Note: Descriptions are shown in the official language in which they were submitted.
57~0
The present invention relates to a novel composite sheet material
having an appearance like that of a high-class napped woolen woven fabric.
More particularly, the present invention relates to a novel sheet-like material
especially suitable for clothes, having an appearance like that of a high-
class napped woolen woven fabric, being soft and pliant, having a soft touch
and a crush-resistant nap which is relatively erect as compared with the nap
of suede, being deep color, ha~ing proper sliding and smoothness, luster and
good resistance to cigarette burns, being free from fray of a selvage like
that of a woven fabric, being light weight and crease resistant.
~eretofore, a napped fabric impregnated with an elastic polymer
generally had an appearance like that of suede and not like a napped woolen
woven fabric.
The present invention improves a napped state by the use of a
hardened organic high molecular weight compound such as silicone rubber, giving
a new touch, nap and a good appearance like that of a napped woolen woven
fabric to a napped fabric impregnated with an elastic polymer.
; ~n Laid~o~en Japanese Patent Application No. 401/1974 is described
the application of a specified cationic surface active agent to a non-woven
fabric having a nap consisting of a superfine fiber and containing an elastic
polymer thereby to bind the root portion of said nap. This prior invention
contrives for an improvement of the napped s*ate, however, a sheet obtained
by the prior invention is always suede-like, remarkably bringing about a chalk
mark and never becomes like a napped woolen woven fabric as in the present
inYentiOn.
In Laid-open Japanese Patent Application No. 54501/1974 is described
a process for preparing an artificial leather which comprises, prior to
impregnation and coagulation of a non-woven fabric with an elastic polymer,
impregnating said non-woven fabric with a provisional binding substance con-
sisting of silicone and a water-soluble high molecular weight substance such
as polyvinyl acetate in advance, buffing the impregnated non-woven fabric and
~"~
1(~9570V
thereafter removing said provisional binding substance. The object of using
silicone here consists in shutting off bonding of fibers with said elastic
polymer, utilizing the sliding effect of silicone and raising a uniform and
short nap at the time of buffing, which is entirely different from the object
of binding the nap as in the present invention. Moreover, in the present
invention, it is necessary that the high molecular weight organic compound
should be hardened, whereas in the prior disclosure, such high molecular weight
elastomer is used in a liquid state such as solution or emulsion.
In Japanese Patent Application Publication No. 33797/1970 is des-
cribed a process for preparing artificial leather which comprises impregnating
a preliminarily silicone resin - processed fabric with an elastic polymer and ^
coagulating said fabric. The object of using a silicone resin is the same as
in Laid-open Japanese Patent Application No. 54501/1972, namely reducing the
adhesiveness of the fibers to said elastomer, which is different from the
object of the present invention.
Laid-open Japanese Patent Application No. 4460/1972 achieves a
similar object similar to that of the Publication No. 33797/1970 by the use of
wax in place of silicone.
In each of these prior art documents, nothing is referred to or
suggested about preparing a fabric having an appearance like that of a high-
class napped woolen woven fabric by binding many naps to a single unitary
strand with a hardened organic high molecular weight compound.
An object of the present invention is to provide a novel material
having an appearance like that of a high-class napped woolen woven fabric
suitable for clothes, wall material, furniture, e*c.
More particularly, it is an object of the present invention to
provide a novel material improved in the following respects:
(1~ That it may be artificially prepared.
~2~ l~at it has a nice surface touch.
(3) That it has an appearance like that of a high-class napped woolen
~s~7ao
woven fabric.
(4) That it has no fray of a selvage like a woven
fabric and it can be sewn without a hemstitch.
(5) That a hole is not readily made in it by a
lighted cigarette.
(6) That it has a smooth touch7 bulkiness and puffy
hand.
~ 7) That it has little sound like that of leather.
~ 8) That it has little nap reversibility like that
of suede (a suede effect is unlikely to come out on it).
(9) That it is light weight, its appearance and
dimensions are stable after it is washed, and especially it can
be washed with water.
(10) That its nap is unlikely to be entangled and
spills are unlikely to occur on it.
(11) That it is durable.
(12) That it is rich in easy-care properties and
crease-resistant and it has packability such that when it is
folded and put into a bag and thereafter taken out therefrom,
it is immediately ready to wear.
Accordingly, one aspect of the invention provides a
composite sheet which comprises a fabric impregnated with an
elastic polymer and a hardened high molecular weight organic
compound~ containing a plurality of naps formed from the ends
of fibers constituting the fabric on at least one surface of the
sheet, each of said naps being a bundle of fibers having a root
portion and a tip portion, said root portion in most naps hav-
ing the shape of a single unitary strand and said tip portion
including at least some individually dis~inct fibers.
Another aspect of the invention provides a process for
preparing a composite sheet which comprises applying a harden-
able high molecular weight organic compound to a fabric~ harden-
C ~- 3 -
1~95700
ing said compound, subsequently applying an elastomer to said
fabric and thereafter buffing and/or raising said fabric,
wherein the adherence between the fibers and the hardened
organic compound is greater than the adherence between the
hardened organic c:ompound and the elastomer.
Embodiments of the invention will be described, by
way of example, with ---
- 3a -
57~)
reference to the accompanying drawing, in which:
Figure 1 is a schematic view showing the nap of a composite sheet;
Figure 2~a) and Figure 2(b) are partial enlarged views of Figure 1,
Figure 3 is a schematic view showing ~he condition of the nap of
a conventional suede-like sheet;
Figure 4 is a diagrammatic cross-sectional view showing the
relation between a fib~r and two kinds of high molecular weight compound;
Figure 5 shows in cross-section examples of fibers suitable for
preparing a superfine fiber.
