U.S. patent number 3,627,567 [Application Number 04/843,990] was granted by the patent office on 1971-12-14 for leatherlike material and process of making same.
This patent grant is currently assigned to Kanegafuchi Boseki Kabushiki Kaisha. Invention is credited to Tomio Tensho.
United States Patent |
3,627,567 |
Tensho |
December 14, 1971 |
LEATHERLIKE MATERIAL AND PROCESS OF MAKING SAME
Abstract
This invention is directed to a tenacious and moisture permeable
leatherlike sheet material having breatheability and water
absorbability and which is comparable to natural leathers in
durability and wearing comfort. It comprises: a base fabric having
a large content of its void spaces; a microporous and aqueous
insoluble polyvinyl acetal resin, adhering to and entirely covering
the structural fibers of said fabric, in the form of a unitary
three dimensional network; and a layer of a different resin
covering said polyvinyl acetal resin. The sheet material may have a
grain side layer on at least one surface side thereof. A process
for manufacturing such a sheet material comprises steps of:
impregnating a base fabric with an aqueous solution of polyvinyl
acetal; heating the impregnated fabric at 50.degree.-130.degree.
C.; further impregnating said fabric with liquid comprising
different resin; and curing. The resultant article is particularly
useful for inner parts of shoe, such as insole, sole pad, inner
lining and the like.
Inventors: |
Tensho; Tomio (Osaka,
JA) |
Assignee: |
Kanegafuchi Boseki Kabushiki
Kaisha (Tokyo, JA)
|
Family
ID: |
12925584 |
Appl.
No.: |
04/843,990 |
Filed: |
July 23, 1969 |
Foreign Application Priority Data
|
|
|
|
|
Jul 23, 1968 [JA] |
|
|
43/52824 |
|
Current U.S.
Class: |
428/85; 12/142V;
36/3A; 427/245; 427/353; 427/379; 427/412; 428/91; 428/315.5;
428/904 |
Current CPC
Class: |
D04H
1/587 (20130101); D04H 1/68 (20130101); D04H
1/64 (20130101); D06N 3/04 (20130101); Y10S
428/904 (20130101); Y10T 428/249978 (20150401); Y10T
428/2395 (20150401) |
Current International
Class: |
D06N
3/04 (20060101); D04H 1/68 (20060101); D04H
1/64 (20060101); D06N 3/00 (20060101); B44c
003/02 (); B44d 001/14 (); D06n 003/04 () |
Field of
Search: |
;117/76T,135.5,161UE
;161/227 ;36/3A ;12/142V |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Goolkasian; John T.
Assistant Examiner: Dawson; Robert A.
Claims
What is claimed is:
1. A leatherlike sheet material comprising a base fabric, a resin
adhering to and entirely covering the structural fibers of said
fabric, said resin consisting essentially of microporous
water-insoluble poly(vinyl formal) in the form of a porous unitary
three-dimensional network in the fabric in a ratio by weight of
poly(vinyl formal) to fabric of 1:10 to 2:1 and a continuous layer
of at least one polymer selected from the group consisting of
polyurethane, polyacrylonitrile, poly(acrylic ester), polyamide,
and melamine-formaldehyde polymer in an amount of the polymer of 5-
100 percent by weight based on the weight of the fabric covering
the surface of said resin, said material being produced by
impregnating said base fabric with an aqueous solution containing a
water-soluble poly(vinyl formal) having an average degree of
formalization of 10- 30 mole percent, heating the impregnated
fabric to 50.degree. to 130.degree. C. to increase the
formalization of said poly(vinyl formal) to yield a microporous,
water-insoluble poly(vinyl formal) having an average degree of
formalization of 50- 75 mole percent and then impregnating the
resultant fabric with at least one of said polymers.
2. A leatherlike material as claimed in claim 1, wherein the base
fabric has a large content of void spaces formed among its
structural fibers and said poly(vinyl formal) resin extends from
the surface of the structural fibers towards said void spaces,
interconnecting adjacent structural fibers.
3. A leatherlike material as claimed in claim 1, wherein the base
fabric comprise its structural fibers which are compatible to the
poly(vinyl formal) resin. 4. A leatherlike material as claimed in
claim 1, wherein the base fabric comprise structural fibers
consisting of a fiber forming material selected from the group
consisting of nylon-6, nylon-66,
polyvinyl acetal and regenerated cellulose. 5. A leatherlike
material as claimed in claim 1, wherein the base fabric consists of
nonwoven fabric,
pile fabric with projecting filaments, napped fabric, terry or
plush. 6. A leatherlike material as claimed in claim 1, wherein the
ratio by weight of
said poly(vinyl formal) resin to said base fabric is 1:5 to 1:1. 7.
A leatherlike material as claimed in claim 1, wherein the amount of
the said resin is 10-50 percent by weight based on the weight of
the base fabric.
A leatherlike sheet material as claimed in claim 1, wherein the
fabric bound with the said poly(vinyl formal) resin and said
polymer has a grain side layer superimposed on a surface thereof
comprising a resin selected from synthetic polymers, synthetic
rubbers, regenerated cellulose and natural resins, the grain side
layer being formed by further applying and coagulating a liquid
containing the resin on the fabric after the curing
step. 9. A leatherlike sheet material as claimed in claim 8,
wherein resin
forming the grain layer is a polyurethane or poly(vinyl butyral).
