TRANSPARENT VAPOR-DEPOSITED FILM
5 Technical Field
[0001] The present invention relates to a vapordeposited
film having a transparent property, and to a
packaging material using the same.
More specifically, it relates to a
0 transparent vapor-deposited film having transparency
and high adhesiveness, and reinforced adhesiveness
with plastic substrates and inorganic oxide vapordeposited
films composed mainly of aluminum oxide,
which is suitable for use as a packaging material to
5 be used for packaging in a wide range of fields
including foods and retort foods, drugs and electronic
parts, as well as to a packaging material using the
same .
Background Art
0 [0002] As wrapping materials for filling and packing
of foods and beverages, chemical products, sundry
goods and the like in the prior art, there have been
developed substrates with gas barrier properties in a
variety of forms that block or shield the passage of
5 oxygen gas, water vapor and the like, in order to
prevent alteration or discoloration of the contents.
[0003] Typical materials that have been proposed are
2
aluminum foil or metal aluminum vapor-deposited films,
that are largely unaffected by temperature or humidity,
and although these exhibit highly stable gas barrier
properties, when they are incinerated as waste after
5 use, they are poorly suited for incineration and are
not easy to dispose of after use, while another
problem is that they have low transparency.
[0004] As a solution it has been attempted, for
example, to use resin films comprising polyvinylidene
10 chloride-based resin, ethylene-vinyl alcohol copolymer
or the like, that have barrier properties that block
or shield the passage of oxygen gas, water vapor and
the like.
However, because polyvinylidene chloride-
15 based resins contain chlorine in the structure, when
they are incinerated as waste after use they generate
harmful chlorine gas, which is undesirable from the
viewpoint of environmental sanitation.
[0005] On the other hand, ethylene-vinyl alcohol
2 0 copolymers have the advantage of both Low oxygen
permeability and low absorption of flavor components,
but when contacted with water vapor their gas barrier
properties are significantly reduced. It is therefore
necessary at the current time to employ a complex
25 layered structure of an ethylene-vinyl alcohol
copolymer as a substrate with a barrier property, in
order to block water vapor, and this tends to increase
3
production cost.
[0006] This has led to development of substrates
having a barrier property comprising a barrier layer
that comprises a thin-film of an inorganic oxide such
as silicon oxide or aluminum oxide, as a plastic with
a gas barrier property, exhibiting a stable high gas
barrier property and having transparency.
In addition, in fields that require hightemperature,
high-pressure retort treatment or
sterilization treatment of foods, drugs and the like,
there has been a desire for substrates having a
barrier property that is not affected by temperature
or humidity and being able stably exhibit higher gas
barrier properties, in order to prevent alteration of
contents and maintain their functions and properties,
and this has spurred development of substrates with
barrier properties, having a multilayer structure
comprising a barrier layer made of a thin-film of an
inorganic oxide such as silicon oxide or aluminum
oxide, and a coating film layer with a gas barrier
property.
[0007] However, plastic substrates that are easily
affected by temperature and humidity easily undergo
dimensional change, and therefore an inorganic oxide
vapor-deposited film layer such as a transparent
silicon oxide thin-film layer or aluminum oxide vapor
deposition layer that is formed thereover cannot
4
easily follow the expansion and contraction that takes
place with dimensional change of the plastic substrate.
Consequently, the phenomenon of interlayer
separation often occurs between the plastic substrate
5 and the inorganic oxide vapor-deposited film layer
such as a transparent silicon oxide thin-film layer or
silicon oxide vapor deposition layer in high
temperature, high humidity environments and the like,
and cracking or generation of pinholes can also occur.
0 As a result, the original barrier performance
is significantly lost, and it is extremely difficult
to retain barrier performance.
[0008] When the aforementioned vapor deposition
method is used to form a transparent vapor-deposited
5 film of an inorganic oxide, such as aluminum oxide, on
a plastic substrate, the method generally employed to
obtain high adhesiveness between the plastic substrate
and the formed vapor-deposited film layer is inline
plasma preprocessing with a parallel flat plate-type
0 apparatus, or modification of the plastic substrate
surface by formation of an undercoat treatment layer
(see PTL 1 and PTL 2, for example).
