U.S. patent application number 09/735313 was filed with the patent office on 2003-04-24 for method for coating a plastic container with vacum vapor deposition.
Invention is credited to Ehrich, Horst, Plester, George, Rule, Mark.
Application Number | 20030077400 09/735313 |
Document ID | / |
Family ID | 25225312 |
Filed Date | 2003-04-24 |
United States Patent
Application |
20030077400 |
Kind Code |
A1 |
Plester, George ; et
al. |
April 24, 2003 |
METHOD FOR COATING A PLASTIC CONTAINER WITH VACUM VAPOR
DEPOSITION
Abstract
A method, composition and system for coating an external surface
of containers and in particular, plastic containers, provides for
low permeability to gases and vapors. The coating applied to the
external surface of the containers is very thin and is comprised of
one or several inorganic substances or layers of substances. For
example, the coating can include silica which is bonded to the
external surface of the container. This coating will be flexible
and can be applied regardless of the container's internal pressure
or lack thereof. The coating will firmly adhere to the container
and possess an enhanced gas barrier effect after pressurization
even when the coating is scratched, fractured, flexed and/or
stretched. Moreover, this gas barrier enhancement will be
substantially unaffected by filling of the container.
Inventors: |
Plester, George; (Brussels,
BE) ; Ehrich, Horst; (Dorsten, DE) ; Rule,
Mark; (Atlanta, GA) |
Correspondence
Address: |
SUTHERLAND ASBILL & BRENNAN LLP
999 PEACHTREE STREET, N.E.
ATLANTA
GA
30309
US
|
Family ID: |
25225312 |
Appl. No.: |
09/735313 |
Filed: |
December 12, 2000 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
09735313 |
Dec 12, 2000 |
|
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|
08818342 |
Mar 14, 1997 |
|
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6223683 |
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Current U.S.
Class: |
427/566 ;
427/255.29; 427/255.31; 427/255.37; 427/579; 427/585; 427/596 |
Current CPC
Class: |
C23C 14/10 20130101;
B29L 2031/7158 20130101; B29B 17/0026 20130101; Y02W 30/62
20150501; B29K 2709/08 20130101; B29K 2995/0067 20130101 |
Class at
Publication: |
427/566 ;
427/579; 427/585; 427/596; 427/255.29; 427/255.31; 427/255.37 |
International
Class: |
C23C 016/00; B05D
003/06; H05H 001/24 |
Claims
We claim:
1. A system for coating an external surface of a container wherein
the container on pressurization possess a gas barrier at least
1.25.times.greater than a similar uncoated container, the system
comprising: a vacuum cell, pressure within the vacuum cell being
reduced as compared to ambient pressure; means for supplying
containers to and withdrawing containers from the vacuum cell; and
at least one source for supplying a coating vapor to the external
surface of the containers in the vacuum cell, the coating vapor
from the at least one source depositing a relatively thin coating
on the external surface of the containers, whereby bonding between
at least a portion of the relatively thin coating deposited on the
container and the external surface of the container occurs.
2. The system for coating as recited in claim 1, wherein the at
least one source supplies the coating vapor from a solid
source.
3. The system for coating as recited in claim 2, wherein the solid
source is a nonpowder.
4. The system for coating as recited in claim 1, wherein the means
for causing coating causes at least one of chemical bonding and
physical bonding with the container.
5. The system for coating as recited in claim 1, further including
a plasma-enhanced device to provide means for causing the
bonding.
6. The system for coating as recited in claim 1, further comprising
a device for degassing the containers prior to deposition of the
relatively thin coating on the external surface of the containers,
the degassing of the containers providing means for causing the
bonding.
7. The system for coating as recited in claim 1, wherein the
container is a temperature sensitive plastic bottle with a neck and
wherein the system includes means for gripping the neck of the
bottle.
8. The system for coating as recited in claim 1, further comprising
means for rotating the containers during transport through the
vacuum cell.
9. The system for coating as recited in claim 1, further comprising
means for supplying at least one gas to an interior of the vacuum
cell, the at least one gas supplied by the means for supplying
being selected from the group consisting of oxygen, nitrogen,
sulfur and halogens.
10. The system for coating as recited in claim 9, wherein the at
least one gas is oxygen.
11. The system for coating as recited in claim 9, wherein said gas
and vapor from the at least one source provide at least one of
color coating for the container, ultraviolet absorbent coating for
the container and a gas barrier for the container.
12. The system for coating as recited in claim 9, wherein said gas
and vapor from the at least one source provide at least one of
color coating for the container and ultraviolet absorbent coating
for the container.
13. The system for coating as recited in claim 1, further
comprising means for coating less than all of the external surface
of the container by the coating vapor from the at least one
source.
14. The system for coating as recited in claim 1, further
comprising a conveying device positioned within the vacuum cell,
the conveying device moving the container through the vacuum cell
past the at least one source.
15. The system for coating as recited in claim 14, wherein the
conveying device includes a container bar for holding the
container, a slow-moving section and a fast-moving section, the
container bar being transferrable between the slow-moving section
and the fast moving section whereby the container on the container
bar can be moved at a first speed and then at a second speed
through the vacuum cell, the first speed being slower than the
second speed.
16. The system for coating as recited in claim 15, further
comprising means for rotating the containers during the transfer
from the slow-moving conveyor to the fast-moving conveyor.
17. The system for coating as recited in claim 15, wherein the
container has a longitudinal axis and wherein the conveying device
further includes means for orienting the longitudinal axis of the
container vertically and horizontally within the vacuum cell, the
longitudinal axis of the container being generally vertically
oriented when the container is being moved at the first speed by
the slow-moving section and being generally horizontally oriented
when the container is being moved at the second speed by the
fast-moving section.
18. The system for coating as recited in claim 17, wherein the
container includes an interior chamber and wherein the system
further comprises an antenna insertable into and removable from the
interior chamber of the container and means for orienting the
antenna to generally face the at least one source during
coating.
19. The system for coating as recited in claim 18, further
comprising magnetic orientating means for orienting the antenna
when the longitudinal axis of the container is generally vertically
oriented.
20. The system for coating as recited in claim 18, wherein the
means for orienting includes a heavy section of the antenna which
is rotatable under the influence of gravity to face a bottom of the
vacuum cell when the antenna and the longitudinal axis of the
container are generally horizontally oriented.
21. The system for coating as recited in claim 18, wherein the
antenna is pivotable toward and away from a wall of the interior
chamber of the container for facilitating insertion and removal of
the antenna into and out of the container.
22. The system for coating as recited in claim 18, further
comprising means for rotating the container around the longitudinal
axis of the container, the antenna being within the container
during rotation by the means for rotating and the antenna being
oriented within the container independent of rotation of the
container.
23. The system for coating as recited in claim 1, wherein the
container includes an interior chamber and wherein the system
further comprises: an antenna insertable into and removable from
the interior chamber of the container; and means for orienting the
antenna when a longitudinal axis of the container is generally
horizontally oriented.
24. The system for coating as recited in claim 1, wherein the
container includes an interior chamber and wherein the system
further comprises: an antenna insertable into and removable from
the interior chamber of the container; and means for orienting the
antenna when a longitudinal axis of the container is generally
vertically oriented.
25. The system for coating as recited in claim 1, further
comprising an antenna provided within the vacuum cell.
26. The system for coating as recited in claim 1, further
comprising means for generating a magnetic field within the vacuum
cell wherein the field acts to direct the coating vapor.
27. A system for coating an external surface of a container wherein
the container on pressurization has enhanced environmental stress
crack resistance, the system comprising: a vacuum cell, pressure
within the vacuum cell being reduced as compared to ambient
pressure; means for supplying containers to and withdrawing
containers from the vacuum cell; and at least one source for
supplying a coating vapor to the external surface of the containers
in the vacuum cell, the coating vapor from the at least one source
depositing a relatively thin coating on the external surface of the
containers, whereby bonding between at least a portion of the
relatively thin coating deposited on the container and the external
surface of the container occurs.
28. The system for coating as recited in claim 27, wherein the at
least one source supplies the coating vapor from a solid
source.
29. The system for coating as recited in claim 28, wherein the
solid source is a nonpowder.
30. The system for coating as recited in claim 27, wherein the
means for causing coating causes at least one of chemical bonding
and physical bonding with the container.
31. The system for coating as recited in claim 27, further
comprising a plasma-enhanced device to provide means for causing
the bonding.
32. The system for coating as recited in claim 27, further
comprising a device for degassing the containers prior to
deposition of the relatively thin coating on the external surface
of the containers, the degassing of5 the containers providing means
for causing the bonding.
33. The system for coating as recited in claim 27, wherein the
container is a temperature sensitive plastic bottle with a neck and
wherein the system includes means for gripping the neck of the
bottle.
34. The system for coating as recited in claim 27, further
comprising means for rotating the containers during transport
through the vacuum cell.
35. The system for coating as recited in claim 27, further
comprising means for supplying at least one gas to an interior of
the vacuum cell, the at least one gas supplied by the means for
supplying being selected from the group consisting of oxygen,
nitrogen, sulfur and halogens.
36. The system for coating as recited in claim 35, wherein the at
least one gas is oxygen.
37. The system for coating as recited in claim 35, wherein said gas
and vapor from the at least one source provide at least one of
color coating for the container, ultraviolet absorbent coating for
the container and a gas barrier for the container.
38. The system for coating as recited in claim 35, wherein said gas
and vapor from the at least one source provide at least one of
color coating for the container and ultraviolet absorbent coating
for the container.
39. The system for coating as recited in claim 27, further
comprising means for coating less than all of the external surface
of the container by the coating vapor from the at least one
source.
40. The system for coating as recited in claim 27, further
comprising a conveying device positioned within the vacuum cell,
the conveying device moving the container through the vacuum cell
past the at least one source.
41. The system for coating as recited in claim 40, wherein the
conveying device includes a container bar for holding the
container, a slow-moving section and a fast-moving section, the
container bar being transferrable between the slow-moving section
and the fast moving section whereby the container on the container
bar can be moved at a first speed and then at a second speed
through the vacuum cell, the first speed being slower than the
second speed.
42. The system for coating as recited in claim 41, further
comprising means for rotating the containers during the transfer
from the slow-moving conveyor to the fast-moving conveyor.
43. The system for coating as recited in claim 41, wherein the
container has a longitudinal axis and wherein the conveying device
further includes means for orienting the longitudinal axis of the
container vertically and horizontally within the vacuum cell, the
longitudinal axis of the container being generally vertically
oriented when the container is being moved at the first speed by
the slow-moving section and being generally horizontally oriented
when the container is being moved at the second speed by the
fast-moving section.
44. The system for coating as recited in claim 43, wherein the
container includes an interior chamber and wherein the system
further comprises an antenna insertable into and removable from the
interior chamber of the container and means for orienting the
antenna to generally face the at least one source during
coating.
45. The system for coating as recited in claim 44, further
comprising magnetic orientating means for orienting the antenna
when the longitudinal axis of the container is generally vertically
oriented.
46. The system for coating as recited in claim 44, wherein the
means for orienting includes a heavy section of the antenna which
is rotatable under the influence of gravity to face a bottom of the
vacuum cell when the antenna and the longitudinal axis of the
container are generally horizontally oriented.
47. The system for coating as recited in claim 44, wherein the
antenna is pivotable toward and away from a wall of the interior
chamber of the container for facilitating insertion and removal of
the antenna into and out of the container.
48. The system for coating as recited in claim 44, further
comprising means for rotating the container around the longitudinal
axis of the container, the antenna being within the container
during rotation by the means for rotating and the antenna being
oriented within the container independent of rotation of the
container.
49. The system for coating as recited in claim 27, wherein the
container includes an interior chamber and wherein the system
further comprises: an antenna insertable into and removable from
the interior chamber of the container; and means for orienting the
antenna when a longitudinal axis of the container is generally
horizontally oriented.
50. The system for coating as recited in claim 27, wherein the
container includes an interior chamber and wherein the system
further comprises: an antenna insertable into and removable from
the interior chamber of the container; and means for orienting the
antenna when a longitudinal axis of the container is generally
vertically oriented.
51. The system for coating as recited in claim 27, further
comprising an antenna provided within the vacuum cell.
52. The system for coating as recited in claim 27, further
comprising means for generating a magnetic field within the vacuum
cell wherein the field acts to direct the coating vapor.
53. A plastic container having an inorganic oxide coating on an
external surface thereof, the coated plastic container possessing a
gas barrier of at least 1.25.times.after pressurization as compared
to a similarly pressurized uncoated container.