10. A shoe made at least in part of the leatherlike sheet material
of claim 1.
. A process of making a leatherlike sheet material as claimed in
claim 1, which comprises: (1) first step of impregnating a base
fabric with an aqueous solution containing water soluble polyvinyl
acetal, (2) second step of heating the impregnated fabric at
50.degree.-130.degree. C. to promote acetalization of said
polyvinyl acetal, whereby resulting a microporous and aqueous
insoluble polyvinyl acetal resin adhering to and entirely covering
the structural fibers of said fabric, (3) third step of further
impregnating the resultant fabric with liquid containing emulsion
or solution of at least one resin different from polyvinyl acetal
selected from the class consisting of synthetic resins and natural
resins and (4)
fourth step of curing the resin impregnated fabric. 12. A process
of making a leatherlike sheet material as claimed in claim 1, which
comprises: (1) first step of impregnating a base fabric with an
aqueous solution containing water soluble polyvinyl acetal, (2)
second step of heating the impregnated fabric to 50.degree.-
130.degree. C. to promote acetalization of said polyvinyl acetal,
whereby resulting a microporous and aqueous insoluble polyvinyl
acetal resin adhering to and entirely covering the structural
fibers of said fabric, (3) third step of further impregnating the
resultant fabric with liquid containing emulsion or solution of at
least one resin different from polyvinyl acetal selected from the
group consisting of synthetic resins and natural resins, (4) fourth
step of curing the resin impregnated fabric and (5) applying liquid
containing at least one resin selected from the class consisting of
synthetic resins and natural resins on at least one surface of the
sheet material obtained by the preceding steps, whereby forming a
grain side
layer thereupon. 13. A process as claimed in claim 11, wherein the
base fabric has a large content of void spaces formed among its
structural
fibers. 14. A process as claimed in claim 11, wherein the water
soluble polyvinyl acetal has an average degree of acetalization of
10- 30 percent
by mole. 15. A process as claimed in claim 11, wherein the aqueous
solution further contains catalyst for acetalization comprising
aldehydes
and acids or their salts. 16. A process as claimed in claim 11,
wherein the aqueous solution further contains catalyst for
acetalization and a
pore forming agent. 17. A process as claimed in claim 11, wherein
the base fabric is impregnated with the aqueous solution in an
amount of 10- 200 percent by weight of its solid ingredients based
on the weight of the
fabric. 18. A process as claimed in claim 11, wherein the base
fabric is impregnated with the aqueous solution in an amount of 20-
100 percent by
weight of its solid ingredients based on the weight of the fabric.
19. A process as claimed in claim 11, wherein the heating
temperature in the
second step is in the range of 70.degree.- 100.degree. C. 20. A
process as claimed in claim 11, wherein the heating in the second
step is conducted for a period of time sufficient to promote the
average degree of acetalization of the polyvinyl acetal which has
been applied to the fabric
in the preceding step, up to 30- 85 percent by mole. 21. A process
as claimed in claim 11, wherein the heating in the second step is
conducted for a period of time sufficient to promote the average
degree of acetalization of the polyvinyl acetal which has been
applied to the fabric
in the preceding step, up to -50- 75 percent by mole. 22. A process
as claimed in claim 11, wherein the heating in the second step is
effected by
steaming. 23. A process as claimed in claim 11, wherein the sheet
material which has been processed in the first and second steps is
rinsed and
washed prior to the third step. 24. A process as claimed in claim
11, wherein the resin employed in the third step is selected from
the group consisting of latex, polyurethanes, polyacrylonitrile,
polyacrylic acid esters, polyamides, polyvinyl chloride and
melamine-formaldehyde polymer.
5. A process as claimed in claim 11, wherein the curing in the
fourth
step is effected at a temperature of 50.degree.-180.degree. C. 26.
A process as claimed in claim 11, wherein the curing in the fourth
step is effected by means of hot pressing under a pressure of 3- 20
kg./cm..sup.2.
7. A process as claimed in claim 11, wherein the said sequential
four steps are carried out continuously.
Description
This invention relates to a leatherlike material and a process for
making the same and, more particularly, to such a leatherlike sheet
material which has a combination of properties including an
excellent air and moisture permeability and a high strength.
Numerous and various proposals in relation to manmade leathers and
their preparation have been made heretofore and some of them have
been accepted as a substitute for natural leather. However, a
majority of manmade leathers in the past has been considerably
inferior to natural leathers in ability to breathe comprising, for
instance, water and moisture absorbability, moisture exhalability,
moisture permeability, etc., so that such prior manmade leathers
have fallen in the public estimation when used as shoes, suitings
and similar protective clothing articles calling for the ability of
the material to breathe, due to their uncomfortable wearing
properties such as moist and humid feels. Particularly, the
moistening or humidification of the inside of a shoe is not only
awfully uncomfortable but also undesirable from the sanitary point
of view, for in most cases, shoes are worn continuously for a long
time throughout all seasons. Furthermore, the previously known
manmade leathers have had such a drawback that when they are used
as chair coverings, wall linings, motor-car panellings, upholstery
materials and the like, those articles are apt to get moist or to
have dew-drops condensed on their surface especially under moist
atmospheric conditions, for instance, in a rainy day or in the
rainy season, or owing to some variations in temperature. The
drawback as such of the prior manmade leathers is principally
ascribed to the fact that their hydrophilicity and porosity are so
poor as compared with those of natural leathers that they lack
breatheability by means of which leathers absorb and exhale
moisture in the atmosphere, permeating air therethrough.
