WO1997010147A1

WO1997010147A1 - Production of packaging material using chemical deposition

Info

Publication number: WO1997010147A1
Application number: PCT/US1996/014815
Authority: WO
Inventors: Jacques A. Laurent; Wolfgang Decker
Original assignee: Tetra Laval Holdings & Finance S.A.
Priority date: 1995-09-13
Filing date: 1996-09-09
Publication date: 1997-03-20
Also published as: US5728224A; AU7110496A

Abstract

An apparatus (20) and process are disclosed for depositing a barrier layer, such as an SiOx barrier layer, onto a moving web (40) of substrate material in a continuous process at atmospheric pressure using a gaseous phase precursor (50) and an oxidizer.

Description

Production of packaging material using chemical deposition

FIELD OF THE INVENTION

The present invention relates to an apparatus and method for manufacturing a packaging material that incorporates a barrier layer. More specifically, the present invention relates to an apparatus and method for manufacturing a packaging material using gaseous phase atmospheric photo chemical vapor deposition to apply a barrier layer on a moving web substrate.

BACKGROUND OF THE INVENTION

Flexible and non-flexible packages having at least one layer of a polymer material have been used in the packaging industry for a

substantial period of time. Non-flexible packages are generally manufactured from a laminate material that includes a paperboard support layer and inner and outer layers of thermoplastic materials that are heat sealable to one another. Flexible packaging materials often do

not include a structural support layer (although they may contain a thin substrate layer of, for example, paper) and are often used to form pouch-type containers. Packages made from these laminated materials have the requisite properties for packaging non-aromatic foodstuffs that are generally insensitive to oxygen but are not suitable for aromatic,

oxygen-sensitive foodstuffs, such as orange juice or the like.

Packages for aromatic, oxygen sensitive foodstuffs are generally made from laminated materials incorporating a barrier layer, either as a

product contact layer or as an intermediate layer in a multilayer laminate.

One of the most commonly used barrier layer materials is aluminum.

Another commonly used barrier material is ethylene vinyl alcohol (EVOH) .

Other materials have been found to exhibit excellent barrier

properties. One set of materials that has been shown to exhibit

excellent barrier properties is the silicon based materials. These materials include silicon oxides (SiOx) such as silicon dioxide (SiO₂) and silicon

nitride (Si ₃N ₄). Packaging materials incorporating such silicon based

materials are set forth in U.S. Patent No. 5, 122,410, issued June 1 6,

1992, to L'fgren, the teachings of which are hereby incorporated by

reference. Generally stated, the >410 patent discloses a laminate

material comprising a carrier layer of thermoplastic material and a barrier

layer of inorganic material that is joined to a further carrier/barrier layer

at the faces of the barrier layers by a bonding agent. In one

embodiment, the barrier layers are silicon based layers, each having a

thickness of 50 - 500 C. In the illustrated embodiments, the silicon

based barrier layers are deposited on the respective thermoplastic carrier

layers using a vacuum deposition process. The existing vacuum deposition processes used in the manufacture of the multilayer barrier materials are prohibitively costly due to the equipment, time, and energy needs associated with batch processing the materials in a chamber that has been evacuated to a

pressure that is substantially below atmospheric pressure. One such process that has been utilized to deposit SiOx materials onto a web in a batch process is a plasma-enhanced chemical vapor deposition (PECVD) process described in U.S. Patent No. 5,224,441 . Other CVD processes are shown, for example, in U.S. Patent Nos. 4,495,218 to Azuma et al.; 5,364,667, to Rheiu. These processes tend to be prohibitively costly and have generally not been economical for the production of packaging laminate materials.

SUMMARY OF THE INVENTION

An economical apparatus and method for depositing a barrier layer on a substrate material is set forth which eliminates many of the problems associated with prior processes. In accordance with the method of the present invention, a continuous web of substrate material is provided on which the barrier layer is to be deposited. The web of substrate material is driven, either continuously or in an indexed fashion, through a reaction chamber of a deposition apparatus wherein there is provided a flow of precursor gas and oxidizer gas. The reaction chamber has an internal pressure of about one atmosphere. The continuous web of substrate material, the precursor gas, and the oxidizer gas are exposed to ultraviolet radiation in the reaction chamber as the continuous web of substrate material is driven therethrough to thereby provide a barrier layer on the web of substrate material. In accordance with one embodiment of the method, the precursor is a silicon precursor and the barrier layer is a silicon-based barrier layer. The

method allows a continuous web of substrate material to be

continuously processed at a reaction pressure of about one atmosphere thereby making the production of the resulting packaging material more economical than the batch processing at low pressure that is required of the prior processes.