54. The plastic container as recited in 53, wherein the plastic
container is subjectable to internal pressures between 1 to 100
psig.
55. The plastic container as recited in 53, wherein the gas barrier
is substantially unaffected by changes in internal gas
pressure.
56. The plastic container as recited in claim 53, wherein the gas
barrier enhancement is substantially unaffected by temperature.
57. The plastic container as recited in claim 53, wherein the gas
barrier enhancement is substantially unaffected by filling of the
container.
58. The plastic container as recited in claim 53, wherein the
inorganic oxide coating is greater than or equal to 50% and up to
but less than 100% SiOx where x is in the range of 1.7 to 2.0.
59. The plastic container as recited in claim 58, wherein the
plastic container is subjectable to internal pressures between 1 to
100 psig and wherein the coating is adhered to the container to
withstand the internal pressure of the container and to withstand
application and withdrawal of the internal pressure to and from the
container whereby the gas barrier will be substantially unaffected
by the internal pressure and by changes in the internal pressure of
the container.
60. The plastic container as recited in claim 53, wherein the
container is a plastic bottle having a threaded opening, a side and
a bottom, the bottom being opposed to the threaded opening, the
exterior of the threaded opening being free of the inorganic oxide
coating, substantially all of the external surface of the bottle
except at the threaded opening having the coating thereon such that
the coating is on both the side and the bottom of the bottle.
61. The plastic container as recited in claim 53, wherein the
container is a plastic bottle having a threaded opening, a side and
a bottom, the bottom being opposed to the threaded opening, the
exterior of the threaded opening being free of the inorganic oxide
coating, substantially all of the external surface of the bottle
except at the threaded opening and the bottom thereof having the
coating thereon such that the coating is on the side of the
bottle.
62. The plastic container as recited in claim 53, wherein the
inorganic oxide coating further includes a pigment for coloring the
external surface of the container.
63. The plastic container as recited in claim 53, wherein the
coating absorbs ultraviolet radiation.
64. The plastic container as recited in claim 53, wherein the
coating contains 0.01 to 50% of one or more elements selected from
the group consisting of Li, Na, K, Rb, Cr, Mg, Ca, Sr, Ba, Ti, Al,
Mn, V, Cr, Fe, Co, Ni, Zn, Cu, Sn, Ge and In.
65. The plastic container as recited in claim 53, wherein the
coating contains 0.01 to 5% of one or more elements selected from
the group consisting of Li, Na, K, Rb, Cr, Mg, Ca, Sr, Ba, Ti, Al,
Mn, V, Cr, Fe, Co, Ni, Zn, Cu, Sn, Ge and In.
66. The plastic container as recited in claim 53, further
comprising a second coating, the second coating comprising a
different inorganic composition from the first coating.
67. The plastic container as recited in claim 53, wherein more than
one layer of coating is provided on the external surface of the
container, the inorganic coating being one of the layers of coating
provided on the external surface of the container.
68. The plastic container as recited in claim 53, wherein the
plastic container is a PET container and wherein the coating has a
thickness of greater than 1 nm.
69. The plastic container as recited in claim 68, wherein the
coating thickness is 10-100 nm.
70. A method for coating a plastic container comprising the steps
of: introducing said container into a vacuum cell; applying an
inorganic composition to an external surface of the container in
the presence of at least one reactive gas and at sub-atmospheric
pressure; and removing the container from the vacuum cell.
71. The method as recited in claim 70, further comprising the step
of reducing pressure within the container prior to introducing the
container to the vacuum cell.
72. The method as recited in claim 70, wherein the container has an
interior chamber and wherein the method further comprises the step
of sealing the container at least when in the vacuum cell to
thereby prevent air within the interior chamber from escaping.
73. The method as recited in claim 70, further comprising the step
of vaporizing a solid source to form vapor within the vacuum cell,
the vapor being a part of the inorganic composition.
74. The method as recited in claim 70, wherein the step of applying
further comprises at least one of chemically and physically bonding
the inorganic composition to the external surface of the
container.
75. The method as recited in claim 70, further comprising the step
of degassing the container, the degassing taking place at the
following time: prior to the step of applying the inorganic
composition; during the step of applying the inorganic composition;
or both prior to and during the step of applying the inorganic
composition.
76. The method as recited in claim 70, further comprising the step
of producing a plastic container with a first plastic content, the
plastic container being the container introduced into the vacuum
cell, the step of applying the inorganic composition bonding the
inorganic composition to the external surface of the plastic
container whereafter the plastic container upon pressurization has
a gas barrier at least equal to a similar plastic container having
a second plastic content, the first plastic content being less than
the second plastic content such that weight of the plastic
container is reduced without loss of gas barrier effectiveness.
77. The method as recited in claim 76, further comprising the step
of using up to or including one of 10%, 20% or 50% less plastic
with the plastic container having the first plastic content than
with a second plastic container having the second plastic
content.
78. The method as recited in claim 70, wherein the container is a
temperature sensitive plastic bottle with a neck and wherein the
method includes the step of gripping the neck of the bottle at
least when the bottle is in the vacuum cell.
79. The method as recited in claim 70, further comprising the step
of rotating the containers during transport through the vacuum
cell.
80. The method as recited in claim 70, further comprising the step
of supplying at least one gas to an interior of the vacuum cell,
the at least one gas supplied being selected from the group
consisting of oxygen, nitrogen, sulfur and halogens.
81. The method as recited in claim 80, wherein the at least one gas
supplied in the step of supplying is oxygen.
82. The method as recited in claim 80, further comprising the step
of providing at least one of color coating for the container,
ultraviolet absorbent coating for the container and a gas barrier
for the container from said gas and from the inorganic
composition.
83. The method as recited in claim 70, further comprising the step
of coating less than all of the external surface of the container
by the inorganic composition.
84. The method as recited in claim 70, further comprising the step
of conveying the containers in the vacuum cell at different
speeds.
85. The method as recited in claim 84, further comprising the step
of rotating the containers during the step of conveying, the step
of rotating includes continuing to rotate the containers when a
speed of conveying changes.
86. The method as recited in claim 84, wherein the container has a
longitudinal axis and wherein the method further comprises the step
of changing the orientation of the longitudinal axis between a
vertical and horizontal orientation during the step of
conveying.
87. The method as recited in claim 70, wherein the container is a
temperature sensitive container and wherein the method further
comprises the steps of: placing an inert inorganic material inside
said vacuum cell; generating a vapor from said inorganic material;
and forming a plasma of said vapor, the step of applying includes
depositing a relatively thin coating of said inorganic composition
over said external surface of said temperature sensitive container,
the step of applying further includes bonding the thin coating to
the external surface of the container.
88. A method for producing recycled content plastic comprising the
steps of: providing a batch plastic, at least a portion of the
plastic having a coating thereon; grinding the plastic to produce
flakes; and melt extruding the flakes.
89. The method as recited in claim 88, wherein the batch plastic
provided is transparent and wherein the method further comprises
the step of maintaining transparency of the plastic throughout the
steps of grinding and melting such that transparency of plastic
from the melt extruding is substantially the same as transparency
of the batch plastic.
90. The method as recited in claim 88, further comprising the step
of forming the melted extruded flakes to form plastic articles.
91. The method as recited in claim 90, wherein the step of forming
forms plastic bottles and wherein the step of providing a batch
plastic comprises using plastic bottles as the recycled content
plastic for the batch plastic.
92. The method as recited in claim 90, further comprising the step
of one of injection molding, blow molding and extrusion molding the
melted extruded flakes in ultimately forming the plastic
articles.
93. The method as recited in claim 88, further comprising the steps
of: providing uncoated and coated plastic; and avoiding a step of
separating the coated plastic from the uncoated plastic prior to
the step of grinding.
94. The method as recited in claim 93, further comprising the step
of using plastic containers as the coated plastic and as the
uncoated plastic.
95. The method as recited in claim 93, further comprising one of
the steps of injection molding, blow molding and extrusion molding
the plastic after the step of mixing.
96. The method as recited in claim 88, further comprising the step
of using plastic containers as the coated plastic.
97. The method as recited in claim 88, further comprising the step
of using plastic bottles as the coated plastic.
98. The method as recited in claim 88, further comprising the step
of washing the flakes produced in the step of grinding.
99. A method for producing recycled content plastic comprising the
steps of: providing at least some coated plastic; depolymerizing
said at least some coated plastic; and re-polymerizing said
depolymerized plastic.
100. The method as recited in claim 99, wherein the at least some
coated plastic used in the step of providing is transparent and
wherein the method further comprises the step of maintaining
transparency of the plastic throughout the steps of depolymerizing
and repolymerizing such that transparency of plastic after
repolymerizing is substantially the same as transparency of the
plastic initially provided.
101. The method as recited in claim 99, further comprising the
steps of: providing uncoated plastic along with the step of
providing at least some coated plastic; and mixing the coated
plastic and uncoated plastic thereby avoiding a step of separating
the coated plastic from the uncoated plastic.
102. The method as recited in claim 99, further comprising the step
of forming the re-polymerized plastic into plastic articles.
103. The method as recited in claim 102, wherein the step of
forming forms plastic bottles and wherein the step of providing at
least some coated plastic comprises using plastic bottles.
104. The method as recited in claim 102, wherein the step of
forming comprises one of the steps of injection molding, blow
molding and extrusion molding the re-polymerized plastic in
ultimately forming the plastic articles.
105. The method as recited in claim 99, further comprising the
steps of: providing coated and uncoated plastic; and avoiding a
step of separating the coated plastic from the uncoated plastic
prior to the step of depolymerizing.
106. The method as recited in claim 105, further comprising the
step of using plastic containers as the coated plastic and as the
uncoated plastic.
107. The method as recited in claim 105, wherein mixing of uncoated
plastic and coated plastic occurs either before the step of
depolymerizing or between the depolymerizing and re-polymerizing
steps and wherein the method further comprises one of the steps of
injection molding, blow molding and extrusion molding the plastic
after the step of mixing and after the step of repolymerizing.
108. The method as recited in claim 99, further comprising the step
of using plastic containers as the at least some coated
plastic.
109. The method as recited in claim 99, further comprising the step
of using plastic bottles as the at least some coated plastic.
110. A plastic container having an exterior inorganic coating that
has an equivalent gas barrier and reduced weight compared to a
plastic container of similar surface area and volume and without
said exterior inorganic coating.
111. A method of extending shelf life of a plastic container
comprising the steps of: providing a plastic container, the plastic
container having an inorganic coating on an external surface
thereof; filling the plastic container with a pressurized beverage;
sealing the plastic container after the step of filling; preventing
escape of pressurized gas from the plastic container, the coating
being utilized in prevention of escape of the pressurized gas;
holding the pressurized gas within the container for a longer time
period than a similarly sized and shaped container without the
inorganic coating, the inorganic coating being utilized in the
holding of the pressurized gas; and permitting at least one of
flexing and stretching of the inorganic coating without
substantially affecting the step of holding.
112. A device for coating containers, the device comprising: an
electron gun; a receptacle for holding material, the electron gun
vaporizing at least a portion of the material held in the
receptacle; and means for conveying containers through an area
having vapor produced by the electron gun vaporizing the material,
the vapor being deposited on the containers to thereby coat an
exterior of the containers.
113. The device for coating containers as recited in claim 112,
further comprising a shield for the electron gun, the shield being
between the electron gun and the receptacle, material of the shield
being selected such that erosion of the shield by the electron gun
produces a desired component in the vapor.
114. The device for coating containers as recited in claim 112,
wherein the shield is an electron emitting plate and is constructed
from one of a desired metal and a mixture of metals.
115. The device for coating containers as recited in claim 112,
further comprising means for cooling the shield and wherein a
degree of erosion of the shield is controllable by at least one of
adjusting a distance between the receptacle and the electron gun,
by adjusting a degree of cooling applied for the shield and by
adjusting voltage applied to the electron gun.
116. The device for coating containers as recited in claim 112
further comprising means for moving the electron gun toward and
away from the receptacle and means for moving the electron gun
toward and away from the containers on the means for conveying.
Description
BACKGROUND OF THE INVENTION
[0001] This invention relates to pressurized plastic containers
that have enhanced barrier performance and methods to provide said
containers and to the coatings. The enhanced barrier performance is
obtained by application of inorganic coatings to the external
surface of the container. The coatings exhibit enhanced adhesion
relative to prior art coatings.
DESCRIPTION OF THE BACKGROUND ART
[0002] Plastic containers currently comprise a large and growing
segment of the food and beverage industry. Plastic containers offer
a number of advantages over traditional metal and glass containers.