[0009] However, the commonly used method of inline
plasma processing method with a parallel flat piate-
5 type apparatus described in PTL 1 introduces
functional groups such as hydroxyl or carbonyl groups
into the plastic surface, creating adhesiveness with
5
the vapor-deposited film via the functional groups.
However, when adhesiveness is produced by hydrogen
bonding with hydroxyl groups, the adhesiveness is
notably reduced in the high temperature, high humidity
5 environments required for electronic device use, such
as in the case of electronic paper, because of
destruction of the hydrogen bonds.
Furthermore, since plasma processing merely
passes the film under a plasma atmosphere generated in
10 air, it is currently not possible to achieve
sufficient adhesiveness between substrates and vapordeposited
films.
[0010] Furthermore, the undercoat treatment method
described in PTL 2 is usually carried out by providing
15 an undercoat layer as an adhesive layer on the plastic
film surface, and this increases cost due to a greater
number of steps during the production process.
[ 0011] A technique for improving adhesiveness is
therefore employed, in which the electrode for plasma
20 generation is situated on the substrate side and a
reactive ion etching (RIE) system that generates
plasma is used for preprocessing {PTL 3).
This plasma RIE method produces adhesiveness
by simultaneously generating two effects, a chemical
25 effect that includes introduction of functional groups
onto the surface of the substrate, and the physical
effect of ion etching of the surface causing fly-off
6
of impurities and smoothing.
[0012] In RIE methods, unlike the aforementioned
inline plasma processing, adhesiveness is not
exhibited by hydrogen bonding and therefore no
reduction in adhesiveness is seen in high temperature,
high humidity environments.
However, since RIE methods introduce
functional groups onto the plastic substrate, the
resistance to cold water and hot water that can cause
hydrolysis at the interface has still remained
insufficient. In addition, in order to obtain
sufficient adhesiveness it is necessary for the Ed
value (= plasma density x processing time) to be at or
above a certain value.
In RIE methods as well, it is necessary for
the Ed value (= plasma density * processing time) to
be at or above a certain value in order to obtain
sufficient adhesiveness. An Ed value at or above a
certain value using the same method can be achieved by
increasing the plasma density or lengthening the
processing time, but increasing the plasma density
requires a high output power source, which can
increase damage to the substrate, while lengthening
the processing time can lower productivity {see PTL 4
and Patent Publication 5).
[0013] Furthermore, the following problems may arise,
depending on the film-forming method used in
7
combination with the preprocessing.
In vacuum vapor deposition methods, the thinfilm
formation speed is not slow, but the precision of
thin-film homogeneity is poor, leading to poor yields.
In sputtering, despite satisfactory precision
of thin-film homogeneity, the thin-film forming rate
is very low and productivity is poor.
In thermal CVD processes, a source gas is
oxidized and decomposed by the heat energy of the
substrate to form a thin-film, and they require the
substrate to be at high temperature, and when the
substrate is a plastic film, decomposition and
oxidation of the plastic film can occur, making it
impossible to form a homogeneous thin-film on the
plastic substrate.
[ 0014] In methods of forming a vapor-deposited film
on a plastic substrate that has been subj ected to
preprocessing by conventional preprocessing means,
problems have arisen such as insufficiency of the
barrier property of the inorganic oxide vapordeposited
film formed on the plastic substrate, even
if the substrate with a gas barrier property
previously had resistance to moist heat, or problems
such as insufficiency of adhesiveness between the
vapor-deposited film and the plastic substrate.
[0015] Also, when a vapor-deposited film is formed
by a film forming device combined with the
aforementioned preprocessing, formation of the vapordeposited
film is accomplished in a continuous manner
but without uniform formation of the vapor-deposited
film, and attempts to maintain adhesiveness have
5 resulted in a slower vapor-deposited film-forming
speed and lower productivity.
In addition, when using conventional vapordeposited
films there has been limited success in
obtaining sufficient resistance to moist heat while
0 maintaining adhesiveness.
[0016] A need therefore exists for a transparent
vapor-deposited film having high adhesiveness, that
can solve the problems encountered with plastic
substrates having vapor-deposited films with a barrier
5 property, when an inorganic oxide vapor-deposited film
is formed on the surface of a plastic substrate that
is being transported as described above, and that
allows production of a vapor-deposited film wherein
the vapor-deposited film is reliably bonded even at
0 high film-forming speed, while improv.i ng the
adhesiveness between the plastic substrate surface and
the inorganic oxide vapor-deposited film and stably
exhibiting barrier performance.