It is, therefore, an important object of the present invention to
provide a novel and improved leatherlike material having air and
moisture permeability, moisture absorptivity and moisture
exhalability equivalent or superior to those of natural
leathers.
Another object is the provision of a process of making flexible and
tenacious moisture permeable sheet materials having a microporous
polymeric component in adherence with fibers in their
substrate.
Still another object is the provision of an economical process of
making such sheet materials which are comparable with natural
leathers in durability and comfort characteristics.
Other important objects will be apparent from the description of
the invention which follows.
The above objects are accomplished according to the present
invention by forming a leatherlike material comprising a base
fabric and a microporous and aqueous insoluble resin consisting
essentially of acetalized product of polyvinyl alcohol (hereinafter
referred to as "polyvinyl acetal") adhering to and entirely
covering the structural fibers of the said base fabric, the said
resin forming a unitary three dimensional network containing a
number of pores therein, the surface of the said resin being
covered continuously by a layer comprising at least one resin
different from the aforementioned resin. In particular, such a
leatherlike material comprises a base fabric having a large content
of void spaces and a microporous and aqueous insoluble polyvinyl
acetal resin, specifically polyvinyl formal resin, adhering to and
entirely covering the structural fibers of the said base fabric,
which resin extending from the surface of the fibers towards void
spaces formed among the fibers, interconnecting adjacent fibers and
forming a unitary three dimensional network containing a number of
pores therein, the said network uniformly existing in and extending
over the fabric, the surface of the said resin being covered
continuously by a layer comprising at least one resin different
from the aforementioned polyvinyl acetal resin.
Another embodiment of the present invention is a leatherlike
material comprising a substrate consisting of the above obtained
leatherlike material, and a grain side layer formed on the surface
of the substrate, which grain side layer comprising at least one
resin selected from the class consisting of synthetic resins and
natural resins.
The invention further comprises a process of making a leatherlike
material which comprises first step of impregnating a base fabric
with an aqueous solution containing water soluble polyvinyl acetal,
second step of heating the impregnated fabric at
50.degree.-130.degree. C. to promote acetalization of said
polyvinyl acetal, whereby resulting microporous and aqueous
insoluble polyvinyl acetal resin adhering to and entirely covering
the structural fibers of the said fabric, third step of further
impregnating the resultant fabric with liquid containing emulsion
or solution of at least one resin different from polyvinyl acetal
selected from the class consisting of synthetic resins and natural
resins and fourth step of curing the thus resin impregnated
fabric.
It is a still further preferable embodiment of the present
invention to make a leatherlike material by a process which
comprises a coating liquid containing at least one resin selected
from the class consisting of synthetic resins and natural resins on
the surface of the material obtained through the aforementioned
four steps, whereby forming a grain side layer thereupon.
The above and other features of the leatherlike material of the
present invention will be more fully understood from the following
description when read in connection with the accompanying drawings
wherein:
FIG. 1 is a magnified schematic cross-sectional view, somewhat
diagrammatic and fragmentary in character, illustrating conditions
of fibers when the base fabric is impregnated with a treating
solution.
FIG. 2 is also a magnified schematic cross-sectional view,
illustrating the structure of leatherlike material of the present
invention, wherein the base fabric has been bound and entirely
covered with the microporous, water-insoluble polyvinyl formal
resin and the other polymer consolidated after the course of fourth
step of the invention.
FIG. 3 is a diagrammatic side elevational view of an apparatus
suitable for carrying out the process of the present invention.
FIGS. 4 and 5 are diagrams showing the relation between time
elapsed from impregnation of water and water content with respect
to insoles manufactured from the leatherlike material of the
present invention and those in the market.
FIG. 6 is a perspective view, with a part broken away, of an
ordinary shoe for gentlemen.
FIG. 7 is a vertical cross-sectional view of the shoe shown in FIG.
6.
Important characteristics called for by a base fabric to be
employed in preparing the leatherlike material according to the
process of the present invention are:
1. its thickness and strength sufficient to impart to the resulting
leatherlike material durability, including resistance to tearing,
repeated flexing and abrasion, and further its appropriate void
content; and
2. its excellent adhesivity or compatibility to polyvinyl
acetal.
As structural fibers of the base fabric, effectively applicable are
natural fibers such as cotton, silk, wool and the like, artificial
fibers such as cellulose acetate fibers, viscose rayons, cupra and
the like, and synthetic fibers consisting of such a polymer as
polyacrylonitrile, polyamide, polyester, polyvinyl alcohol,
polyvinyl chloride, polyvinylidene chloride, polyolefin and the
like. In particular, polyamide fibers such as nylon-6, nylon-66 and
the like, polyvinyl alcohol fiber what is called Vinylon or the
like and viscose rayon are suitable among the others.
It is desirable that the structure of the base fabric has a large
content of void spaces and from this point of view, nonwoven
fabrics such as web and batt, pile fabrics with projecting
filaments, napped fabrics, terry, plush and the like are
advantageously applicable.