They are lightweight, inexpensive, nonbreakable, transparent and
easily manufactured and handled. However, plastic containers have
at least one significant drawback that has limited their universal
acceptance, especially in the more demanding food applications.
That drawback is that all plastic containers are more or less
permeable to water, oxygen, carbon dioxide, and other gases and
vapors. In a number of applications, the permeation rates of
affordable plastics are great enough to significantly limit the
shelf-life of the contained food or beverage, or prevent the use of
plastic containers altogether. Shelf-life is the time needed for a
loss of seventeen percent of the initial carbonation of a
beverage.
[0003] It has been recognized for some time that a container
structure that combines the best features of plastic containers and
more traditional containers could be obtained by applying a
glass-like or metal-like layer to a plastic container, and
metallized plastic containers. For example, metallized potato chip
bags have been commercially available for some time. However, in a
number of applications, the clarity of the package is of
significant importance, and for those applications metallized
coatings are not acceptable. Obtaining durable glass-like coatings
on plastic containers without changing the appearance of the
container has proven to be much more difficult.
[0004] A number of processes have been developed for the purpose of
applying glass-like coatings onto plastic films, where the films
are then subsequently formed into flexible plastic containers.
However, relatively few processes have been developed that allow
the application of a glass-like coating onto a preformed,
relatively rigid plastic container such as the PET bottles commonly
used in the U.S. for carbonated beverages, and heretofore no
process has been developed that allows the application of a
glass-like coating onto the external surface of a plastic container
that is sufficiently durable to withstand the effect of
pressurization of the container, retain an enhanced barrier to
gases and vapors subsequent to said pressurization, and not affect
the recyclability of the containers. Pressurized beverage
containers currently comprise a very large market world-wide, and
currently affordable plastics have sufficiently high permeation
rates to limit the use of plastic containers in a number of the
markets served.
[0005] Such pressurized containers include plastic bottles for both
carbonated and non-carbonated beverages. Plastic bottles have been
constructed from various polymers, predominant among them being
polyethylene terephthalate (PET), particularly for carbonated
beverages, but all of these polymers have exhibited various degrees
of permeability to gases and vapors which have limited the shelf
life of the beverages placed within them. For example, carbonated
beverage bottles have a shelf-life which is limited by loss of
CO.sub.2. While this limitation becomes increasingly important as
the size of the bottle is reduced, because of the increasing
surface to volume ratio, small containers are needed for many
market applications, and this severely limits the use of plastic
bottles in such cases. Generally, based upon this surface to volume
ratio, as a bottle becomes smaller, carbonation retention in the
beverage becomes more difficult.
[0006] For non-carbonated beverages, similar limitations apply,
again with increasing importance as the bottle size is reduced, on
account of oxygen and/or water-vapor diffusion. It should be
appreciated that diffusion means both ingress and egress (diffusion
and infusion) to and from the bottle or container. The degree of
impermeability (described herein as "gas barrier") to CO.sub.2
diffusion and to the diffusion of oxygen, water vapor and other
gases, grows in importance in conditions of high ambient
temperature. An outer coating with high gas barrier can improve the
quality of beverages packed in plastic bottles and increase the
shelf life of such bottles, making small bottles feasible, and this
in turn presents many advantages in reduced distribution costs and
a more flexible marketing mix.
[0007] Some polymers, for example PET, are also susceptible to
stress cracking when they come in contact with bottle-conveyor
lubricants used in bottle filling plants, or detergents, solvents
and other materials. Such cracking is often described as
"environmental stress cracking" and can limit the life of the
bottle by causing leaks and prevent damage to adjacent property. An
impermeable outer surface for plastic bottles, and prevent damage
to adjacent property which resists stress-cracking-inducin- g
chemicals, will extend the shelf life of plastic bottles in some
markets.
[0008] Another limitation to shelf life and beverage quality is
often UV radiation which can affect the taste, color and other
beverage properties. This is particularly important in conditions
of prolonged sunshine. An outer coating with UV absorbing
properties can improve the quality of such beverages and make
plastic bottles much more useable under such conditions.
[0009] Additional functionality can be incorporated into the
inorganic coating by incorporating visible light absorbing species,
rendering the plastic container cosmetically more appealing.
[0010] An additional benefit of the present invention is ease of
recycling. Prior art barrier enhancing coatings generally are
organic in nature and are much thicker than the coating of the
present invention. Consequently, when post-consumer scrap
containing containers coated with prior art organic coatings are
recycled, significant deterioration in the appearance and
properties of the plastic occur. In contrast, because of the inert
nature and thinness of the coatings of the present invention, the
coated containers can be processed in any conventional recycling
system without modification of the process.
[0011] Moreover, haziness in recycled articles can occur when large
sized particles are used in a coating. However, such a haze is
avoided in the present invention because relatively small particles
are used as will be described. Moreover, the coating is acceptable
for food contact and therefore will not adversely affect the
recycling effort when ground or depolymorized in the recycling
process.
[0012] Along the lines of recycling, the present invention provides
for a method of recycling coated plastic which has results
heretofore unattainable. In particular, separation of coated and
uncoated plastics is unnecessary whereby modifications to existing
recycling systems are unnecessary or whereby extra process steps
(separating coated bottles from uncoated bottles) can be avoided.
Moreover, it is possible to produce a transparent plastic from
coated plastic while avoiding the above-noted problem of haziness
in the final recycled product. While the present invention can be
used in recycling many types of plastic, it is contemplated that
this invention can be used with plastic articles, such as
containers or bottles and more particularly, with plastic beverage
bottles. Bottle-to-bottle recycling remains unaffected with the
present invention.
[0013] Recycling in the instant invention can be carried out in
both a chemical process and a physical process. The plastic
subjected to recycling processes can be molded or extruded. Even if
a coated plastic is initially introduced in the recycling process,
the coating of the present invention will not interfere with the
downstream injection molding or blow molding.
[0014] Finally, the cost of applying a coating to the outside of a
bottle, which has a gas barrier which significantly increases the
shelf-life of beverage container in that bottle, and/or which
significantly reduces product spoilage of beverage container in
that bottle, and/or which significantly reduces product spoilage
due to UV radiation, and/or virtually eliminates environmental
stress cracking, and/or provides a specific color, must not add
significant cost to the basic package. This is a criterion, which
eliminates many processes for high gas barrier coatings, because
plastic bottles are themselves a very low cost, mass produced
article. Affordability implies in practice that the cost of the
coating must add minimal or no increase to the cost of the whole
package and in fact, the cost can be less.
[0015] A coating on the outside of plastic bottles must be capable
of flexing. When bottles are used for pressurized containers, the
coating preferably should be able to biaxially stretch whenever the
plastic substrate stretches. In addition it is preferable that the
coating be continuous over the majority of the container surface.
However, in the present invention, unlike prior art devices, the
continuous coating is not essential because of the high level of
adhesion of the inorganic coating to the surface of the plastic
container. In other words, even though the coating of the present
invention may be non-continuous because of scratches or fractures
therein, for example, the coating will continue to effectively
adhere to the substrate such as an underlying plastic bottle. The
present invention can therefore provide an effective gas barrier
even if the surface is highly fractured. A high gas barrier of
1.25.times.greater than a similar uncoated container can be
obtained with the present invention and this barrier can even be
1.5.times.or preferably 2.times.greater.
[0016] Adhesion is particularly important in the case of carbonated
beverages, since the CO.sub.2 within the bottle exerts some or all
of its in-bottle pressure on the coating. This pressure can rise to
above 6 bar, exerting considerable forces on the coating/plastic
interface. The coating must also resist scuffing, normal handling,
weathering (rain, sun climate, etc.), and the coating must maintain
its gas barrier throughout the bottle's useful life.
[0017] There are several plasma-enhanced processes which apply an
external, inorganic coating to a range of articles, which in some
cases includes bottles. Many of the processes are targeted to
provide coating properties which are quite different, and far less
onerous than high gas barrier bottle coatings. Such processes
target, for example, abrasion resistance, where the coating
continuity is not a major factor, since the coating can protect the
microscopic interstices. Other processes target cosmetic or
light-reflection properties and some processes have a pure handling
protection role. Often the substrate does not flex nor stretch and
the article itself is higher priced than plastic bottles so that
cost is not a benefit of the design. In some cases, the substrate
allows far higher coating temperatures than those allowed by PET,
the most common plastic-bottle material. Such processes do not, in
general, provide the coating continuity, adhesion, flexibility
needed for high gas barrier coatings, nor do they provide a
solution to the other problems relating to high gas barrier
coatings, described above.
[0018] Prior art also exists for gas barrier processes for bottles,
but the lack of commercially available, coated bottles for
pressurized application is due to the fact that these processes
lack the desirable attributes described above and fail to provide a
coating with adequate adhesion, continuity and/or flexibility under
high in-bottle pressure or a coating which avoids recycling
problems, or the low cost necessary to make the coating
affordable.
[0019] U.S. Pat. No. 5,565,248 to Plester and Ehrich describes a
method for coating containers internally. However, external
coatings require far greater adhesion than internal coatings,
because in-bottle pressure acts against external coatings, and
internal coatings are not subject to the same handling and/or
abrasion in use. For these, and other reasons, coating bottles
externally differs from coating them internally and the present
invention is therefore substantially different.
SUMMARY OF THE INVENTION
[0020] Accordingly, it is an object of the present invention to
provide an outer coating or layer for a container such as a heat
sensitive plastic bottle, and particularly for the non-refillable
bottles used for carbonated beverages.
[0021] It is a further object of the present invention to provide a
coating and a system and method for coating which can provide an
external glass-like coating that is flexible, durable and possess
sufficient adhesion to withstand the effects of pressurization
without significant loss of enhanced barrier properties.
[0022] An additional object of the present invention is to provide
an externally coated container which will avoid environmental
stress cracking such as when the container comes into contact with
conveyor lubricants during filling, detergent, cleaners or solvents
or similar substances during its life cycle. Such lubricants can
include 409.TM., Mean Green.TM. or other commercially available
cleansers or lubricants, etc.
[0023] Yet another object of the present invention is to provide a
lighter container and a system and method for making the container
whereby an amount of plastic utilized in making the container as
compared to a conventional container can be reduced without
adversely effecting or while improving the gas barrier
effectiveness of the container.
[0024] It is another object of the present invention to provide a
coating that comprises an inorganic oxide layer on the external
surface of a plastic container, the inorganic oxide layer being
further distinguished by being comprised of greater than or equal
to 50 and up to but less than 100% SiOx (x=1.7 to 2.0).
[0025] Another object is to provide a coating which possesses
sufficient adhesion to the external surface of the plastic
container so that the barrier enhancement provided by the inorganic
oxide layer is not substantially reduced upon pressurization of the
container to a pressure between 1 and 100 psig.
[0026] A further object of the present invention is to provide a
method for applying an inorganic layer as described above, the
method resulting in a robust inorganic oxide layer that provides an
effective level of barrier enhancement to the plastic container and
does not result in significant physical distortion of the
container.
[0027] It is a further object of the present invention to provide a
system and method for manufacturing a container whereby the
aesthetic appeal of the container will be enhanced by applying a
colored inorganic layer that further contains visible-light
absorbing species.
[0028] Yet another object of the present invention is to provide a
coating for a container with UV absorbing capabilities.
[0029] Still another object of the present invention is to provide
a container with a colored or clear coating which can easily be
recycled without significant or abnormal complications to existing
recycling systems.
[0030] Another object of the present invention is to provide a
system and method for inexpensively manufacturing an externally
coated container.
[0031] Yet another object of the present invention is to provide a
method which the thickness and composition of the applied coating
on a container can be rapidly and easily determined and whereby
process control and insurance of enhanced barrier performance can
be obtained.
[0032] A further object of the present invention is to provide a
method to determine the condition of the surface of a plastic
container at least with regards to its suitability for applying
glass-like coatings.
[0033] Another object of the present invention is to provide a high
gas barrier which considerably increases the shelf life of the
containers such as plastic bottles and to provide the containers
with good transparency so as not to affect the appearance of a
clear plastic bottle.
[0034] Yet another object of the present invention is to provide a
container with enhanced barrier performance both when the container
walls flex or stretch under pressure and when the walls are
indented.
[0035] Still another object of the present invention is to provide
a container with adequate durability and adhesion during working
life, when the outer surface of the container is subjected to
environmental conditions such as severe weather, rubbing, scuffing,
or abrasions (for example, during transportation) or when the outer
coating is subjected to internal pressure and with the ability to
maintain a gas barrier while remaining stressed by in-bottle
pressure throughout the container's useful life.