In addition, there is a need for a water-
5 resistant adhesive transparent vapor-deposited film
having a vapor-deposited film with reinforced waterresistant
adhesion after hot water treatment at 121° C,
9
60 min, on a plastic substrate having a vapordeposited
film with a barrier property, wherein the
adhesiveness between the film and the inorganic oxide
vapor deposition layer is not decreased after hot
5 water treatment at 121°C, 60 min.
There is additional need for a highly
adhesive transparent vapor-deposited film with
resistance to moist heat, on a plastic substrate
having a vapor-deposited film with a barrier property,
10 the vapor-deposited film being such that a sufficient
gas barrier property is maintained and the
adhesiveness between the film and the inorganic oxide
vapor deposition layer is not reduced, even after
storage for 500 hours in an environment of 60°C x 90%
15 RH (a high temperature, high humidity environment).
There is yet further need for a transparent
vapor-deposited film that is suitable for retort
purposes .
Citation List
20 Patent literature
[0017]
[PTL 1] Japanese Unexamined Patent Application
Publication HEI No. 7-233463
[PTL 2] Japanese Unexamined Patent Application
25 Publication No. 2000-43182
[PTL 3] Japanese Unexamined Patent Application
Publication No. 2005-335109
10
[PTL 4] Japanese Patent Publication No. 4461737
[PTL 5] Japanese Patent Publication No. 4135496
Summary of Invention
Technical Problem
5 [0018] The present invention has been accomplished
in light of the problems mentioned above, and its
object is to provide a highly adhesive transparent
vapor-deposited film that has excellent homogeneity
and excellent adhesiveness between the plastic
0 substrate and the vapor-deposited film, and can
exhibit barrier performance, humidity-resistant
barrier performance and prolonged storage stability,
without being affected by the temperature and humidity
of the vapor-deposited film even when the barrier
5 layer is formed while conveying the substrate at high
speed, as well as a highly adhesive transparent vapordeposited
film that allows stable formation of a
vapor-deposited film in terms of the production method,
and that can improve productivity.
0 Solution to Problem
[0019] In order to achieve this object, the
invention produces a highly adhesive transparent
vapor-deposited film with reinforced adhesiveness at
the interface between the plastic substrate and the
5 inorganic oxide vapor-deposited film, by using a
continuous vapor-deposited film forming device wherein
a preprocessing chamber containing a specific plasma
11
preprocessing device and a film-forming chamber are
separated, for plasma processing of the plastic
substrate by a plasma preprocessing device that
differs from conventional RIE plasma processing,
5 wherein the inorganic oxide vapor-deposited film that
is composed mainly of aluminum oxide being formed
continuously and at high speed {360 m/min-10 0 0 m/min)
on the plasma preprocessing side.
[0020] According to the invention, plasma
0 preprocessing of a plastic substrate is carried out on
the surface of a preprocessing roller under reduced
pressure using a specific plasma preprocessing device,
and a roller-type continuous vapor-deposited film
forming device is used in a continuous manner to form
5 an inorganic oxide vapor-deposited film on the
preprocessed surface of the plastic substrate formed
by the plasma processing, over a film-forming roller,
to form an inorganic oxide vapor-deposited film
containing Al-C covalent bonds at the lamination
0 interface between the plastic film and the inorganic
oxide vapor-deposited film that is composed mainly of
aluminum oxide, and a highly adhesive transparent
vapor-deposited film is obtained that has reinforced
adhesiveness between the plastic substrate and the
5 inorganic oxide vapor-deposited film.
Also, an inorganic oxide vapor-deposited film
containing Al-C covalent bonds at the lamination
12
interface between the plastic film and the inorganic
oxide vapor-deposited film that is composed mainly of
aluminum oxide is formed, to obtain a water-resistant
adhesive transparent vapor-deposited film that has
5 adhesiveness between the plastic substrate and the
inorganic oxide vapor-deposited film even after hot
water treatment, wherein the bonding strength between
the plastic substrate and the vapor-deposited film is
3.0 N/15 mm or greater based on measurement of the
10 lamination strength after hot water treatment at 121°C,
60 min.