In the first step of the process of the present invention, the
aforementioned base fabric which has been relevantly prepared and
selected is impregnated with an aqueous solution containing water
soluble polyvinyl acetal as its principal ingredient. The treating
solution i.e., and above-mentioned aqueous solution can be prepared
in the following manner. An aqueous solution of polyvinyl alcohol
is admixed with aldehydes such as formaldehyde, acetaldehyde,
butylaldehyde, glyoxal, benzaldehyde and the like, and acids such
as hydrochloric acid, sulfuric acid, hydrobromic acid, phosphoric
acid, trichloroacetic acid, organic sulfonic acids and the like, to
acetalize the polyvinyl alcohol. When the degree of acetalization
has reached a range of 10- 30 percent by mole, an alkali is added
to the reaction mixture to stop the reaction and water-soluble
polyvinyl acetal, in this instance, a partially acetalized product
of polyvinyl alcohol results. An aqueous solution of the thus
obtained water-soluble polyvinyl acetal can be used as the
above-mentioned treating solution, to which a catalyst for
acetalization comprising aldehydes and the above-mentioned acids or
their salts, a pore forming agent such as starch, dextrine and the
like, or a coloring agent is incorporated, if required.
The treating solution may be applied to the base fabric by any
conventional method, such as pad-squeezing, doctor coating, roll
coating, brush coating and spraying. The application or
impregnation of the solution may be effected from one side or both
sides of the fabric. Generally, the amount of the solution adhered
to the fabric is preferably 10- 20 percent by weight of its solid
ingredients based on the weight of fabric, and more preferably 20-
100 percent by weight, although it differs according to the kind of
fabric or its outlets;
The first step wherein the base fabric is impregnated with the
treating solution, is successively followed by the second step in
which the fabric is heated to promote acetalization of the
polyvinyl acetal which has been applied to the fabric in the
preceding step, up to a degree of acetalization of 30- 85 percent
by mole, preferably 50- 75 percent, whereby the polyvinyl acetal is
consolidated to form a microporous and water-insoluble polyvinyl
acetal resin of a unitary three dimensional network in the base
fabric. The heating is conducted preferably at a temperature of
50.degree.-130.degree. C., more preferably of
70.degree.-100.degree. C. As a manner of heating, either dry
heating or steam heating may be adoptable and in general, the
latter is more preferable. A heating period can be determined
appropriately according to the temperature as well as the heating
manner.
The fabric thus heat treated in the second step as mentioned above
may be neutralized, washed to extract excess aldehydes, catalysts
for acetalization, other water soluble substances and nonreacted
substances therefrom, squeezed and dried, if required.
The method of thus forming the aqueous insoluble polyvinyl acetal
in and over the base fabric in the manner mentioned above will be
illustrated hereafter with reference to the accompanying
diagrammatic drawings.
In FIG. 1, structural fibers 1 are impregnated with treating
solution 2. If such a fabric is subjected to a heat treatment, then
as is shown in FIG. 2, insolubilized and consolidated acetalized
product 3 having a microporous structure is formed therein,
adhering to and entirely covering the structural fibers 1 as a
unitary three dimensional network. The acetalized resinous product
3 extends from the surface of the structural fibers 1 towards void
spaces formed among structural fibers, interconnecting adjacent
structural fibers and occupies a part of said void spaces forming
pores or cavities 4. The acetalized resinous product 3 now formed
is water insoluble, comparatively hydrophilic and extremely
microporous and which composes a unitary three dimensional network
extending on and along the structural fibers. Accordingly, the
product resulting from the aforementioned second step exhibits
excellent water and moisture absorbability as well as moisture
exhalability and furthermore displays superior water retentiveness
and air permeability due to its numerous pores or cavities 4.
Now, the third step of the present invention will be described in
details hereafter.
The product manufactured by the foregoing two steps may have its
top surface buffed or abraded, or may be sliced or pressed so as to
be as thick as is desired, by an appropriate method prior to being
subjected to the third step. As preferable resins to be applicable
for the preparation of the treating liquid used in the third step,
mention may be made of: addition polymers such as acrylic and
vinylic polymers; condensation polymers such as polyamides,
polyesters, polyurethanes and the like; synthetic rubbers such as
styrene/butadiene rubber, nitrile/butadiene rubber and the like;
and natural rubber. Furthermore, materials for producing
condensation resins, for instance, prepolymers of such condensation
resins as a urea-formaldehyde resin, melamine-formaldehyde resin,
phenols-formaldehyde resin and the like are also preferably
applicable for the preparation of the treating liquid. Latex, and
solution in organic solvent, of polyurethanes, polyacrylonitrile,
polyacrylic acid esters, polyamides or polyvinyl chloride, and
aqueous solution of precondensate of melamine-formaldehyde are
especially preferable among the others.
The above-mentioned resins and their materials can be used either
solely or in combination of more than one, in the form of emulsion,
aqueous solution or solution in organic solvent according to their
characteristics. Moreover, to the treating liquid, if required,
other additives may be added, for instance: plasticizers such as
butyl lauryl phthalate, butyl phthalyl butyl glycolate, dibutyl
phthalate, diethyl phthalate, di-2-ethyl hexyl phthalate, dimethyl
phthalate, di-n-octyl phthalate, tricresyl phosphate, ethylene
glycol, glycerine and the like; catalysts for condensation reaction
such as hydrochloric acid salts of organic amine, magnesium
chloride, zinc nitrate, ammonium chloride and primary ammonium
phosphate; coloring agents; softening agents; and hardening
agents.