As a fiber constituting a fabric in the present invention, a bundle
of superfine fibers of less than 0.7 denier, especially less than 0.5 denier
is preferable.
~; There are various processes for obtaining a bundle of superfine
fibers, however, in the present inven~ion, what is obtained from a multi-
component fiber described in, for example, United States Patent 3,531,368 and
commonly called an "islands-in-a~sea" type fiber is most preferable based on
many reasons such as easiness to prepare, yield, dispersibility, qualitative
stability, reproducibility, easily controllable structure and easiness to make
it an intertwined body.
This fiber is a multi-component fiber and when at least one com-
ponent (sea component) is chemically or mechanically removed therefrom,
superfine fibers consisting of the remaining (island) components are obtained
as a bundle. For example, the cross-sections of such fibers are shown in
parts (A), ~D) and ~F) of Figure 5. When cross-sections of such "islands-in-
a-sea" type fibers are observed, many island components are divided so as to
be dispersed and distributed in a sea component and the island components are
continuous in the direction of the fiber axis. Any number (n) of island com-
ponents may be taken, however, usually n is selected within the range of
n <10000.
As island components, polyester such as polyethylene terephthalate
gS'7~0
and a copolymer thereof ~a homopolymer or copolymer for mixing like isophthalic
acid and sodium sulfonate isophthalate) and polybutylene terephthalate; poly-
amide 6, 66 and 6-10; polypropylene, polyethylene and polyacrylonitrile are
often used.
Such "islands-in-a-sea" type fiber is not limited in shape as to
whether it is hollow or it has a transformed cross-section.
Many studies of fibers similar thereto have been carried out since
then, which include the following. Namely, there are polymer blend spun
fibers obtained by selecting the characte istics of polymers, their blending
conditions and their spinning conditions so that one component is continuous
slenderly and lengthily in another component, a bundle of fibers bound by a
binding agent of a yarn spun by a method of spinning which comprises passing
two kinds of polymer through a labyrinthian mixer (vib-mixer, static mixer,
etc.) to promote division and integration of the two kinds of polymer, there-
after, passing these polymers through a filter to change their filmy state to
a dot-like state and-spinning, namely superdraw spinning and drawing or by
superfine wet spinning or a multi-component fiber becoming a bundle of super-
fine ibers or fibrillated by dynamically strongly rubbing or a fiber exhibit-
ing characteristics similar to those of said multi-component fiber, for
example, having a cross-section such as (B) or ~C) of Figure 5 or (A~ of
Figure 5 wherein the ratio of island components is large. Using these fibers,
fabrics are prepared.
The kind of fabric is not particularly limited, and may be any one
of woven, knitted and non-woven fabrics. Especially, in case the fabric is a
non-woven fabric, it is possible ~o make its appearance like that of a napped
woolen woven fabric despite it being a non-woven fabric. The most typical
non-woven fabric is that obtained by needle punching a laminated web or mono-
layer web with a cross lapper and a random webber~ What is especially prefer-
able is to slice and halve the fabric later and to combine buffing.
When the obtained fabric consists of an "islands-in-a-sea" type
lf~l95~V
multi-component fiber, except in the case in which the ratio of the sea com-
ponent is small, it is necessary to remove or separate the sea component. It
is necessary to remove or separate the sea component before the hardenable
organic high molecular weight compound is imparted to the fabric. When the
sea component is removed or separated, the fabric becomes soft. However, when
the overall fiber density is low, the fabric becomes too sof~ sometimes when
the postprocessing handling is taken into account. In such case, it is pre-
ferable to impart or apply to the fabric in advance, a water-soluble or hot
water-soluble sizing agent such as polyvinyl alcohol, a partly saponified
polyvinyl alcohol, carboxymethyl cellulose, methyl cellulose, sodium poly-
acrylate, polyacrylamide and starch; such method being what has been provided
by the present inventors. Imparting naturally includes usual means such as
dipping, coating, sa.ueezing and drying. The sizing agent is removed when the
necessity for fixing the shape of the fabric disappears. Said agent is
normally removed after the elastic polymer is imparted, however, it may be
removed prior thereto as the case may be. In case the sea component of the
"islands-in-a-sea" type multi-component fiber is polystyrene or a copolymer
of polystyrene and another known monomer of the vinyl series, one kind or a
combination of at least two kinds selected from the group of the solvents
therefore such as trichloroethylene, perchloroethylene, toluene, xylene and
benzene is used as a removing agent.
To the so obtained fabric is imparted a hardenable organic high
molecular weight compound and thereafter, said compound is hardened. As such
hardenable organic high molecular weight compound, there are an organosilicone
compound (in a solution or emulsion state) and a self-crosslinking type acryl
resin emulsion, of which the most effective compound for the present invention
is a high molecular weight organosilicone compound.
A typical example of forming a hardened high molecular weight
organosilicone compound is a combination of polyorganosiloxane with a medicine
(chemical) necessary for hardening (which may be called vulcanization in the
~9S7(~)
case of a rubber, which is included here). What is especially useful in the
present invention is silicone rubber.
