U.S. patent number 3,778,251 [Application Number 05/125,055] was granted by the patent office on 1973-12-11 for shoe stiffener materials.
This patent grant is currently assigned to Bixby Box Toe Co., Inc.. Invention is credited to Blair D. Trask.
United States Patent |
3,778,251 |
Trask |
December 11, 1973 |
SHOE STIFFENER MATERIALS
Abstract
Improved shoe stiffener materials such as box toe blanks and
counter blanks are formed of a base layer of an impregnated fabric
carrying a polystyrene-type impregnant in incompletely coalesced
particle form. At least one and preferably both sides of the base
layer carries a polycaprolactone thermoplastic layer. The shoe
stiffener material is solid and non-tacky at standard room
temperature and has sufficient softness and flexibility to permit
ease of use in conventional box toe and shoe back part forming
apparatus. Heat is used to form a continuous thermoplastic film of
the polymers in the shoe stiffener when formed into
three-dimensional box toes and counters. The heat also acts to
adhesively unite the stiffener with surrounding layers such as shoe
uppers and shoe linings.
Inventors: |
Trask; Blair D. (Haverhill,
MA) |
Assignee: |
Bixby Box Toe Co., Inc.
(Haverhill, MA)
|
Family
ID: |
22418001 |
Appl.
No.: |
05/125,055 |
Filed: |
March 17, 1971 |
Current U.S.
Class: |
428/215; 12/146D;
36/68; 156/245; 427/389.9; 427/417; 428/334; 442/286; 442/304;
442/326; 442/394 |
Current CPC
Class: |
B32B
27/12 (20130101); A43D 11/00 (20130101); B32B
27/00 (20130101); B32B 27/36 (20130101); B32B
27/08 (20130101); Y10T 428/263 (20150115); B32B
2437/02 (20130101); Y10T 442/59 (20150401); B32B
2325/00 (20130101); Y10T 428/24967 (20150115); B32B
2367/00 (20130101); Y10T 442/40 (20150401); Y10T
442/674 (20150401); Y10T 442/3854 (20150401); B32B
2260/046 (20130101); B32B 2260/021 (20130101) |
Current International
Class: |
A43D
11/00 (20060101); B32B 27/00 (20060101); B32b
027/12 (); A43d 031/00 () |
Field of
Search: |
;117/76T,76A,122H,68.5,161K,68 ;260/78.3R |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Husack; Ralph
Claims
What is claimed is:
1. A thermoplastic shoe stiffener sheet comprising,
a base layer of an impregnated fabric carrying an incompletely
coalesced thermoplastic polymer impregnant and having first and
second outer surfaces,
an outer layer adhered to a surface of said base layer and
consisting essentially of polycaprolactone.
2. A thermoplastic shoe stiffener sheet in accordance with claim 1
and further comprising a second outer layer adhered to a second
surface of said base layer and consisting essentially of
polycaprolactone.
3. A thermoplastic shoe stiffener sheet in accordance with claim 2
wherein said sheet is capable of being treated with heat at a
temperature of from 140.degree.F to 360.degree.F to activate said
sheet to form a continuous film thereof and render it adhesive.
4. A thermoplastic shoe stiffener sheet in accordance with claim 3
wherein said thermoplastic polymer impregnant comprises
polystyrene.
5. A thermoplastic shoe stiffener sheet in accordance with claim 4
wherein said thermoplastic polymer impregnant consists essentially
of a mixture of styrene-butadiene copolymer and a styrene polymer
wherein the ratio of total styrene to butadiene is not less than
75:25 and does not exceed 95:5.
6. A thermoplastic shoe stiffener sheet in accordance with claim 5
wherein said thermoplastic polymer impregnant and said fabric are
in the ratio of at least 2:1 by weight and said polycaprolactone
has a molten viscosity of at least 7,000 cps at 350.degree.F.
7. A thermoplastic shoe stiffener sheet in accordance with claim 5
wherein said polycaprolactone has a weight average molecular weight
of from 25,000 to 50,000.
8. A thermoplastic shoe stiffener sheet in accordance with claim 7
wherein said polycaprolactone of said first and second outer layers
is blended with from 10 to 40 percent by weight of a viscosity
depressant selected from the group consisting of rosin derivatives,
terpene phenolics and waxes.