To impregnate the sheet material which has been obtained in the
aforementioned two steps with the treating liquid, all of the same
manners as applicable to the first step are also applicable to the
third step.
The sheet material which has been treated in the third step is then
subjected to the fourth step, wherein said sheet material is heated
preferably at 50.degree.- 180.degree. C., although the suitable
heating temperature varies depending upon characteristics of the
resin impregnated to the material in the foregoing step. According
to the fourth step, the applied resin covers the surface of the
aforementioned polyvinyl acetal resin which uniformly exists in and
extends over the base fabric, whereby interconnection or
conjunction of structural fibers is secured, resulting in a
tenacious and tough leatherlike material, which retains appropriate
air and moisture permeability.
An amount of the resin to be fixed onto the sheet material in the
fourth step is preferably 5- 100 percent by weight based on the
weight of the base fabric and more preferably 10- 50 percent by
weight, although the above stated preferable range may somewhat
vary according as the kinds of resin and intended outlets of the
product. At the above-mentioned heat treatment in the fourth step,
the sheet material may be pressed on a cylinder heating apparatus
or compressed by and between two hot plates under a pressure of 3-
20 kg./cm..sup.2, simultaneously with heating.
The aforementioned first to fourth steps can be carried out
continuously and its embodiment will be illustrated with reference
to the drawing. Referring now to FIG. 3, base fabric 5 is passed
through a first saturator 6, impregnated with treating solution 7
and squeezed by squeeze rolls 8 to control the pickup. During its
travel in steamer 9, the fabric is subjected to a heat treatment,
then squeezed again by squeeze rolls 10 to remove an excess
treating solution, fed into washer 11 consisting of first washing
bath 12 and second washing bath 13, wherein the fabric is
successively washed, and squeezed by squeeze rolls 14. The fabric
which has been thus through the first and second steps of the
invention, is continuously subjected to the third step, wherein it
is led into a second saturator 15 to impregnate with treating
liquid 16, squeezed by squeeze rolls 17 to regulate the pickup and
wound up on a roll by a batch-up device 18. Thus processed and
batched-up sheet material is then subjected to the fourth step of
heating with or without pressing according as its contemplated
outlets. In conventional methods for manufacturing manmade
leathers, their process and steps have been so complicated that
they have been difficult to carry out continuously, while according
to the process of the present invention, a continuous process can
be readily realized utilizing conventional equipments and
machineries.
Leatherlike materials thus manufactured are extremely excellent,
compared with conventional manmade leathers, in air and moisture
permeability, strength and toughness, and moreover do not provide
any wearing discomfort or dew formation, so that they are suitable
broadly for insole, sole pad, vamp, quarter lining and toe lining
for shoe, wall lining, motor-car panelling, substrate for synthetic
leather, etc.
The fifth step of the process of the invention will be explained
hereafter. In this step, resin is applied onto the surface of the
sheet material which has been prepared by and through the foregoing
four steps and which is used as a substrate in the instant step, to
form a grain side layer on the top side thereof. Resins to be
employable to form the grain side layer are: synthetic polymers
such as polyurethanes, polyamides and vinyl polymers; synthetic
rubbers such as styrene/butadiene rubber, nitrile/butadiene rubber
and the like; artificial resins such as cellulose acetate,
cellulose nitrate and the like; and natural resins such as natural
rubber. A treating liquid in the form of emulsion, aqueous solution
or solution in organic solvent, of the above-mentioned resin is
prepared, using the resin either solely or in combination of more
than one, and which treating liquid is applied and coagulated on
the top side of the substrate which has been obtained by the
aforementioned four steps, to form a grain side layer thereupon.
The kinds and amount of the resin to be applied may be properly
selected and determined according to the kinds of structural
fibers, the texture of base fabric, the kinds of resin employed in
the third step, outlets of product and the type of machinery. To
apply the liquid of resin onto the substrate, doctor coating, roll
coating or any other conventional coatings are employable.
Leatherlike materials thus obtained have its flesh side and grain
side layers resembling natural leathers and moreover, exhibit
excellent moisture absorptivity, moisture exhalability, air
permeability and hands comparable to natural leathers, so that they
are suitable broadly for coats, chair coverings, bags, shoe uppers,
wall materials, etc.
One of the most important applications of the leatherlike material
of the present invention is insole and linings of shoe, which will
be described in more detail. A shoes having its insole and linings
composed of the leatherlike material of the present invention can
provide its inner surface with microporous polyvinyl acetal resin
layers having exceedingly numerous micropores therein, so that it
exhibits highly intensified capillary action with the aid of the
hydrophilic properties inherent to the polyvinyl acetal resin.
Furthermore, the sheet material of the present invention possesses
appropriate strength even if it absorbs water and therefore, in
case it absorbs a lot of sweat, it can keep its original
configuration unchanged. Thus an improved shoe providing an
excellent wearing comfort with dry feel and having a light weight,
as well as a compact size can be manufactured by employing the
sheet material of the present invention as the insole and inner
linings. Moreover, it is further an important advantage of the
present invention that the process of the invention permits the
rapid and economical production of continuous lengths of the sheet
material in any desired width, is relatively easy to control and
consistently yields a high quality product.
