U.S. patent number 3,804,663 [Application Number 05/147,120] was granted by the patent office on 1974-04-16 for method of internally coating rigid or semi-rigid plastic containers.
This patent grant is currently assigned to The Dow Chemical Company. Invention is credited to Dale E. Clark.
United States Patent |
3,804,663 |
Clark |
April 16, 1974 |
METHOD OF INTERNALLY COATING RIGID OR SEMI-RIGID PLASTIC
CONTAINERS
Abstract
A method for spin coating the interior of a generally rigid or
semi-rigid plastic hollow article, such as a container or parison,
with a synthetic organic resinous material to provide a protective
coating therein. The method comprises placing a quantity of a
dispersion of synthetic organic resinous material, preferably a
latex or solution, in a hollow article, spinning the article at
high speed thereby causing centrifugal force to distribute and hold
a coating of the dispersion uniformly on the interior surfaces of
the same and then heating the coating while continuing to spin the
article. The result of the spin coating method is an article with a
substantially uniform interior protective film providing improved
article characteristics such as gas and liquid barrier properties,
color and appearance, taste and flavor protection and the like.
Inventors: |
Clark; Dale E. (Midland,
MI) |
Assignee: |
The Dow Chemical Company
(Midland, MI)
|
Family
ID: |
22520360 |
Appl.
No.: |
05/147,120 |
Filed: |
May 26, 1971 |
Current U.S.
Class: |
427/542; 264/512;
264/535; 426/106; 427/233; 427/240; 427/498; 427/522; 427/553;
428/336; 220/62.18; 264/503; 264/516; 264/537; 427/231; 427/393.5;
427/512; 427/541; 427/558; 428/413; 215/12.2 |
Current CPC
Class: |
B05D
7/227 (20130101); B29C 49/22 (20130101); B05D
2201/00 (20130101); B29B 2911/14106 (20130101); B29B
2911/1404 (20130101); B05D 1/002 (20130101); B05D
3/0263 (20130101); B29B 2911/1402 (20130101); B29B
2911/14053 (20130101); B29B 2911/14026 (20130101); B29B
2911/14033 (20130101); Y10T 428/31511 (20150401); B29B
2911/14066 (20130101); B29B 2911/1408 (20130101); B29B
2911/14093 (20130101); B29B 2911/14113 (20130101); Y10T
428/265 (20150115) |
Current International
Class: |
B29C
49/22 (20060101); B05D 7/22 (20060101); B05D
3/02 (20060101); B44d 001/02 () |
Field of
Search: |
;117/95,96,101,105.4,66,161ZB,162,161UZ,161R ;220/64 ;264/94 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
handbook of Material Trade Names, Zimmerman and Lavine (1953),
pages 503 and 504..
|
Primary Examiner: Whitby; Edward G.
Attorney, Agent or Firm: Young; Arthur J.
Claims
1. A method for internally coating a generally rigid or semi-rigid
plastic container or parison type hollow article comprising:
a. placing a quantity of a dispersion of synthetic organic resinous
material into said article;
b. spinning said article at a rate of speed sufficient to
distribute and hold a coating of said dispersion uniformly on
interior wall surfaces of said article; and
c. heating said coating sufficient to dry or fuse the same while
continuing
2. The method of claim 1 wherein said article is formed of a
polymer which
3. The method of claim 1 wherein said article is a parison which is
blow molded into an internally coated container contemporaneously
with and immediately after said heating step c thereby utilizing
said drying or fusion heat from step c to help soften said parison
before blow molding
4. The method of claim 3 wherein said blown container has a wall
substrate
5. The method of claim 1 wherein said dry coating has gas and
liquid
6. The method of claim 5 wherein said dispersion comprises a latex
the major resin component of which is a copolymer having
copolymerized therein at least about 70 weight percent vinylidene
chloride and a remainder of
7. The method of claim 5 wherein said dispersion comprises a
suspension the major resin component of which is a copolymer having
copolymerized therein at least 70 weight percent vinylidene
chloride and a remainder of one or
8. The method of claim 5 wherein said dispersion comprises an
emulsion the
9. The method of claim 5 wherein said dispersion comprises a
suspension the
10. The method of claim 5 wherein said dispersion comprises a latex
the
11. The method of claim 5 wherein said dispersion comprises a
suspension
12. The method of claim 1 wherein said heating of said coating is
accomplished by inserting an infrared heating element or other
like
13. The method of claim 1 wherein said heating of said coating
is
14. The method of claim 1 wherein said heating of said coating
is
15. The method of claim 1 wherein said heating of said coating
is
16. The method of claim 1 wherein said dry coating has a range from
about
17. The method of claim 1 wherein said parison or container is spun
at a
18. The method of claim 1 wherein said placing said dispersion into
said article is accomplished by spraying.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method of coating hollow articles, with
particular reference to spin coating the interior of plastic
containers or parisons, for forming the same, with a dispersion of
synthetic organic resinous material which will enhance the end use
characteristics of the containers or parisons.
