U.S. patent number 3,616,047 [Application Number 04/855,878] was granted by the patent office on 1971-10-26 for bonding propylene polymers to metal surfaces.
This patent grant is currently assigned to Continental Can Company, Inc.. Invention is credited to Alfred W. Kehe.
United States Patent |
3,616,047 |
Kehe |
October 26, 1971 |
BONDING PROPYLENE POLYMERS TO METAL SURFACES
Abstract
This disclosure relates to bonding a propylene polymer article,
such as a removable closure member for a container, to a metal
surface, such as the metal end portion of the container, which
contains an opening for removal of the contents of the container.
The metal surface is first coated with a thermosetting enamel
coating composition. Next there is applied to the enamel coated
surface a heat activatable adhesion promoting layer containing a
carboxyl modified polypropylene resin having a particle size of
less than 5 microns. The propylene polymer article is heat sealed
to the carboxyl modified polypropylene containing coated surface
and the resultant assembly is then immediately cooled to ambient
temperature.
Inventors: |
Kehe; Alfred W. (Berkeley,
IL) |
Assignee: |
Continental Can Company, Inc.
(New York, NY)
|
Family
ID: |
25322327 |
Appl.
No.: |
04/855,878 |
Filed: |
September 8, 1969 |
Current U.S.
Class: |
156/334; 156/69;
156/311; 428/462 |
Current CPC
Class: |
B29C
66/742 (20130101); B29C 66/1122 (20130101); B65D
17/502 (20130101); B32B 15/08 (20130101); B29C
66/24241 (20130101); B29C 66/534 (20130101); B29C
66/71 (20130101); B29C 65/368 (20130101); B29C
65/3656 (20130101); B29C 66/242 (20130101); B29C
66/72321 (20130101); B29C 65/02 (20130101); B29C
66/7392 (20130101); C08J 5/124 (20130101); B29C
66/71 (20130101); B29K 2023/12 (20130101); B65D
2517/0013 (20130101); B65D 2517/5027 (20130101); B29C
65/18 (20130101); B65D 2517/0086 (20130101); B29L
2031/717 (20130101); B29C 66/74283 (20130101); Y10T
428/31696 (20150401); B29C 65/46 (20130101); B29L
2031/565 (20130101); B29C 66/7426 (20130101); B65D
2517/5081 (20130101); B29C 65/223 (20130101); C08J
2323/12 (20130101); B29C 66/7422 (20130101) |
Current International
Class: |
B29C
65/00 (20060101); B32B 15/08 (20060101); C08J
5/12 (20060101); B65D 17/00 (20060101); B65D
17/50 (20060101); C09j 003/14 () |
Field of
Search: |
;156/332,334,311,69,283
;260/878 ;161/216 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Quarforth; Carl D.
Assistant Examiner: Miller; E. A.
Claims
What is claimed is:
1. A method of preparing a metal article having a propylene polymer
article adhered to the surface thereof which comprises the
sequential steps of:
a. applying an enamel coating composition to the surface of the
metal;
b. applying to the enamel coated metal surface a heat activatable
thermoplastic bond promoting layer containing a carboxyl modified
polypropylene resin, said resin being the graft copolymer of
polypropylene and an unsaturated dicarboxylic acid or anhydride
having a particle size less than 5 microns;
c. heat sealing to the bond promoting layer, a layer of a propylene
polymer; and then
d. rapidly cooling the heat sealed assembly to ambient temperature
immediately after heat sealing.
2. The process of claim 1 wherein the carboxyl modified
polypropylene resin contains about 0.05 percent to about 5 percent
carboxyl groups.
3. The process of claim 1 wherein the unsaturated anhydride is
maleic anhydride.
4. The process of claim 1 wherein the carboxyl modified
polypropylene resin has a particle size ranging from 0.1 to 3
microns.
5. The process of claim 1 wherein the bond promoting layer is an
admixture of a carboxyl modified polypropylene resin and a
polypropylene resin, both having a particle size less than 5
microns.
6. The process of claim 1 wherein the propylene polymer is
polypropylene.
7. The process of claim 1 wherein the propylene polymer is a
propylene/ethylene copolymer.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates in general to bonding propylene polymer
articles to metal surfaces, and more particularly to bonding
closure members fabricated from propylene polymers to the surfaces
of metal containers.