Especially important properties of the sheet material with respect
to its utility as a shoe material are as follows:
1. Since it has a strong capillary action, sweat is rapidly
absorbed and spread out in a broad range, so that a wearing comfort
such as dry feel is retainable even under perspiration.
2. Since the absorbed sweat is rapidly spread out broadly as
mentioned above so that the contact surface of the sweat with air,
namely the surface area of the sweat is rapidly increased and
evaporation of the sweat is accelerated, taking a latent heat out
of the environment of the foot, whereby cooling the foot and
keeping it dry.
3. The material has a highly increased water retentiveneness and an
extremely small so-called equilibrium moisture regain at 25.degree.
C., 65 percent R.H. as compared with conventional shoe materials,
so that it has considerably increased capacity for absorbing sweat.
Accordingly, even one who has a plenty of perspiration can keep
one's feet in dry condition and feel.
4. In case the shoe is used on a rainy day and is quite wet, it can
be dried up within a comparatively short period, for instance,
overnight.
The above mentioned advantages and outstanding features of the
present invention are further evidenced by the following
comparative experimentations.
Equilibrium moisture regains at 25.degree. C. and 65 percent R.H.,
and percent saturated waters based on the weight of the sheet
material with respect to the sheet material manufactured by the
process of the present invention and those available in the market
are given in table 1. It can be clearly understood from the
experimental data given in table 1 that the insole of the present
invention has a remarkably large capacity of absorbing water among
all others, as was described in the above feature 3. ##SPC1##
Further, experimental data in relation to the water absorbing rate
of sheet material, that is, heights (mm.) of water absorbed at a
certain time (second) after the bottom end of the sheet material
set upright is dipped in water are given in table 2, from which it
is now clear that the material prepared according to the process of
the invention is far superior to any of the conventional materials
or even to the natural leather, in absorbed amount as well as
absorbing time. ##SPC2##
In FIG. 4 of the attached drawings, the diagram shows water
exhaling abilities with respect to insole H of the present
invention, that F of natural leather, those A, B and C of
regenerated material which are available in the market and those D
and E of synthetic leather also available in the market, which were
determined by the following manner:
Each specimen having a size of 100 mm..sup.2 taken from the above
mentioned insoles was entirely soaked in water at 20.degree. C. for
24 hours, taken out of water and squeezed to remove excess water
therefrom. The specimen was then allowed to stand in an atmosphere
at 15.degree. C. and 65 percent R.H. under atmospheric pressure and
change of water content in the insole according to elapsed time was
measured. As is apparent from the diagram, the excellency in water
exhaling ability of the product of the invention is evidenced by
the fact that the line H relating to the insole of the present
invention has the largest inclination among the other lines.
FIG. 5 shows the same lines indicating the water content with
respect to the above mentioned insoles as shown in FIG. 4, being
somewhat rearranged only with their parts below a water content of
67 percent. Thus, lines A, D and B show water exhaling abilities of
the corresponding insoles A, D and B beginning at their respective
water content of 40 percent, 36 percent and 53 percent, and each of
the beginning points is made to accord with the point of the same
value of water content on the line H for the purpose of comparison
with each other. As is clearly understood from FIG. 5 above, the
leatherlike material of the present invention is extremely superior
in water exhaling ability to any other conventional materials.
Accordingly, the materials of the invention can provide shoes
having such a wearing comfort that even though they are wet with
water on a rainy day, they can be dried thoroughly by standing
overnight and worn comfortably again on the next morning.
Moreover, from those diagrams shown in FIGS. 4 and 5 features the
outstanding feature and merit of the invention as already described
hereinbefore are clear, i.e. that absorbed sweat is rapidly spread
out broadly and evaporation of the absorbed sweat is commenced
instantaneously and rapidly, so that a latent heat of evaporation
is taken out of an environment adjacent to the foot, thereby
cooling the foot, preventing its further perspiration and keeping
it in a dry and sanitary condition.
FIGS. 6 and 7 show a structure of an ordinary shoe for gentlemen,
wherein between outsole 110 and circumference of slipsole 111, toe
cap 112, vamp 113, counter 114, toe lining 116 and quarter lining
117 are tightly fastened and secured at their circumferences. Toe
box is indicated as 115. Insole or inner sole 118 is placed upon
the slipsole 111, heel pad 119 is superimposed upon a heel portion,
120 is a lace and 121 indicates a surface of the insole which is to
be in contact with a foot. A leatherlike material of the invention
having a continuous microporous structure comprising polyvinyl
acetal, specifically polyvinyl formal may be employed to constitute
at least a part of the insole 118 of the shoe as illustrated above,
and further is applicable to form the toe lining 116, quarter
lining 117, heel pad 119 or a sole pad (not shown in FIGS. 6 and
7).
The microporous resin of which the leatherlike material of the
present invention is composed has numerous fine projections, such
as coralline branches, on the surface of its pore, so that it
exhibits an increased void content as well as a tremendously large
surface area per unit volume. Thus the particular microstructural
feature of the resin as such, greatly enhances the effects and
merits of the leatherlike material of the present invention.
The examples which follow are given for the purpose of illustrating
the invention in more detail but are not to be construed as
limitative or as indicating that the products obtained are fully
equivalent.