2. Description of the Prior Art
Coating the interior walls of a container with a protective film is
well known. Generally the methods used in the past to internally
coat plastic, metal and paper containers are dipping, brushing or
spraying. Also, in the metal can and paper container coating
methods of the prior art, the coatings may be either sprayed or
brushed into the containers as they are rotated or placed in the
bottom of the containers and forced up the walls of the same
utilizing the centrifugal force generated by a subsequent
rotational operation. The containers are then removed from the
coating apparatus and dried in conventional hot air or infrared
ovens.
One of the primary problems associated with the prior art coating
methods, including spin coating, is their inability to form uniform
coatings without coating sag substantially in excess of 0.1 mil in
thickness on the walls of a container without the addition of
thickeners which are detrimental to the properties of the resulting
film. Another problem is their inability, when used to coat a
latex, to completely wet-out and maintain a wetted surface of a
nonporous substrate such as a plastic without the addition of
substantial amounts of wetting agents which are also detrimental to
the properties of the resulting film.
SUMMARY
In general, the present invention provides a method for uniformly
spin coating the interior walls of generally rigid or semi-rigid
plastic hollow articles such as a container or parison, for forming
the same, with a synthetic organic resinous material, hereinafter
commonly referred to as plastic material, which will result in an
article having an interior protective coating providing improved
characteristics. The method comprises placing, preferably spraying
or brushing, a quantity of a dispersion of plastic material in a
hollow article, spinning the same at a high speed thereby causing
centrifugal force to distribute and/or hold a coating of the
dispersion uniformly on the interior wall surfaces of the article
and then heating the coating to dry or fuse the same while
continuing to spin the article. The dispersion of synthetic organic
resinous material may be a latex, emulsion, suspension, solution or
the like but is preferably a latex or suspension. The article is
spun at a high rate of speed of at least 100 r.p.m., preferably
from about 1,000 to 5,000 r.p.m., with the resulting centrifugal
force distributing and/or holding the dispersion uniformly on the
walls of the article. The coating may be dried or fused by
inserting an infrared or other like heating element into the
article, blowing hot air into the article, dielectric heating,
microwave heating or other known heating means or combinations
thereof while continuing to spin the same with the coating being
held to the container walls by the centrifugal force. The drying
time of the coating is dependent on thickness of coating, amount
and type of heating and the like. Application of multiple layers of
coating, including adhesive or tie coatings applied before the
protective coatings, fall within the scope of the invention.
The plastic dispersion is preferably a latex or suspension of
saran, polyvinyl chloride, polyamide, olefins, acrylonitrile, epoxy
or other like plastic resins or copolymers or blends thereof which
will form the desired protective coating in the parison or
container. The hollow articles may be thermoformed by extrusion,
injection molding, vacuum forming, blow molding and the like from
polymers such as polystyrene, polypropylene, polyethylene,
acrylonitrile butadiene styrene, styrene acrylonitrile, vinyl
chloride, arylonitrile or like high structural strength polymers or
copolymers or blends thereof which will not, in most cases, meet
the necessary requirements for the products contained therein. The
polymers in the article walls may be multiaxially molecular
oriented or unoriented depending on desired end product. A more
detailed description of various useful polymers will be discussed
later.