An apparatus for implementing the method of the invention is also set forth. The apparatus comprises a web dispenser supporting a

continuous web of substrate material and a deposition apparatus. The deposition apparatus comprises a) a reaction chamber; b) a web inlet portion for accepting the continuous web of substrate material from the web dispenser into the reaction chamber; c) an ultraviolet energy source disposed to radiate ultraviolet energy into the reaction chamber; d) at least one gas inlet for conducting a flow of a precursor gas, an oxidizing gas, and a carrier gas into said reaction chamber, pressure within the reaction chamber being about one atmosphere, the precursor gas, oxidizing gas, and continuous web of substrate material being exposed to the ultraviolet light energy from the ultraviolet lamp to thereby cause deposition of a barrier layer on the web of substrate material; e) a web outlet portion for allowing passage of the continuous web of substrate material from the reaction chamber; and f) a gas outlet for allowing gases to exit the reaction chamber. The apparatus further comprises a web driving mechanism for driving the web of substrate material through the reaction chamber.

In accordance with further enhancements to the apparatus and method of the present invention, the temperature of the moving web of substrate material is controlled, at least in part, by passing the web over a cooling table as it is processed in the reaction chamber. Additionally, the precursor, oxidizer, ultraviolet light intensity, substrate material, and web speed through the reaction chamber may be chosen so that the deposition of the barrier layer takes place at a temperature of less than about 200E C within the reaction chamber. Selective deposition of the barrier material may take place using photo masking

techniques.

The foregoing apparatus can be used in any one of a variety of system configurations. For example, the foregoing apparatus can be

used in a modular fashion to better regulate the thickness of the barrier

layer deposited on the substrate. To this end, a plurality of deposition

device modules may be arranged so that the continuous web of

substrate material is passed through a series of the devices, each device

contributing to a predetermined thickness of the barrier layer material.

Additionally, the apparatus can be utilized in a first web converting system wherein the barrier layer is, for example, the product contact

layer of the packaging material or in a second web converting system

wherein a further material layer is joined on or over the barrier layer of

the substrate/barrier material after processing by the deposition

apparatus. In either instance, the resulting laminate material may be

taken up onto a rewinder roll for transport and use in subsequent

converting or packaging operations. In accordance with a still further

system utilizing the foregoing apparatus, the apparatus is disposed at

the input of a packaging machine wherein the resulting substrate/barrier

material is transported after the deposition of the barrier layer to the

input of the packaging machine for forming the material into a package

which is both filled and sealed. Other objects, features, and advantages of the present method and apparatus will become apparent on review of the following drawings and accompanying description.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 is a schematic cross-section of a deposition device

constructed in accordance with one embodiment of the present invention.

Fig. 2A is a cross-section side view of one embodiment of a web

inlet suitable for use in the deposition device of Fig. 1 .

Fig. 2B is a cross-section side view of a further web inlet suitable for use in the deposition device of Fig. 1 .

Fig. 3 is a system diagram illustrating the use of a plurality of serially disposed deposition devices of the general type shown in Fig. 1 .

Fig. 4 is a system diagram illustrating one embodiment of a web

handling system for use with a deposition device such as the one set

forth in Fig. 1 .

Fig. 5 is a system diagram of a packaging system employing a

deposition device and web handling system that feeds a material web

directly from the output of a deposition device to the input of a

packaging machine.

Fig. 6 is a system diagram illustrating one embodiment of a

system wherein a further web of material is applied over the barrier layer

of the substrate/barrier material exiting the deposition device using

adhesive lamination.

Fig. 7 is a system diagram illustrating one embodiment of a

system wherein a further layer of material is extruded over the barrier

layer of the substrate/barrier material exiting the deposition device. Figs. 8 and 9 are schematic cross-sections illustrating a further embodiment of the deposition device of the present invention.

Fig. 10 is a schematic cross-section of a deposition device of the type shown in Figs. 8 and 9 and further including a masking apparatus.

Figs. 1 1 and 12 illustrate one embodiment of a heating apparatus which heats the reaction chamber to a desired, reaction temperature.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

With reference to Fig. 1 , there is shown a deposition device 20

constructed in accordance with one embodiment of the present invention. The deposition device 20 includes a web inlet portion 25, a

reaction chamber 30, and a web outlet portion 35. A continuous web

of substrate material 40 extends from a location exterior to the web inlet

portion 25, through reaction chamber 30, to a location exterior to the web outlet portion 35. The continuous web substrate 40 is driven in

the direction illustrated by arrows 45 in a continuous manner or in an

indexed fashion so as to enter the deposition device 20 at the web inlet

portion 25, enter the reaction chamber 30, and exit the deposition

device 20 at the web outlet portion 35. The continuous web of

substrate material 40 may be a single polymer, such as polyethylene

(LDPE, VLDPE, LLDPE, etc.), polyethylene terephthalet (PET), etc., or a

multilayer laminate, for example, a paperboard based material coated

with at least one layer of polyethylene. Numerous polymers and

polymer layer combinations are suitable for use as the web substrate 40.

A known surface treatment, such as corona or flame treatment, may be

performed on the web substrate 40 prior to processing within the

deposition device 20.