2. The Prior Art
Easy opening containers are known to the art. These containers are
generally formed of metal and are provided with a pour opening. The
pour opening generally occupies only a portion of the end panel of
the container. Heretofore, the pour opening has generally been
formed by scoring to define a tear strip. A pull tab is attached to
the tear strip, and upon the application of a force, the pull tab
is operative to separate the tear strip along the weakening line
from the panel.
Although easy opening containers have been readily accepted by the
public, deficiencies still remain in this type of container. One of
these deficiencies is that the removable tear strip which is torn
from the can end in the opening of the can has sharp edges, and
when thrown on the ground or otherwise improperly disposed of,
remains as a nuisance on which an individual may be readily
cut.
It has been proposed to replace the metal tear strip with a plastic
closure member which will eliminate the cutting hazard in that the
removed portion does not have sharp edges on which a person may be
cut. The plastic closure member fabricated from a thermoplastic
resin, such as polypropylene, is detachably and sealably secured to
the outer periphery of the pour opening in the end panel by bonding
with a suitable adhesive. Container end panels used for beverages
and the like have been coated with a heat activatable adhesive
layer to provide a surface for bonding a plastic closure member to
the container end panel to seal the pour opening. In this manner,
the plastic closure member is heat sealed to and fixed about the
periphery of the opening until a pulling force is applied
thereto.
Although sealing the pour opening of a container with a plastic
closure of this type has been proven feasible, the rigid standards
of the food industry require that the sealing bond between the
plastic closure and the end panel be greater than has heretofore
been achieved.
SUMMARY OF THE INVENTION
In accordance with the present invention, there is provided a
method of improving the bond strength of propylene polymers heat
sealed to metal surfaces which comprises first coating the metal
surface with a thermosetting enamel coating, followed by coating
the enameled surface with heat activatable, adhesion promoting
layer containing a carboxyl modified polypropylene resin having a
particle size of less than 5 microns, to which is heat sealed the
propylene polymer. The heat sealed surface is then immediately
cooled to ambient temperature.
As will hereinafter be illustrated, the combination of the use of a
carboxyl modified polypropylene resin having a particle size of
less than 5 microns and the immediate cooling of the metal surface
after heat sealing the propylene polymer layer thereto causes an
unexpected and substantial increase in the bond strength of the
resultant assembly.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top plane view of a container having an easy opening
structure provided with a propylene polymer closure member.
FIG. 2 is an enlarged cross-sectional view taken generally along
the lines 2-2 of FIG. 1 showing the propylene polymer closure
member secured to the end panel surface in accordance with the
present invention.
PREFERRED EMBODIMENTS
In the process of the present invention, any of the thermosetting
resins or mixtures of thermosetting resins conventionally used in
the coating art may be employed for enamel coating the metal
substrate.
Typical thermosetting resins which may be employed as enamel
coatings include epoxy resins of the type which are polymeric
reaction products of polyfunctional halohydrins with polyhydric
phenols having the structural formula:
wherein x represents the number of molecules condensed. Typical
polyfunctional halohydrins are epichlorohydrin, glycerol
dichlorohydrin and the like. Typical polyhydric phenols are
resorcinol and a 2,2-bis(4-hydroxyphenyl)alkane, the latter
resulting from the condensation of phenols with aldehydes and
ketones, including formaldehyde, acetaldehyde, propionaldehyde,
acetone, methyl ethyl ketone and the like, which result in such
compounds as 2,2-bis(4-hydroxyphenyl)propane and the like
compounds. These epoxy resins normally contain terminal epoxy
groups but may contain terminal epoxy groups and terminal hydroxyl
groups.
In place of or in admixture with the epoxy resins, any of the
well-known class of heat-hardenable phenolic resins produced by
condensing a phenolic compound with an aldehydic compound may be
employed as thermosetting enamel coating materials.
Exemplary phenols suitable for the preparation of
phenol/formaldehyde resins include phenol itself, the ortho, para
and metacresols, the xylenols, the dihydroxy benzenes, such as
resorcinol, and polynuclear phenols, such as the naphthols, and the
various alkylated, aralkylated, carboxylated, alkylolated, etc.,
derivatives of these types, such as o-ethyl phenol, carvacrol,
salicylic acid and the like.
Formaldehyde is the aldehydic compound preferred for condensation
with the phenolic compound, but in general, any
methylene-containing agent, such as formaldehyde, paraformaldehyde,
hexamethylene tetramine, acetaldehyde, and the like may be
used.