It is known that such silicone rubber is prepared by the following
reactions. There are, for example, a monoliquid type and a biliquid type, for
each of which, there are a condensation reaction type, an addition reaction
type and a ring-opening reaction type, ther are effectively used. When
chemical formulae of the main reactions only are shown, they are as follows.
In many cases, they react at a relatively low temperature such as room tempera-
ture, to say nothing of reacting by moisture and by a high temperature.
Monliquid group:
(1) Acetic acid-removing condensation type:
O ,.
....... . , , . ....................................... .
-Si-OH+CH CO-Si- ~ -$i-0-Si-0-Si-+CH C-COH
3 , , . , 3
~2) Oxime-removing condensation type:
-Si-OH+,C=NO-Si- ~ -Si-0-Si-+`C=NOH
.
(3) Alcohol-removing condensation type:
-Si-OH+R0-Si~ Si-0-Si-+ROH
(4) Amine-removing condensation type:
$ R N -~ -si-o-si-+R>NH
(5) Amide-removing condensation type:
O O
.. , , ,
-Si-OH+RCN-Si-~ -Si-0-Si-+RCNH
t
R R
Monoliquid addition reaction type:
(1) Vinyl-addition reaction type:
-Si-CH=CH +HSi-> -Si-CH~CH2-Si-
2 . Cat.
~2~ peroxide type:
-Si-CH +CH3=CHSi- -~ Si-CH -CH -CH Si
- , 3 peroxide ~ l
``` l~;~9S7~)
~iliquid condensation reaction type:
~1) Alcohol-removing condensation type:
-SiQH~ROSi- Cat.> -Si-O-Si+ROH
Example Cat.: metal salt of fatty acid
(2) Oxylamine-removing condensation type:
-SiOH+R>NOSi- ~ si-o-si-+R~NoH
(3) Dehydrogenation condensation type:
-Si-OH+HSi- ~ -Si-O-Si-+H2
Cat.
Biliquid reaction type:
(1) Vinyl-addition reaction type:
t
-Si-CH=CH2+HSi- . _ ~ -Si-CH2_CH2_Si_
Cat.
Example Cat.: platinum compound, etc.
(2) Ring-opening reaction type:
(A) ,NH~cH2/cH-cH2-oR-si- ~ ,N-cH2-cH-cH2-oR-si
o OH
-Si-OH ~ C\H2/cH-cH2-oR-~ -t-si-o-cH2-cH-cH2-oR-si
OH
The main skeleton is polysiloxane, and polydimethyl siloxane is most
representative, besides which, that a little or considerable part of which is
made phenyl group, hydrogen or vinyl group as crosslinking reactivity or epoxy
group as ring-opening reactivity is well known also. What has -OH, -CH=CH2,
-OR, -CH3 and ~O-CH2-CH-CH2 at a terminal is general. These terminal groups
o
react between or among themselves or with various silanes. In the reaction,
water including water vapor, a platinum compound such as chloro-platinic acid,
peroxide, an organometallic compound such as a metal salt of fatty acid, a
radical-releasing compound and an aminosilane con~pound are used in conformity
with the reaction.
-8-
~957(~)
The molecular weight of the main skeleton is 10,000 - 1,000,000 in
the case of what is most often used.
What is most often used for advancing the physical properties of a
hardened (organic high molecular weight) compound is silicon oxid~ such as
aerosol silica. Besides, there are titanium oxide, carbon black, calcium
carbonateJ diatomaceous earth, quartz powder, asbestos, zinc oxide and
zirconium silicate.
They are preferably treated with chain or cyclic silane, silanol,
siloxane and silazane. It goes without saying that besides these, various
additives such as a coloring pigment and an extracting agent for making porous
may be used.
Information in these areas is obtainable from many patents owned by
Dow Corning Co. of U.S.A. J and various technical papers from Toray Silicone Co.,
Toshiba 5ilicone Co. and Shinetsu Chemical Industries Co., all of Japan.
As examples of the latest literature, there may be mentioned
Japanese Patent Application Publications Nos. 27704/1976, 27705/1976 and
27706/1976 ~Dow Corning Co.), Laid-open Japanese Patent Application No.
94295/1975 ~Dow Chemical Co. of Great Britain), Japanese Patent Application
Publication No. 27703/1976 (Kuraray Co. of Japan), Japanese Patent Application
Publication No. 24303/1976 ~Toshiba Silicone Co.), Japanese Patent Application
Publications Nos. 24301/1976, 24302/1976, 23977/~976, 23979/1976, 25069/1976,
28308/1976, 28309/1976 and 28310/1976 (Shinetsu Chemical Industries Co.) as
well as Laid-open Japanese Patent Appiica~ions Nos. 34291/1976, 39773/1976
and 49995/1976 (Shinetsu Chemical Industries Co.), in which resinification for
various objects is disclosed. These knowledges and arts are effectively and
preferably used in the present invention.
In the present invention, at first a fabric is applied to or im-
pregnated with a hardenable organic high molecular weight compound such as an
organosilicone compound. Said compound has a viscosi~y at which it is easy
to impregnate the same in an unreacted state in many cases, therefore, it is
_ g _
~957~0
possible to directly apply or impregnate the same, however, it is preferable
to make said compound a solution or emulsion (dispersion) because in such
state, not only it is easy to apply or impregnate said compound, but also
such state is excellent in uniformity, controllability of an imparting amount
and operability. It is a matter of course that a solvent and a dispersion
medium are removed later by drying. Subsequently, in an applied or impregnated
state, a hardening reaction of said hardenable organic high molecular weight
compound is caused to proceed9 fixation of emulsion particles is caused to
proceed or the reaction and the fixation are caused to simultaneously
proceed. For example, when hardening is effected by heating, a sheet is
passed through a heating zone, and when a reaction proceeds by moisture in
the air, the sheet is allowed to stand in the air for a sufficient period
of time, by which hardening of said compound is achieved. An imparting
operation of said compound is generally carried out in a place where there
is air, therefore, it is more excellent from the industrial and stabilizing
viewpoints to clearly harden said compound by heating than to harden said
compound by moisture.