A barrier material is deposited on the continuous web of substrate material 40 as it passes through the reaction chamber 30. To this end,

a precursor gas, oxidizing gas, and carrier gas are supplied at a first gas

inlet 50. These gasses are directed through region 55 in the direction indicated by arrow 60 under the guidance of baffle wall 65. Baffle wall 65 terminates in a curved section 70 at an open region where the gasses are deflected in a direction indicated by arrows 80 and 85 over the upper surface 90 of the web 40. The gasses entering the reaction

chamber 30 may be heated, for example, in a manner that will be described below. Although the precursor, oxidizing, and carrier gasses are illustrated as entering the reaction chamber 30 through a single inlet 50, it will be recognized that multiple inlets may be used for communication of these gasses to the reaction chamber 30. An ultraviolet radiation module, shown generally at 100, is disposed to irradiate the web of substrate material 40 and the oxidizing and precursor gasses so as to result in the deposition of a barrier layer

onto the upper surface 90 of the web substrate 40. In the illustrated embodiment, the ultraviolet radiation module 100 includes one or more ultraviolet lamps 102 disposed beneath a reflector hood 103 within a housing 105. Cooling ports (not illustrated) may be used to conduct a cooled air flow through region 107 to cool the reflector hood 103 and UV lamp 102. An ultraviolet transparent window 1 10 is disposed at one end of the housing 105 proximate the upper surface 90 of the web substrate 40. One type of ultraviolet lamp that may be utilized is a model EPIQ 6000 lamp available from FUSION UV Curing Systems of Rockville, Maryland. Such a lamp has a generally broad spectrum extending from 200 nm to 450 nm and has a power output of about

600 Watts/inch. Another type of lamp suitable for use in the present - 12 -

system is an excimer (KrCI) lamp such as one sold by Hereus Noblelight. Such an excimer lamp is characterized by a narrow wavelength

centered, for example, at 222 nm and has a power output of about 170 Watts/inch. The choice of ultraviolet lamp type is principally determined by the absorption spectrum of the precursor and oxidizing gas molecules that have to react with one another and, further, by the absorption

spectrum of the web of substrate material 40.

The precursor and oxidizing gasses react with one another under the influence of the ultraviolet radiation emanating through the window 110. The reactions, however, also take place at the window surface

1 15 as well as at the upper surface 90 of the web 40. To reduce the deposition of the barrier material on the window surface 115, a further flow of carrier gas is introduced through a second gas inlet 120 and an optional third gas inlet 121. This flow of carrier gas is directed through region 125 and is separated from the precursor/oxidizing/carrier gas stream in region 55 by the baffle wall 65. In the illustrated embodiment,

the curved portion 70 assists in directing the carrier gas from region 125 in a direction, illustrated here by arrows 130, across window surface 1 15 to purge the precursor and oxidizing reactants from the region adjacent the window surface 115. A further flow of carrier gas is

directed through inlet 121 and into region 131 in the direction of arrows

132 where it is directed to the window surface 1 15 by further baffle

133 to further assist in separating the flow 85 of the precursor and oxidizing gasses from the flow 130 of the carrier gas. The carrier gas, residual gas, and byproduct gasses ultimately flow into region 135 where they are removed through exhaust outlet 140, for example, to be

released into the atmosphere, to be stored in a containment vessel, to

be separated and recycled, etc.

The pressure within the reaction chamber 30 will typically be

about one atmosphere and, preferably, slightly greater than one

atmosphere. As such, it is necessary to ensure as tight a seal as

possible at the web inlet and outlet portions 25 and 35 while still

allowing the web of substrate material 40 to readily pass therethrough.

To accomplish this, the inlet and outlet portions 45 and 50 may be

provided with a web sealing device 1 50, such as shown in Fig. 2A.

The web sealing device 1 50, shown here at the inlet portion 45, includes a channel guide member 1 55 that extends through a sidewall

1 60 of the reaction chamber module 20. The channel guide member

1 55 is elongated in the direction of web movement and defines a

channel region 1 65 through which the web 40 passes from the liquid

coating module 25 to the reaction chamber module 30. Flexible sealing

members 170 and 175 are disposed at opposite ends of the channel

region 165 and, for example, may be integrally formed with the channel

guide member 155. The flexible sealing members 170 and 175 may be

of sufficient length to contact the upper surface 90 of the web 40 and

urge the web 40 against a lower wall 175 of the channel region 1 65

without significantly disturbing the liquid precursor at the surface 40. ln this manner, the web 35 passes through a generally sealed antechamber (or in the case of a web sealing device at the web exit

portion 55, a generally sealed post-chamber) which assists in isolating the reactant and carrier gasses within the reaction chamber 50 from the atmospheric gases. Such a partial seal also increases the integrity of the barrier layer by reducing the possibility of the entry of contaminants into the reaction chamber 30.

To avoid contamination of the precursor at the surface 40 as it passes between the liquid coating module 25 and the reaction chamber module 30, it may be desirable to have end 187 of the web sealing apparatus 150 sealed with the outlet portion 188 of the liquid coating module 25 (see Fig. 1 ). Similarly, the web inlet 189 to the liquid coating module 25 may be provided with a web sealing device 150. Such modifications are dependent on the particular configuration of the system 20 and may be implemented based on the teachings herein.