Amine-aldehyde resins may also be employed in preparing
thermosetting enamel coatings, either separately or in combination
with epoxy and/or phenolic resins.
The term "amine-aldehyde" resin includes aldehyde condensation
products of melamine, urea, aceto-guanamine, or a similar compound.
Generally, the aldehyde employed is formaldehyde, although useful
products can be made from other aldehydes, such as acetaldehyde,
crotonaldehyde, acrolein, benzaldehyde, furfural, and others.
Condensation products of melamine or urea are the commonly employed
amine-aldehyde resins.
For application to metal surfaces, the above-described resins or
mixtures of these resins are dissolved in suitable solvent systems,
such as organic ketones, such as methyl ethyl ketone, methyl
isobutyl ketone, isophorone, cyclohexanone, and aromatic
hydrocarbons, such as xylene and toluene, and mixtures thereof, to
provide a coating solution of the necessary viscosity for
application to the metal surfaces.
The thermosetting enamel coating compositions are applied as a
liquid solution to the metal surface by any of the conventional
methods employed by the coating industry. In the coating of metal
sheet used in container fabrication, roller coating is a preferred
method as the deposited coating weight is easily and conveniently
applied in a single coat. For general coating purposes, spraying,
dipping, and flow coating are useful methods of application.
The applied coating after substantial volatile loss of solvent is
cured to a hard film by heating the coated substrate at a
temperature between about 150.degree. and about 250.degree.C for
about 1 to 10 minutes. The preferred coating weight for use as an
enamel for containers is in the range of about 1 to 5 milligrams of
dry coating per square inch of substrate surface.
The metal sheet stock, coated with the hardened enamel coating, in
accordance with the present invention, is coated with an adhesion
promoting layer containing a carboxyl modified polypropylene
resin.
The carboxyl modified polypropylene which is utilized in the
practice of the present invention is prepared by grafting an
unsaturated dicarboxylic acid or anhydride onto a polypropylene
backbone. Unsaturated dicarboxylic acids or anhydrides which can be
employed to prepare the carboxyl modified polypropylene resins of
the present invention include maleic, tetrahydrophthalic acid,
fumaric acid, itaconic, nadic, methyl nadic and their
anhydrides.
The amount of unsaturated dicarboxylic acid or anhydride which can
be grafted onto the polypropylene ranges from about 0.05 to about
10 percent by weight based on the total weight of the grafted
polymer. It has been found, however, that only small amounts of the
acid or anhydride are required to impart adhesion promoting
properties to the polymer and generally, the amount of grafted
dicarboxylic acid or anhydride ranges from about 0.5 to about 5.0
percent.
The modified polymers can be prepared by reacting the unsaturated
dicarboxylic acid, or anhydride such as maleic anhydride, with a
polypropylene containing active sites which are capable of
anchoring the dicarboxylic acid or anhydride thereon. Active
centers at which anchoring will occur can readily be induced on the
polypropylene in known ways, as for example, by subjecting the
polypropylene to the action of high energy ionizing radiations or
by contacting the polymer, either as a solid or in solution in a
solvent, with a free radical producing material, such as dibenzoyl
peroxide, dilauroyl peroxide, dicumyl peroxide, t-butyl perbenzoate
and the like. Preferably, the carboxyl modified polypropylene resin
is prepared by reacting maleic anhydride with a solution of the
polypropylene in an organic solvent containing a free radical
producing material, such method being described in Belgian Pat. No.
607,269. The polypropylene resin used as a starting material for
the preparation of the carboxyl modified polymers can either be the
amorphous polymer, otherwise known as atactic polypropylene, or a
crystalline polymer, otherwise known as a syndiotactic or isotactic
polypropylene. In the case of maleic anhydride modified
polypropylene, amorphous polypropylene is generally preferred as
the starting material as the carboxyl modified product is soluble
at ordinary temperatures in a variety of common organic solvents
and thus, the application of the modified polymer by ordinary
solution techniques is possible. Maleic anhydride modified
crystalline polypropylene is not soluble in common solvents, except
at relatively high temperatures, and therefore is generally applied
as a dispersion following which the coating is baked to effect
fusion.
It is a critical and essential feature of the present invention
that the particle size of the adhesion promoting carboxyl modified
polypropylene layer applied to the enamel metal surface be less
than 5 microns and preferably be in a particle size range of 0.1 to
4 microns. As will hereinafter be illustrated, when the particle
size of carboxyl modified polypropylene is substantially above 5
microns, the bond strength between a propylene polymer bonded to a
carboxyl modified polypropylene coated surface is substantially
reduced.