[0036] Also, another object of the present invention includes the
ability to enable coating to heat sensitive plastic containers with
coating materials, which can only be vaporized at very high
temperatures without an acceptable increase in the plastic's
temperature and which must remain in many cases below 60.degree.
C.
[0037] The foregoing and other objects of this invention are
fulfilled by a method, apparatus and process control procedure for
plasma-assisted deposition of a very thin, typically 10-100 nm,
inorganic outer surface coating on a container such as a plastic
bottle using inorganic substances.
[0038] Although not bound to any particular theory, the formation
of a highly adherent, dense, continuous coating may be achieved in
the present invention by producing a high energy plasma which
further provides good coating adhesion by enabling penetration of
the coating beneath the surface of the plastic. This penetration is
additionally assisted by a biasing energy using RF or HF. Formation
of a dense coating is further enhanced by the ability to coat under
conditions of high vacuum (generally in range 10.sup.-3 to
10.sup.-5 mbar) which avoids unwanted gas molecules being
incorporated into the coating and is still further enhanced by the
ability to cause the reaction components of the coating to react
stoichiometrically.
[0039] Furthermore, the method described herein enables surface
pretreatment for the activation of the plastic surface by forming
free radicals which can react with and attach to the coating and
enhance adhesion before coating begins. The method further includes
surface cleaning, where necessary. The method identifies the need
to apply surface activation during pretreatment, and to control
this, since activation can be counter productive by damaging the
surface. The method also describes means of inspecting the bottle
surface for coating suitability and identifies factors which lead
to the preference to coat containers (particularly PET bottles)
quickly, or immediately, after molding. The method describes means
of degassing the plastic, so as to avoid vapor emission from the
plastic surface which interferes with the coating, and reduces its
adhesion or density.
[0040] The form of deposition provides for an approach angle of
plasma particles to the surface which does not exceed 70.degree. to
the vertical, so as to enhance coating adhesion. It also provides
for mixtures of substances to be deposited, and particularly for
the trace of addition (up to 50%) of metal ions into silica, which
increases silica's gas barrier for pressurized packages. The form
of deposition also enables heat sensitive containers to be coated
without significant temperature rise, and at all times maintaining
a bottle temperature well below 60.degree. C.
[0041] While this angle of 70.degree. to the vertical was noted
above, it is important to recognize that there may be certain
situations where this limitation would not apply. For example, if
bottles or containers surrounded a vapor source, then no limitation
on the angle would be desired. In other words, plasma particles
could be moving 360.degree. from their source if the bottles or
containers to be coated surrounded the source. Alternatively, if
two parallel conveyors were provided for moving the bottles or
containers past a given source with the source being between the
conveyor lines, then plasma particles could also move 360.degree.
from this source in order to reach the bottles or containers on
both conveyor lines. Other situations are envisioned whereby the
angle would not be limited to 70.degree..
[0042] The method enables mixtures and layers of substances to be
applied which can be chosen for their color, or UV-absorbing
properties, or additional gas barrier properties. Further, the
method enables coatings, such as silica, which are fully
transparent and clear, and would therefore not affect the
appearance of an otherwise clear bottle. The coating materials are
inert and remain solid when the plastic bottle is melted for
recycling.
[0043] The method for coating the outer surface of a container
according to the present invention comprises the steps of (1)
conveying the containers to a loading/unloading station where they
are placed into a holding crate ("holder"); (b) conveying the
holder/containers into a "tool" station which applies in-bottle
antennas and seals the containers with caps, which enable the
inside of the container to stay under pressure during coating and
provide for the containers to be gripped, rotated and released at
the appropriate parts of the coating cycle; (c) locating
holder/containers in an evacuation cell which brings the
holder/containers to the pressure of a vacuum cell; (d) conveying
holder/containers into the vacuum cell to a container
loading/unloading table and raising holder/bottles to permit the
containers to be gripped and located in a conveyor chain; (3)
conveying containers while continuously rotating them in a vertical
position within the vacuum cell through stages, which enable
degassing of plastic, then pretreatment to clean/activate the
container surface, then container base coating; (f) conveying
containers while continuously rotating them in a horizontal
position within the vacuum cell to enable the container sidewall to
be coated; (g) returning the coated containers to the container
loading/unloading table where they are replaced in the holder; (h)
returning holder/containers to the evacuation cell where they are
brought back to normal atmospheric pressure; (i) conveying the
holder/containers to the "tool" station where the antennas and caps
are removed; (j) conveying holder/containers to the container
loading/unloading station where the coated containers are removed
from holder and replaced by uncoated containers so that the cycle
can be repeated.
[0044] Within the vacuum cells, a plasma at very low pressures is
created using a conventional electron gun. While the gun itself is
known, the method of using this gun in the present invention is new
as will be described below. Trace metals can be added to a silica
coating by sacrificial erosion of the electron gun. The solid
deposit will stoichiometrically and on-surface react with the
reactive gas to ensure that surplus gas molecules cannot be build
into the coating, thus avoiding porosity. The coating is at high
vacuum-to reduce interference of ambient gas molecules with the
coating process and to avoid gas molecules being built into the
coating, causing porosity. A very thin coating, generally below 100
nm is deposited on the container. Optionally, RF and HF energy is
used to bias the coating particles and an in-cell antenna and RF or
HF or DC energy is optionally used to create a pretreatment plasma
within the vacuum cell. The plastic container is degassed to avoid
vapor emerging from the plastic which can interfere with the
coating process. Multiple plasma-making systems can be used
whenever more than one solid material is needed for the coating
process.
[0045] An apparatus for performing the above-mentioned method steps
comprises: (a) a holder and means of loading containers into it;
(b) a cap which seals the container opening and which incorporates
a screw driver-type slot and quick-snap-in-release connection for
gripping, releasing and turning the containers; (c) an antenna
which can be erected inside the container, maintain a minimal gap
with the walls of the container without touching the walls, and can
be orientated to face in the desired direction either magnetically
or by gravity; (d) means of inserting antenna into the containers
and applying the cap; (e) means of sealing holder/containers in a
cell which can either be pumped down to coating pressure so as to
enable the holder/containers to enter the vacuum cell, or can be
repressurized to enable holder/containers to exit the vacuum call;
(f) means of conveying holder/containers into the vacuum cell and
means for gripping the containers in a conveyor system which runs
within the vacuum cell; (g) a vacuum cell with an internal
conveying system which conveys the containers, while continuously
rotating them, first in vertical position, then in horizontal
position; (h) a plasma-making system having a conventional
electron-gun and coating-materials that are to be deposited; (i) a
biasing system using RF or HF energy and applying it to the
in-container antenna, and use of this system both for pretreatment
and for densifying the coating by biasing the coating particles;
(j) an optional in-vacuum cell mounted antenna which can create a
pretreatment plasma by using RF or HF or DC energy; and (k) means
of introducing a gas or mixture of gases into the vacuum cell.
[0046] These and other objects of the present invention are
fulfilled by a system for coating an external surface of a
container wherein the container on pressurization possess a gas
barrier at least 1.25.times.greater than a similar uncoated
container, the system comprising:
[0047] a vacuum cell, pressure within the vacuum cell being reduced
as compared to ambient pressure;
[0048] means for supplying containers to and withdrawing containers
from the vacuum cell; and
[0049] at least one source for supplying a coating vapor to the
external surface of the containers in the vacuum cell, the coating
vapor from the at least one source depositing a relatively thin
coating on the external surface of the containers,
[0050] whereby bonding between at least a portion of the relatively
thin coating deposited on the container and the external surface of
the container occurs.
[0051] Moreover, these and other objects of the present invention
are fulfilled by a system for coating an external surface of a
container wherein the container on pressurization has enhanced
environmental stress crack resistance, the system comprising:
[0052] a vacuum cell, pressure within the vacuum cell being reduced
as compared to ambient pressure;
[0053] means for supplying containers to and withdrawing containers
from the vacuum cell; and
[0054] at least one source for supplying a coating vapor to the
external surface of the containers in the vacuum cell, the coating
vapor from the at least one source depositing a relatively thin
coating on the external surface of the containers,
[0055] whereby bonding between at least a portion of the relatively
thin coating deposited on the container and the external surface of
the container occurs.
[0056] In addition, these and other objects of the present
invention are fulfilled by a plastic container having an inorganic
oxide coating on an external surface thereof, the coated plastic
container possessing a gas barrier of at least 1.25.times.after
pressurization as compared to a similarly pressurized uncoated
container.
[0057] These and other objects of the present invention are also
fulfilled by a method for coating a plastic container comprising
the steps of:
[0058] introducing said container into a vacuum cell;
[0059] applying an inorganic composition to an external surface of
the container in the presence of at least one reactive gas and at
sub-atmospheric pressure; and
[0060] removing the container from the vacuum cell.
[0061] In addition, these and other objects of the present
invention are fulfilled by a method for producing recycled content
plastic comprising the steps of:
[0062] providing a batch plastic, at least a portion of the plastic
having a coating thereon;
[0063] grinding the plastic to produce flakes; and
[0064] melt extruding the flakes.
[0065] A method for producing recycled content plastic fulfills
these and other objects of the present invention with the steps
of:
[0066] providing at least some coated plastic;
[0067] depolymerizing said at least some coated plastic; and
[0068] re-polymerizing said depolymerized plastic.
[0069] Moreover, these and other objects of the present invention
are fulfilled by a plastic container having an exterior inorganic
coating that has an equivalent gas barrier and reduced weight
compared to a plastic container of similar surface area and volume
and without said exterior inorganic coating.
[0070] In addition, these and other objects of the present
invention are fulfilled by a method of extending shelf life of a
plastic container comprising the steps of:
[0071] providing a plastic container, the plastic container having
an inorganic coating on an external surface thereof;
[0072] filling the plastic container with a pressurized
beverage;
[0073] sealing the plastic container after the step of filling;
[0074] preventing escape of pressurized gas from the plastic
container, the coating being utilized in prevention of escape of
the pressurized gas;
[0075] holding the pressurized gas within the container for a
longer time period than a similarly sized and shaped container
without the inorganic coating, the inorganic coating being utilized
in the holding of the pressurized gas; and
[0076] permitting at least one of flexing and stretching of the
inorganic coating without substantially affecting the step of
holding.
[0077] Still yet these and other objects of the present invention
are fulfilled by a device for coating containers, the device
comprising:
[0078] an electron gun;
[0079] a receptacle for holding material, the electron gun
vaporizing at least a portion of the material held in the
receptacle; and
[0080] means for conveying containers through an area having vapor
produced by the electron gun vaporizing the material, the vapor
being deposited on the containers to thereby coat an exterior of
the containers.
[0081] Further scope of applicability of the present invention will
become apparent from the detailed description given hereinafter.
However, it should be understood that the detailed description and
specific examples, while indicating preferred embodiments of the
invention, are given by way of illustration only, since various
changes and modifications within the spirit and scope of the
invention will become apparent to those skilled in the art from
this detailed description.
