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Патент USA US2405602

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Aug. lß, i946.
2,405,602
F.V{NUGENT
VADHESIVE ACTIVATION
Filed Sept. 23, 1944
_
A
»1M/eww?
i: _Frederick VÃfulgen‘Ú
A
1
Patented Aug. 13, 1946
2,405,602 l
UNITED STATES PATENT OFFICE
2,405,602
ADHESIVE ACTIVATION
Frederick V. Nugent, Abington, Mass., assigner to
B. B. Chemical Co., Boston, Mass., a corpora
tion of Massachusetts
1
.
Application September 23, 1944, Serial No. 555,579
2 Claims. (Cl. 154-40)
This invention relates to improvements in the
joining together of fibrous surfaces with cements
or adhesives and more particularly to the joining
of shoe parts, such as leather soles to shoe uppers
by means of synthetic rubber-like adhesives.
that a cemented portion- has been activated or
softened prior to its assembly or joinder with
another cemented part.
In the manufacture of shoes in which the soles
are attached to the uppers by means of adhesives
it is conventional practice to apply a suitable ad
from one hour to eighteen hours before the at
'
Fig. 1 shows a perspective view of a shoe sole
showing the marginal portion to which adhesive
cement has been applied for attaching the sole
to a shoe; and
hesive to the over-lasted edge of the shoe upper
tachment and to cement the marginal portion of
l
The invention will be explained with reference
to the accompanying drawing, in which
10
Fig. 2 shows an elevation view of the main por- y
tion of a machine adapted to carry out the meth
the shoe sole from five hours to one week prior
to attachment. The adhesive on the uppers and
soles is therefore hard and dry when it becomes
od of this invention.
>be avoided, it is necessaryin alternative custom
Patent No. 2,061,296, granted November 17, 1936,
'
I have discovered that by applying an activator
or solvent lightly to hardened synthetic rubber
convenient to join the parts together. When the 15 like adhesive cement by spraying, the cement is
parts are to be assembled the dry and hardened
temporarily restored to attaching condition sub
adhesive on the sole is activated or softened by
stantially immediately, that is to say, no waiting
a suitable solvent the volatility of which must
is required between the activation of the cement
be so adjusted Áas to allow the operator suiiicient
and the sole attaching operation (for example)
time to assemble the parts before placing them in 20 even with ordinary activators such as toluene.
a pressure device. In the present practice for
When spraying is used it is possible to activate
temporarily restoring normal adhesiveness it is
merely the surface of the cement and no excess
customary to apply the activator or softener by
solvent need be dissipated ,before the parts are
means of a brush and in so doing the quantity
ready for attachment. It’has been found that
of the solvent or activator applied is so excessive 25 in spray activation of neoprene or polymerized
that the soles must be set aside for about an hour
chloroprene cement, for example, an initial bond
before they are applied to the shoe uppers, neces
strength of 15 to 20 pounds may be obtained as
sitating care in timing the operations of shoe
compared with the five-pound bond ordinarily
manufacture and contributing to the uncertainty
obtained with liquid solvent activation. The
as to whether the cement is properly activated. 30 neoprene or chloroprene cement spoken of is of
If such delay preliminary to sole attachment is to
the type as described in United ,States Letters
ary practice, for the shoes to remain in the pres
sure device for a considerable time to permit sub
stantially complete removal of the volatile mate
rial in the softener or until the adhesive has set
completely. In other words, a considerable delay
has been heretofore essential in shoe manufac
on an application filed in the name of W. H.
Wedger'. By “initial bond” is meant the strength
l tested immediately after a time dwell in an at
taching press of from 8 to 60 seconds. The light
spray activation is very economical of solvent.
It has been found that by the spray method 5000
turing procedure either before or after sole lay
pairs> of shoe soles may be activated per vgallon
ing. Another diñiculty that has arisen is that 40 of solvent as compared with 1000 pairs per gal
when a machine is used to apply the activator
lon of solvent by the brush method of solvent
or solvent to the margin of the soles the operator
may not notice that the supply of solvent has
given out or is irregular with the result that the
attachment of the sole to the upper Vis neither
secure nor reliable.
Y
t .One object of this invention is the provision
of an improved method of joining fibrous sur
activation.
Spray activation is advantageous
with other adhesive cements, among them Ibeing
butadiene-acrylonitrile copolymer in the form
known as “Hycar” (type O. R.) manufactured by
the H_ycar Chemical Company, Akron, Ohio.
