthetic high
molecular weight materials, or in the presence of materials
suspended in the water, such as talcum, magnesium carbonate, or
aluminum hydroxide, and is then polymerized under the influence of
an accelrator soluble in the monomer. In the polymerization, the
droplets, which are liquid at first, become rubbery and, finally,
solid. The goal of the suspension polymerization has until now in
all cases been the preparation of solid products which can be
separated from the aqueous phase in a simple way, for example by
filtration, and which are bead-like particles which are "hard",
i.e. which do not adhere to each other. The preparation of
suspension polymers from "soft resins", i.e. the preparation of
products which adhere together on separation of the aqueous phase,
has appeared until now to be contrary to the desired end in
suspension polymerizations, namely the easy separation and drying
of the polymer. However, the use of just such bead polymers as
binding agents for web structures comprising fibers is the object
of the present invention.
It is not necessary to go into more detail concerning the technique
of suspension polymerization to explain the present invention. It
suffices to note that one skilled in the art can influence the size
of the pearls, or beads, obtained by choice of the polymerization
conditions, particularly by the intensity of stirring and by the
kind and amount of the suspension stabilizer, and that by these
measures he can prepare beads having a diameter from, for example,
0.01 mm to several millimeters.
In general, for purposes of the present invention average bead
diameters between about 0.05 mm and 0.5 mm are preferred.
Although it is necessary to add the aforementioned suspension
stabilizers or dispersing agents to the system in order to form
defined monomer droplets and to hinder the adhesion, during the
polymerization process, of the spherical polymer particles formed,
it may be suitable additionally to stabilize the finished
suspension to inhibit a precipitation of the solid particles (in
case their density is greater than that of the aqueous phase), or
to inhibit floating of the particles (when they have a lesser
density than that of the aqueous phase). Also, possible adhesion
which may occur on long storage is hindered.
Such a stabilization is achieved with beads whose density is
greater than 1, for example by adding watersoluble salts such as
sodium chloride, or other materials influencing the density of the
aqueous phase.
Another possibility for stabilization lies in thickening the
aqueous phase. For this purpose, high molecular weight natural
pruducts (starch, alginate, pectin), modified forms of these
materials (methyl cellulose, carboxylmethyl cellulose, etc.), or
synthetic macromolecular products can be employed. Exemplary of the
last-mentioned class of materials are copolymers containing
carboxyl groups (or salts of the same) such as copolymers of
acrylic acid or methacrylic acid, or polyvinyl pyrrolidone.
Monomers which can be used according to the present invention and
which can be converted into bead polymers according to a suspension
polymerization process include, principally, acrylic esters having
1-18 carbon atoms in the alcohol portion; methacrylic esters having
from 4-18 carbon atoms in the alcohol portion; butadiene;
vinylidene chloride; and vinyl acetate. These monomers can be
copolymerized with one another or, also, with monomers producing
hard homopolymers. In the latter case, the proportion in which
those monomers forming hard homopolymers can be employed is limited
by the requirement that the glass transition temperature of the
resulting copolymer should not exceed the limiting value which is
characteristic of the present invention. As monomers of this type
forming hard homopolymers can be mentioned, for example, methyl and
ethyl methacrylate, methacrylonitrile, acrylonitrile, acrylamide,
methacrylamide, and styrene.
It should also be noted that the characteristic glass transition
temperature, T.sub.g, for a suspension polymer to be used according
to the present invention can be imparted by the use of so-called
"external plasticizers", such as pthalic acid esters, even in those
cases in which monomer or monomer mixture to be polymerized would
give a polymer having a higher glass temperature in the absence of
such a plasticizer.
Monomers effecting a cross-linking can be employed in the
preparation of the suspension polymers to be used according to the
present invention. However, they must be used with the proviso that
cross-linking of the suspended particles may only occur to such an
extent that the thermoplastic "welding" of the web fibers by fusion
of the binder resin on heating of the deposited web is not
impaired. The use of methylol compounds or methylol ether compounds
of acrylamide or methacrylamide, or the use of monomers having at
least two carbon-carbon double bonds in the molecule as comonomers
is exemplary of such a cross-linking mechanism. Also, a
cross-linking of macromolecular compounds can be brought about by
graft copolymerization reactions.