9. A thermoplastic shoe stiffener sheet in accordance with claim 8
wherein said viscosity depressant is a terpene phenolic in an
amount of from 10 to 40 percent by weight, and from 5 to 15 percent
by weight of a compatible polymeric material selected from
polymeric acetates and vinyl materials is uniformly incorporated in
said polycaprolactone to prevent embrittlement by said terpene
phenolic.
10. A thermoplastic shoe stiffener sheet in accordance with claim 4
wherein said base layer has a thickness of from 0.020 to 0.090 inch
and said first and second outer layers each have a thickness of
from 0.001 to 0.005 inch.
11. A thermoplastic shoe stiffener sheet in accordance with claim 1
wherein said thermoplastic polymer impregnant consists essentially
of a mixture of styrene-butadiene copolymer and a styrene polymer
wherein the ratio of total styrene to butadiene is not less than
75:25 and does not exceed 95:5, and said sheet is capable of being
treated with heat at a temperature of from 140.degree.F to
360.degree.F to activate said sheet to form a continuous film
thereof and render it adhesive.
12. A method of forming a shoe stiffening sheet for use as shoe
counter blanks and shoe box toe blanks,
said method comprising,
impregnating a fibrous material with an aqueous dispersion of a
mixture of a styrene-butadiene copolymer and a styrene polymer
wherein the ratio of total styrene to butadiene is between 75:25
and 95:5 to form an impregnated base layer,
drying said base layer without causing complete coalescence of the
polymers,
and applying an adherent film coating consisting essentially of
polycaprolactone on outer surfaces of said base layer.
Description
BACKGROUND OF THE INVENTION
A large variety of thermoplastic shoe stiffener materials have long
been known in the shoe art for use as box toe blanks and counter
blanks in conventional shoe molding and lasting procedures. A type
of shoe stiffener material which has been highly successful and
extensively used in recent years is described in U.S. Pat. No.
2,840,492. Such shoe stiffener materials are formed into a box toe
blank or counter blank having a fibrous base impregnated with
incompletely coalesced particles of polystyrene-type impregnant.
The term "polystyrene-type" is used herein to mean conventional
shoe stiffener polystyrene-containing thermoplastics which are
preferably mixtures of styrene-butadiene copolymer and a styrene
polymer wherein the ratio of total styrene to butadiene is between
75:25 and 95:5. Such shoe stiffeners as in the form of a box toe
blank are used in accordance with conventional practice wherein a
shoe upper and liner are sewn together, the box toe blank is
softened by a liquid solvent and inserted between the liner and
upper and the assembly applied to a last. The box toe blank remains
pliable at least through the lasting operation. The liquid solvent
acts to cause the impregnant to firmly adhere to the upper and
liner while coalescing the impregnant particles to form a
continuous film so that by the time the shoe is removed from the
last, the liner, box toe blank and upper are integrated into a
relatively rigid structure having high resistance to impact.
Such shoe stiffeners provide box toe and counter blanks which can
be readily softened by application of selected solvents which are
capable of adhesively integrating the upper and liner to provide a
stiffened shoe structure having good impact resistance. The blanks
are formed so that the plastic impregnants are incompletely
coalesced and incompletely film formed in order to allow ease of
handling and rapid solvent penetration.
Problems connected with the use of such shoe stiffeners include
that of obtaining outstanding adhesion to liners and uppers which
requires difficult to obtain ideal solvent activation conditions.
Handling of solvent soaked blanks is messy and time consuming. The
manufacturing time for forming the stiffeners in shoe making
operations is usually long since often several hours are required
for the solvent to evaporate. The timing in back part molding and
lasting operations is critical since solvent activated shoe
stiffeners must be molded while sufficient solvent is still present
which requires juggling of solvent blends to fit particular sets of
factory conditions. Moreover, use of the solvents can cause
problems of toxicity and flammability normally associated with the
handling of solvents.
SUMMARY OF THE INVENTION
It is an object of this invention to provide a shoe stiffening
material in sheet form which can be molded into three-dimensional
box toes and shoe counters having good flexibility, stiffness and
impact resistance with excellent adhesion to conventional shoe
upper and shoe lining materials.