The method described herein is directed towards, but not limited
to, the fabrication of a pressurized or nonpressurized container
for packaging food products, oil and greases, beverages, medicine
and the like where the protective coating helps provide improved
container characteristics such as a barrier to oxygen, carbon
dioxide, nitrogen, water or water vapor and organic vapor or liquid
transmission into or out of the container.
In addition to the above gas and liquid barrier properties,
improved container characteristics such as color and appearance,
taste and flavor protection, stress crack and chemical resistance
and the like may also be achieved. The method herein described
provides many advantages over more conventional prior art coating
methods such as a symmetrically uniform coating thickness without
coating sag, improved adhesion of the coating to the container or
parison wall substrate due to forced wetting, reduced need for
wetting agents, thickeners or other additives in the coating
formulation, a more continuous layer of coating with substantially
fewer pinholes therein due to a high degree of coalescence of the
wet coating during spinning of the container or parison and a
reduced drying time of the coating as, for example, where the
polymer in a latex or suspension is of higher density than the
suspending agents, such as a saran latex, the polymer is forced to
the container or parison wall leaving the suspending agent at the
heated surface during spinning of the container where it can be
more easily removed by drying.
As previously noted, the parisons coated by the method herein
described may be used to form containers having an interior
protective coating. Beneficially, coated containers can be formed
from coated parisons by conventional blow molding. However, an
additional advantage is obtained by combining the spin coating
method with a blow molding operation to form an internally coated
container. By blow molding a container contemporaneously with and
immediately after the spin coating of a parison, the heat used to
dry the coating can be also used to soften the inside parison walls
prior to the actual blowing of the container. The interior heat in
the spin coated parison need only be retained while additional
external heat is applied to soften the parison before the container
blowing step. By using this sequence of steps, the time required to
heat parisons for blow molding can be substantially reduced.
Accordingly, it is an object of the present invention to provide a
new and improved method of coating the interior walls of rigid or
semi-rigid plastic hollow articles such as parisons or containers.
Another object of the present invention is to provide a method of
spin coating the interior walls of hollow articles with a plastic
material having protective properties. A further object of the
present invention is to provide a method for coating the interior
walls of articles which will result in a substantially uniform
coating thickness without coating sag, improve adhesion of coatings
to article wall substrates and provide a more continuous layer of
coating with a substantially fewer number of pinholes therethrough.
A still further object of the present invention is to provide a
combined method for spin coating the interior of parisons with
protective coatings and then blow molding said coated parisons into
coated containers utilizing the heat for drying or fusing the
coatings in the parisons to help soften the parisons for subsequent
blowing of the containers. Other objects of the present invention
will be apparent to those skilled in the art from the
specification, drawing and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
The preferred embodiments of the present invention are shown in the
accompanying drawings where:
FIG. 1 is an exaggerated cross-sectional view of a cup shaped
container for food products and the like constructed according to
the principles of the present invention;
FIG. 2 is a side elevation view, with portions broken away, of a
parison which may be used to make a container and which is
constructed according to the principles of the present
invention;
FIG. 3 is a view like FIG. 1 only showing a modified bottle shaped
container;
FIG. 4 is a schematic representation of the sequence of steps
followed in accordance with the principles of the present invention
showing spin coating of a container similar to that shown in FIG.
1; and
FIG. 5 is a schematic representation of the sequence of steps
followed in accordance with the principles of the present invention
showing spin coating of a parison similar to that shown in FIG. 2
and then blow molding of the same into an internally coated
container utilizing the heat for drying or fusing the coating to
help soften the parison prior to blowing the container.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following description illustrates the manner in which the
principles of the invention are applied but are not to be construed
as limiting the scope of the invention.
More specifically referring to FIGS. 1-3, plastic containers 10 and
30 and parison 20 illustrate the resulting interior coating
obtained from the spin coating method herein described.