Similar copolymers may also be obtained com- '
mercially under the trade name “Chemigum”
faces together with synthetic rubber-like adhe
manufactured by Goodyear 'I‘ire and Rubber
sive cement previously applied to the surfaces 50 Company, Akron, Ohio, or under the trade name
and allowed to dry in which method no undue
delay or interruption in manufacturing procedure
need be encountered,
A further object of the invention is to provide
` “Perbunan” manufactured by the Standard Oil
Company of New Jersey. For butadiene-acrylo
nitrile type cements, suitable illustrative solvents
for application by spray are acetone and methyl
a method for clearly indicating by means of color 55 ethyl ketone. With the use of any of these ce
à
,
five days; the aging results in the oxidation of
The necessity for
aging may be obviated by dissolving diphenyl
carbazide in toluene and oxidizing the carbazide
ments spray activation necessitates prompt join
the carbazide to carbazone.
der >of the parts, that is, a period not in excess '
of approximately three minutes should intervene
between the step of activation and the attach
ment of the parts.
to carbazone by means of quinone. The formula
for symmetrical diphenyl carbazide is as fol
It has been found that a time dwell not in eX
cess of one minute is sufìcient in the attaching
lows: (CsHsNH-NH-CO-NH-NH-CsHs). The in
dicator as dissolved in the solvent presents a
machine by means of Which the parts are held
bright red color but when this is sprayed on an
together with suitable pressure. In the case of
attachment of an outsole and shoe upper it is 10 Auncoated shoe sole it is practically invisible.
preferable that they be maintained under sole '
Wherever the indicator contacts a hardened ce
attaching pressure for at least 40 to 60 seconds,
and this may be accomplished conveniently in a
machine such as shown in UnitedStates Letters
Patent No. 2,047,185, granted July 14, 1936, on an 15
an instantaneous chemical reaction which im
parts a distinct red color to the cement. This
ment which includes magnesium oxide there is
vcolor 'fades ina few days if the parts are not
' attached together by means of the cement. Use
application filed in the namev of Milton H. Bal
'of the. indicator inthe activator does not hinder
lard et al.
reactivation of the cement at a later date. In
When it is desired that a sole be molded or..V
employing an indicator as set_forth in this in
Vention it is necessary to omit any accelerators
of curing from the activator because such ac
of time elapses between the sole forming or mold
celerators would react with the cli-phenyl car
ing and the sole attaching operations the-sole
bazone. The use of such indicator is greatly
may be brought again into temper just prior to
superior to the use of dyes as dyes tend to mi
the sole attaching operation. Before the appli
cation of an activator or softener to the sole, 25 grate and are apt to discolor the objects treated,
such as the uppers or soles of shoes. There is no
Whether or not the sole is formed or molded, the
migration or discoloration in the use of diphenyl
sole is preferably mulled or tempered in order
carbazone.
to make the same more iiexible, and to reduce
In carrying out the method a shoe, to which
the tendency of the sole to pull away 'from the
upper after the release of the scle~attaching 30 a sole is `to be applied, may have its upper llasted
over its insole in any usual manner. YFor ex
pressure. The step of activation is not adversely
ample, the heel seat portion may be lasted `with
affected by the prior tempering operation.
tacks and at the shank portion the upper may
I have avoided uncertainties in the prior meth~
be Worked over the last and secured in position
ods of activation, whether such methods be by
brush or spray application of a solvent, by 'in 35 with staples by means of a machine such as the
staple lasting machine disclosed in Letters Pat»
corporating a color indicator in the activator or
ent of the United States No. 1,815,295, granted
solvent. A small quantity of a substance is placed
J uly 21, 1931, on an application ñled in the name
in the activator, which substance will react with
of George Goddu. The Iforepart may be similarly
an' ingredient such as a ñller in the cement and
thereby constitute a color indication of4 the ce 40 lasted or the upper may be held in lasted position
by cement alone. The »overlasted margin of the
ment activation. The use of a color >indicator
upper is preferably roughened before synthetic
enables an operatorl by casual Vobservation to ob
rubber-like adhesive cement is applied thereto
serve immediately whether or not a hardened- ce
by hand or byv means of »a cement applying ma
ment'lias been activated andV jhe can therefore
proceed immediately to carry out the attaching 45 chine such as disclosed in Letters Patent No.
2,100,341, granted November 30, 1937, on an ap
step (if spray activation is used) or can proceed
plication filed »in the name of Wilbur L. Mac
with his timing `(if brush activation isV used) and
formed the cement coated sole is mulled or tem'--- ‘
pered and shaped. If la relatively long period
with greater certainty of result.
ì _'
Kenzie.
i
~
An outsole llll is prepared as shown in Fig. 1,
The use of the color indicator of this -inven
tion is especially and peculiarly adapted for com 50 the » marginal portion of its inner -face being
roughened at I2 for the receptiony of synthetic
bination with the spray activation feature'for the
rubber-like cement which is shown» `as having
reason that spray activation requires vsuch a
been applied to the margin. The roughing may
small amount of activator or solvent> that an in
be done by any of the usual roughing machines
dicator isV particularly advantageous to Warn an
employed in themanufacture of cemented shoes.
operator from proceeding'with cement attaching
The, cement may be applied to the outsole by
Without proper activation.