The adhesion promoting carboxyl modified polypropylene resin is
generally applied to the enamel coated metal article surface as a
dispersion in a high-boiling volatile organic solvent, such as
kerosene, in order to achieve satisfactory coalescence of the resin
particles. Preferably, the carboxylated polypropylene is applied to
the enamel coated substrate in admixture with a polypropylene resin
having approximately the same particle size, i.e., 0.1 to 5
microns. The incorporation of the polypropylene resin in the
dispersion improves the flow and viscosity characteristics of the
dispersion required in commercial coating methods. Generally, the
polypropylene resin is incorporated in the dispersion at a weight
ratio to the carboxyl modified polypropylene resin in a range from
about 85:15 to 99:1.
The dispersion containing the carboxyl modified polypropylene resin
can be satisfactorily applied at a solids content ranging from
about 15 percent to about 25 percent by weight, based on the total
weight of the dispersion composition. Generally, a solids content
of 18 percent to about 23 percent by weight is preferred.
The dispersion containing the adhesion promoting carboxyl modified
polypropylene composition can be satisfactorily applied by any of
the conventional methods employed by the coating industry. However,
for coating of enameled sheet metal used in container fabrication,
gravure or direct roller coating are preferred methods, as the
desired coating weight is easily and conveniently applied in a
single coat. Spraying, dipping and flow coating are also useful
methods of applying the coating dispersion.
After applying the dispersion, the solvent is volatilized by
heating the coated substrate. Generally, the substrate is heated at
a temperature of about 175.degree. to about 200.degree. C. for
about 2 to about 6 minutes to volatilize the solvent.
In the case of propylene polymer closure members, to provide enamel
coated metal sheet substrates with an adequately adhesion promoting
coating containing the carboxyl modified polypropylene resin, the
dry film weight of the bond promoting coating should be in the
range of 1.5 to 3.5 milligrams of dry coating per square inch of
enamel coated surface.
Propylene polymers which are bonded to the carboxyl modified
polypropylene coated metal surface in accordance with the practice
of the present invention include polypropylene, and
propylene/ethylene copolymers containing about 1 percent to 10
percent ethylene.
The propylene polymer is bonded to the carboxyl modified
polypropylene coated metal surface by heat sealing at a temperature
of about 175.degree. to about 225.degree. C., and preferably at a
temperature of 180.degree. to 200.degree. C. Heat sealing may be
accomplished by any means known to the art, such as heated bars or
wires, induction and RF heating.
After the propylene polymer is heat sealed and bonded to the
carboxyl modified polypropylene coated metal surface, the assembly
is immediately and rapidly cooled or chilled to ambient
temperature, as, for example, room temperature, in any suitable
manner, as by air cooling, flooding with water, plunging into a
water bath, or by any other appropriate procedure that does not
disturb the applied propylene polymer.
Referring now to the drawings, and in particular to FIG. 1, there
is shown a container top end assembly 10 of a container. The end
assembly 10 is made of metal such as tin plate, tin-free steel or
aluminum. The end assembly 10 comprises a central panel 12 having a
bead formed adjacent the outer periphery from which there depends a
peripheral flange 13. The peripheral flange 13 is curled and double
seamed with an outwardly flap flange at the upper end of a
container body in the usual manner.
The panel 12 in the embodiment is shown with a pour opening 14
through which the contents of the container are poured.
The opening 14 may be formed by blanking or the like. It is to be
understood that the opening 14 may assume any configuration, and is
not limited to the conventional tear drop design shown.
The top surface of the end assembly 10 is coated with a first layer
of a thermosetting enamel coating, such as an
epoxy-urea/formaldehyde resin 15. To the thermosetting enamel
coating is applied a second layer of an adhesion promoting layer 16
containing a carboxyl modified polypropylene resin, such as a
polypropylene/maleic anhydride graft copolymer.
Detachably and sealably secured to the periphery of the opening 14
is propylene polymer closure member 17. The propylene polymer
closure member 17 has a sealing flap 18 for closing the opening 14.
Integrally extending from the sealing flap 18 is a pull ring
portion 19. The sealing flap 18 of closure member 17 is heat sealed
to the coated periphery of the opening 14 at a temperature of
180.degree. to 200.degree. C.