As mentioned above, when a sizing agent is used for an intertwined
sheet, it is necessary to effect heating so as not to insolubilize said agent
or melt a fiber per se.
In such way, silicone is hardened, fixes and adheres around a space
among bundles of fibers as a main body. From the nature of surface tension,
silicone tends to adhere to the inside and around bundles of fibers and to the
intersecting points of bundles of fibers. In order to further promote this
tendency, it is preferable to use a silane coupling agent in advance and in
admixture from a reason to be mentioned later.
Next, various elastic polymers such as polyurethane are imparted.
The elastic polymers are preferably imparted in the state of a solution or
emulsion. When said silicGne is silicone rub~er, the result becomes a two-
stage impregnation of two specified elastomers. After proceeding coagulation
-- 10 ~
11~'957~
and fixation (solidiication) J removal of a sizing agent is caused to proceed
by washing,if necessary. When a solvent is used, it is preferable that a
greater part or substantially all of the solvent used is removed together with
said sizing agent.
As such elastic polymers polyurethane of the ether series, poly-
urethane of the ester series (polyurethane is considered including a urea
bond, containing block- and co-polyurethane), polyurethane of the ether series,
and all of various rubbers such as natural rubber, chloroprene rubber, SBR
and NBR are used. That which withstands a dyeing temperature is preferable.
One example of the most preferable combination in preparation of a
composite sheet of the present invention is when polyester is used as a fiber,
partly or completely saponified polyvinyl alcohol as a sizing agent, a material
for a silicone rubber - forming reaction as hardenable high molecular weight
organic compound and polyurethane as anelastic polymer.
Polyurethane is most often prepared from a reaction of polyole
with diisocyanate. As polyole: polytetrahydrofuran, polycaprolactone and poly-
hexanediol adipate are used alone or in admixture: as isocyanate: diphenyl-
methane~,4'-diisocyanate (MDI) and hydrogenated MDI are used alone, in admix-
ture or in a multi-stage reaction; as a chain extender: ethylene glycol,
butylene glycol, hydrazine and meth~lene bis-aniline (MBA) are used alone, in
admixture or in a multi-stage reaction.
The so completed composite sheet is buffed thereafter. As occasion
demands, it is sliced, buffed and napped. Sometimes it is buffed after
necessary treatments are carried out. A napped grey fabric, when not spun
dyed, is commonly dyed subsequently. When the material is polyester, it is
dyed with a dispersed dye. When the material is improved in properties to be
dyeable with a basic dye, it is dyed with a basic dye. Nylon such as nylon 6
and nylon 66 is dyed with an acid dye in a wide sense.
After the composite sheet is dyed, it is preferable to carry out
reduction washing.
57QO
It goes without saying that a proper known finishing agent is
commonly used on sheet after it is dyed. Sometimes a finishing agent is not
used. However, in order to further improve the slime, luster, touch and soft-
ness, it is preferable to use such a finishing agent.
After dyeing, upon drying the fabric, it is preferable to wet comb
(smooth down with a brush) the nap in a direction parallel with (positive to)
or contrary to the passing direction of the dyeing machine and/or the direction
of buffing.
When the napping state of the so finished novel material having an
appearance like that of a high-class napped woolen woven fabric is observed,
what is sketched in Figure 1 may be taken as one example. This nap is greatly
differe~t from that of a conventional material prepared for a suede-like fabric.
In this example, nap is bound as strands with hardened silicone. ~ome strands
decrease in number of fibers halfway and are tapered by buffing. In Figure 1,
(1) shows a tip of a superfine fiber, (2) shows a part where fibers are bound,
but decrease in number, becoming a slender bundle, and (3) shows a part where
superfine fibers are bound.
On the other hand, as a comparison for reference, an example where-
in a silicone compound is not used, but polyurethane only is used, is shown.
In this case also, the fabric becomes like suede, however, the napped state of
said fabric becomes like, for example, what is shown in Figure 3. The same as
a part close to the tip of nap (4), a root portion of nap (5) is slender
Cordinarily~ this fabric having a suede effect, nap is seen in a more fallen
state than is shown in many cases).
As sucn, in a composite sheet of the present invention, the root
portion of nap is bound and thick, while the tip becomes slender or branches
to become slender, at any rate, the tip is slender, having a nice touch. The
main structure of bundles is a bundle of fibers obtained by removing or
mechanically peeling the sea component from an "islands-in-a-sea" type multi-
component fiber, however, as the case may be, thicker bundles each comprising
- 12 -
57~
several blmdles of fibers brought about at the time of needle punching are con-
tained. The root portion being thickJ the nap becomes firm. Therefore, as
compared with that in which fibers are not bound, namely, a suede-like fabric,
a fabric of the present invention changes to one very unlikely to show a
reversible falling state of nap, namely, free from a suede effect, which is
considered one reason why a napped woolen woven fabric-like appearance is
given. Taper is considered to be brought about by using bundles of originally
slender fibers, the fact that tips are scraped off by buffing and the fact
that the unity of bundles is released by division. On the other hand, an
elastic polymer such as polyurethane is naturally located around hardened
silicone which first occupies a place around fibers. When adhesion of such
elastomer to hardened silicone is poor, the elastic polymer such as polyure-
thane on the nap is considered to have been stripped off and removed at the
time of buffing. The unity of fibers with silicone is weak sometimes, in
such case the composite sheet becomes suede-like leaving behind a hardly melt-
able efect because hardened silicone is removed at the time of buffing and
nap is formed rom only the fibers, but is not bound with said silicone.