Specifically, FIG. 1 illustrates a plastic cup-shaped container 10
having a side wall 12 and a bottom wall 14. Container 10 is formed
from a high structural strength thermoplastic material 16. A
plastic coating 18 is bonded to interior of walls 12 and 14. FIG. 2
illustrates a parison 20 used to blow mold a container, similar to
that shown in FIG. 3, having a thermoplastic wall 22 to which a
coating 24, similar to coating 18 shown in FIG. 1, is bonded. FIG.
3 illustrates a bottle shaped container 30 having a side wall 32, a
bottom wall 34 and a neck portion 36 which is formed from a
thermoplastic material 38. A coating 39, similar to coating 18
shown in FIG. 1, is bonded to the interior of walls 32 and 34 and
the neck portion 36.
Referring now to FIGS. 4 and 5, the steps of the method utilized in
the present invention are illustrated. Specifically in FIG. 4, step
1 illustrates the selection of a container, similar to that shown
in FIG. 1, which is then spun and sprayed on the interior walls
with a synthetic organic resinous dispersion, as shown in step 2.
Step 3 of FIG. 4 illustrates the drying or fusion of the
distributed coating while being held to the container walls by the
centrifugal force with an infrared heating element which is
inserted into the container while continuing to spin the same. Step
4 illustrates the resulting container with an internal protective
coating adhered to the walls of the container. Steps 1 and 2 of
FIG. 5 illustrate the selection and spin coating of a parison,
similar to that shown in FIG. 2, following the same procedure
represented by FIG. 4. In step 3, the parison is held by a heated
mandrel to retain the drying or fusion heat within the parison and
is externally heated in an oven utilizing any known heating means.
Step 4 of FIG. 5 illustrates the subsequent blow molding of the
internally coated parison and step 5 illustrates the resulting
internally coated blown container which is similar to the container
shown in FIG. 3.
For a more complete understanding of the nature and scope of the
invention and to better demonstrate its advantages, reference may
now be had to the following detailed examples thereof.
Example 1
To illustrate the method herein described, a plastic cup-shaped
container, like container 10 shown in FIG. 1, having a wall
thickness of about 50 mils, a diameter of about 31/4 inches and a
height of about 4 inches formed of a general purpose polystyrene
material was selected. A variable speed motor fitted with a spindle
wihch holds the container was used to spin the container. The
container was placed in the spindle and 3 grams of a saran latex
poured into the same. The container was then spun for 10 seconds at
about 5,000 r.p.m. with the excess latex allowed to flow out the
mouth of the container. While continuing to spin the container, a
600 watt infrared heating element was inserted into the container
for 10 seconds to dry the latex. The dried coating thickness was a
uniform 0.4 mils on the side wall and 0.1 mils on the bottom
wall.
The saran latex used in this example was formulated with about 57
weight percent solids and 2 weight percent wetting agent. The saran
component comprises about 80 weight percent of a copolymer of
vinylidene chloride with the balance being acrylonitrile and methyl
methacrylate copolymers. The wetting agent is of the type generally
referred to as an alkylphenoxypoly(oxyethylene)ethanol having the
general formula RC.sub.6 H.sub.4 O(CH.sub.2 CH.sub.2 O).sub.n
CH.sub.2 CH.sub.2 OH in which R may be C.sub.8 H.sub.17 or a higher
homolog.
The coating on the container side wall demonstrates very good
adhesion and could be removed with a 1/2 inch wide strip of No. 810
Scotch tape only after three attempts in the same area of the wall.
The dried film exhibited complete wet-out on the container
walls.
For comparative purposes, a flat sheet of a similar general purpose
polystyrene material was coated with the same saran latex using a
wire wound rod and then dried for 10 seconds with a 600 watt
infrared heating element. The dried film exhibited incomplete
wetting out on the flat sheet. A 0.4 mil thick portion of the
coating was easily removed with tape from the sheet with only one
attempt. The difference in adhesion and wet-out were attributed to
the forced wetting of the walls of the container when the spin
coating method herein described was used.