In special cases it can be advantageous to combine the binders
according to the present invention with resin dispersions known in
the prior art, for example in order to increase the film-forming
properties of the resin. Also, the use of mixtures of different
resin suspensions which are differentiated according to
composition, particle size, or molecular weight, can be
advantageous.
Resin suspensions according to the present invention can be
advantageously prepered with a solids content of from 50-70 percent
by weight. The materials can be stored and shipped in this form,
optionally after taking the stabilizing measures discussed earlier
herein. The resin suspensions can be added to fiber suspensions in
this concentrated form, particularly if good stirring is provided,
or can be diluted before addition if this is more convenient.
The amount of the suspension polymer to be added to the web-forming
fiber suspension can vary between wide limits according to the
nature of the fiber web to be prepared. In general, an amount of
suspension is employed which contains resin solids which are from
10 to 100 percent by weight of the suspended fibers.
A better understanding of the present invention will be had by
referring to the following specific examples, given by way of
illustration.
Measures available to one skilled in the art, such as the addition
of dyes, pigments, and the like, the selection of synthetic,
natural, or inorganic fibers which are not described herein in
greater detail, and the use of homopolymers and copolymers which
are not specifically described -- providing these can be obtained
as suspension polymers and have a glass transition temperature
below the characteristic limiting value described herein -- expand
the scope of specific embodiments of the binders according to the
present invention without taking them outside the scope of the
invention. It should particularly be mentioned that by appropriate
choice of the suspension polymer and of its average particle size,
products which are substantially "made to order" for a particular
use can be prepared. It is common to all of these products that
they can be stored for a long period of time, optionally using
supplemental stabilizing measures; that they deposit on fibers even
at extraordinarily low concentrations, calculated on the water
phase; and, in the drying process, lead to a uniform punctiform,
adhesion of the fibers on which they are deposited. When the resin
suspensions described above are employed, the disadvantage of
"vagabond" binder portions involved with the use of dispersions of
the prior art is not encountered, whereby losses of the binder as
well as waste-water problems are avoided.
EXAMPLES
I. Preparation of Resin Suspensions Suitable for Use According to
the Invention
The bead polymers listed in Table 1 are prepared either in a
two-liter round glass vessel having a triangular stirrer or in a
100-liter kettle with an impeller-type stirrer and wave breaker.
Heating in the first case is with a water bath: in the second case
a heating mantle having circulating water is employed. The
apparatus in each case is equipped with temperature sensors, a
reflux condenser, and an arrangement for flushing with inert gas.
The speed of stirring is variable by a gear arrangement. For the
polymerization of monomers which are gaseous at the polymerization
temperature (for example, vinylidene chloride), the 100-liter
kettle is sealed pressuretight.
The polymerization is carried out in the following manner.
The suspending agent (suspension stabilizer) is dissolved or
suspended in an already-present total amount of de-ionized water
while stirring, introducing inert gas (e.g. nitrogen or carbon
dioxide), and heating to polymerization temperature (65.degree.
-80.degree.C.). As is evident from Table 1, a partially-hydrolyzed
polyvinyl acetate (commercially available under the tradename
"Mowiol N 70- 88") or the sodium salt of a copolymer of methacrylic
acid and one of its higher alkyl esters (more than four carbon
atoms in the alcohol portion), characterized in Table 1 as PMAA
copolymer, are used as water-soluble suspending agents. For the
preparation of a water-insoluble suspending agent, aluminum
hydroxide is precipitated from a solution of aluminum sulfate with
a soda solution. To improve the suspending effect, 5 percent, by
weight of the aluminum hydroxide, of a C.sub.14 -C.sub.16 alkyl
sulfonate sodium salt (commercially available under the tradename
"Statexan K 1") is added.
The monomer phase, which contains the initiator and optional
molecular weight regulators, as well as other additives such as
plasticizers, dyestuffs, and the like in dissolved form, is
introduced into this solution or suspension of the suspending agent
and is dispersed in the form of fine droplets by the shearing
action of the stirring. The form and the speed of rotation of the
stirrer are variable over wide limits. What is necessary is that
the stirring system bring about such a strong vertical circulation
of the kettle contents that, in addition to the dispersion of the
monomer as droplets of the desired size, any rising or sinking of
the monomer droplets brought about by density differences between
the water phase and the monomer phase is hindered. As monomers
suitable for bead polymerization, water-insoluble compounds or
compounds difficulty soluble in water are principally employed.