Another web sealing device is shown in Fig. 2B. As illustrated,

the web sealing device 177 is disposed through sidewall 160 of the deposition device 20 and includes an upper roller 179 and a lower roller 180 that extend along at least the width of the web 40. The web 40 proceeds between the rollers 179 and 180 and into the interior of the deposition device 20. The edge portions 182 and 184 of the sidewall 160 may be provided with gaskets to further seal the interior of the deposition device 20 from external contaminants. With reference again to Fig. 1 , it is possible to select a precursor gas, oxidizing gas, web material, and web speed that allows the

deposition of the barrier material to take place in the reaction chamber

30 at temperatures about or below 200E C. Depending on the

material(s) used for the web substrate 40, such temperatures may cause

one or more layers of the web substrate 40 to go to a molten state. To

prevent this from occurring, and to facilitate deposition of the barrier

material on the upper surface 90 of the web 40, a cooling table 185 is

provided over which the web substrate 40 is transported as it passes through the reaction chamber 30. The cooling table 185 functions as

a heat sink for the web 40 and, for example, may be cooled by water

tubes or the like extending throughout its interior. Other cooling

mechanisms may likewise be employed to cool the cooling table 185 and/or the web substrate 40.

Fig. 3 illustrates a modular approach to utilizing the deposition

device 20 of Fig. 1 in a system. In the modular system shown in Fig.

2, a plurality of deposition devices 20 are arranged in a serial fashion

along the direction of travel of the web substrate 40. The deposition

devices 20 are connected to a common carrier gas source 195, an

oxidizing gas source 200, and a precursor gas source 205 which

includes a vaporizer for the precursor. Pressure regulating valves 210

are disposed between each of the sources 195, 200, and 205 and their

respective common lines 21 5, 220, and 225. A mass flow controller

230 is disposed between the first gas inlet 50 of each deposition device 20 and the common line 225 carrying the precursor gas. Flowmeters

235 are disposed in the oxidizing gas line 220 to monitor flow of the

oxidizing gas to the first gas inlet 50 of each of the deposition devices 20. Flowmeters 240 are also disposed in each interconnect line 245

that connects the line 21 5 supplying carrier gas to the first gas inlet 50.

Similarly, flowmeters 250 are disposed in line with the second gas inlet

120 to monitor the flow of carrier gas that is used for purging of the window surface 1 1 5 (Fig. 1 ). Flowmeters 252 may also be used to monitor carrier gas flow at inlet 1 21 . Flowmeter information may be in

a digital format suitable for monitoring by a central controller. Similarly,

the mass flow controllers 230 may be of the type that may be digitally controlled monitored by a central controller.

Using the deposition devices 20 in a tandem fashion gives rise to several advantages over the use of a single deposition device. For

example, the tandem deposition devices can provide more accurate

control of the thickness of the barrier layer since a single barrier layer

may be deposited on the web substrate 40 by depositing a series of

thinner layers whose thickness are easier to control. Additionally, the

speed of the web substrate 40 through the deposition devices 20 for a

given barrier layer thickness may be increased for large scale production.

Also, the modular set-up facilitates quick and economical adaptation of

the production line to accommodate for the production of different

packaging materials having different substrate/barrier characteristics.

Further, the process parameters (flows, gas types, irradiation, etc. ) may be different from one module to the next thereby providing a greater

degree of flexibility in forming a multilayer structure coating.

Various web handling systems are suitable for driving the web

substrate through one or more deposition devices. One such system

suitable for initial material production or converting operations is shown

in Fig. 4. As illustrated, the system, shown generally at 260, includes

a web dispenser 265 and web recoil roll 270. The web of substrate material 40 extends between the web dispenser 265 and web recoil roll

270 and through the deposition device 20 in the illustrated manner over

a plurality of idler rollers 275 and dancer rollers 280. Each dancer roller

280 is connected to a tension cylinder 285 that assists in adjusting the tension of the web substrate 40 as it passes through the deposition

device 20.

The web handling system 260 may be controlled by a central

controller 300 which, for example, includes one or both a programmable

logic controller, a programmable axis manager, or other type of

controller capable of controlling an electric motor, such as a servomotor.

The controller 300 receives position information along one or more lines

305 and 310 indicative of the position of dancer rollers 280. This

information is used by the controller 300 to control the speed of motors

31 5 and 320 (i.e., servomotors) which are connected to drive the web

dispenser 265 and web recoil roll 270, respectively, and motor 320

which is connected to output drive roller 325. The controller 300

effects control by sending signals along lines 330, 335, and 340, to maintain the speed of the web 40 through device 20 at the desired rate while further maintaining the tension of web 40 at the requisite tension. Tension of the web 40 may also be monitored using a tension sensor 345 that supplies a signal indicative of tension on the web 40 along one

or more lines 350. Web tension should be chosen to ensure that the barrier material does not crack or otherwise create flaws in the barrier material.