Example 2
To demonstrate the uniformity and lack of coating sag achieved by
the spin coating method, a cup-shaped container similar to that
described in Example 1 was spin coated at 1,800 r.p.m. The same
saran latex and spinning and drying times were used. The resulting
dried coating on the interior side wall of the container was a
uniform 0.4 mil thick. A second container was spin coated following
the same procedure except that the spinning step was discontinued
before the coating was dried with the infrared heating element. The
resulting dried coating on the side wall of the container exhibited
severe coating sag and nonuniformity.
Example 3
To demonstrate the improved barrier properties of a container
coated with the method herein described, a cup-shaped container,
like container 10 in FIG. 1, having a wall thickness of about 40
mils, a diameter of about 31/2 inches and a height of about 31/2
inches formed of a high density polyethylene material was selected.
The same procedures and equipment used in Example 1 are employed
here. Three grams of a saran latex was placed in the container, the
container was spun at about 5,000 r.p.m. for 10 seconds and then
dried for 15 seconds while continuing to spin the container.
The high density polyethylene forming the container walls was
polymerized by Ziegler catalysts and had a density of about 0.959,
a melt index of about 0.5 and a flexual modulus of about 170,000.
The saran latex used here was the same as that used in Example 1
except it was formulated with about 4 weight percent wetting
agent.
The resulting dried coating was a uniform 0.3 mil thick on the side
wall of the container. The average oxygen transmission rate
determined by mass spectrometer analysis of two samples taken from
the side wall of the container was found to be 0.63 cubic
centimeter per 100 square inches per day at atmospheric pressure
and 23.degree.C. The average oxygen transmission rate, tested in
the same manner, of four 40 mil thick samples taken from the side
wall of a similar uncoated container was found to be 2.78 cubic
centimeters per 100 square inches per day at atmospheric pressure
and 23.degree.C.
Example 4
To illustrate the method of spin coating and blow molding of a
parison, like the parison with a tapered side wall shown in FIG. 5,
into an internally coated container, like container 30 of FIG. 3,
an injection molded, closed end, multiaxially oriented, general
purpose polystyrene parison was selected which had a wall thickness
of about 40 mils, a base diameter of 11/4 inches and an upper
diameter just below the neck of 11/2 inches and an overall height
of 41/8 inches. The same procedures and equipment used in Example 1
are employed here. Two grams of a saran latex was poured into the
parison, the parison was spun for 2 seconds at 5,000 r.p.m. and
then a 500 watt infrared heating element was inserted into the
parison for 4 seconds to dry the latex while continuing to spin the
parison. A second coating of the latex was applied over the first
coating using the same conditions and procedures as described
above. The dried coating had an evenly distributed thickness of 0.4
mil at the bottom and 0.6 mil at the top of the parison with the
average being 0.5 mil.
The saran latex used in this example was formulated with about 50
weight percent solids and 2 weight percent wetting agent. The saran
component comprised about 92 weight percent of a copolymer of
vinylidene chloride with the balance being an acrylonitrile
copolymer. The wetting agent was the same general type employed in
Example 1.
The coated parison was then blow molded using conventional
equipment. To heat soften the parison, it was placed on a mandrel,
similar to that shown in FIG. 5, which had a surface, temperature
of 220.degree.F. External heating was accomplished by placing the
parison and mandrel for 14 seconds in an oven heated by radiant
heating elements having a surface temperature of 1,000.degree.F.
The parison was then placed in a mold and blown into a container,
like container 30 shown in FIG. 3, with an air pressure of 60
p.s.i. for a period of 5 seconds. The dwell time of the container
in the mold was 3 seconds. The blow molded container had an average
side wall thickness of about 10 mils, a body diameter of 3 3/16
inches, a neck diameter of 15/8 inches and height of 43/8 inches.
The coating on the side wall of the container was reduced in
thickness proportionally with the reduction in thickness of the
side wall substrate and had an average thickness of about 0.125
mils.