It is another object of this invention to provide a shoe stiffener
material in accordance with the preceding object which comprises a
thermoplastic impregnated fabric having at least one coating of
polycaprolactone whereby the material can be molded within standard
shoe making temperature limits to form a continuous film and
adhesively unite with conventional shoe upper and shoe lining
materials.
Still another object of this invention is to provide a shoe
stiffener material which can be activated and molded by heat
without the use of liquid solvents and which is economical to
manufacture and use efficiently in shoe making procedures.
According to the invention a thermoplastic shoe stiffening material
in sheet form comprises a base layer of an impregnated fabric
carrying a thermoplastic impregnant in the form of incompletely
coalesced particles. At least one outer layer comprises
polycaprolactone. The material is capable of being heat treated at
a temperature of from 140.degree.F to 360.degree.F and preferably
175.degree.F to 250.degree.F to form a continuous plastic film
having adhesive properties.
Preferably the incompletely coalesced thermoplastic impregnant is
of a styrene type preferably comprising a mixture of
styrene-butadiene copolymer and a styrene polymer with the ratio of
total styrene to butadiene being between 75:25 and 95:5. The
polycaprolactone has a molding temperature between 140.degree.F and
360.degree.F and preferably 175.degree.F to 250.degree.F with a
softening point of from about 140.degree.F to 180.degree.F.
Preferably the polycaprolactone is applied to both sides of the
impregnated fabric as a thin layer in a continuous film having a
thickness of between 0.001 and 0.005 inch and the impregnated
fabric has a thickness of from 0.020 to about 0.090 inch.
The polycaprolactone can be modified with suitable viscosity
depressants which preferably do not affect the desired flexibility
of the polycaprolactone. Such viscosity depressants include rosin
derivatives, terpene phenolics and waxes. Conventional modifiers,
fillers and the like can also be incorporated in the
polycaprolactone.
In an alternate embodiment of this invention, the impregnated
fabric coated on both sides with a polycaprolactone film has one of
the polycaprolactone films further coated with a barrier layer.
This embodiment can be used in unlined shoe manufacture where the
barrier coating prevents adhesion of the polycaprolactone to lasts
during formation of the shoe stiffeners into three-dimensional
configurations.
In the method of using the shoe stiffeners of this invention, a
shoe stiffener blank having an incompletely coalesced thermoplastic
particle impregnated fabric with outer coatings of
polycaprolactone, is preheated while pressed against a shoe upper
and/or liner in a conventional shoe box toe of back part forming
apparatus. Preferably a machine temperature of from 250.degree.F to
350.degree.F is used to obtain a blank temperature of 175.degree.F
to 250.degree.F for from 5 to 20 seconds. The preheated blank is
then placed in the box toe or heel seat lasting section. The blank
is thus adhesively united with a shoe upper and/or lining while
simultaneously forming the shoe stiffener blank into a continuous
film. As soon as the laminate so formed is cooled to room
temperature, a solid shoe part is obtained having the required
stiffness.
It is a feature of this invention that adhesion to conventional
shoe lining and shoe upper materials is extremely good and in fact
far better than obtained by solvent activated materials under
normal operating conditions. Shoe making operations are greatly
simplified since manufacturing time is decreased by orders of
magnitude due to elimination of the time necessary for the solvent
to evaporate. Critical timing in back part molding and lasting
operations is not necessary since the materials of this invention
are permanently re-moldable at reason-able temperatures which can
easily be attained by normal steaming operations. Problems of
toxicity and flammability associated with handling of solvents are
avoided. Firmness, i.e., the resistance to deformation of molded
box toe and counter shapes, is greater for the material of this
invention than with comparable solvent activated shoe stiffeners.
Molded shoe counters or shoe box toes made from the material of
this invention have good impact strength and high resistance to
fracture. Use of polycaprolactone layers on both sides of the base
fabric provides for moisture seals of the material which minimizes
the softening effect of moisture if present.