The central controller 300 may also be used to monitor and

control the flow of gases through the deposition device 20 and the temperature within the reaction chamber. To this end, signals indicative of the flow of the respective gasses through the deposition device 20 are provided to the controller along one or more lines 350. The controller 300 also provides output signals along one or more lines 355 to, for example, mass flow controllers and other flow control valves to automatically regulate the supply of gasses in response to the sensed

gas flows. Gas flows may be set to and maintained at a predetermined constant level or dynamically changed in response to barrier layer thickness as monitored, for example, by a barrier thickness sensor 360 that supplies a signal indicative of barrier thickness along one or more lines 365. As will be readily recognized, web speed, tension,

temperatures and gas flows will vary depending on the barrier material,

substrate material, desired barrier material thickness, etc.

The use of one or more deposition devices in a single integrated

packaging system is illustrated in Fig. 5. The packaging system, shown generally at 500, includes a deposition subsystem 510 and a packaging machine 51 5. The deposition subsystem 510 deposits a barrier

material layer on the web substrate 40 and provides the substrate/barrier

material 520 to the input of the packaging machine 515. The packaging

machine 515 may, for example, be a TBA-9J aseptic packaging machine

available from Tetra Pak, Inc. The packaging machine 51 5 receives the

web of substrate/barrier material 520 and forms the material into a container, for example, a brik-type container, that is filled and sealed.

Other packaging machine types may also be utilized, the TBA-97

machine being merely exemplary.

The barrier layer of the web substrate/barrier material need not be the product contact layer of any resulting package found from the

material. Rather, the substrate/barrier material 520 may have a further

material joined to it at the face of the barrier layer. Figs. 6 and 7

illustrate two mechanisms that may be used to join the substrate/barrier material 520 to a further material. In the apparatus of Fig. 6, a web of,

for example, a multilayer material (e.g., paperboard and polymer, multi¬

layer polymer, etc.) or single polymer material 535 proceeds from a web

dispenser 530 and is laminated to the substrate/barrier material 520 as

the substrate/barrier material 520 and material 535 pass between a lay-

on rollers 540 and a heating and combining drum 545. An adhesive

material may be applied to one or both of the materials 520 and 535 in

a known fashion. A known surface treatment, such as corona or flame

treatment, may also be utilized to enhance adhesion between the - 20 -

material surfaces. The resulting laminate packaging material 550 is directed over a plurality of heated rollers 555 to, for example, a recoil roll or a packaging machine.

In the apparatus of Fig. 7, a polymer material 557 is extruded through an extruder 560 onto the barrier layer of the substrate/barrier material 520 in a known manner as it passes between a rubber roller 565 and a pinch roller 570. A known surface treatment, such as corona or flame treatment, may be utilized to enhance adhesion between the material surfaces. The resulting laminate packaging material 575 is directed over a plurality of cooling rollers 580 to, for example, a recoil roll or a packaging machine.

Figs. 8 and 9 illustrate a further embodiment of the deposition device 20. This embodiment principally differs from embodiment of Fig. 1 in the manner of delivering the precursor, oxidizing, and carrier gasses to the reaction chamber 30. In the illustrated embodiment, a mixture of precursor gas, oxidizing gas, and carrier gas is supplied through an inlet pipe 600 to a manifold 605. A plurality of outlet pipes 615 first extend downward from the manifold 605 and then in a direction that is generally parallel to the web of substrate material 40. Each of the outlet pipes 615 of the plurality of outlet pipes terminates in a diffuser 620 that, for example, may include a heating element for heating the gas mixture as it enters the reaction chamber 30. A similar arrangement

including inlet pipe 625, manifold 630, outlet pipes 635, and diffusers 640 are utilized to supply the purging flow of carrier gas over the window surface 1 1 5. The outlet pipes 635 for the purging flow of

carrier gas do not extend as far downward as the outlet pipes 61 5

carrying the gas mixture so as to assist in keeping the flow of the gas

mixture and the flow of purging carrier gas separate.

In accordance with one modification to the deposition device 20

of Figs. 1 and 8, the device of Fig. 10 is provided with an endless belt

mask 640 which facilitates selective exposure of the upper surface 90 of the web substrate 40 to ultraviolet radiation. The endless belt mask

640 is driven, for example, by one or more drive rollers 645 at the same

speed as the web of substrate material 40 and includes a repeating

pattern which only allows the ultraviolet radiation from the ultraviolet energy module 100 to irradiate selected areas of the web substrate 40.

In this manner, only selected portions of upper surface 90 of web

substrate 40 have the barrier layer deposited thereon. Selective deposition is particularly desirable when the barrier layer is to be the

product contact layer of a package formed from the substrate/barrier

material. The portions of upper surface 90 that do not have the barrier

material deposited thereon can be used to provide a heat sealing surface

to facilitate front-to-back and back-to-back heat sealing of the substrate/barrier material.

An alternative selective deposition construction may be used if

the web of substrate material 40 is driven through the deposition device 20 in an indexed manner. In such instance, a mask may be fixed

between the UV energy source and the web of substrate material 40, - 22 -

for example, on the window 1 10. The ultraviolet energy source may then be gated on during the time in which the web dwells beneath the

ultraviolet source and gated off as the web is moved.