'
hand but preferably bya'machine such 'as dis
It is customary in the use of adhesive lcements
closed in Letters Patent of the United States No.
to incorporate therewith a quantity of mag
2,042,479, granted June 2, 1936, on an application
nesium oxide which usually functions as a filler.
In‘the use of such cements l have found it` aol 60 ñled in the name of Carl A. Newhall.
After the outsole and shoe -have been coated
vantageousto use an activator containing a small
with adhesive cement they are aliowed'to dry in
quantity of symmetrical diphenyl carbazone
the-customary manner and the outsole may then
(CeHaN-N- CO -NH -NH' Cel-lla) .
Approximately
be mulled and formed before the use of a softener'
three grams of this material is used per gallon
or-activator for the cement.
of solvent when activation is by means of a spray.
The application of the softener `or activator
Approximately one gram per gallon of solvent
may be done by a spray gun mounted in place of
is used for brush activation. A suitable sol
. a brush- Von a coating applying machine as dis
vent composition With a color indicator for the
closed inlLetters Patent of the United States No.
activation has been found to be as follows:
2,073,647 granted March 15, 1937, on an> appli
70
ASixrounces____`____________ __ Denatured alcohol
cation- filed-in the name of Carl A. Newhall. The
Six ounces__,_1 _______ __, _____ ___„_ Ethyl acetate
substitution of a spray gun on such a machine is
One or three grams ______ __ Diphenyl carbazide
shown in Fig. 2 in which a spray gun 20>is shown
Dilute to one gallon with toluene.
¿
’ «This solution 'should be'subjected to -agingfor
15'
mountedat an angle to the horizontal on an-arm
22 extending from `the machine frame and'inpo
2,405,602
sition to direct a light spray of activator mate
rial on the margin of the outsole as the outsole
is manipulated between the upper and lower feed
rolls 24 and 26, Customary air and liquid feed
connections 3l and 33 are shown. The spray
as new and desire to -secure by Letters Patent of
`the United States is:
l. In the art of adhering fibrous materials to
gether, that improvement which comprises add
ing a filler material yto a synthetic rubber-like
adhesive, applying the adhesive to areas of the
parts to be joined and permitting the adhesive
to harden, providing a solvent activator for said
adhesive and adding thereto an agent capable
of subsequent reaction with said filler material
for producing a color, applying the agent carry
ing activator to the hardened adhesive on at
gun is so adjusted that there is a ñow of approx
imately four-tenths of one cubic centimeter of
the activator to each sole. The spray may easily
be maintained light by adjusting the gun to re
tain a large volume of air as compared with the
amount of activator. 'I‘he trigger 30 of the spray
gun may be operated by connecting it through
arm 32 to the horizontal and sectional rod 34
least one of said areas to render the adhesive
which is rotated by the rod and lever system 36
tacky and with a resulting reaction between the
upon depression of a foot treadle (not shown) to
agent and the filler giving a visual indication of
which a vertical rod 38 is attached. The feed 15 the condition of the adhesive, and thereafter
ing of an outsole and application of an activator
pressing the parts together to effect an adhesive
to the outsole during feeding are both under the
bond.
control of the treadle.
2. In the art of adhering ñbrous materials to
The activating medium preferably includes a`
small quantity of diphenyl carbazone and in such
case the cement on the outsole is a cement con
taining a quantity of magnesium oxide.
Prcmptly after activation of the outsole ce
ment (preferably evidenced by the color pro
duced in the cement), the outsole and shoe bot
tom are brought into juXtaposition and under
attaching pressure in a sole attaching machine
gether, that improvement which comprises add
ing magnesium oxide to a synthetic rubber-like
adhesive, applying the adhesive to areas of the
parts to be joined and permitting the adhesive
to harden, providing a solvent activator solution
25 for said adhesive, said solution containing di
phenyl carbazone, lightly spraying the said ac
tivator solution on the hardened adhesive of at
least one of said areas to render the adhesive
of a type before referred to. The pressure is
tacky and with a resulting Vreaction between the
maintained for 50 seconds and then the shoe may
diphenyl carbazone and the magnesium oxide
30
be removed from the machine as the strength of
giving a visual indication of the condition of the
the initial bond is suñiciently great to be reliableeven -though the last be immediately pulled from
the shoe.
Having described my invention, what I claim
adhesive, and thereafter pressing the parts to
gether to effect an adhesive bond.
35
FREDERICK V. NUGENT.
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