In addition, by laminating a coating film
with resistance to moist heat and a gas barrier
property on the formed vapor-deposited film, to form
15 an inorganic oxide vapor-deposited film containing Al-
C covalent bonds at the lamination interface between
the plastic substrate and the inorganic oxide vapordeposited
film that is composed mainly of aluminum
oxide, there is obtained a highly adhesive transparent
20 vapor-deposited film having adhesiveness between the
plastic substrate and the inorganic oxide vapordeposited
film even in high temperature, high humidity
environments and having a bonding strength of 3.0 N/15
mm or greater based on measurement of the lamination
25 strength after storage for 5 00 hours in an environment
at 60°C * 90% RH.
[0021] The highly adhesive transparent vapor13
deposited film of the invention is produced in a
manner that requires using a conventionally known RIE
plasma processing device, or a roller-type continuous
plasma preprocessing device incorporating plasma
5 preprocessing means different from RIE processing, for
plasma preprocessing, and forming a vapor-deposited
film.
Furthermore, the plasma preprocessing
structure has a plasma preprocessing roller that
0 conveys a substrate, and plasma supply means and
magnetism forming means facing the preprocessing
roller, the plasma being formed on the substrate
surface and concentrated, with a gap to entrap the
plasma, wherein the supplied plasma source gas is
5 introduced as plasma near the substrate surface, while
the plastic substrate is subjected to plasma
preprocessing by a roller-type plasma preprocessing
device that allows plasma preprocessing while holding
it with a desired voltage applied between the plasma
0 preprocessing roller and the plasma supply means.
[002 2] The invention employs a roller-type
continuous vapor-deposited film forming device having
a structure in which a roller-type plasma
preprocessing device and a roller-type vapor-deposited
5 film forming device that forms an inorganic oxide
vapor-deposited film on the substrate surface that has
been plasma processed by the preprocessing device, are
14
provided in series, wherein low-temperature plasma is
used to maintain a powerful plasma state on the plasma
processing section while forming a powerful magnetic
field, and the substrate surface of a plastic material
5 or the like is treated with the plasma to form a
treated surface on the plastic substrate, after which
an inorganic oxide vapor-deposited film that is
composed mainly of aluminum oxide is formed on the
treated surface of the plastic substrate.
0 [0023] Furthermore, it was found that by forming an
inorganic oxide vapor-deposited film that is composed
mainly of aluminum oxide after the plasma
preprocessing, using a continuous vapor-deposited film
forming device that separately comprises a
5 preprocessing chamber where a plasma preprocessing
device of the invention is provided, and a filmforming
chamber, it is possible for the highly
adhesive transparent vapor-deposited film of the
invention to have Al-C covalent bonds reliably formed
0 at the interface between the plastic substrate and the
inorganic oxide vapor-deposited film that is composed
mainly of aluminum oxide, thereby reinforcing the
adhesiveness between the vapor-deposited film and the
plastic substrate by the bonded structure containing
5 Al-C covalent bonds, and obtaining a layered
transparent vapor-deposited film.
[0024] The roller-type continuous vapor-deposited
15
film forming device that produces a highly adhesive
transparent vapor-deposited film of the invention is a
multiple roller-type continuous vapor-deposited film
forming device comprising a pressure reduction chamber,
conveying means that transports the substrate in the
pressure reduction chamber, means that separates the
pressure reduction chamber interior into at least a
preprocessing chamber and a film-forming chamber, a
preprocessing roller provided in the pressure
reduction chamber for at least plasma processing of
the taken-up substrate, a plurality of substrate
processing rollers including a film-forming roller for
film formation of a vapor-deposited film on the
preprocessed surface of the substrate, plasma
preprocessing means comprising plasma supply means
that supplies a plasma source gas composed of oxygen,
nitrogen, carbon dioxide gas or a mixture of one or
more of these with argon and magnetism forming means,
and vapor-deposited film-forming means for forming a
vapor-deposited film on the p]asma-preprocessed
substrate surface.