As previously described, the gasses flowing into the reaction

chamber 30 may be heated. One manner of heating the gasses to the desired temperature is illustrated in Figs. 1 1 and 12. In the illustrated

embodiment, heated diffusers 705 and 710 are disposed in regions 55

and 65, respectively, and extend along the entire width of the respective

chamber. A diffuser may also be disposed in region 131 in a similar fashion. The diffusers may be heated by passing an electric current therethrough or in any other known manner.

If a barrier layer of SiOx material is desired to be deposited on the

web of substrate material 40, the precursor may be an organic silane

such as tetraethoxysilane (TEOS), triethoxysilane, tetraacetoxysilane, or

a siloxane such as hexamethyldisiloxane (HMDSO). Other silicon

precursors may also be utilized, although organic silanes and organic

siloxanes are preferable since they tend to be safer for use in large scale

processing. The oxidizing gas may, for example, be an oxidizer such as

N₂O or O₂. The carrier gas may be an inert gas such as N₂, Ar, or He.

As previously noted, web speed, gas types, and gas flows are

system dependent. In accordance with one system, a 20 nm silicon

dioxide barrier layer was deposited on a PET substrate. The PET

substrate was 1 2 Fm thick and 30 cm wide. The web speed was set

to 30m/min at a tension of 1 kg and the web was irradiated by three, 1 .7 KW excimer lamps having a narrow spectrum at 222 nm. The distance between the window 1 15 and the surface 90 of the web was set to 1 cm. The reaction gas flows were set to 95 slm of ₂, 9.5 slm N ₂O, and 0.5 slm of HMDSO, through inlet 50. A nitrogen gas flow of 105 slm through inlet 120. The temperature of the precursor gas lines and diffusers 705 and 710 were set to 150EC and the PET was passed over cooling table 185 which was water cooled to 10EC.

While particular elements, embodiments and applications of the present invention have been shown and described, it will be understood, of course, that the invention is not limited thereto since modifications may be made by those skilled in the art, particularly in light of the

foregoing teachings. It is therefore contemplated by the appended claims to cover such modifications as incorporate those features which come within the spirit and scope of the invention.

Claims

What is claimed is:

1. A method of forming a packaging material comprising the steps of: a) providing a continuous web of substrate material; and b) processing the continuous web of substrate material in a continuous process at about atmospheric pressure to form a silicon oxide barrier layer on a surface of the continuous web of substrate material.

2. A method as claimed in Claim 1 wherein the web of substrate material is a multilayer laminate material.

3. A method as claimed in Claim 1 wherein the web of substrate

material is a paperboard based laminate material.

4. A method as claimed in Claim 1 wherein the processing of the

continuous web of substrate material to form the silicon oxide

barrier layer occurs at a temperature below about 200E C.

5. A method of forming a packaging material comprising the steps ! of: a) providing a continuous web of substrate material; I- b) driving the continuous web of substrate material through a deposition apparatus having a reaction chamber through which the continuous web of substrate material passes as it is driven through the deposition apparatus;

c) providing a flow of a silicon precursor gas and oxidizer gas through the reaction chamber, pressure within the reaction chamber being about one atmosphere; and d) exposing the web of substrate material, the precursor gas, and the oxidizer gas to ultraviolet radiation as the continuous web of substrate material is driven through the reaction chamber to thereby provide a silicon-based barrier layer on the continuous web of substrate material.

6. A method as claimed in Claim 5 and wherein the continuous web of substrate material is driven in a continuous manner.

7. A method as claimed in Claim 5 and wherein the continuous web of substrate material is driven in an indexed manner.

8. A method as claimed in Claim 5 wherein the web of substrate material is a multilayer laminate material.

9. A method as claimed in Claim 5 wherein the web of substrate material is a paperboard based laminate material.

10. A method as claimed in Claim 5 wherein the silicon-based barrier layer is both an oxygen barrier layer and a flavor barrier layer of the packaging material.

1 1. A method as claimed in Claim 5 wherein the temperature within the reaction chamber is below about 200E C.

12. A method as claimed in Claim 5 wherein the silicon precursor is a silane and the barrier layer is an SiOx material.

13. A method as claimed in Claim 5 wherein the silicon precursor is a siloxane and the barrier layer is an SiOx material.

14. A method as claimed in Claim 5 and further comprising the step of passing the continuous web of substrate material over a cooling table in the reaction chamber.

15. A method as claimed in Claim 5 wherein the continuous web of substrate material is provided on a roll.

16. A method as claimed in Claim 5 and further comprising the step of extracting the continuous web of substrate material from the deposition apparatus onto a recoil roll.

17. A method as claimed in Claim 5 and further comprising the steps of: a) extracting the continuous web of substrate material from the deposition apparatus; and b) supplying the continuous web of substrate material to a further deposition apparatus as the continuous web of substrate material is extracted from the deposition apparatus.

18. A method as claimed in Claim 5 and further comprising the steps of: a) extracting the continuous web of substrate material from the deposition apparatus; and b) joining the barrier layer of the continuous web of substrate material with a polymer material.