In the present invention, it is preferable that the bonding strength
between a bundle of superfine fibers and a hardened high molecular weight
organic compound is stronger than that between the hardened high molecular
weight organic compound and anelastic polymer.
The bonding strength between the bundle Gf superfine fiber and the
hardened high molecular weight organic compound may be such that after buffing
and/or raising, more preferably after dyeing9 adherence of the hardened high
molecular weight organic compound to the bundle of superfine fibers is recog-
ni~ed under a microscope.
~rom such point of view, it can be said that the fo]lowing condi-
tions are preferable, Namely, if A and B are defined as:
A: the relation betwe~n the fiber and hardened silicone
B: the relation between the hardened silicone and the elastic polymer
1~9~7~V
as will be seen from observation of nap of an actually prepared sheet, it is
preferable that A is sufficiently high in adherence and affinity, and from the
viewpoint of a feel and a touch of said fabric, it is preferable that B is
sufficiently low in adherence and affinity. The balance between A and B is
important, and when A is sufficiently high, the higher is B, and the less nap
fall out and touch other clothes.
From such point of view, it is preferable that bundles of fibers
are treated with a silane coupling agent or added with said agent before they
are spun. Various silane compounds, especially a silane coupling agent
ordinarily treat aerosol silica and diatomaceous earth with silane and are
used for improving adherence to silicone resin and another high molecular
Weight substance. However, an inverse case of treating a fiber with a~silane
coupling agent in advance is carried out for the first time by the present
invention. At this time, it is possible to add a silane coupling agent to
bundles of fibers so as to make good its fitting to hardened silicone upon
spinning said fiber.
From the similar way of thinking, it is preferable to add a silane
coupling agent to silicone to be hardened or use hardenable type silicone add-
ed with a substance playing a role as a silane coupling agent for a hardening
reaction. Thus, what is excellent in the physical properties and adhesive
strength to fibers of hardened silicone required in A, is preferable.
Examples of silane coupling agents for polyesters are as follows.
a. CH2-CHCH20CH2CH2CH2Si(OcH3)3
Cl
b. CH2=C-COOCH2CH2N(CH2)3Si(OcH3)3
CH3 (CH3)2
,
2 ~ CH2NH-(CH2)2NH(CH2)3Si(OCH3~3
HCl
d. CH2=CHSi(0OccH3)3
e- (CH30)3Si(CH2)3NHC~2CH2NH2
~9~ o
Por polyamides, for example, c. above is used together with a
reaction promotor or alone.
As mentioned above, in case bundles of superfine fibers and harden-
able silicone are caused to bond strongly, it is necessary to reduce the
ratio of the hardenable silicone to (another later imparted) elastic polymer
to be mentioned below.
On the other hand, as regards B, it had better have no strong
adherence from the viewpoint of a feel and a nap's touch, however, from the
viewpoint of preventing nap from falling out and touching clothes, the ad-
herence must not be too low. Originally, hardenable silicone and another high
molecular weight elastomer are poor in adherence therebetween and not much
consideration is necessary. However~ in order to make it poorer, it is pre-
ferable to add to ~hese two in advance, what increases mold-releasing and
sliding easiness such as polyorganosiloxane or a fluorine compound which is
not of a hardenable type, but of a commonly mold-releasing type. Upon using
the silane coupling agent, it is preferable to pay attention so as not to in-
crease adherence of hardenable silicone to the elastic polymer. When, for
example, a silane coupling agent is mixed with hardenable silicone and used,
when a fiber is, for example, polyester, it is necessary to pay attention upon
selecting such agent so that; even if it is possible to make high the adhesive
strength of such agent to polyester, when the high molecular weight elastomer
is polyurethane; said agent does not adhere too strongly to such polyurethane.
In case further attention is paid to proceed a reaction, it is preferable to
treat a sheet as a whole with various fiber treating agents advancing mold-
releasing and sliding easiness such as silicon and paraffin after completing
the treatment of said sheet with hardenable silicone, by which a feel after
the subsequent treatment of said sheet with an elastic polymer advances or it
becomes easy to carry out buffing.
In case emphasis is placed on making nap unlikely ~o fall out at
the sacrifice of a feel of the fabric to some exten~, it is preferable to
- 15 -
~9~7~
raise the bond (unity) of a fiber with silicone on the contrary. For ex-
ample, in order to prevent nap of a product after it is dyed from falling out,
it is preferable to treat the product with a self-crosslinking acryl emulsion
and a silicone rubber (resin) - forming liquid or emulsion thereof, examples
of such case will be shown in Examples later.
Although it is apparent that if such treatment for preventing nap
from being lost becomes excessive, it would hurt a feel, nap and a touch
thereof, it is possible to control such treatment by changing -the extent of
the treatment according to one's desire, for example, by changing the concen-
tration at the time of the treatment.