Determinations of moisture absorptivity, moisture exhalability and
water content were conducted as follows:
1. Moisture absorptivity
A specimen was conditioned in an atmosphere having 65 percent R.H.
at 20.degree. C. for 24 hours and its weight W.sub.1 was
determined. The thus conditioned specimen was allowed to absorb
moisture in a moist atmosphere having 100 percent R.H. at
30.degree. C. for an arbitrary period of time and its weight
W.sub.2 was weighed. Then the moisture absorptivity of the specimen
is given by the following equation:
2. Moisture exhalability
A specimen was allowed to stand in an atmosphere having 100 percent
R.H. at 30.degree. C. for 24 hours and its weight W.sub.3 was
determined. The thus treated specimen was placed in an atmosphere
having 65 percent R.H. at 20.degree. C. for an arbitrary period of
time and its weight W.sub.4 was determined. The moisture
exhalability of the specimen is calculated according to the
following equation:
3. Water content
A specimen having an initial weight of W.sub.5 was soaked in water
at 20.degree. C. for 24 hours, taken out of the water and after
removing excess water from its surface, the weight W.sub.6 of the
wet specimen was determined. Then the water content is calculated
according to the following equation:
4. Moisture permeability or water vapor permeability
The moisture permeability was determined in accordance with JIS
(Japanese Industrial Standard) K6549-1965.
5. stiffness in flexure
The stiffness in flexure of the product of the invention was
measured by the tentative method designated in ASTM-D-747-58T.
The word "part" used in the examples means "part by weight," unless
otherwise indicated.
EXAMPLE 1
A web having a thickness of 6 mm. and a weight of 700 g./m..sup.2
which had been prepared from nylon-6 staples of 1.5 denier having
fiber length of 38 mm. was employed as a base fabric. Prior to the
first step of the process of the invention, a water soluble
formalized product of polyvinyl alcohol having a degree of
formalization of 20 percent by mole was prepared with a polyvinyl
alcohol having an average degree of polymerization of 1,500,
formaldehyde and sulfuric acid, and then a treating solution
consisting of 40 parts of 10 percent solution of the above obtained
formalized product of polyvinyl alcohol, 6 parts of formaldehyde of
an industrial grade having its concentration of 37 percent, 5 parts
of sulfuric acid of an industrial grade having its specific gravity
of 50.degree. Be and 15 parts of water was prepared in advance.
Into the above treating solution soaked was the aforementioned base
fabric, which was then squeezed so as to retain the treating
solution of 5 times the weight of fabric, passed through a steamer
having its effective heating length of 10 meters in which the
fabric was steamed at 100.degree. C. for 10 minutes and subjected
successively to rinsing, washing and dehydrating. The amount of the
formalized polyvinyl alcohol consolidated and adhered onto the
fabric was 32 percent by weight based on the base fabric.
The fabric thus treated in the foregoing two steps, i.e., the first
and second steps, was transferred to the third step, wherein it was
led and soaked into a treating liquid composed of 20 parts of
Beckamin PM (a trade name of a material of resin, containing 80
percent of nonvolatile ingredients and comprising trimethylol
melamine as its principal component, manufactured by Dainihon Ink
Kogyo K.K.), 4 parts of Catalyst C-376 (a trade name of a catalyst
for condensation reaction of Beckamin PM, comprising an organic
amine salt and containing 30 percent of nonvolatile ingredients,
manufactured by Dainihon Ink Kogyo K.K.) and 80 parts of water,
impregnated with 100 percent by weight of the treating liquid based
on the fabric and subjected to 5 minute cure at 130.degree. C. in
the fourth step. The amount of the resin further adhered onto the
fabric in the third and fourth steps was 16 percent by weight based
on the fabric.
Properties of the thus obtained leatherlike material are given in
tables 3, 4 and 5, comparing with those of conventional articles
wherein comparative instance 1 is for an insole made of tanned
natural oxhide, comparative instance 2 for that made of a
regenerated leather available in the market, comparative instance 3
for that made of paper board available in the market and
comparative instance 4 is for an intermediate product manufactured
by the first and second steps in the process of the present
invention. ##SPC3##
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TABLE 4
Water content and moisture permeability
Item Water content Moisture (%) permeability Specimen
(mg./cm..sup.2 /hr.)
__________________________________________________________________________
Example 1 315.0 10.2 Comparative 1 152.6 6.5 Comparative 2 60.9 3.0
Comparative 3 47.8 3.2
__________________________________________________________________________
##SPC4##
As is apparent from tables 3 and 4 above, the leatherlike material
obtained in this example of this invention is extremely high in
moisture absorbing and exhaling abilities, water absorbability and
water vapor permeability as compared with conventional manmade
leathers prevailing in the market and moreover, exhibits rather
greater values of those properties than natural leathers.
Furthermore, although the leatherlike material prepared by all four
steps of the process of the invention shows a slight decrease with
respect to the water absorbability and water vapor permeability,
yet it exhibits a considerable improvement in all other mechanical
properties, as compared with the intermediate product prepared by
only the first and second steps of the process of the invention, so
that the utility of the leatherlike material of the present
invention is greatly improved.
The leatherlike material manufactured according to the process as
described in example 1 is suitable for insole and sole pad of
shoes, wall linings, motor car panellings and the like.