19. A method as claimed in Claim 5 and further comprising the steps of:

a) extracting the continuous web of substrate material from the deposition apparatus; and b) extruding at least one layer of polymer material over the barrier layer of the continuous web of substrate material with a polymer material.

20. A method as claimed in Claim 5 and further comprising the steps of: a) extracting the continuous web of substrate material from the deposition apparatus; and

b) adhesive laminating at least one layer of polymer material over the barrier layer of the continuous web of substrate material with a polymer material.

21 . A method of forming a package comprising the steps of: a) providing a continuous web of substrate material; b) driving the continuous web of substrate material through at least one deposition apparatus having a reaction chamber through which the continuous web of substrate material passes; c) providing a flow of a precursor gas and oxidizer gas through the reaction chamber of the at least one deposition

apparatus, pressure within the reaction chamber being about one atmosphere; d) exposing the continuous web of substrate material, the precursor gas, and the oxidizer gas to ultraviolet radiation

as the continuous web of substrate material is driven through the reaction chamber of the at least one deposition apparatus to thereby provide a barrier layer on the continuous web of substrate material; e) supplying the continuous web of substrate material from the at least one deposition apparatus to a web input of a packaging machine as the continuous web of substrate material exits the at least one deposition apparatus; and f) forming the extracted web of substrate material into a sealed and filled package using the packaging machine.

22. A method as claimed in Claim 21 wherein the precursor is a silicon precursor and the barrier layer is a silicon-based barrier layer.

23. A method as claimed in Claim 22 wherein the precursor is a silane and the barrier layer is an SiOx material.

24. A method as claimed in Claim 22 wherein the precursor is a siloxane and the barrier layer is an SiOx material.

25. A method as claimed in Claim 21 wherein the web of substrate material is a multilayer laminate material.

26. A method as claimed in Claim 21 wherein the web of substrate material is a paperboard based laminate material.

27. A method as claimed in Claim 21 wherein the barrier layer is both an oxygen barrier layer and a flavor barrier layer of the filled package.

28. A method as claimed in Claim 21 wherein the temperature for reactions within the reaction chamber is below about 200E C.

29. A method as claimed in Claim 21 and further comprising the step of passing the web of substrate material over a cooling table in the reaction chamber of the at least one deposition apparatus.

30. A method as claimed in Claim 21 wherein the step of driving the continuous web is further defined by driving the continuous web of substrate material through a plurality of deposition apparati, each having a reaction chamber through which the continuous

web of substrate material passes.

31. A method as claimed in Claim 21 and further comprising the steps

of: a) extracting the continuous web of substrate material from the at least one deposition apparatus; and b) joining the barrier layer of the continuous web of substrate material with a layer of polymer material.

32. A method as claimed in Claim 21 and further comprising the steps

of: a) extracting the continuous web of substrate material from the at least one deposition apparatus; and b) extruding at least one layer of polymer material over the barrier layer of the continuous web of substrate material.

33. A method as claimed in Claim 21 and further comprising the steps

of: a) extracting the continuous web of substrate material from the at least one deposition apparatus; and b) adhesive laminating at least one layer of polymer material

over the barrier layer of the continuous web of substrate material.

34. An apparatus for forming a packaging material, the apparatus comprising: a) a web dispenser supporting a continuous web of substrate

material; b) a deposition apparatus comprising i. a reaction chamber, ii. a web inlet portion for accepting the web of substrate material from the web dispenser into the reaction chamber, iii. an ultraviolet radiation source disposed to radiate ultraviolet light energy into the reaction chamber,

iv. a gas inlet for conducting a flow of a precursor gas, an oxidizing gas, and a carrier gas into the reaction chamber, pressure within the reaction chamber being about one atmosphere, the precursor gas, oxidizing gas, and continuous web of substrate material being exposed to the ultraviolet light energy from the ultraviolet radiation source to thereby cause deposition of a barrier layer on the continuous web of substrate material, v. a web outlet portion for allowing passage of the web of substrate material from the reaction chamber, and

vi. a gas outlet for allowing gases to exit the reaction chamber; and

c) driving means for driving the continuous web of substrate material through the reaction chamber.

35. An apparatus as claimed in Claim 34 wherein the precursor is a silicon precursor and the barrier layer is a silicon-based barrier

layer.

36. An apparatus as claimed in Claim 35 wherein the precursor is a silane and the barrier layer is an SiOx barrier layer.

37. An apparatus as claimed in Claim 36 wherein the precursor is

TEOS.

38. An apparatus as claimed in Claim 36 wherein the precursor is triethoxysilane.

39. An apparatus as claimed in Claim 36 wherein the precursor is

tetraacetoxysilane.

40. An apparatus as claimed in Claim 35 wherein the precursor is a siloxane and the barrier layer is an SiOx barrier layer.

41 . An apparatus as claimed in Claim 40 wherein the precursor is

HMDSO.

42. An apparatus as claimed in Claim 34 wherein the driving means

drives the continuous web of substrate material in a continuous

manner.

43. An apparatus as claimed in Claim 34 wherein the driving means ! drives the continuous web of substrate material in an indexed manner.