When the relation of bundles of fibers with the two kinds of highmolecular weight compound which is the essence of the structure of the com-
posite sheet is diagrammatically shown in Figure 4, wherein 6 shows fibers,
hardened silicone and 8 polyurethane; 8 surrounds 7 on the spot (locally),
partly or entirely (in Figure 4, entirely). Accordingly, what is similar to
this diagram sectional view is formed in all or a considerable part of an
intertwined sheet and of a napped portion alike. Par-ts which become nap by
buffing consist of 6 and 7, while 8 comes off at the time of buffing; 6 and 7
are held at the roots, but at tips 7 comes off or parts of 6 and 7 are simul-
taneously scraped off, becoming slender or separate, taking a tapered s-tate or
disperses toward the tip. Because the n~p becomes like this, a composite
sheet according to the present invention has an appearance like that of a
high-class woolen woven fabric.
As regards the amounts of a hardened organic high molecular weight
compound a~dan elastic polymer to be imparted to a fabric, it is preferable
that the total of the two is about 15 - 70 parts by weight based on 100 parts
by weight of the composite sheet as a whole. ~he imparting ratio of the har-
dened organic high molecular weignt compound to the elastic polymer is 0.5 -
30% by weight, especially 0.5 - 20% by weight of the former to 100~ by weight
of the latter.
A composite sheet according to the present invention is effectively
- 16 -
lC~9~t7~
used as clothes such as coats, blazers, sport shirts, hats, furni~cures such as
upholsteries and bed covers, wall materials, carpeting, ornaMents, shoes such
as boots, handiwork materials and pouches such as bags.
Hereinbelow, the present invention will be illustrated by reference
to non-limitative Examples.
Example 1.
Using cut fibers of an "islands-in-a-sea" type fiber whose cross
section was like Figure 4, whose sea component was a blend of polystyrene 47.5/
polyethylene glycol 2.5 whose island component was polyethylene terephthalate,
having a sea/islands ratio of 50/50, number of islands of 16, a denier of the
"islands-in-a-sea" type fiber of 3.2 d, number of crimps of 13 mounts/inch and
a cut length of 51mm, a web was formed by a cross lapper method, which was
needle punched at 3300 punches/cm2 to obtain an intertwined non-woven fabric
having a weight per unit area of 500 g/m2 and an apparent density of 0.19 g/cm3.
When this non-woven fabric was further contracted in hot water ~at 97 - 100C),
its weight per unit area became 833 g/m2 and its apparent density became
Q.379 g~cm3 in a dried state. One hundred parts of this non-woven fabric (of
the ~l~slands-in-a~sea" type fiber) was iMpregnated with about ~0 parts (cal-
culated as solid) of a solution of polyvinyl alcohol whose degree of saponi-
fication was about 80%, dried and using trichloroethylene, 99.2% of the sea
component was removed.
This non-woven fabric from which almost a'l of the sea component had
been removed was impregnated with about 250% ~in wet weight) of a silicone
treating liquid prepared by dissolving in advance, 30 parts by weight of a
, composition containing
1 f~ te~
' ~ j Ca) 95 parts by weight of polydimethylsiloxane having Ll tcr~inal of -OH
and a molecular weight of about 25,000 (25C, 3000 CS) and
(b) 5 parts by weight of partly condensed CH3Si(OCH3)2 which could be
expressed by the general formula
(OMe)n
MeSiO
2 ( ~ - O to 3
- 17 -
~9~o
in 967 parts of trichloroethylene, next while stirring the resultant solution,
adding 3 parts by weight of (CH30)3Si (CH2)3NHCH2CH2NH2 thereto-
At about 70C, a greater part of trichloroethylene was scatteredoff and the impregnated non-woven fabric was allowed to stand in the air at
room temperature of 25C and a relative humidity of 60% for 24 hours to com-
plete hardening of silicone. The adhered amount of silicone was 7.9% calculat-
ed as solid and the adhered amount of silicone per unit area was 59.3 g/m2 at
this time.
This non-woven fabric was further impregnated with a dimethyl form-
amide solution of po]yurethane so that the adhered amount of polyurethane
calculated as solid became about 60 parts based on 100 parts of the island
components, coagulated in a water bath and removed of polyvinyl alcohol, and
then sliced into 2 non-woven fabrics so that the thickness of the two might
become the same, each of which was buffed on the non-sliced face (surface)
to nap, made into a non-woven fabric having a napped surface and dyed under
pressure with a dispersed dye at 125C.
This product looked like a woolen woven fabric, having a puffy
appearance~ at the same time, a soft pliant feel, being different from the
conyentional material and artificial suede products.
A comparison of a product according to the present invention and
another product prepared without passing through a silicone-treating step
will be shown in Table 1.
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7(~0
Table I Characteristics of the product
.
.. , I
Product A product according to the A comparative product
present invention obtained without passing
Characteristics through a silicone treat-
ment
. . _ _
Overall appearance Deep in color, like that Like that of leather
of a puffy woolen woven suede
fabric
.__... _ . _ . .
Feel Soft and puffy Like that of leather suede
~ .
Nap Hardly having direction- Having directionality,
ality, consisting mainly consisting of nap as
of nap as shown in Fig. 1 shown in Figure 3
_ _ _ ..