While the exact mechanism that takes place during heating and
molding of the shoe stiffener material of this invention is not
fully understood, it is believed that the polycaprolactone acts as
an adhesive to bond the shoe stiffeners to the upper and/or lining
material of the shoe. In the molten state, the coating is believed
to cause some activation of the polystyrene impregnant, i.e., it
causes the impregnant to swell and coalesce at least partially into
a continuous film. Moreover, the coating of polycaprolactone
penetrates and flows into the impregnated fabric and around
polystyrene particles which have not coalesced. Because
polycaprolactone and polystyrene are quite compatible, it is
believed that there is a dissolution of the polystyrene into the
molten polycaprolactone. These actions bond the incompletely
coalesced particles into a uniform continuous film. The result of
molding in conventional box toe and counter apparatus is that the
shoe stiffener material after molding is an essentially continuous
resin film reinforced by a fabric which gives the necessary
hardness and durability to the three-dimensional molded
stiffeners.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objects, features and advantages of the present
invention will be better understood from the following description
when read in conjunction with the accompanying drawings in
which:
FIG. 1 is a top plan view of a preferred embodiment of a shoe
stiffener material of this invention in the form of a shoe
counter;
FIG. 2 is a cross sectional view through line 2--2 thereof;
FIG. 3 is an alternate embodiment thereof in the form of a box toe
blank;
FIG. 4 is a cross sectional view showing a step in the molding of
the counter of FIG. 1 between a shoe upper and shoe lining; and
FIG. 5 is a cross sectional view through an alternate embodiment of
a shoe stiffener material in accordance with this invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
With reference now to the drawings, the shoe stiffening material of
this invention is illustrated in sheet form in the shape of a
counter blank 10 in FIG. 1 and a box toe blank 20 in FIG. 3. The
counter blanks and box toe blanks can be of any conventional shape
and the shapes 10 and 20 are shown for illustrative purposes. The
shoe stiffener materials will be referred to with reference to the
counter blank 10, but, it should be understood that whether in a
counter blank or box toe blank shape, the makeup of the shoe
stiffener material is the same.
The counter blank 10 as shown in FIG. 2 is formed of a flat fibrous
base 16 impregnated with polystyrene-type incompletely coalesced
particles 15 to make up a base layer 12. Both the upper and lower
surfaces of the base layer 12 are coated with a thin, continuous
film 11, 13 of polycaprolactone adhered to the base layer.
Preferably the base layer 12 has a thickness of from 0.020 to 0.090
and each film coating 11, 13 has a thickness of from 0.001 to 0.005
inch. However, the thickness of each layer can vary greatly
depending upon particular materials used and particular results
desired.
The counter blank 10, because of the polycaprolactone used is solid
and non-tacky at standard room temperature of 70.degree.F and
remains non-tacky allowing storage at temperatures as high as at
least 138.degree.F.
The impregnated fiber base layer 12 is a conventional shoe
stiffener sheet capable of being activated by a liquid solvent in
conventional box toe and counter blank apparatus. Suitable base
layers are described in U.S. Pat. No. 2,840,492 and are well-known
in the art. As described in that patent, the fibrous material 16 is
a textile material which can be knitted, woven, felted, needle
punched, non-woven or the like from fibers of cotton, felt, jute or
the like. The impregnant is preferably a resinous composition which
is a thermoplastic styrene-type material preferably consisting
essentially of a mixture of styrene-butadiene copolymer and a
styrene polymer wherein the ratio of total styrene to butadiene is
not less than approximately 75:25 and does not exceed approximately
95:5 with a preferred range being between 80:20 and 90:10. The
impregnant can be a styrene copolymer alone or a styrene blend
alone. Styrene copolymers and blends with natural and synthetic
rubbers such as butadiene or with acrylates can be used. As known
in the art, such base layers when used alone as box toe or counter
blanks are formed by impregnation in a conventional manner so that
the fibrous base picks up from approximately 200 percent to 500
percent or more of its weight of the resinous composition (dry
basis) to produce an impregnated sheet with a coating or surface of
the resinous material which is incompletely coalesced and
incompletely film formed. The terms "incompletely coalesced" and
"incompletely film formed" are used to indicate that the resin is
capable of substantial further coalescing and film forming as by
solvent activation in conventional shoe molding procedures.
The impregnating composition is preferably a mixture of aqueous
dispersions of the copolymer and styrene polymer containing
suitable thickening agents which do not undergo bacterial
decomposition and which are preferably relatively water resistant
when dried out. The fabric material is passed through the aqueous
dispersion and the base layer 12, then dried out in any suitable
manner such as conventional oven drying or drying on textile cans
at temperatures of approximately from 180.degree.F to 280.degree.F
and preferably 180.degree.F to 210.degree.F. The time and
temperature of drying is controlled as known in the art to avoid
complete film forming and coalescing which would render the sheet
too rigid for ease of handling in conventional molding.