Nevertheless, water-soluble monomers such as acrylic acid or
methacrylic acid and their amides or, optionally, their substituted
amides, can be employed in minor amounts. It is decisive for the
success of such a bead polymerization that the equilibrium
distribution of these monomers between the water phase and the
monomer phase makes polymerization in the monomer droplets
possible. The ratio between the water phase and the monomer phase
is variable between 4:1 and 1.5:1 (by weight). At the ratio of 3:1
generally used, the following batch sizes are involved: 2 liter
round flask: 900 g water; 300 g monomer; 100 liter kettle: 45 kg
water; 15 kg monomer.
In the choice of auxiliary polymerization agents (initiator, chain
transfer agent), the only limitations observed for the preparation
of soft beads are the same as those which are generally observed
for bead polymerization, for example with respect to solubility
properites of these agents with respect to water and the
monomers.
The compositions of the bead polymers prepared are set forth in
Table 1.
During the polymerization, the exterior temperature (water bath or
circulating heating) is held constant. The inner temperature
increases because of the heat of polymerization which is released
and reaches a maximum which is about 10.degree. - 20.degree.C.
above the starting temperature after about 30- 120 minutes.
The temperature reached is held constant for about 2 hours by
regulation of the heating, after which the batch is cooled to about
25.degree.C. and introduced into a storage container.
By subsequent separation of a portion of the water phase, the
solids content of the bead suspension is adjusted to 50 percent.
Since there are as a rule density differences between the bead
polymer and the water phase, the polymer either settles or rises.
However, the dispersing agent added before the polymerization
generally suffices to hinder adhesion of the beads under these
conditions, even on long storage.
The average particle size of the polymer beads is, to the extend
that the data is given in the Table, determined microscopically.
The average bead size in suspensions O - X is between 0.1 and 0.2
mm.
To characterize the molecular size, the .eta. .sub.sp/c value
[Makromolekulare Chemie 7, 294 (1952)] is given, measured at
20.degree.C. in chloroform. The molecular weights of the polymers
are in excess of 5000.
In the following Table, all parts given are parts by weight.
TABLE 1
__________________________________________________________________________
Composition of the Polymerization Batch Polymer- Stir- Sus- Chain-
ization ring Bead pen- Appa- Transfer Temp. Rate Size .eta..sub.sp
T.sub.g sion ratus Dispersant Monomers Initiator Agent Additive
(.degree.C.) (rpm) (mm) (l/g) (.degree.C)
__________________________________________________________________________
A Kettle 0.4 Al(OH).sub.3 80 Butylacrylate/ 0.3 Lauroyl- 0.2
Dodecyl- -- 75 170 0.05 0.080 -25 20 Acrylonitrile Peroxide
mercaptan B " " " " " -- " 110 0.10 0.078 -25 C " " " " " -- " 90
0.15 0.079 -25 D " " " " " -- " 75 0.20 0.077 -25 E " " " " " -- "
65 0.25 0.080 -25 F " " " " 0.5 Ethyl- -- 75 110 0.050 -25
hexylthio- glycolate G " " " " 0.1 Dodecyl- -- 75 110 0.13 -25
mercaptan H Flask 0.4 Al(OH).sub.3 80 Butylacrylate 0.2 AIBN* 0.2 "
0.1 Blue 75 710 0.10 0.083 -23 20 Methylmeth- Dye** acrylate I " "
" " " " " 610 0.15 0.086 -23 K " " " " " " " 470 0.20 0.087 -23 L "
" " " " " " 390 0.25 0.084 -23 M Flask 0.4 Al(OH).sub.3 60
Butylacrylate/ 0.2 AIBN* 0.2 Dodecyl- -- 75 610 0.1-0.2 0.085 +8 40
Methylmeth- mercaptan acrylate N " " 45 Butylacrylate/ " " -- 75