Also, the highly adhesive transparent vapordeposited
film of the invention can be produced by
using a roller-type continuous vapor-deposited film
forming device, the roller-type continuous vapordeposited
film forming device having a roller-type
plasma preprocessing device, with a plasma
16
preprocessing structure having a plasma preprocessing
roller and plasma supply means and magnetism forming
means facing the preprocessing roller, disposed across
a gap to entrap the plasma, the supplied plasma source
5 gas being introduced as plasma near the substrate
surface, and plasma being formed in a concentrated
manner on the surface of the plastic substrate,
thereby allowing plasma preprocessing while holding it
with a voltage applied between the plasma
0 preprocessing roller and the plasma supply means.
According to the invention, it is possible to
produce a highly adhesive transparent vapor-deposited
film having Al-C covalent bonds at the interface
between the plastic substrate and the inorganic oxide
5 vapor-deposited film that is composed mainly of
aluminum oxide in the transparent vapor-deposited film,
and with more reinforced adhesiveness between the
plastic substrate and the inorganic oxide vapordeposited
film, compared to the prior art.
0 [0025] As a result, the invention not only
reinforces the adhesiveness between the plastic
substrate surface and the inorganic oxide vapordeposited
film that is composed mainly of aluminum
oxide in the highly adhesive transparent vapor-
5 deposited film, improving the gas barrier property and
preventing cracking, but also helps prevent detachment
even after heat treatment such as retort treatment.
17
In addition, the processing system allows
processing at high speed (3 60 m/min-10 0 0 m/min), since
the preprocessing and film-forming processing can be
carried out continuously in a roller-type system.
5 [0026] When a thin-film is to be formed to a high
thickness with a single film forming device, the thinfilm
becomes fragile due to stress and cracking is
also generated, notably lowering the gas barrier
property or causing detachment of the thin-film during
0 conveyance or during take-up, and therefore according
to the invention a plurality of film forming devices
may be provided to obtain a thick layer of the barrier
thin-film, for multiple formation of thin-films of the
same substance.
5 In addition, according to the invention, a
plurality of film forming devices may be used to form
thin-films of different materials, in which case it is
possible to obtain a multilayer film imparted with not
only a barrier property but also various other
0 functions.
[0027] The plasma preprocessing device for
production of a transparent vapor-deposited film
according to the invention comprises plasma
preprocessing means including plasma supply means and
5 magnetism forming means, and a preprocessing roller
for plasma preprocessing of the substrate surface
while conveying the substrate.
18
[ 0 02 8] For plasma preprocessing, the plasma supply
means supplies a plasma source gas comprising an inert
gas such as argon as a plasma source gas that does not
form a coating film, and oxygen, nitrogen, carbon
5 dioxide gas, ethylene or the like, or a mixed gas of
one of more of these gas components, as an active gas
component.
[0029] The plasma source gas used may be one type of
inert gas alone, or a mixture with one or more active
0 gases. Preferably, a mixed gas of an inert gas such
as argon and an active gas is supplied to the plasma
supply means.
[ 0030] The plasma supply means is set at a position
opposite the plasma preprocessing roller and functions
5 as a counter electrode, while a high-freguency voltage
is applied between the counter electrode and
preprocessing roller by a plasma power source to form
plasma, and the plasma is supplied near the supply
port of the plasma supply means with plasma being
0 introduced into the substrate surface treatment region.
[0031] The gas supply means is mounted on the
counter electrode side provided facing the
preprocessing roller that conveys the substrate, and
it supplies gas toward the substrate surface.
5 [0032] The magnetism forming means forms a magnetic
field in order to create concentrated plasma on the
plastic substrate surface and hold the plasma while
19
facilitating discharge, and a magnet is set at a
location opposite the preprocessing roller in the
plasma preprocessing chamber. The magnetism forming
means is set so as to combine the use of the counter
5 electrode and plasma supply means with the magnet, for
suitable concentration of the plasma in an efficient
manner on the substrate surface.
[ 0033] The plasma preprocessing means of the
invention is configured so that a limited and
0 surrounded gap is formed by the counter
electrode/plasma supply means composing the plasma
preprocessing means, the magnetism forming means and
the preprocessing roller, in order to create plasma
from the supplied plasma source gas and form plasma in
5 a concentrated manner near the plastic substrate being
conveyed over the surface of the plasma preprocessing
roller, the plasma being trapped within the space of
the gap, forming a plasma preprocessing region at the
plastic substrate surface where the plasma density is
0 increased and also controllable,
[0034] The plasma power source applies an
alternating current voltage with a frequency of from
10 Hz to 50 MHz between the counter electrode, with
the plasma preprocessing roller set as the ground
5 level, and accomplishes input power control or
impedance control.