The polystyrene thermoplastic impregnant can have suitable fillers
and other compounding materials incorporated therein as known in
the art.
It is conventional to use the base layer 12 as a box toe or counter
blank directly as by soaking such blanks in a solvent and then
molding. However, as pointed out above, several disadvantages
ensue.
In the counter blank 10 of this invention, polycaprolactone film
layers 11 and 13 are deposited on the upper and lower surfaces of
the base layer 12 to form a bonded sheet. The formation of the film
layers or coatings 11 and 13 can be carried out by conventional hot
melt roller coating, extrusion and the like. Preferably the film
layers 11 and 13 are formed as substantially uniform thickness
layers using conventional hot melt, roller coating techniques at a
temperature in the hot melt of about 360.degree.F.
The polycaprolactone polymers of the layers 11 and 13 are known in
the art to have the following structural formula: ##SPC1##
where n preferably varies from 100 to at least 1,000. It has now
been found that such polymers which are solid at room and normal
storage temperatures are ideally suited for use in shoe stiffener
materials to eliminate the need for solvent activation.
Polycaprolactone has good compatibility with styrene-type polymers,
good stiffness, flexibility and impact resistance and excellent
adhesive properties to normal shoe upper and shoe lining materials.
Moreover, the temperatures at which polycaprolactones become
adhesive and flow are ideally suitable for shoe making procedures
since softening and flow can be obtained in a temperature range
which is non-destructive to shoe uppers and high enough to prevent
strike through of the thermoplastic through the shoe upper and
lining materials.
Preferably the polycaprolactone polymers used have weight average
molecular weights of at least 25,000 with a weight average
molecular weight in the range of 25,000 to 50,000 being preferred.
Such polycaprolactone polymers have excellent adhesive properties
and eminently suitable molding temperatures in the range of from
140.degree.F to 360.degree.F and preferably 175.degree.F to
250.degree.F.
Typical molten viscosities for useful polycaprolactone polymers
obtained by Brookfield Model LVT using spindle SC-34 at 0.6 rpm
(Brookfield's Thermosel equipment) are given below:
Polycaprolactone polymer weight average molecular weight 28,000
350.degree.F 7750 cps 375.degree.F 5000 cps Polycaprolactone
polymer weight average molecular weight 40,000 350.degree.F 66,000
cps 375.degree.F 31,000 cps
A preferred polycaprolactone polymer for use in this invention is
available from Union Carbide Corporation of New York, N.Y. and
designated PCL-700. This polymer has a weight average molecular
weight of 40,000 with the viscosity noted above. Other properties
of the polycaprolactone polymer are listed below and are described
in Union Carbide Corporation product information sheets F-42501:
##SPC2##
The PCL-700 polycaprolactone polymer has a viscosity which is too
high to allow application as a thin coating of from 0.001 to 0.005
inch using conventional hot melt, roller coating techniques and it
is therefore extrusion coated when the film layers 11 and 13
consist of this polymer. However, extrusion of the film coatings 11
and 13 can add cost to the shoe stiffener materials of this
invention. Thus, it has been found that it is possible to modify
the polycaprolactone polymers used with suitable viscosity
depressants and preferably viscosity depressants which do not
affect flexibility and are compatible with polycaprolactone. Such
viscosity depressants can be blended with the polycaprolactone in
conventional blending operations such as conventional blending in a
hot melt. Preferably the film layers 11 and 13 comprise at least 60
percent by weight polycaprolactone polymer. Conventional modifiers,
fillers and other additives can also be incorporated in the
polycaprolactone as known in the art.
Useful viscosity depressants include rosin derivatives, waxes and
terpene phenolics alone or in combination with each other. When
terpene phenolics are used as viscosity depressants, a modifying
polymeric material is also used to prevent the terpene phenolics
from brittling the polycaprolactone. Thus, such viscosity
depressants do not change the flexibility of the polycaprolactone.