BRIEF DESCRIPTION OF DRAWINGS
[0082] The present invention will be more readily understood from
the detailed description given hereinbelow and the accompanying
drawings, which are given by way of illustration only and thus are
not limitative of the present invention, and wherein:
[0083] FIG. 1 is a schematic illustration of the basic process and
it parameters;
[0084] FIG. 1A is a schematic illustration similar to FIG. 1, but
showing the receptacle 3 and a supplemental receptacle positioned
on a support 19;
[0085] FIG. 1B is a schematic illustration similar to FIG. 1, but
showing a modified form of the coating chamber;
[0086] FIG. 2A shows the in-bottle antenna and bottle-capping
arrangement before insertion of the antenna;
[0087] FIG. 2B shows a cross-section of the in-bottle antenna and
bottle-capping arrangement of FIG. 2A after insertion of the
antenna;
[0088] FIG. 2C is a cross-sectional view showing a modified form of
an in-bottle antenna prior to insertion;
[0089] FIG. 2D is a cross-sectional view similar to FIG. 2C after
insertion of the in-bottle antenna;
[0090] FIG. 3 is one embodiment of a coating machine in accordance
with the present invention;
[0091] FIG. 4 shows the handling of bottles, holder, caps,
antennas, air-displacing collars of the present invention;
[0092] FIG. 5A shows a system for conveying bottles first
vertically, then horizontally while bottles are continuously
rotated;
[0093] FIG. 5B shows a sectional view of the bottle bar taken along
line V-V of FIG. 5A;
[0094] FIG. 6A is a view of bottles moving past plasma-making and
coating sources;
[0095] FIG. 6B is a side sectional view taken along line VI-VI of
FIG. 6A;
[0096] FIG. 7A shows a scanning electron microscope (SEM)
photograph of a PET bottle surface after in-plastic light molecular
weight components have diffused to the surface;
[0097] FIG. 7B is a photograph similar to FIG. 7A showing a
refillable PET bottle surface;
[0098] FIG. 7C is a similar photograph to FIG. 7A before this
diffusion has taken place;
[0099] FIG. 7D is a similar photograph to FIG. 7C before this
diffusion has taken place, but at a 1/2 magnification of only
10,000 times;
[0100] FIG. 8A shows an SEM photograph of the surface of a PET
bottle, which has been stretched when the bottle was pressurized to
a pressure of 6.5 bar, and whose coating has good adhesion and good
coverage in spite of this stressing;
[0101] FIG. 8B is a similar photograph to FIG. 8A, but the view at
4 times magnification (20,000 times);
[0102] FIG. 8C is a similar photograph to FIG. 8A of a coating
which has poor adhesion and stretchability;
[0103] FIG. 8D is a similar photograph to FIG. 8C of a coating
which has poor adhesion and stretchability, but at 100 times
magnification;
[0104] FIG. 9 is a graph showing improvements in gas barrier factor
with increasing content of Zn or Cu;
[0105] FIG. 10 is a flow chart illustrating the steps of physical
recycling; and
[0106] FIG. 11 is a flow chart illustrating the steps of chemical
recycling.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0107] Coatings with good adhesion to a surface of a container,
good gas barriers, and providing the necessary stretchability and
flexibility can be produced by the process and systems of the
present invention. Throughout the present specification, a
container or bottle 10 will be described. While this container will
generally be described with reference to a plastic bottle, any
suitable container can be treated by the method and system of the
present invention. Accordingly, soft drink bottles of various
sizes, other food containers or any other suitable container can be
treated using the disclosed method and system.
[0108] FIG. 1 shows a source 1 used as typical evaporation and
plasma-making system for this present invention. A conventional,
water-cooled electron gun 2 is used to convey energy to a
conventional receptacle 3, which holds the coating solids 4. This
receptacle 3 is constructed of a material suitable for melting and
evaporating the particular coating solid chosen, and must be both
inert and resistant to the temperature necessary for generating the
quantities of vapor needed. For example, for evaporating silicon,
carbon has been found to be a suitable material. The receptacle 3
is suspended from a receptacle holder 5, which is water cooled or
cooled by other methods.
[0109] By using these conventional components (i.e., electron gun 2
and receptacle 3, and by varying the position of the electron gun 2
relative to the horizontal surface of the receptacle 3, the
proportion of energy available for plasma-making and evaporation
can be adjusted. For example, in position A, a large portion of the
energy is available for plasma-making, while in position B, almost
all energy is used for evaporation and hardly any plasma is formed.
The degree of energy to the source 1 is adjusted by the voltage V
to give the particular deposition rate on the external bottle
surface 6 which enables coating solids 4, after evaporation, to
deposit and react completely (i.e., stoichiometrically) with the
gaseous substance 7 (or mixture of substances) introduced into the
coating chamber 8, thus ensuring that no significant amounts of
unreacted gas can be occluded within the coating 9. For example, in
one of the preferred embodiments, which uses silicon as coating
solid 4 and oxygen as gaseous substance 7, deposition rates onto
the coating surface of 2 to 20 nm/s can give fully transparent
coatings, with virtually x=2 in SiO.sub.x, while avoiding surplus
oxygen (or air) and maintaining high vacuum in the coating cell (in
region of 10.sup.5 mbar to 10.sup.3 mbar).
[0110] For producing good gas barrier results, it is beneficial to
ensure that an on-surface reaction between coating solids 4 and
gaseous substance 7 takes place after coating solids 4 have been
deposited and formed a solid lattice, since the gaseous substance 7
then densifies the coating 9 by reacting into the solid lattice.
The distance H between a surface 6 of a container 10 and the
receptacle 3 is important when avoiding the coating solids 4 which
react with the gaseous substance 7 before the coating solids 4 are
deposited onto the container surface 6. Equally, the condition of
the coating solids 4 is important in securing maximum on-surface
reaction. When these coating solids 4 are to be oxidized on the
container surface 6, as in case of silicon, large chunks with low
oxidized surface areas give best results. A distance H is chosen so
as to give optimal use of source 1 (thus enabling it to coat as
many bottles 10 as possible) while at the same time providing a
collision-free path (thus limiting reaction prior to the container
surface 6). Distance H is dependent on vacuum and deposition rate,
but generally in region 0.50 m to 2 m. Also, increasing distance H,
within the limitations described, enables high-energy plasmas to be
created at source 1 without heat-damaging the container 10.
[0111] It is usually important to ensure that the individual
particles of the coating solids 4 strike the container surface 6 at
high speed and temperature, so that the first molecular layers of
coating 9 break into container surface 6 thus forming an embedded
foundation for the coating 9, which in turn helps the adhesion of
the coating to the container 10 and the coating's flexibility,
stretchability and resistance to the internal pressure generated
with soft drink bottles, for example (which acts onto the bottle
surface 6 and stresses the coating 9). High-energy
plasma-generation (determined by position of electron gun 2,
voltage V and distance between electron gun 2 and receptacle 3) is
an important parameter, together with the coating angle a. A
coating angle a in region 0-70.degree. helps provide adequate
adhesion, while angles above approximately 70.degree. give poorer
gas barrier results, since in such a case, the coating-solids 4
impinge at an angle to the surface which reduces surface
impact.
[0112] Biasing energy, provided by locating an antenna 11 inside
the bottle or container 10 and connection it to an RF or HF source,
also helps to improve the adhesion and density of coating 9 by
accelerating and directing the ionized portion of the plasma toward
the bottle surface 6. Depending on the material of bottle 10,
biasing energies of up to 2000 V improve gas barrier, while
normally these are in region 100-800 V. Excessive bias voltage can
be detrimental by overheating and damaging the bottle surface 6.
The antenna 11 must remain oriented in line with source 1 and means
of achieving this, while bottle 10 rotates, are described
below.
[0113] Rotation of bottle 10 enables the bottle 10 to be coated
over its entire surface at a high rate of deposition of coating
solids 4 while allowing time for reaction with gaseous substance(s)
7. When coating the sidewall, the rate of deposition of coating
solids 4 onto the part of the surface of bottle 10, which is
directly opposite source 1 and which is the only surface receiving
significant deposition of coating solids 4, can be adjusted by
rotating bottle 10 at an adequate rate, so that this deposition
comprises only a few molecular layers. These molecular layers can
be easily reacted with gaseous substance(s) 7, thus achieving the
desired criterion of on-surface reaction with a solidified deposit,
since this helps provide the required dense, continuous coating
which gives good gas barrier. Also, since that part of the surface
of bottle 10, which is not opposite source 1, can continue to react
while not receiving deposition of coating solids 4, this procedure
brings the whole 360.degree. circumference of bottle 10 into the
deposition/reaction cycle and reduces coating time. Therefore,
correct setting of rotation rate (R) helps secure full reaction at
optimal coating rate conditions. Conditions of high vacuum (e.g.
10.sup.-5 mbar to 10.sup.-3 mbar) and very thin coatings (usually
below 100 nm) help to provide coatings which are continuous and
exhibit no cracks, if stretched under pressure or flexed, when
studied under high magnification using an scanning-electron
microscope.
[0114] Small or trace additions of certain metals in silicon
dioxide and other coatings can increase gas barrier. Such metals
include Ag, Al, Ca, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Sn, Ti, and Zn,
and are added to form a proportion of metal in coating 9 of 0.01 to
5%. For example, such additions to a coating 9 mainly composed of
SiO.sub.2 increase the gas barrier by a factor of 2, or more. Such
metals are added either to receptacle 3, or are provided by the
sacrificial erosion of the electron emitting plate or shield 12 of
the electron gun 2, this being constructed out of the desired
metal, or mixture of metals.
[0115] Alternatively, as shown in FIG. 1A, a separate receptacle 16
can be provided for holding a source 16' of metals. The receptacles
3 and 16 can be supported on the floor of the coating chamber 8 as
shown in FIG. 1, or on a support 19 as shown in FIG. 1A or at any
suitable location. The electron gun 2 can act on the materials 3',
16' in both respective receptacles 3, 16 or two separate electron
guns can be provided. Also, the spacing between the receptacles 3,
16 can be relative close as shown in FIG. 1A or they can be further
apart or the spacing can be varied.
[0116] In FIG. 1B, an alternative embodiment of the coating chamber
8 is used. Instead of using in-bottle antennas 11 or coating cell
antenna 14 or in addition to these antenna 11, 14, an external
biasing antenna 28 is used. This antenna 28 is for biasing during
coating. Of course, this is separate to the already shown
out-of-bottle antenna 14 for pretreatment. While not indicated in
FIG. 1B, appropriate means are provided for holding and/or
transporting the containers 10. While a continuous or
semi-continuous process for treating the bottles or containers 10
is discussed below, it should be evident that the present invention
is also applicable to batch processing.
[0117] While not shown in FIGS. 1, 1A or 1B, an automatic source
for supplying the material to receptacle 3 and/or 16 can be
provided. These materials can be supplied as a rod or other solid
structure or in any other form. It is contemplated that material in
the receptacle 3 will be in solid form and in particular will be in
a chunky or nonpowder form. By minimizing the surface area of this
material, detrimental affects of oxidization can be avoided. The
material in--the receptacle 3 (and 16, if present) will be a source
of vapor in the coating chamber when acted upon by the electron gun
2. This vapor will be deposited on the bottles or containers 10 as
will be described below. It should be noted that wiring 17 is
indicated in FIG. 1A attached to the receptacle 16. This wiring 17
can be used to supply current to the receptacle 3 and/or 16 as
described in U.S. Pat. No. 5,565,248, if so desired. Of course,
such wiring can be omitted.
[0118] When the shield or plate 12 is used as a source, the degree
of erosion can be approximately controlled by adjusting distance D
between receptacle 3 and electron gun 2, and by the degree of
cooling applied to plate or shield 12 by the means for cooling 15.
This means for cooling 15 can cool one or both of the electron gun
and the plate or shield 12. Water cooling or any other suitable
cooling can be provided by this means for cooling 15. The other
main variable affecting erosion of plate 12 is the voltage V
applied to the electron gun 2, but this is normally adjusted
independently according to the plasma generation and evaporation
rate requirements.
[0119] The choice of coating solids 4 and gaseous substance 7
depends on the process criteria (cost, coating color, degree of gas
barrier necessary size of bottle and particularly the type of
plastic used in the bottle). Good gas barriers have been obtained
by procedures described above by means of on-surface reaction of
silicon with oxygen, giving SiO.sub.x where x is greater than 1.8,
and normally insignificantly less than 2 and thus, glass-like
transparent. Also, the blending-in of significant proportions (i.e.
about 1-50%) of Ti and/or Al and/or B and/or mono-valent metals
(such as Na K) and/or divalent metals (such as Mg, Ca) have
increased gas barrier in certain conditions, whereby in case of Ca,
Mg, Na or K these can be introduced in-the form of a salt (e.g.
CaF.sub.2 or MgF.sub.2), and in case of B the introduction can be
in the form of the solid oxide. Alternatively, the process
conditions described can provide good gas barriers, using metals
(such as Ag, Al, Cr, Ge, Ti, Sn, An, Zr), or mixtures of metals,
instead of silicon, and reacting these with gaseous substances T
other than oxygen, such as N, S or halogens. To such metallic
coatings, silicon may be beneficially added. It is contemplated
that the coating contains 0.01 to 50% of one or more elements
selected from the group consisting of Li, Na, K, Rb, Cr, Mg, Ca,
Sr, Ba, Ti, Al, Mn, V, Cr, Fe, Co, Ni, Zn, Cu, Sn, Ge and In.
[0120] Use of metals and other gaseous substances also enables
colored coatings, or UV-absorbent coatings (by choosing the
reactants appropriately). More than one layer, each layer
comprising a different composition, can also be beneficial,
particularly when producing colored coatings, since combining
colored and transparent layers enables a good gas barrier to be
obtained with minimum thickness of colored coating, thus enhancing
recyclability. When more than one type of substance is used as
coating solid 4 it is often necessary to provide more than one
source 1, since differences in vapor pressure between substances
can result in fractionation and uncontrolled proportions of each
substance in the coating 9.