Sewing properties Like those of a napped Like those of leather
woolen woven fabric suede
_ . . . _
Melt resistance l)* About 10 seconds (about About 3 seconds~Time until a hole 3 times that of the
was opened by a comparative product)
lighted cigarette)
_... . _ _
Tear strength L.* _ 2.02 _ _ __ _ 0.68
(kg) B.* 2 81 0.59
..
Tensile stren- L.* 55 4 74.8
gth 2 _
(kg/cm ) B.* _ 56.3 _ _ 65.2
Tensile elon- L.* 90 , ~. . _ 74
gation ~%) B * 116 107
. .
Brush abrasion
strength index 164 100
21*
. . .
Light resistance
(fade-o-meter, 20 Above grade 5 Grade 5
hrs ~ 3)*
_ ... _ . _
Washing fastness
(discoloration, Grade 5 Grade 5
fading)
Dry cleaning
(discoloration, Grade 5 Grade 5
fadin~)
~ _ ~
Note l)* Time for a lighted "Hi-lite" cigarette to make a hole in the
sample by self-weight of the cigarette.
2)* Frequency of revolution of a round nylon brush until a hole began
to be made thereby, shown by an index based on that of a
comparative compound which was made 100.
- 19 -
1~95~0
L.* Length
B.* Breadth
3)* Grade 5 ~ Grade 1
Hardly discolored Much discolored
or faded
Example 2.
The same fiber as in Example l was treated in the same manner to
prepare a non-woven fabric of an "islands-in-a-sea" type fiber, from which the
sea component was removed. The so obtained non-woven fabric was impregnated
with about 250% in wet weight of a silicone treating liquid prepared by dis-
solving in advance, 80 parts by weight of a composition containing
(a) 95 parts by weight of polydimethylsiloxane having a terminal of
-OH and a molecular weight of about 25,000 ~25C, 3000 CS) and
(b) 5 parts by weight of partly condensed CH3Si~OCH3)3 which could be
expressed by the general formula
~OMe)n
MeSiO3_
2 (~ = O t~3)
in 912 parts by weight of trichloroethylene, next while stirring the resultant
solution, adding 8 parts by weight of ~CH30)3Si~CH2)3NHCH2cH2NH2 thereto-
~fter scattering off a greater part of trichloroethylene at about
70C, the impregnated non-woven fabric was allowed to stand in the air at room
2a temperature of 25C and a relative humidity of 60% for 48 hours to complete
hardening of silicone. The adhered amount of silicone calculated as solid was
19.3% and the adhered amount of silicone per unit area was 142.5 g/m2 at this
time.
This non-woven fabric was further impregnated with a dimethyl
formamide solution of polyurethane containing a black pigment ~about 8% of a
carbon black preparation based on the solid component of polyurethane) so that
the adhered amount of polyurethane calculated as solid became about 60 parts
based on 100 parts of the island components. Thereafter~ said fabric was
processed according to Example 1.
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1~957~0
The non-woven fabric was dyed in a deep color using a dispersed
dye with pressure at 125C. Because silicone did not contain carbon black,
it was feared if the color of the product became indistinct, however, the
color of the product was unexpectedly deep, becoming a tint increased with
high-class feeling. The other properties were about the same as those of
Example 1.
The characteristics of a product obtained in accordance with the
present invention will be shown in Table 2.
Table 2 Characteristics of the product (for the characteristics
of a comparative product, refer to Table 1)
duct A product according to the present
~ invention
Characteristics
_
Overall appearance Deep in color, a puffy appearance
like that of a woolen woven fabric
. . ~
Feel Soft and liant
. . - P
Nap Having no directionality, consisting
. mainly of nap as shown in Figure 1
Sewin ro erties Like those of a woolen woven fabric
g P P _ - -
~elt resistance Ctime until About 12 seconds
a hole was opened by a
lighted cigarette)
~ear strength ~kg) L.* 1.43
. B- . 1.70
Tensile strength L.* 41.8
~kg/cm ~ B.* 51.0
Tensile elongation L.* 65
(%) B.* 89
Schiefer
abrasion strength index 108
Light resistance (fade- Grade 5
o-meter~ 20 hrs.)
Washing fastness (discolora- Grade 5
tion9 fading) -- _ _
Dry cleaning (discoloration, Grade 5
fading)_ _ _ ___ _ _
~57(~)
Note: L.* Length
B.* Breadth
The testing methods were the same as those of Example 1.
Example 3.
The same fiber as in Example 1 was used in preparing a non-woven
fabric of an "islands-in-a-sea" type fiber, from which the sea component was
removed and said fabric was treated with a reaction type silicone all in the
same manner as in Example l. Next, this non-woven fabric was further impreg-
nated with a dimethyl formamide solution of polyurethane containing a black
pigment (8% of a carbon black preparation based on the solid component of
polyurethane) so that the adhered amount of polyurethane became about 60 parts
solids based on 100 parts of the island components. Thereafter, said fabric
was processed according to Example 1.
The non-woven fabric was dyed a deep color using a dispersed dye
with pressure at 125C. As in Example 1, the color of the product was deep,
and a napped product increased with high-class feeling in tint, having an
appea~ance like that of a woolen woven fabric was obtained.
Example 4.