The rosin derivatives are preferably used in amounts of from 10 to
40 percent by weight and can be resin esters including but not
limited to pentaerythritol esters of hydrogenated rosin, methyl
esters of hydrogenated rosin, glycerol esters of polymerized rosin
and glycerol esters of hydrogenated rosin. The waxes can be
natural, microcrystalline and ester waxes having melting points
above the melting point of the polycaprolactone polymer and
preferably above 160.degree.F. Such waxes are preferably used in
amounts of from 1 to 5 percent by weight of blends useful in this
invention. The waxes act to depress viscosity and also improve
blocking characteristics thus preventing counter blanks and box toe
blanks from sticking to one another when stacked for shipment and
storage even though environmental temperatures may be high.
The terpene phenolics when used are preferably blended with
polycaprolactone with or without rosin and waxes in preferred
amounts of from 10 to 40 percent by weight of the blends. The
terpene phenolics act as blocking agents as well as viscosity
depressants as do the waxes. Since the terpene phenolics tend to
embrittle polycaprolactone, when used, they are used in conjunction
with a polymeric material such as ethylene vinyl acetate acting as
a softening agent. Other acetates and vinyl materials can be
used.Ethylene vinyl acetate does not appreciably affect the
flexibility of blends of terpene phenolics and polycaprolactone.
Such polymeric materials are preferably used in amounts of from 5
to 15 percent by weight of the blends.
The particular amount of the viscosity depressants and modifiers
added to the polycaprolactone can vary depending upon the molecular
weight of the polycaprolactone used and its initial viscosity. In
most cases, it is preferred that the viscosity depressants and
modifiers used be used in amounts of from 10 to 40 percent by
weight of the blend with polycaprolactone. In all cases, the
additives are compatible with polycaprolactone in that they do not
significantly adversely affect the desirable properties of the
polycaprolactone.
In the method of using the shoe stiffener material of this
invention, as suggested in FIG. 4, a counter blank 10 is formed
into a three-dimensional molded counter in a conventional shoe back
part forming machine such as a United Shoe Machinery UBMA. Other
conventional molding equipment such as International Shoe Machinery
Corporation Model CHT with Model TA activator can be used. The
counter blank 10 as shown in FIG. 4 is heated after positioning
between a show upper layer 21 and shoe lining 22 for shaping, at
conventional machine temperatures and times. For example, at
275.degree.F cycle times are normally 12 to 20 seconds while at
350.degree.F cycle times are normally 6 to 10 seconds. After
heating, the laminated counter, shoe lining and shoe upper which
are pulled down over a last as in conventional practice, are
transferred to a second station and then allowed to cool. The
counter 10 easily conforms to the shape of the last and is easily
molded. During the molding operation, the counter blank 10 is
formed into a continuous film throughout and adhesively unites to
the leather upper and leather lining without strike through of the
thermoplastic material to the outer surfaces of the lining 22 or
upper 21. After molding, the shoe parts can be air-cooled or
allowed to cool at room temperature so that a complete molded box
toe structure or counter structure is rapidly formed and which
maintains its shape well. This procedure avoids the long time
periods ordinarily used to evaporate solvents after lasting.
FIG. 5 illustrates an alternate embodiment of this invention where
the box toe blank 20 with layers 11, 12 and 13 as previously
described is formed with an adherent layer 14 of a blocking film.
The film 14 can for example be a film of styrene acrylonitrile
applied to the lower layer 13. Thus, layer 11 can be applied to a
shoe upper in a molding operation with layer 14 directly contacting
the last. The layer 14 provides a barrier to prevent adhesive
attachment of the blank to the last during the lasting operation
while allowing adhesive attachment to the shoe upper.
In most cases, it is preferred to use the shoe blanks of this
invention with dual coatings 11 and 13 as described in laminated
constructions between a lining and shoe upper. Use of dual coating
assures continuous film formation of the molded blank. However, in
some cases, only one coating 11 or 13 need be used.
The shoe counter blanks 10 and box toe blanks 20 are compatible
with a wide variety of conventional shoe uppers and linings. For
example, the shoe upper can be leather, cloth, or other materials
including synthetic polymeric materials such as poromeric shoe
upper materials, polyvinyl chloride coated fabrics, or polyurethane
coated fabrics. The shoe linings can be conventional sheet or
textile materials of cotton, jute, felt, leather, synthetic
polymeric materials such as poromeric materials, and the like. In
all cases, the adhesive properties of polycaprolactone are
outstanding.