[0121] Surface pretreatment, aimed at activating bottle surface 6
by forming free radicals on the surface, assists in providing
continuous coatings and good adhesion, leading to durable gas
barriers. Such pretreatment is possible using a gaseous
pretreatment substance 13 (which can often be the same as the
gaseous substance 7 or substances) and at same cell pressure
conditions. The pretreatment time is adjusted so as to lightly
activate the surface only, since heavy activation is accompanied by
degradation of the bottle surface 6, in turn leading to poor
adhesion rather than the improved adhesion, which is the aim of the
pretreatment process.
[0122] Pretreatment is carried out either by using the in-bottle
antenna 11 with RF or HF energy to create a gas-plasma on bottle
surface 6, or by connecting a coating cell antenna 14 to a DC or HF
or RF source and creating a plasma within the entire cell.
[0123] It is desirable that the bottle surface 6 is degassed to
remove absorbed moisture and low molecular weight materials. This
is achieved by holding the bottle 10 in a vacuum for a period of
5-180 s. The time required for degassing is dependent on the
condition of bottle 10 (in relation to its temperature and absorbed
vapors). Bottles 10 blown immediately after blow molding can be
degassed relatively quickly, and location of coating process beside
a blow molder is desirable. Also, degassing can be accelerated
using energy, by applying either RF or HF to the internal antenna
11, or DC/RF/HF to the coating cell antenna 14, or from an IR
source located near bottle surface 6, not shown.
[0124] For certain compositions of coating 9, it is desirable to
apply the coating on a bottle 10, which during the coating process
has an internal pressure significantly higher than the cell
pressure. This gives improved gas barrier by enabling coating 9 to
relax/contract when bottle 10 is not under pressure while also
enabling coating 9 to resist cracking due to stretching when bottle
10 comes under pressure in normal use.
[0125] Some plastic surfaces, particularly those of PET, which is a
polymer most commonly used in plastic bottles, deteriorate after
blow molding due to the migration to the surface of low molecular
weight components. It is important to determine the quality of the
bottle surface 6 prior to coating. Under scanning electron
microscope, these migrating components can be observed on bottle
surface 6, and an important quality control can thus be
applied.
[0126] FIGS. 7A and 7B show a typical PET bottle surface after
surface diffusion of low molecular weight components and FIGS. 7C
and 7D show, by way of comparison, a PET bottle surface soon after
the blow molder, when no diffusion has taken place. For quality
control, it has also been demonstrated that Rutherford-Back-Scatter
(RBS) is able to determine the thickness of very thin coatings
(e.g. 50 nm) and also their composition, the latter being important
when coating with more than one solid component. X-ray fluorescence
also can be used to measure coating thickness, and, because this is
a relatively simple process, X-ray fluorescence can be applied as
an in-line quality control system after a coating machine. Finally,
observing the surface of coated bottles 10 under a scanning
electron microscope after these bottles 10 have been subjected to
gas pressure, enables a first indicator of coating performance,
since coatings 9, with poor gas barrier performance, have tendency
to crack/peel.
[0127] FIGS. 8A and 8B show the surface of a coated PET bottle
after the bottle was subjected to an in-bottle pressure of over 6
bar and part of the coating was deliberately scratched to enable
its continuous coverage and its adherence, even close to the
damage, to be observed. For comparison, FIGS. 8C and 8D show a
coating with poor surface adhesion, where distinct peeling and
splitting in the coating has been caused by the stretching of the
PET.
[0128] FIG. 2 shows an antenna and bottle capping arrangement, as
an example. Other similar arrangements achieving the same result
are possible. A cap 20 incorporates a sealing ring 21, a threaded
portion 22, a snap-in, quick-release connector 23 and a contact
ring 24 for the biasing voltage which can be applied either by RF
(radio frequency) or HF (high frequency). The contact ring 24 has
an electrical connection 25 which has a sliding contact with the
antenna stem 26. The antenna stem 26 is mounted in a bearing 27,
which is in turn mounted inside the cap 20, and is free to rotate
within the cap. The antenna 30 has the antenna stem 26, hinged arms
31a, 31b, light antenna segments 32a, 32b and a heavy antenna
segment 33. Hinged arm 31b also acts as antenna for the base of
bottle 10 when extended. At the base of the antenna stem 26 is a
ball bearing 34, which can rotate freely, and is pressed downward
by a spring 35 and a pin 36. When antenna 30 is outside the bottle
10, the antenna segments 32, 33 are folded against the antenna stem
26, due to the action of the spring 35, as shown in FIG. 2A. Pin 36
has a base stop 37 and a swivel 38 to which the hinged arm 31b and
the antenna segment 32b are connected. As pin 36 moves up/down,
hinged arm 31b and antenna segment 32b extend outward or fold
against antenna stem 26. When the antenna 30 is inserted into the
bottle 10, the ball bearing 34 is forced to compress the spring 35
and this extends the hinged arm 31b outwardly from the antenna stem
36, which erects the antenna 30 so that all its segments 32a, 32b
and 33 approach the walls of bottle 10. A gap between walls of
bottle 10 and antenna 30 is maintained which is as close to the
walls of bottle 10 as possible, but without touching, and is in
practice between 3 and about 15 mm.
[0129] Cap 20 is screwed onto the threaded finish (mouth) of bottle
10 and the gaseous content of bottle 10 is thereby sealed by
sealing ring 21. A tool (not shown), enters the connector 23 in cap
20 and provides the screw driver action for turning the cap 20 to
screw it onto bottle 10. The same tool holds the bottle 10 (until
released by connector 23) and makes contact with the RF/HF biasing
voltage on contact ring 24. Of course, a snap-in, quick-release
connector or other known connections for cap 20 instead of a screw
connection could also be used. When the bottle 10 is held and
turned horizontally, the heavy antenna segment 33 ensures that the
antenna 30, which has no contact with the walls of bottle 10, is
able to maintain a position facing vertically downwards and
therefore acts as means for orienting the antenna to generally face
the at least one source during coating. When antenna 30 is
orientated while bottle 10 is rotated in vertical position, use of
a magnetic material in antenna segment 33 and an external magnet,
appropriately positioned, enable the antenna 30 to face in the
correct direction. Accordingly, this magnet will act as magnetic
orientating means for orienting the antenna when the longitudinal
axis of the container is generally vertically oriented.
[0130] The principle demonstrated by FIGS. 2A and 2B can also be
applied to a multi-segment design. In such a multi-segment design,
where a plurality of antenna-segments 32a, 32b, 33 and hinged arms
31a, 31b enable a folding arrangement which can pass through the
finish of bottle 10 and can be erected within bottle 10 giving a
360.degree. C. antenna-coverage of its walls. In such a case, the
need for antenna orientation is eliminated and a greater portion of
the bottle is subject to biasing energy, enabling shorter coating
times in certain applications.
[0131] Moreover, apart from using the antenna 11 or 30 a back plate
18 in the vacuum cell can be provided as indicated in FIG. 1. The
bottles or containers 10 are positionable between this back plate
18 and the source 1. When used, this back plate can result in the
insertion of an antenna 11 or 30 into bottles 10 unnecessary. This
can speed the overall process, reduce the need to have an inventory
of antennas and can provide other benefits.
[0132] Alternatively, a portion or all of the vacuum cell50 or
coating chamber 8 can be used as an antenna. For example, the back
plate 18 can be omitted and the ceiling alone or the ceiling and
some of the walls or the entire chamber 8 can be used as the
antenna. Other arrangements are also possible.
[0133] Another potential for avoiding the antennas 11 or 30
comprises providing a magnetic source within the vacuum cell 50 as
generally indicated by numeral 58 in FIG. 3. The number of magnetic
sources 58 and there location within vacuum cell 50 can readily be
varied. This magnetic source 58 acts as a means for generating a
magnetic field within the vacuum cell 50 wherein the field directs
the coating vapor.
[0134] This magnetic source could alternatively be used to
selectively direct the coating vapor going to the bottle surface,
thereby avoiding some or all of the need to mechanically rotate or
translate the bottles. This magnetic source will therefore act as
means for generating a field to direct the coating vapor.
[0135] While still using an in-bottle antenna, FIGS. 2C and 2D show
another possible type of antenna 69. This antenna 69 is straight
and therefore is more easily inserted into and removed from the
bottle or container 10. This antenna 69 simply runs as a straight
"peg" from the cap to within a few millimeters of the base of the
bottle or container 10. This antenna 69 also simplifies the
operation because no pivoting, orientation, folding-out to fit the
walls of the bottle or container 10, etc. are needed. While antenna
69 is shown as being generally coextensive with the longitudinal
axis of the respective bottle or container 10, it is contemplated
that a skewed orientation is also possible. In other words, antenna
69 would be angled relative to the longitudinal axis of the bottle
or container 10. In such an angled position, the antenna 69 may or
may not intersect the longitudinal axis of the bottle or container
10.
[0136] Alternatively, a corkscrew antenna could also be used. This
antenna would be screwed into the bottle or container 10, yet would
be closer to the sidewalls than the straight antenna 69 without
touching these sidewalls. Other possible antennas are, of course,
also possible.
[0137] It is normally desirable to avoid coating the threaded
finish of a beverage bottle, because this may affect the closure
performance characteristics and because this can come in contact
with the beverage and perhaps the mouth of the consumer. Although
all of the coatings used in this invention are safe in contact with
food, it is nonetheless desirable to restrict beverage contact to
the main bottle material. Cap 20 covers the finish portion of
bottle 10 and prevents the coating 9 from spreading to it.
[0138] FIG. 3 shows one embodiment of a coating machine in
accordance with this invention, which enables continuous, economic
coating of the bottles. In view of the fact that bottles are
inexpensive, mass produced, single use packages, it is important to
arrive at an embodiment which provides a very low cost operation,
is compact (because preferred location is beside a bottle blow
molder), and is suitable for mass production (i.e. preferably
continuous rather than batch processing).
[0139] In FIG. 3, the sequence of operation of the present
invention is illustrated. Bottles or containers 10 will move
through the various stages A through H. Initially, the bottles are
supplied via conveyor 39 to a loading/unloading station 40. The
bottles or containers 10 can be fed immediately from a forming
machine 29 to the coating system. This forming machine includes a
blow molding machine, injection molding machine, extrusion molding
machine or any other known machine for forming containers or
bottles 10. As will be described below with reference to FIGS.
7A-7C, the surface of a PET bottle, for example deteriorates over
time. If the containers or bottles 10 are quickly coated after
being formed, then potential obstructions to improved adhesion on
the surface of the bottles or containers 10 are absent.
[0140] From conveyor 39, an operator can manually move or other
suitable equipment can automatically move the bottles or containers
10 to the loading/unloading station 40. The conveyor 39 can feed
bottles from a molding machine or any other upstream process.
[0141] At the loading/unloading station 40, the bottles or
containers 10 are placed into or removed from a holder 41. This
holder can have open interior or it can have segmented sections for
receiving individual bottles 10. The arrangement of the holder 41
will be discussed in more detail below. The holder 41 used in FIG.
3 has four bottles in two rows for a total of eight bottles. Of
course, this configuration could be modified so as to meet the
needs of the system.
[0142] The holder 41 with the loaded bottles or containers 10 can
be manually or automatically moved from the loading/unloading
station 40 at stage A to the tool station 42 at stage B as noted
above. The operation of this tool station 42 will be explained in
more detail below with reference to FIG. 4. At this tool station
42, an antenna 30, cap 20 and an air-displacement collar 60 can be
inserted into or removed from the bottles or containers 10. The cap
20, antenna 30 and collar 60 will be collectively designated as
"tools". The tools as well as the holder 41 should be made of a
non-gassing (low-absorbent) material whose surface cannot damage
the surface of the coated or uncoated bottles or containers 10.
[0143] From the tool station 42 at stage B, the holder 41 with the
bottles or containers 10 can be manually or automatically moved
into the evacuation cell 43 at stage C. Some door, air lock or
other feature is provided for enabling a vacuum to be formed within
the evacuation cell 43. As will be explained in more detail below,
the displacement collar 60 which had previously been applied to the
bottles or containers 10 can be removed or reapplied in the
evacuation cell 43. Also, a vacuum is either created or released in
this evacuation cell 43 as will be described below.
[0144] From the evacuation cell 43, the holder 41 and bottles or
containers 10 move into the loading/unloading table 44 at stage D.