The bond that is formed permits the closure member or flap to be
separated by the application of a pulling force at the ring portion
19. Preferably, the pull ring portion 19 is formed with an opening
sized to receive the finger of a user. The heat to achieve bonding
is preferably applied by RF heating of the metal surface. RF
heating is used so as to localize the heat in the peripheral edge
portion of the opening 14, thereby to minimize the buckling of the
relatively thin metal from which the end 10 is made. In this
manner, the sealing closure member 17 is firmly fixed about the
peripheral portion of the opening 14 and remains adhered
thereto.
After the closure member 17 is heat sealed to the peripheral
portion of the opening, the end assembly 10 is rapidly cooled to
room temperature.
To illustrate the manner in which the present invention may be
carried out, the following example is given. It is to be
understood, however, that the example is for the purpose of
illustration, and the invention is not to be regarded as limited to
any of the specific materials or conditions recited therein.
EXAMPLE
A solution of a mixture consisting of 85 percent by weight of an
epoxy resin EPON 1009, available from the Shell Chemical Company,
and 15 percent of a urea/formaldehyde resin BEETLE 216-18,
available from the American Cyanamid Company, in a volatile solvent
was applied to the surface of a chrome plated steel sheet by means
of a roller to deposit an enamel coating at a coating weight of 3.5
mg/in.sup.2 of steel surface. The coating was heated for 8 minutes
at 213.degree. C. to remove the solvent and to cure the epoxy
resin-urea/formaldehyde resin mixture to a hard enamel film.
A bond-promoting coating formulation was prepared using a carboxyl
modified polypropylene resin admixed with a finely divided
unmodified polypropylene resin at a weight ratio of 5:95. The
carboxyl modified polypropylene resin was HERCOPRIME PA-672
available from Hercules, Inc., which is a maleic anhydride modified
polypropylene having an inherent viscosity of about 1.7, a carboxyl
content of 0.6 percent to 1 percent, and a particle size range of
0.1 to 3 microns. The polypropylene resin was HERCOTUF PB-681,
available from Hercules, Inc., having a melt index of 6 and a
particle size range of from 0.1 to 2 microns. A 20 percent solids
dispersion of the carboxyl modified polypropylene-unmodified
polypropylene resin mixture in kerosene was applied to the enamel
coated surface of the steel.
After application of the carboxyl modified polypropylene-unmodified
polypropylene dispersion, the coated sheet was baked at 180.degree.
C. to volatilize the solvent, fuse and coalesce the dispersed
particles into a continuous film. A 1inch .times.1 inch
.times.0.050 inch strip molded from SHELL V521, a
propylene/ethylene copolymer having an ethylene content of 4.0
percent, a melt index (D1238) of 0.55, and a density of 0.895 to
0.905 (D1505) was inserted between the carboxyl modified
polypropylene coated sides of two 1 inch .times.1inch .times.0.006
inch strips cut from the coated metal sheet. The assembly was then
laminated by heat sealing at a temperature of 240.degree. C. for a
3.5 second dwell time at 20 p.s.i.
Immediately after heat sealing, the laminated assembly was chill
quenched with water to cool the assembly to room temperature.
The above procedure was repeated using a laminated assembly wherein
the intermediate layer was fabricated from DIAMOND 8620, a
polypropylene resin having a melt index of 4.0 and a density of
0.905, available from the Diamond Shamrock Chemical Company.
The peel strength of the cooled assembly was then determined. The
peel strength of the assembly, i.e., a measure of the load required
to peel apart the laminate assembly was determined by pulling the
outer steel layers of the assembly apart at an angle of 180.degree.
to the bond in an Instron machine at a rate of 0.5 inches per
minute.
For purposes of contrast, the above procedure was repeated with the
exception that in separate runs, the heat sealed assembly was not
chilled, or a carboxyl modified polypropylene having a particle
size greater than 5 microns was used.
The peel strengths of the assemblies are summarized in the table
below. ##SPC1##
By referring to the table, it is at once apparent that the peel
strengths of propylene polymers bonded to metal surfaces coated
with an adhesion promoting layer containing a carboxyl modified
polypropylene resin in accordance with the present invention (Run
Nos. 1 and 4) are substantially greater than the peel strengths
over the contrasting or control runs (Run Nos. 2, 3, 5 and 6) in
which the heat sealed assembly was not cooled immediately after
heat sealing or a carboxyl modified polypropylene having a particle
size greater than 5 microns was used.
* * * * *