EXAMPLE 2
The intermediate prepared in example 1 was impregnated with 40
parts of an emulsion (comprising 40 percent of solid component) of
an acrylonitrile/acrylic acid butyl ester copolymer and 60 parts of
water and squeezed to retain 100 percent by weight of the treating
solution based on the fabric, as the third step of the process of
the invention. As the fourth step, the impregnated fabric was
subjected to a 3-minute hot press on a hot pressing machine at a
surface temperature of 150.degree. C. and with a pressure of 4
kg./cm..sup.2, followed by drying. The amount of the resin adhered
and fixed onto the fabric in this step was 16 percent by weight
based on the fabric.
The top surface of the resultant sheet material was thereafter
abraded and a leatherlike material having its thickness of 2 mm.
was obtained. Properties of the obtained leatherlike material were
as follows:
Water absorbability (%) 296 Moisture permeability (mg./cm..sup.2
/hr.) 9.6 Tensile strength at break in dry state (kg./mm..sup.2)
1.16 Elongation at break in dry state (%) 58 Tensile strength at
break in wet state (kg./mm..sup.2) 1.09 Elongation at break in wet
state (%) 68.0 Tearing strength in dry state (kg./mm.) 3.3
Stiffness in flexure in dry state (cm.g.) 140
The resultant leatherlike material had desirable properties for
insoles, sole pads, side linings, quarter linings and toe linings
of shoes.
EXAMPLE 3
The leatherlike sheet material manufactured in example 2 was sliced
into sheets of 1 mm. thick, and which sheets were employed as
substrates to be subjected to the fifth step according to the
process of the present invention.
A colored treating liquid which had been prepared by admixing a
black toner (a pigment paste) with Crisvon (a trade name of a
N,N-dimethylformamide 30 percent solution of polyurethane of 35
percent ester type, manufactured by Dainihon Ink Kogyo K.K.) was
applied to the top surface of the above-mentioned substrate by 0.6
mm. thick by means of a roll coater. Then the coated sheet was
introduced into water and the liquid applied thereupon was
coagulated and solidified to form a grain side layer. The sheet was
thereafter subjected to a drying process, followed by an embossing
process whereby a leatherlike superficial appearance was imparted
to the product. The amount of resin adhered onto the substrate in
the fifth step was 14 percent by weight based on the substrate.
Properties of the resultant leatherlike sheet material were as
follows:
Water absorbability (%) 210 Moisture permeability (mg./cm..sup.2
/hr.) 4.0 Tensile strength at break in dry state (kg./mm..sup.2)
1.8 Elongation at break in dry state (%) 63
It had often happened in conventional manmade leathers that their
grain side layer was readily split off the substrate, while since
the grain side layer of the above manufactured sheet material of
the invention had been bonded fastly to the substrate, as a matter
of fact, it was impossible to split them off. The leatherlike sheet
material thus obtained exhibited hands and feels resembling those
of natural leathers, and suitable for shoe uppers, bags, chair
coverings and the like.
EXAMPLE 4
A terry composed of polyamide staples having a cut length of 5 mm.
was employed as a base fabric. Prior to the first step of the
process of the invention, a water soluble formalized product of
polyvinyl alcohol having a degree of formalization of 22 percent by
mole was prepared with a polyvinyl alcohol having an average degree
of polymerization of 1700 , and then a treating solution consisting
of 40 parts of 10 percent solution of the above obtained formalized
product of polyvinyl alcohol, 6 parts of formaldehyde of an
industrial grade having its concentration of 37 percent, 5 parts of
sulfuric acid of an industrial grade having its specific gravity of
50.degree. Be and 15 parts of 5 percent aqueous solution of potato
starch was prepared in advance. Into the thus prepared treating
solution soaked was the aforementioned base fabric which was then
squeezed so as to retain 500 percent by weight of the treating
solution based on the fabric, passed through a steamer having its
effective heating length of 10 meters in which the fabric was
steamed at 100.degree. C. for 7 minutes and subjected successively
to rinsing, washing and dehydrating.
The fabric thus treated in the foregoing two steps, i.e., the first
and second steps, was subjected to the third step wherein it was
soaked in a treating liquid composed of 100 parts of Hydran F-24 (a
trade name of a water soluble polyurethane resin, containing 30
percent of nonvolatile ingredients, manufactured by Dainihon Ink
Kogyo K.K.), 10 parts of Beckamin PM, 2 parts of Catalyst C-376 and
300 parts of water, squeezed so as to retain 100 percent by weight
of the treating liquid based on the fabric, followed by the fourth
step wherein the fabric was cured at 130.degree. C. for 5
minutes.
In the fifth step, on the top surface of the resultant sheet
material applied was a treating liquid consisting of 100 parts of
30 percent N,N-dimethylformamide of S-lec BH-2 (a trade name of a
polyvinyl butylal resin having an average degree of polymerization
of 1600 and an average degree of butylalization of 65 percent,
manufactured by Sekisui Kagaku Kogyo K.K.) and 10 parts of butyl
phthalyl butyl glycolate, in the same manner as in the fifth step
of example 3, to form a grain side layer on the sheet material. The
thus obtained leatherlike material had its properties as
follows:
Water absorbability (%) 235 Moisture permeability (mg./cm..sup.2
/hr.) 4.2 Tensile strength at break in dry state (kg./mm..sup.2)
1.6 Elongation at break in dry state (%) 58
The resultant leatherlike material exhibited appropriate softness
and preferable hands and was suitable for clothings such as a coat,
chair coverings and bags.
* * * * *