Loading of the bottles from holder 41 to bottle-carrying bars 51 is
carried out on this table 44. Also, the bottles or containers 10
are unloaded from the bottles carrying bars 51 back into the holder
41 as will be described in more detail below.
[0145] When the bottles or containers 10 are mounted on the
bottle-carrying bars 51 at stage D, they are then passed to the
degassing and pretreatment sections 45 and stage E. The antenna 30
which can be within the interior of the bottles or containers 10
will be oriented by a magnet 46 in the degassing and pretreatment
sections 45. The bottles or containers 10 have their longitudinal
axes generally vertically aligned when in the degassing and
pretreatment sections 45 of stage E.
[0146] From the degassing and pretreatment sections 45, the bottles
or containers 10 on the bottles carrying bars 51 will move to the
base coating section 47 at stage F. Then the bottles or containers
10 will move the sidewall coating section 48 at stage G. It should
be noted that the bottles or containers 10 move from a generally
vertically orientation in stage F to a generally horizontally
orientation in stage G. This arrangement will be described in more
detail below. From stage G, the bottles return to the
loading/unloading table 44. The bottles or containers 10 are
removed from the bottle-carrying bars 51 and reinserted into the
holders 41. The holders 41 are then moved through the evacuation
cell 43 at stage C to an intermediate holding position 49 at stage
H.
[0147] Now after this general description, a more detailed
description of the arrangement of FIG. 3 will now be given. First,
the bottles or containers 10 are loaded into holder 41 at stage A
as noted above. An operator can manually insert the tools, cap 20,
antenna 30 and collar 60, onto the bottles or containers 10 or this
step can be automatically carried out with appropriate equipment.
This operation is carried out at the tool station 42 at stage
B.
[0148] When the holders 41 and bottles or containers 10 are moved
into the evacuation cell 43 at stage C, a vacuum will be created in
this cell 43. The collar 60 previously applied at tool station 42
during stage B will be used to evacuate the interior of the bottles
or containers 10 prior to the evacuation of pressure from cell 43.
The purpose of collar 60 is reduce the amount of air brought into
the evacuation cell 43. Together with the holder 41 into which
bottles or containers 10 tightly fit, the pre-evacuation of the
containers or bottles 20 reduces the amount of air which must be
evacuated from the cell 43. In other words, the bottles or
containers 10 tightly fit into the holder 41. This holder 41
tightly fits within the walls of the evacuation cell 43 in order to
minimize the amount of air exterior of the containers or bottles
10.
[0149] Before or during insertion of the holder 41 with the bottles
or containers 10 into the evacuation cell 43, the collar 60 is
utilized to remove air from the interior of the bottles or
containers 10. Therefore, the vacuum system for evacuating cell 43
need only evacuate the little amount of air existing in the cells
exteriorly of the containers or bottles 10. Therefore, the vacuum
system capacity can be reduced. This is an important economic
consideration in view of the low operating pressure of the vacuum
cell 50. This also helps to prolong the life of the vacuum system
and helps to minimize the amount of energy consumed with the
instant system.
[0150] From the evacuation cell 43 at stage C, the holder 41 with
the bottles or containers 10 is moved to the loading/unloading
table 44 at stage D. This loading/unloading table 44 is within the
vacuum cell 50. The vacuum cell 50 and the evacuated cell 43 are
both connected to a conventional vacuum system (not shown). When,
the evacuation cell 43 reaches the appropriate pressure, various
steps are undertaken including opening of door 55 to permit entry
of the holder 41 with the bottles or containers 10.
[0151] Within the vacuum cell 50, the bottles or containers 10 are
degassed and pretreated in section 45 at stage E. This degassing at
stage E can take sixty seconds, for example. It should be noted
that degassing of the containers or bottles 10 actually starts in
the evacuation cell 43 at stage C. The degassing is completed
during the pretreatment in section 45 of stage E. The bottles or
containers 10 are moved out of the holder 41 at the
loading/unloading table 44 and onto bottle-carrying bars 51 which
will be described in more detail below. The bottles are moved from
the loading/unloading table 44 area in stage D to the subsequent
stages within the vacuum cell 10 by movement of the bottle-carrying
bars 51.
[0152] While a conveyor arrangement will described below for moving
these bottle-carrying bars 51, it should be appreciated that many
different arrangements could be used in order to convey the bottles
or containers 10 through the vacuum cell 50.
[0153] In the degassing and pretreatment sections 45, orienting
magnets 46 can be used to orient the antennas 11 or 30 as desired.
The antennas could be stationary relative to a certain point on the
container or bottles 10 or can be movable relative to the bottles
or containers 10. In the degassing and pretreatment section 45 at
stage E as well as in the downstream base coating section 47 of the
stage F, the bottles or containers 10 have their longitudinal axes
vertically oriented.
[0154] In the pretreatment loading/unloading table 44 area at stage
D or in the degassing and pretreatment section 45 of stage E,
heating of the bottles or containers 10 can be carried out if
appropriate. At these stages D or E or throughout the vacuum cell
50, radiant or infrared heaters (not shown) could be provided such
that the bottles or containers 10 would be at an appropriate
temperature. For example, this temperature could be ambient to
60.degree. C.
[0155] Apart from the bottles or containers 10 being at an
appropriate temperature to facilitate degassing, the antennas 11 or
30 with the containers can be used to accelerate the degassing as
has previously been noted. In particular, either RF or HR energy is
applied to the internal antenna 11 or 30. Alternatively, as noted
with regard to FIG. 1, a coating cell antenna 14 can be provided.
DC/RF/HF energy can be applied to this coating cell antenna 14 or
from an infrared source located near the bottle surface 6. All of
these features can accelerate degassing. Also, the provision of a
vacuum aids in the degassing process. It should be noted again that
the antennas 11 or 30 inserted into the bottles or containers 10
are also used in the pretreatment steps.
[0156] In particular, pretreatment is carried out either by using
the in-bottle antenna 11 or 30 with RF or HF energy to create a
gas-plasma on the bottle or container surface 6, or by connecting a
coating cell antenna 14 as shown in FIG. 1 to a DC or HF or RF
source in creating a plasma within the entire cell 50.
Alternatively, this cell 50 could be segmented into sections such
that the plasma is only created in the degassing and pretreatment
section 45 of stage E. The pretreatment will lightly activate the
surface of the bottle or container 10 in order to improve the
downstream coating. This pretreatment forms free radicals on the
surface 6 of the bottle or container 10 to assist in providing
continuous coating and good adhesion leading to durable gas
barriers. The pretreating step can last for 60 seconds, for
example.
[0157] The bottle bars 51 holding the bottles or containers 10 can
allow for rotation of the bottles through the degassing and
pretreatment section 45 of stage E. For example, the bottles or
containers 10 could be rotated at two revolutions per minute, for
example. The IF bias used in pretreatment can be 700 volts with a
50 watt antenna. The gas within the degassing and pretreatment
section 45 of stage E is contemplated as being O.sub.2 but any
desired gas can be used. The gas flow will be controlled so as to
maintain correct pressure within the area of degassing and
pretreatment section 45. This pressure can be 2.times.10.sup.-4
mbar. The duration could be, however, anywhere from 20-120 sec.
with the bottles being rotated at 1-10 revolutions per minute.
Also, the pressure can be from 1-5.times.10.sup.-4. The flexibility
in these ranges are given only as an example to indicate the
required scope. For example, the pretreatment duration can be
achieved by varying the machine speed without an accompanying
change in machine size, whereby the accepted results would be a
change in output. Therefore great flexibility is obtainable with
the system of the instant invention.
[0158] The coating process is carried out in two parts. First,
there was the previously noted base coating section 47 at stage F.
Then the sidewall coating section 48 at stage G completes coating
of the bottles or containers 10. In this base coating section 47,
the bottom or base of the bottles or containers 10 are coated. Then
as will be described in more detail below, the longitudinal axes of
the bottles are changed from the vertical to a horizontal
orientation. This is achieved by increasing space between bottle
bars 51. As will be described below with reference to a fast-moving
chain 53 and a slow-moving chain 52, this reorientation of the
bottles or container 10 can take place. Throughout their vertical
and horizontal orientations, the bottles or containers 10 are close
to each other to give best utilization to the evaporators or source
1, but they do not touch. The bottles in the horizontal orientation
are then moved through a sidewall coating section 48 at stage G. As
the bottles move through the section, they can be rotated about
their longitudinal axis.
[0159] The bottles or containers 10 can be coated throughout
movement in the sidewall coating section 48 or only in a portion
thereof. The distance of the coating section 48 over which the
bottles are coated can be influenced by the amount of coating
desired to be deposited on the bottles. For example, various
sources 1 can be provided in the vacuum cell 50 for supplying the
coating vapor to the bottles or containers 10. If a thicker
external coating is desired, then more of the sources 1 could be
activated as opposed to when a thinner coating is desired. Of
course, other criteria can be modified in order to influence the
thickness of the coating on the exterior of the bottles or
containers 10.
[0160] Similarly to the pressure in the degassing and pretreatment
section 45 of stage E, the pressure in both the base coating
section 47 and the sidewall coating section 48 of stages F and G
can be 2.times.10.sup.-4 mbar and can be in the range of 1 to
5.times.10.sup.-4 mbar. It is contemplated that the base coating in
stage F will take 15 seconds but can be in the range of 10-30
seconds. The sidewall coating in stage G can take 60 seconds but be
in the range of 20-120 seconds. The bottles will rotate two
revolutions per minute in both sections 47 and 48 but can rotate
from 1-10 revolutions per minute. The bottle energy (RF-bias) will
be 700 volts with a 50 watt antenna for at least the first 20% of
the coating cycle. These numbers are merely given by way of example
and can be varied.
[0161] Within the coating cell 50, an evaporator system can be
provided. This evaporator system was described with reference to
FIG. 1 and will also be described in more detail with reference to
FIGS. 6A and 6B. In particular, evaporators or source 1 are
provided in order to provide the coating which will be deposited on
the exterior of the bottles or containers 10.
[0162] The evaporators can be arranged in rows so that the
evaporator fluxes overlap their paths, giving an even longitudinal
deposition rate R. This rate can be 3 nm/s and be in the range of
1-10 nm/s. The angle of contact a which was previously discussed
therefore only applies to row ends and to the row cross sections
where there is no overlap. This angle of contact a is indicated in
FIGS. 6A and 6B and can be 30.degree. or at least in the range of
30-60.degree., for example. However, as previously noted this angle
should not be greater than 70.degree.. This will help to enhance
coating adhesion.
[0163] It is desired that the evaporators layout must result in a
minimum number of evaporators or sources 1 with the most effective
use thereof. In other words, material loss should be minimized. The
presentation of bottle rows to the evaporator or source 1 can be
four in a row as indicated in FIG. 3 but this number can be varied
as desired. It is merely desired that the evaporator or source 1
utilization will be optimized.
[0164] As will be described below for FIGS. 6A and 6B, dust screens
or shields 93 can be provided. These shields or dust screens should
be removable and easily cleaned. They will catch particles from the
evaporator or source 1 which are not flowing to the bottle
surface.
[0165] In order to avoid the need for switching off the evaporators
or sources 1 during short cycle pauses, provision can be made for
swing covers or similar covers to collect coating vapors during
non-coating periods of the cycle. This will reduce the dust coating
of the internal coating cell. Automatic function controls and
automatic detection of malfunctioning evaporators or sources 1 can
also be provided. It is estimated that the parameters specified
will result in a coating thickness of about 50 nm. On this basis,
the evaporation rate is estimated as follows. With the weight of
the bottle being 30 grams and the PET thickness being 0.35 mm, the
coating thickness can be 50 nm. Therefore, the proportion coating
to PET (V/V) will equal 0.00014. The Si proportion of SiO.sub.2
(W/W) will equal 0.467. The density of the SiO.sub.2 will be 2.5
with the density of PET being 1.3. Therefore, the weight of Si of
coating will be 0.004 g/bottle. At about 3,000 bottles per hour,
the Si evaporated for bottle coating only (not including losses)
will be about 11.5 g with about 30 g/h including the total
losses.
[0166] As has been described with reference to FIG. 1, the distance
between the evaporator or source 1 and the bottle surface (H) can
be 0.5 and be in the range of 0.3 to 1 m. It should also be
possible to remove sources 1 from the vacuum cell 15 for inspection
and/or maintenance without releasing the coating or vacuum. A
tandem evaporator system operating through vacuum locks is one
possibility. In view of this, no automatic material feed to the
evaporators would be needed. Of course, such an automatic material
feed could be used, if so desired. The evaporating function must be
monitored by instruments and can be visible from outside of the
vacuum cell 50 by means of sight glasses, for example.