The same iber as in Example 1 was used in preparing a non-woven
fabric of an "islands-in-a-sea" type fiber, from which the sea component was
removed all in the same manner as in Examp]e 1. The resultant non-woven fabric
was impregnated with about 250% wet weight of a silicone treating liquid
which was reactive upon heating prepared from the following components:
(a) 942 parts by weight of trichloroethylene
(b) 50 parts by weight of a mixture
HO ~ S O ~ H _ (CH3~35io ~ Si ~ SitCH3)3 = 100/6
Cm=loo ~ 500, n=10 - 40)
(c) 1 part by weight of
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1~57(~0
(CH3) 3siot si~sioJsi (CH3)3
R = alkylstyrene (~-methylstyrene type)
(d) 7 parts by weight of ~CH3CH2CH2CH2)2Sn(OCOCH3)2
Next, after driving off a greater part of the trichloroethylene at
about 70C. J said fabric was heat-treated at 130C for 7 minutes. The adhered
amount of silicone calculated as solid was 12.7% and the adhered amount of
silicone per unit area was 92 g/m2 at this time.
The non-woven fabric was further impregnated with a dimethyl form-
amide solution of polyurethane containing a black pigment (8% of a carbon
black preparation based on the solid component of polyurethane) so that the
adhered amount of polyurethane became abou~ 60 parts based on 100 parts of the
island components.
Thereafter, the fabric was processed according to Example 1 and
dyed a deep color. The dyed product had about the same appearance, properties
and feel as those of Examples 1 - 3 although it was somewhat inferior in deep-
ness of the color as compared with those of Examples 1 - 3.
Example 5
Using cut fibers of an "islands-in-a-sea" type fiber whose cross-
section was like Figure 4, whose sea component was polystyrene, whose island
component was polyethylene terphthalate~ having a sea/islands ratio of 43/57,
number of islands of 16, denier of the "islands-in-a-sea!' type fiber of 3.4 d,
numb0r of crimps of 13 mounts/inch and a cut length of 51 mm, a web was formed
by a cross lapper method, which was needle punched at 3500 punches/cm2 to
obtain an intertwined non-woven fabric having a weight per unit area of 540
g/m and an apparent density of 0.185 g/cm3. When this non-woven fabric was
further contracted in hot water (at 97 - 100C), its wei~ht per unit area be-
came 820 g/m2 and its apparent density became 0.372 g/cm3 in a dried state.
One hundred parts of this non-woven fabric ~ of the "islands-in-a-
sea" type fiber) was impregnated with about 23 parts ~calculated as solids)
-23-
~957~
of a solution of polyvinyl alcohol whose degree of saponification was about
80%, dried and using trichloroethylene, 99.8% of the sea component was removed.
This non~woven fabric ~rom which almost all of the sea component
had been removed was impregnated with about 250% wet weight of a silicone
treating liquid prepared by dissolving in advance, 50 parts by weight of a
composition containing:
~ a) 95 parts by weight of partly condensed polydimethyl siloxane having
a terminal of -OH and a molecular weight of about 25,000 (at 25C, 3000 CS),
and
(b) 5 parts by weight of partly condensed CH3Si(OCH3)3
in 945 par~s by weight of trichloroethylene, next while stirring the resultant
solution, adding 5 parts by weight of (CH30)3Si (CH2)3NHCH2CH2NH2 thereto-
At about 70C, a greater part of trichloroethylene was driven off
and then the impregnated non-woven fabric was allowed to stand in air at room
temperature of 25C and relative humidity of 60% for 24 hours to complete
hardening of the silicone. The adhered amount of silicone calculated as
solids was 12.9% and the adhered amount of silicone per unit area was 82 g/m2
at this time.
This non-woven fabric was further impregnated with a dimethyl form-
amide solution of polyurethane containing a black pigment (8% of a carbon
black preparation based on the solid component of the polyurethane) so that
the adhered mount of polyurethane calculated as solids became about 48 parts
based on 100 parts of the island components~ coagulated in a water bath,
freed from polyvinyl alcohol and dried.
Next, to this processed non-woven fabric was imparted 6 - 9% cal-
culated as solids of a self-cross inking type emulsion resin ("Ultrasol -
2613", a product of Takeda Pharmaceutical Industries Co~ of Japan) added with
a small amount of a migration preventing agent with a view ~o decreasing the
number of nap lost, from which the moisture was removed and thereafter said
fabric was heat-treated at 140C for 6 minutes.
_ ~
~, .
9~7~
The processed non-woven fabric which had been treated so as to
prevent nap from being lost was sliced in two so that the thickness thereof
might become the same, and thereafter, said fabric was processed into a napped
non-woven fabric and dyed a deep color according to Example 1.
The dyed product became a product having a capacity of preventing
nap from being lost in addition to the appearance, feel and properties of the
products of Examples 1 - 3.
The results of testing the products in respect of their capacity
to prevent nap from being lost will be shown in Table 3 below.
Table 3. Properties of products after being treated for preventing
nap from being lost.
\ ~ pp* Nap losing Surface Feel
T ~ ~ ;~`~ \ ~ resistance properties
.
This 12.9 O ~ O O
Exampl l
I~ 6.1 ~ - O O O
., 7.1 O O O
ll 8.8 O O O
. _
Control 7.8 O ~ O O
5.2 ~ - O O O
7.8 O O O
11.6 O O ~ - O
:
18.4 O ~ O O
ll 5.1 ~ O O
6.4 ~ - O O O
8.6 . __ O
Note: Nap losing resistance 0: Few naps were lost
~: more naps were lost
Surface properties 0: good
and feel ~: somewhat poor
~," _~_
, ~ , ., . . _ .
57~0
Note: T* Test
S* Adhered amount of silicone (%)
M* Adhered amount of a migration preventing agent (%)
PP* Properties of the product
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