Examination of the blown container showed that it exhibited the
characteristic increased toughness of a multiaxially molecular
oriented container. Also, the coating had sufficient adhesion to
the container wall substrate to flow therewith without any
detachment when the container was blown. The coating in the blown
container was continuous and pinhole free as determined by placing
a mineral spirits and red dye solution into coated and uncoated
blown containers for a period of one-half hour. The uncoated
general purpose polystyrene containers were stained red whereas the
coated containers remained unchanged. The average oxygen
transmission rate determined by mass spectrometer analysis of three
samples taken from the side wall of the coated containers was found
to be 0.93 cubic centimeter per hundred square inches per day at
atmospheric pressure and 23.degree.C. The average oxygen
transmission rate, tested in the same manner, of three samples
taken from the side walls of similar uncoated containers is found
to be 23.0 cubic centimeters per hundred square inches per day at
atmospheric pressure and 23.degree.C.
It is emphasized that a wide variety of materials may be employed
in coating containers in accordance with the present invention.
Particularly suited polymers are vinylidene chloride, vinyl
chloride, acrylonitrile, vinylidene fluoride and/or combined
mixtures thereof. Especially advantageous and beneficial are
compositions of vinylidene chloride polymers, wherein the polymers
contain at least about 70 weight percent vinylidene chloride, the
remainder being one or more olefinically unsaturated monomers
copolymerizable therewith. Suitable vinylidene chloride polymers
are prepared utilizing such comonomers as methyl, ethyl, isobutyl,
butyl, octyl and 2-ethylhexyl acrylates and methacrylate; phenyl
methacrylate, cyclohexyl methacrylate, p-cyclohexylphenyl
methacrylate, chloroethyl methacrylate, p-cyclohexylphenyl
methacrylate, chloroethyl methacrylate, 2-nitro-2-methylpropyl
methacrylate, and the corresponding esters of acrylic acid, methyl
alphachloro-acrylate, octyl alphachloroacrylate, methyl isopropenyl
ketone, acrylonitrile, methacrylonitrile, methyl vinyl ketone,
vinyl chloride, vinyl acetate, vinyl propionate, vinyl
chloroacetate, vinyl bromide, styrene, vinyl naphthalene, ethyl
vinyl ether, N-vinyl phthalimide, N-vinyl succinamide, N-vinyl
carbazole, isopropenyl acetate, acrylamide, methacrylamide or
monoalkyl substitution products thereof, phenyl vinyl ketone,
diethyl fumarate, diethyl maleate, methylene diethyl malenate,
dichlorovinylidene fluoride, dimethyl itaconate, diethyl itaconate,
dibutyl itaconate, vinyl pyridine, maleic anhydride and allyl
glycidyl ether. It is also frequently advantageous and beneficial
to incorporate therein a minor portion of a plasticizer and a heat
and/or light stabilizer. Other compositions which may be used with
benefit in coatings in accordance with the present invention are
vinyl chloride polymers which contain a predominant amount of vinyl
chloride therein. Fluorocarbon polymers, fluorohydrocarbon polymers
and fluorohalohydrocarbon polymers may also be used with benefit.
Such materials as polyvinylidene fluoride, chlorinated polyethylene
and polymers of such materials as vinylidene fluoride, vinylidene
fluoride and chlorotrifluoroethylene, chlorotrifluoroethylene and
vinylidene fluoride, chlorotrifluoroethylene and vinyl chloride,
chlorotrifluoroethylene-vinylidene fluoride and tetrafluoroethylene
and the like might also be useful. Generally for economic reasons,
the vinylidene chloride polymers are employed, as they are most
readily available at a low cost.
It is conceivable that a variety of article configurations such as
a cup-shape, frustoconical shape, cylindrical shape and the like,
which are rotationally symmetrical and which have any desired wall
thickness and plastic composition, may be internally coated by the
method herein disclosed. Also, the dried interior coating thickness
has a preferred range of about 0.1 to 1.0 mils, but can be varied
considerably by changing the coating formulation and the spinning
rate and time used.
Thus, while certain representative embodiments and details have
been shown for the purpose of illustrating the invention, it will
be apparent to those skilled in the art that various changes and
modifications can be made therein without departing from the spirit
and scope of the invention.
* * * * *