610 " 0.088 +33 55 Methylmeth- acrylate O " 0.1 PMAA 75
Butylacrylate/ 0.5 Lauroyl- 0.4 Ethyl- -- 75 610 " 0.10 -15
Copolymer 20 Acrylonitrile/ Peroxide hexylthio- 5 Methacrylamide
glycolate P " 0.4 Al(OH).sub.3 95 Ethylacrylate/ 0.2 Lauroyl- 0.2
Dodecyl- not 3 Methylolmeth- Peroxide mercaptan -- 75 610 " mea-
-20 acrylamide/ 2 surable Methacrylamide Q Pres- 65 Vinylidene- 0.3
" -- -- 80 110 " 0.078 +15 sure 0.4 Al(OH).sub.3 chloride/ 35
Kettle Ethylacrylate R Flask 1.0 poly- 75 Ethylacrylate/ 0.3 AIBN*
0.2 Thioglycol -- 75 610 " not +20 vinyl ace- 15 methylmeth- mea-
tate acrylate/ 10 meth- surable acrylic acid S " 0.4 Al(OH).sub.3
80 Butylacrylate/ 0.5 Lauroyl- 0.2 Dodecyl- -- 75 610 " 0.13
<-30 20 Vinylacetate Peroxide mercaptan T " " 100
C.sub.12.sub.-18 -Alkyl- 0.5 " 0.2 " -- 75 610 " 0.031 "
methacrylate U " " 100 C.sub.12.sub.-18 -Alkyl- 0.5 " 0.2 " 75 610
" 0.048 " acrylate V Flask 0.4 Al(OH).sub.3 100 2-Ethylhexyl- 0.5
Lauroyl- 0.2 Dodecyl- acrylate Peroxide mercaptan 75 610 " 0.062
<-30 W " 0.1 PMAA- 70 Methylmeth- 0.2 t-Butyl- 0.1 " 30 Dibu-
Copolymer acrylate perpivalate tyl- phthalate 65 610 " 0.075 +30 X
" " 50 Methylmeth- 0.2 " 0.1 " 50 " 65 610 " 0.053 -13 acrylate
__________________________________________________________________________
*Azo-isobutyronitrile **Commercially available as "Makrolex-blau
R
II. Preparation of Web Structures from Fibrous Materials Using
Resin Suspensions According to I as a Binder
The following process is generally employed.
The binder is added in the form of an aqueous 50 percent suspension
of bead-like resin particles to a 0.1 percent aqueous fiber
suspension. (In those cases where a different fiber concentration
is employed, this is specifically noted.) The amount employed
depends on the desired binder deposit. After thorough mixing, the
suspension is deposited in web form on an inclined sieve (sieve
mesh number 0.16; DIN 4188 ), and water is removed. The surface
weight of the web is determined by the rate of web formation. In
all cases investigated, a clear waste water was obtained.
The web formed is then subjected to a heat treatment, for example
on heated cylinders, in order to evaporate the remaining water and
to adhere the resin particles to the fibers. In this step, the
temperatures employed are determined by the hardness or softness of
the resin employed as a binder, and may vary from about
80.degree.C. to about 180.degree.C.
EXAMPLE 1
Using cellulose fibers (1.7 dtex; length: 6 mm; and binders A - G,
webs having a weight of 50 g/m.sup.2 and a binder deposit of 30
percent are prepared and dried. Subsequently, they are calendered
at a pressure of 1 metric ton/cm.sup.2 at 20.degree.C. and then
treated on a flat-iron press for about 1 minute at 170.degree.C.
under a pressure of 13 gf/cm.sup.2. All the non-woven products show
a pleasant soft and textile-like hand. Their resistance to tear is
determined on samples which are 5 cm in width according to DIN
53857. The values obtained are collected in the following
Table.
TABLE 2 ______________________________________ Sus- Average
particle Average Load pen- Size of the Resin .eta..sub.sp /c (l/g)
on Tearing sion Particles (mm) (kgf)
______________________________________ A 0.05 1.0 B 0.10 1.1 C 0.15
ca. 0.08 2.1 D 0.20 1.4 E 0.25 0.7 F 0.10 0.05 1.0 B 0.10 0.08 1.1
G 0.10 0.13 1.3 ______________________________________
EXAMPLE 2
Example 1 is repeated using binder C, with the difference that
differing amounts of deposited binder are employed. In this case
also, the strength properties of the material are determined
according to DIN 53857.