44. An apparatus as claimed in Claim 34 wherein the continuous web ! of substrate material is a multilayer laminate material.

45. An apparatus as claimed in Claim 34 wherein the continuous web i of substrate material is a paperboard based multilayer laminate material.

46. An apparatus as claimed in Claim 34 wherein the barrier layer

1 serves as both an oxygen barrier and a flavor barrier layer.

47. An apparatus as claimed in Claim 34 and further comprising . means for heating the reaction chamber.

48. An apparatus as claimed in Claim 45 wherein the temperature in . the reaction chamber is maintained at a temperature below about

200E C.

49. An apparatus as claimed in Claim 34 and further comprising a

2 cooling table disposed in the reaction chamber and in contact with the continuous web of substrate material as it passes through the reaction chamber.

50. An apparatus as claimed in Claim 34 and further comprising:

a) a housing for the ultraviolet radiation source; and b) a window disposed on the housing for passing ultraviolet

radiation therethrough for exposure of the precursor gas,

the oxidizing gas, and the continuous web of substrate

material.

51 . An apparatus as claimed in Claim 50 and further comprising

means for supplying a purging flow of carrier gas to assist in

preventing reaction of the precursor gas and oxidizing gas on a

surface of the window.

52. An apparatus as claimed in Claim 50 and further comprising

means for accepting the continuous web of substrate material

from the deposition apparatus and for disposing a further layer

of material over the barrier layer.

53. An apparatus as claimed in Claim 50 and further comprising a

further deposition apparatus disposed to accept the continuous

web of substrate material from the web outlet portion of the

deposition apparatus.

54. A packaging system comprising: a) a web dispenser supporting a web of substrate material; b) at least one deposition apparatus comprising i. a reaction chamber,

ii. a web inlet portion for accepting the web of substrate material from the web dispenser into the reaction chamber, iii. an ultraviolet energy source disposed to radiate ultraviolet light energy into the reaction chamber,

iv. a gas inlet for conducting a flow of a precursor gas, an oxidizing gas, and a carrier gas into said reaction chamber, pressure within the reaction chamber being about one atmosphere, the precursor gas, oxidizing gas, and web of substrate material being exposed to the ultraviolet light energy from the ultraviolet energy source to thereby cause deposition of a barrier layer on the continuous web of substrate

material, v. a web outlet portion for allowing passage of the web of substrate material from the reaction chamber, and vi. a gas outlet for allowing gases to exit the reaction chamber; and c) driving means for driving the web of substrate material through the reaction chamber; and d) a packaging machine disposed to receive the web of substrate material from the web outlet portion of the at least one deposition apparatus, the packaging machine using the web of substrate material to form a container that is filled with a product.

55. A packaging system as claimed in Claim 54 wherein the precursor is a silicon precursor and the barrier layer is a silicon-based barrier layer.

56. A packaging system as claimed in Claim 55 wherein the precursor is a silane and the barrier layer is an SiOx barrier layer.

57. A packaging system as claimed in Claim 54 wherein the precursor

is TEOS.

58. An apparatus as claimed in Claim 55 wherein the precursor is triethoxysilane.

59. An apparatus as claimed in Claim 55 wherein the precursor is tetraacetoxysilane.

60. A packaging system as claimed in Claim 55 wherein the precursor is a siloxane and the barrier layer is an SiOx barrier layer.

61 . A packaging system as claimed in Claim 60 wherein the precursor is HMDSO.

62. A packaging system as claimed in Claim 54 wherein the driving

means drives the continuous web of substrate material in a continuous manner.

63. A packaging system as claimed in Claim 54 and further comprising: a) a housing for the ultraviolet radiation source; and b) a window disposed on the housing for passing ultraviolet radiation therethrough for exposure of the precursor gas,

the oxidizing gas, and the continuous web of substrate material.

64. A packaging system as claimed in Claim 54 wherein the driving means drives the continuous web of substrate material in an indexed manner.

65. A packaging system as claimed in Claim 63 and further comprising means for supplying a purging flow of carrier gas to assist in preventing reaction of the precursor gas and oxidizing

gas on a surface of the window.

66. A packaging system as claimed in Claim 54 wherein the packaging machine is an aseptic packaging machine.

67. A packaging system as claimed in Claim 66 wherein the packaging machine forms and fills brik-type containers.

68. A packaging system as claimed in Claim 54 and further comprising means for applying at least one layer of material to the barrier layer of the continuous web of substrate material.

69. A packaging system as claimed in Claim 68 wherein the at least one layer of material is a polymer material.

70. A packaging system as claimed in Claim 54 and further comprising laminating means for laminating at least one material layer over the barrier layer of the substrate material.

71 . A packaging system as claimed in Claim 70 wherein the at least one layer of material is a polymer material.

72. A packaging system as claimed in Claim 54 and further ! comprising extruder means for extrusion coating at least one material layer on the barrier layer of the substrate material.

73. A packaging system as claimed in Claim 68 wherein the at least : one layer of material is a polymer material.