Illustrative examples for preparing and using the shoe stiffener
materials in accordance with the present invention are given
below:
EXAMPLE 1
An aqueous dispersion of 88.5 parts of a 60-40 styrene-butadiene
copolymer (Polyco 2415, a Borden Chemical Company product) is mixed
with 144 parts an aqueous dispersion of polystyrene (Polyco 220NS,
a Borden Chemical Company product) to produce a latex mixture
having a total solids content of about 47 3/4 percent and a total
styrene to butadiene ratio of about 83/17. A 28 percent ammonium
hydroxide solution is then added in an amount sufficient to produce
a pH of 10 to 11, followed by gentle heating to a temperature
between 120.degree. and 150.degree.F, after which 1 percent
thickening agent (Lytron 820, a styrene-maleic anhydride copolymer
having an average molecular weight of 20,000 and an acid number of
180, a Monsanto Chemical Co. product), based on the weight of
resin, is added and the mixture is stirred until a uniform
dispersion is produced. The mixture is then cooled to room
temperature (70.degree.-90.degree.F) and then run into the
impregnating apparatus.
A double nap flannel, 4 1/2 ounce -- 3/3 double nap, is then run
through the treating composition, passed through squeeze rolls or
between doctor blades to remove the excess, and dried at a
temperature of 180.degree. to 210.degree.F, the pick-up of latex
solids being 260 percent of the fabric base.
EXAMPLE 2
The same procedure as set forth in Example 1 was followed, except
that 85 parts of the styrene-butadiene copolymer of 70-30 ratio
(Polyco 2410, a Borden Chemical Company product), 126 parts of the
polystyrene and 0.67 percent of the thickener were used to produce
a 47.4 percent dispersion having a total styrene to butadiene ratio
of 87:13 and the pick-up of latex solid was 250 percent of the
fabric base.
EXAMPLE 3
A base layer as formed in Example 1 is coated with a uniform
continuous film of polycaprolactone (PCL-700) on each side with the
film having a uniform thickness of 0.002 inches on each side of the
base layer. The coating film is applied by conventional extrusion
coating at 225.degree.F and line speeds of 20 to 70 feet per minute
and are allowed to cool to room temperature. The polycaprolactone
film has a molten viscosity of 31,000 cps at 375.degree.F.
EXAMPLE 4
Example 3 is repeated using the base layer formed in Example 2
rather than that formed in Example 1 and varying the extrusion
conditions. Extrusion was carried out at 200.degree.F at line
speeds of from 10 to 40 feet per minute. Both sides of the base
layer are coated with a continuous film having uniform thickness of
0.004 inch.
EXAMPLE 5
The base layer formed in Example 1 is coated with a
polycaprolactone mixture on both sides with each film having a
thickness of 0.0035 inch. A coating mixture is formed by mixing
together in a hot melt at 360.degree.F, 65 percent by weight
polycaprolactone (PCL-700), 21 percent by weight terpene phenolic
resin (SP-560, a Schenectady Chemical, Inc., of Schenectady, New
York product) having a melting point,(ball and ring ASTM E-28) of
150.degree.C, an acid number of 65 and a specific gravity at
25.degree.C of 1.10 with a viscosity of (60 percent in toluol) 130
cps, 10 percent by weight 82-18 ethylene vinyl acetate with
inherent viscosity of 0.48 at 0.25 grams per 100 ml toluene (Elvax
410, an E. I. DuPont de Nemours Co., Inc. product) and 4 percent by
weight microcrystalline wax (Mobil Wax 2305, a Mobil Oil
Corporation product) having a melting point, ASTM, of 178.degree.F
and a needle penetration ASTM at 77.degree.F of 25/30 with a
viscosity of 70-85 at 210.degree.F, SUS. The coating is applied by
conventional hot melt roller coating at 360.degree.F using a line
speed of the base layer of 20 to 120 feet per minute. The coating
formed has a viscosity of 17,000 cps at 375.degree.F.
EXAMPLE 6
Example 5 is repeated; however, the base layer used is that formed
in Example 2. The terpene phenolic used is LTP-135, a product of
Pennsylvania Industrial Chemical Corporation having a softening
point (ring and ball) of 135 with a specific gravity of 1.03 and a
0 acid number. The resultant film coatings 11 and 13 have a molten
viscosity of about 16,500 cps at 375.degree.F.