TABLE 3 ______________________________________ Binder Deposit Load
on Tearing Extension on Tearing (%) (kgf) (%)
______________________________________ 20 1.2 20 25 1.4 25 30 2.1
30 35 2.8 45 40 3.3 55 ______________________________________
EXAMPLE 3
Example 1 is repeated with the difference that nonwoven products
having a surface weight of 100 g/m.sup.2 are prepared from
cellulose fibers or from mixtures of cellulose fibers with
polyamide or polyester fibers using binder C at a binder deposit of
80 percent. The density of solids in the solid suspension in this
case is 0.3 percent. The strength values determined according to
DIN 53857 are given in following Table 4.
TABLE 4 ______________________________________ Mix Load Extension
Ratio on on (Parts by Tearing Tearing Fiber or Fiber Mixture
Weight) (kgf) (%) ______________________________________ Cellulose
Fiber (1.7 dtex; length = 6mm) 100 17.3 65 Cellulose fiber (1.7
dtex; length = 6mm)/poly- 70/30 13.5 60 amide (6 dtex; length =
3mm) Cellulose fiber (1.7 dtex; length = 6mm)/polyester 70/30 19.7
68 (1.7 dtex; length = 6mm)
______________________________________
EXAMPLE 4
Example 1 is repeated with the difference that colored binders H -
L are employed. In the finished web, the colored resin particles
clearly make evident the uniform dispersion of the punctiform
adhesion sites.
TABLE 5 ______________________________________ Suspension Average
Particle Size of the Resin Particles Load on Tearing (mm) in (kgf)
______________________________________ H 0.10 0.2 I 0.15 0.7 K 0.20
0.2 L 0.25 0.3 ______________________________________
EXAMPLE 5
Example 1 is repeated with the difference that fabrics having the
binding agents I, M, and N are prepared. It is clearly evident from
manual handling of the finished nonwoven product that an increasing
fraction of methylmethacrylate produces a harder hand.
EXAMPLE 6
Example 1 is repeated with the difference that binders C, O, and P
are employed as binding agents. The weight of the non-woven product
was 50 g/m.sup.2 and the binder fraction was 50 percent. The
finished non-woven products are subjected to laundering according
to DIN 54014 (30 minutes at 40.degree.C. with 5 g of soap per liter
of wash water in the ABK-Lavatest) and to drycleaning according to
DIN 54024 (30 minutes at 30.degree.C. in perchloroethylene with the
addition of 3 grams of cleaning intensifier per liter of bath in
ABK-Lavatest). After laundering, the web adhesion is maintained in
all the non-woven products.
The web prepared using binder C is completely destroyed on
drycleaning. The web containing biner O still shows a certain
maintenance of the web adhesion. The non-woven product prepared
with binding agent P, typifying a self-cross-linking acrylic resin,
is resistant to the rigors of drycleaning according to DIN
54024.
EXAMPLE 7
Non-woven fabrics are prepared as in Example 1, using binding agent
Q at increasing concentrations of the binder. At a binder deposit
of 30 percent, a flame-inhibiting effect is observed [DIN-Standard:
Determination of Burning and Smoldering Properties of Inflammable
Textiles (Arc Tester); presently in draft].
EXAMPLE 8
A non-woven fabric is prepared as in Example 1 using binder R. The
finished article is tested for resistance to water according to H.
Joerder, Textil-Industrie 71, 302 (1969). The test show that a time
of only 60 seconds is necessary for destruction of the web prepared
using this carboxy group-containing copolymer as a binder. Such
limited resistance to water is of significance for many hygienic
articles.
EXAMPLE 9
Example 1 is repeated using binders S - V. The resultant webs
(binder deposit = 50 percent) are carefully dried at 80.degree. -
100.degree.C. They have a tacky hand and can be adhered to one
another by calendering under pressure.
EXAMPLE 10
Non-woven products are prepared as in Example 9 using binders W and
X. The binder deposit is 50 percent. Both non-woven fabrics can be
heat sealed, i.e., they can be adhered under pressure at
temperatures of 140.degree.C. to cotton fabric. It can clearly be
seen that better adhesion is obtained with binder X than with
binder W.
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