[0167] After moving through the sidewall coating section 48 at
stage G, the bottles 10 will reenter the holder 41 at the
loading/unloading table 44. This arrangement will be described in
more detail with regard to FIG. 4. From the loading/unloading table
44 at stage D, the holders 41 with the reinserted bottles or
containers 10 will back into the evacuation cell 43 at stage C.
Prior to moving into this evacuation cell 43, the collars 60 will
be placed on the containers at stage D.
[0168] When the holder 41 and bottles or containers 10 are
reintroduced into the evacuation cell 43, the vacuum can be
released. Then, the holder 41 containing the coated bottles or
containers 10 will exit the evacuation cell 43. The holder 41 with
the bottles 10 can then be slid to the intermediate holding
position 49. At this position, the entry to the evacuation cell 43
will be clear such that another loaded holder 41 with uncoated
bottles or containers 10 can be quickly reinserted into the
evacuation cell 43. This helps to keep the continuous operation of
the coating system. After evacuation cell 43 is reloaded, the
holder 41 can return to stage B whereat the tools are automatically
or manually removed. In other words, the cap 20, antenna 30 and
collar 60 will be removed from the bottles or containers 10. Then,
at the loading/unloading station 40 at stage A, the coated bottles
or containers 10 can be removed from the holder 41 and returned to
the conveyor 39 for subsequent processing. New uncoated bottles or
containers 10 can be placed into the emptied holder 41 enabling the
described cycle of operation to repeat.
[0169] When bottles 10 and holder 41 are viewed separately, bottles
10 first pass through stages A to G, and then return through stages
C to H to A. There are two holders 41, and these first pass through
stages A to G, and return by passing through stages C to H to A.
There are sufficient sets of tools to cover all bottles in stages B
through H. The tools are applied at stage B and return to stage B
having passed through all the stages B to H.
[0170] Stages D, E, F, G are housed in a vacuum cell 50. Bottles 10
are gripped by bottle bars 51 and processed through the vacuum cell
50 by conveyor chains, one slow moving chain 52 and one fast moving
chain 53. The slow moving chain 52 pushes the bottle bars 51 in a
closely packed arrangement, during the cycle of operations when the
bottles 10 are held in vertical position (for degassing and
pretreatment at stage E and base coating at stage F) and the fast
moving chain 53 pushes the bottle bars 51 with greater bar-to-bar
spacing while the bottles 20 are in a horizontal position (for
sidewall coating at stage G). The bottle bars 51 run in carrier
rails 54 which firmly locate and carry the bottle bars 51 as will
be described in more detail with reference to FIG. 5A.
[0171] The evacuation cell 53 is equipped with conventional
mechanized doors 55 which open/close to enable holder 41 to
enter/exit. A ceiling door 55a in FIG. 5 allows the collar 60 to be
removed and/or reapplied) by conventional means prior to the holder
41 moving into the main section of vacuum cell 50. The compartment
above the evacuation cell 53, where the collar 60 is held after
removal, is part of vacuum cell 50, and both this compartment and
the main part of vacuum cell 50 are permanently under vacuum.
Evacuation cell 43 is evacuated to enable holder 41 to enter vacuum
cell 50 and is returned to normal pressure to allow holders 41 to
exit the coating system.
[0172] Bottles 10 are conveyed conventionally along conveyor 39 to
the coating machine (preferably directly from the blow molder), and
to the bottle palletizing system after coating.
[0173] FIG. 4 shows the handling of bottles 10 and tools. Bottles
10 enter a holder 41 at stage A. Bottles 10 fit tightly into
cavities within the holder 41 to reduce the air gaps as much as
possible, as this in turn reduces vacuum pump duty. At stage B, a
collar 60 is applied to reduce the air gaps around the necks of
bottles 10 and the antenna 30 and cap 20 are fitted onto bottle 10.
The caps 20 are screwed onto the bottles 10 by a series of screw
drivers which are part of a tool applicator 61. At stage C, the
holder 41 enters the evacuation cell through door 55. Overhead door
55a opens to allow collar 60 to be lifted off and stored in a
storage compartment 62, within the vacuum cell 50. At stage D, the
holder 41 is elevated to the bottle bars 51 which pick up the
bottles 10 by means of the snap-in connector 23 on the caps 20. The
bottle bars 51 now progress through the coating stages D to G.
[0174] After coating, the holder 41 is elevated at stage D to the
bottle bars 51 and the bottles 10 are released into holder 41. The
holder 51 returns to the evacuation cell 43, where the collar 60 is
reapplied, and vacuum is released. Holder 41 exits to stage B,
where the tool-applicator 61 descends, grips caps 20 by the snap-in
connector 23, unscrews caps 20 and lifts caps 20, antennas 30 and
collar 60 as a single unit, the collar 60 being lifted off by the
caps 20, which lock in its underside. The tool-applicator 61 and
the quick release, screw driver devices, comprise conventional
technology and will not be described further.
[0175] FIG. 5A shows details of the bottle bars, bottle turning and
bottle conveying. Bottle bars 51 hold a plurality of bottles 10 in
a row. In FIG. 5A, four bottles 10 are shown, as an example only. A
bottle drive shaft 70 on which worm gears 71 are fitted, runs
inside the bottle bars 51, and is suspended by bearings 72 at each
end of bottle bar 51. The cap 20 acts as means for gripping the
neck of the bottle or container 10 to help hold it on bottle bar
51. As seen in FIG. 5B, this cap 20 also covers the neck and/or
threads of the container or bottle 10 whereby coating of this area
of the container can be prevented. The bottle drive shaft 70, also
shown in FIG. 5B, is driven by bevel gears 73, and rotates by
rotating the snap-in connectors 23 which are fitted with a screw
driver end piece (not shown) to thereby act as means for rotating
the containers or bottles 10 during transport through the vacuum
cell 50. The bottle bar 51 is fitted at each end with carrier bars
74 in which it is free to swivel, due to bush bearings 75. The
carrier bars 74 are fitted with carrier wheels 76 which run in a
pair of carrier rails 54. The bottle bars 51 are conveyed by means
of a drive chain 77, to which a pall-finger 78 is attached which in
turn impinges upon an extension arm 79 on carrier bars 74. The
drive chain 77 is attached to a main shaft 80 which is driven by
conveyor motor 81. A bottle rotation motor 82 drives a bottle
rotation sprocket 83 which is free to slide up/down main shaft 80
by means of bearing bushes 84. Bottle rotation sprocket 83 drives
bottle rotation chain 85 which in turn drives the bevel gears
73.
[0176] The bottle bars 51 are attached to a guide wheel 90 which
runs in a guide rail 91. This guide rail 91 is able to turn the
bottle bar 51 from a position holding bottles 10 vertically (as
shown) to a position holding bottles horizontally by means of
guiding the guide wheel up a ramp 92 at the appropriate part of the
conveying cycle. This switch from a vertical orientation to a
horizontal orientation occurs between stages F and G. When the
bottles or containers 10 are horizontally oriented, the bottles or
containers 10 continue to rotate without interruption by means of
bevel gears 73 while the bottle rotation sprocket 83 moves up the
main shaft 80 to accommodate the new position of the bevel gears
73. Dust screens 93 previously noted protect the main parts of the
drive system.
[0177] FIG. 6A is a view of bottle motion past source 1, both for
base coating and sidewall coating. Bottles 10 and caps 20 are held
vertically in the base coating section 47 by bottle bars 51 which
continuously rotate both the bottles 10 and caps 20. After base
coating the bottles 10 are turned to horizontal position for
sidewall coatings as quickly as possible (i.e. with minimum gap
between base coating section 47 and sidewall coating section 48).
The bottles are continuously rotating throughout the conveying
cycle. Bottle bars 51 are designed compactly to minimize spacing
between bottle rows in horizontal position. Sources 1 are
positioned so as to minimize the number of sources 1 needed and
according to the criteria discussed in conjunction with FIG. 1, but
with some overlap as shown in FIG. 6B to ensure full coating
coverage. Dust screens 93, which are easily removable for cleaning,
protect the machine parts from those deposits from source 1 which
do not impinge on bottle 10. Strip brushes with dust screens are
used to separate, whenever possible, the main coating cell of
vacuum cell 50 from the chains, motors, etc. used for transporting
the bottle bars 51.
[0178] FIG. 9 is a graph showing improved barrier effect showing
the importance of coating composition to gas barrier. A small
change in Zn composition can have a large effect on the barrier
enhancement.
[0179] FIG. 10 is a flow chart illustrating a physical recycling
process. In recycling, either physical recycling or chemical
recycling are normally carried out for plastic containers. In
physical recycling, a batch of plastic is provided as indicated in
step 100. While this plastic can include a single type of item, it
is contemplated that both coated and uncoated plastics will be
provided. In a conventional process indicated in step 102, these
coated and uncoated plastics must be separated. This can be a labor
intensive step and will result in increased costs for
recycling.
[0180] With the instant invention, this separating step 102 can be
avoided. In particular, step 104 indicates mixing of coated and
uncoated containers. While this step can certainly be done at the
recycling station, it is contemplated that the actual mixing could
take place prior to the arrival of the plastic at the recycling
station. For example, when the plastic is picked-up by a refuse
vehicle and taken to the recycling center, such mixing could then
occur. An advantage of the instant invention is that when plastic
to be recycled is mixed with coated plastic being with non-coated
plastic, separation of these two plastics is unnecessary. In
practice, this is, in fact, impracticable. Accordingly, when
introducing coated containers into the recycling steam, the
recycling process is unaffected.
[0181] As in a conventional process, the mixed plastics are ground
into flakes in step 106. An optional step of washing the flakes 108
can be carried out. In fact, a washing step could occur at many
other times during the process.
[0182] After the step of washing 108, if it is carried out, or
after the step of grinding 106, the ground flakes are melt extruded
at step 110. A step of forming 112 then occurs which merely
indicates that something is done with the extrusion. For example,
pellets, flakes or other configured plastics could be melt extruded
and then blow molded or injection molded. Many other uses for the
recycled plastic are possible. The blow molded or injection molded
plastic can be reused for containers and in particular, can be used
for beverage containers. In fact, the batch plastic initially
provided in the method at step 100 can be plastic beverage
containers whereby bottle-to-bottle recycling is possible. Of
course, the type of plastic handle and the output of the recycling
process is not limited.
[0183] Apart from the steps of physical recycling, the instant
invention is also applicable to a chemical recycling process as
shown in FIG. 11. Again, plastics are provided in a step 114.
Conventionally, a separating step 116 was necessary. The instant
invention avoids such a separating step 116. Similarly to the
above-described physical recycling, a mixing step 118 for coated
and uncoated plastic is indicated. This mixing can take place at
the recycling station or prior to the plastic's arrival at this
station.
[0184] In chemical recycling, the plastic is depolymerized by
conventional processes as indicated in step 120. To indicate the
flexibility of the instant invention, it is contemplated that
separated coated and uncoated plastic could be provided in the step
114. These separate plastics would be separately depolymerized in
step 120 but would be mixed together in step 122. This optional
mixing step 122 is merely to indicate the flexibility of the
instant invention.
[0185] After the plastic is depolymerized, it is repolymerized in
step 124. This plastic can then be formed into a desired article
such as by blow molding or extrusion molding as indicated in step
126. Similarly to the physical recycling process, the chemical
recycling process can handle and produce many types of plastics.
For example, bottle-to-bottle recycling is possible.
[0186] Another benefit to the recycling process of the instant
invention is that haziness in the final recycled product is
avoided. Because relatively small particles are used in the
coating, a haze in the finally produced recycled product can be
avoided. Moreover, the coating is acceptable for food contact and
therefore will not adversely affect the recycling efforts when
ground or depolymorized in the recycling processes.
[0187] The plastic produced in either recycling process can be
injection molded or blow molded as noted above. Even if a coated
plastic is initially introduced in the recycling process, the
coating of the present invention will not interfere with the
downstream injection molding or blow molding processes.
[0188] While the particular physical and chemical recycling have
been discussed, it should be appreciated that the instant invention
can also be applied in other types of recycling processes.
[0189] The invention being thus described, it will be obvious that
the same may be varied in many ways. Such variations are not to be
regarded as a departure from the spirit and scope of the invention,
and all such modifications as would be obvious to one skilled in
the art are intended to be included within the scope of the
following claims.
* * * * *