EXAMPLE 7
Example 6 is repeated except that the coating hot melt is
substituted with the following mixture: 65 percent by weight
polycaprolactone (PCL-700), 21 percent by weight terpene phenolic
(SP-560), 10 percent ethylene vinyl acetate (Elvax 410, a DuPont de
Nemours & Co., Inc. product) and 4 percent by weight synthetic
wax (Ross Wax 160, a Frank B. Ross Co. of Jersey City, N.J.
product) which is an N, N(-dialkyl-4,4' diaminodephenylmethane).
The coatings formed each have a thickness of 0.0035 inch and a
molten viscosity of about 17,000 cps at 375.degree.F.
EXAMPLE 8
Example 7 is repeated except that the coating hot melt is
substituted with the following mixture: 65 percent polycaprolactone
(PCL-700), 21 percent by weight of a glycerol ester of polymerized
rosin (Poly-Pale ester 10, a product of Hercules Powder Co. of
Wilmington, Del.), 10 percent by weight ethylene vinyl acetate
(Elvax 410), and 4 percent by weight microcrystalline wax (Mobil
Wax 2305). The coatings have a viscosity of 16,000 cps at
375.degree.F.
EXAMPLE 9
Example 6 is repeated except that the following mixture is used for
the coating hot melt: 72 percent by weight polycaprolactone
(PCL-700), 25 percent by weight glycerol ester of polymerized rosin
(Poly-Pale ester 10), and 3 percent by weight microcrystalline wax
(Mobile Wax 2305). The film coatings 11 and 13 formed have a molten
viscosity of 15,000 cps at 375.degree.F.
EXAMPLE 10
Example 6 is repeated; however, the coating hot melt mixture is
substituted with the following mixture: 72 percent by weight
polycaprolactone (PCL-700), 25 percent by weight of a maleic
modified pentaerythritol ester of rosin (Pentalyn G, a Hercules
Powder Co. product) and 3 percent by weight microcrystalline wax
(Mobil Wax 2305). The film coatings formed on either side of the
base layer have a molten viscosity of 15,500 cps at
375.degree.F.
EXAMPLE 11
Example 6 is repeated; however, the hot melt coating mixture is
substituted with the following mixture: 72 percent by weight
polycaprolactone (PCL-700), 25 percent by weight of a glycerol
ester of hydrogenated rosin (Stabelyte Ester-10, a Hercules Powder
Co. product) and 3 percent by weight microcrystalline wax (Mobil
Wax 2305). The coating composition has a molten viscosity of about
14,500 cps at 375.degree.F. The molten viscosities of the coatings
of this invention are determined with the Brookfield technique
described above with relation to PCL-700.
EXAMPLE 12
The shoe stiffener material produced in Example 11 is used. A
counter in the sheet form 10 shown in FIG. 1 is cut from the shoe
stiffener material of Example 11. The sheet counter 10 is then
positioned in contact with a calfskin shoe upper sheet and a
leather shoe liner after which the assembly is pulled down over a
wooden last with the sheets urged into pressing contact, and
processed in a United Shoe Machinery UBMA back part forming machine
using a machine temperature of 275.degree.F and a machine time of
15 seconds. The resultant stiffened shoe part shows good adhesive
lamination of the three layers with good bond strength, and
excellent shape retention properties. When any of the shoe
stiffener materials of Examples 3-10 are used in this process,
similar results are obtained. Variations in temperature and times
of from 275.degree.F to 350.degree.F and 6 to 20 seconds and higher
give desirable results. The specific time and temperature varies
depending upon the specific materials, thicknesses and the like as
known in the art.
While specific embodiments of this invention have been shown and
described, it should be understood that many variations are
possible. In all cases, it is important that the layers 11 and 13
be formed of polycaprolactone having desirable adhesive properties
and capable of forming three-dimensional molded configurations with
desired stiffness and ease of handling without the use of
conventional liquid solvents. The polycaprolactone in all cases
functions as an adhesive and forms a continuous film of the shoe
stiffener material. Preferably the polycaprolactone polymer or
blend of this polymer with suitable modifiers has a molten
viscosity (Brookfield technique as described above) of at least
7,000 centipoise (CPS). When the viscosity is below 7,000 cps,
adhesive properties are adversely affected and strike through
problems can occur.
* * * * *