The plasma preprocessing roller set on the
20
electrical ground level may also be set on the
electrical floating level.
[003 5] According to the invention, a power source is
connected between the plasma preprocessing roller and
5 the plasma supply means, forming a condition in which
a desired voltage is applied between them, and a pulse
voltage of 2 0 0-1000 volts as the applied voltage is
applied to the power source.
By superposing a direct-current voltage with
0 a negative voltage of minus several hundred volts with
the applied pulse voltage it is possible to perform
maintenance of the electrode surface in the plasma,
and this improves the pox-jer efficiency while allowing
efficient plasma preprocessing to be accomplished.
5 [0036] According to the invention, specifically, the
discharge impedance is increased by widening the
distance between the plasma preprocessing roller and
the counter electrode/plasma supply means which are
situated as a pair. As a result, with application of
0 constant power, the discharge voltage is high and the
discharge current is low, such that the plasma ion
implantation effect is increased and a highly adhesive
film can be formed.
[0037] Also, the flux density by the magnetism
5 forming means is from 100 gauss to 10,000 gauss, and
application of a magnetic field to the plasma traps
the plasma near the surface of the plastic substrate,
21
and when held there it has reduced loss due to exhaust
and seal leakage from the partitions, allowing
preprocessing to be carried out at high efficiency
with the desired plasma strength.
[0038] A plasma power source is supplied to the
counter electrode side in the plasma preprocessing
device, but there is no limitation to this, and a
plasma power source may instead be applied only to the
plasma preprocessing roller, or the plasma power
source may be supplied to both the plasma
preprocessing roller and the counter electrode. Also,
while the magnet is shown placed on the counter
electrode side in the attached drawings, this is not
limitative, and the magnet may instead be placed only
at the plasma preprocessing roller, or the magnet may
be placed at both the preprocessing roller and the
counter electrode.
[003 9] The highly adhesive transparent vapordeposited
film of the invention is a highly adhesive
vapor-deposited film having a vapor-deposited film on
a substrate, with a bonded structure at the interface
between the plastic substrate and the vapor-deposited
film that contains Al-C covalent bonds, wherein the
vapor-deposited film has reinforced adhesiveness
achieved by controlling the abundance of Al-C covalent
bonds so as to be between 0.3% and 30% of the total
bonds that include C, as measured by X-ray
22
photoelectron spectroscopy (measuring conditions: Xray
source: AlKot, X-ray output: 120W) .
[0040] In addition, there is obtained a highly
adhesive transparent vapor-deposited film that has
5 much more reinforced adhesiveness than the prior art
and is transparent as well as resistant to moist heat,
with reinforced adhesiveness between the plastic
substrate and the vapor-deposited film achieved by
control so that the Al/O ratio of the inorganic oxide
0 vapor-deposited film that is composed mainly of
aluminum oxide from the interface between the film and
the vapor-deposited film up to 3 nm toward the surface
of the vapor-deposited film is no greater than 1.0.
The present invention has the following
5 features.
1. A transparent vapor-deposited film having
at least a laminar structure with an inorganic oxide
vapor-deposited film that is composed mainly of
aluminum oxide formed on the surface of a plastic
0 substrate, the transparent vapor-deposited film
containing Al-C covalent bonds at the interface
between the plastic substrate and the inorganic oxide
vapor-deposited film that is composed mainly of
aluminum oxide.
5 2. A transparent vapor-deposited film
according to 1. above, wherein a metal alkoxide
hydrolyzable product and a water-soluble polymer mixed
23
solution are coated onto the vapor-deposited film
surface and heat-dried to produce a gas barrier
coating film.
3. A transparent vapor-deposited film
5 according to 1. or 2 . above, wherein the bonding
strength between the plastic substrate and the vapordeposited
film is at least 3.0 N/15 millimeters based
on measurement of the lamination strength after
storage for 50 0 hours in an environment of 60°C * 90%
0 RH.
4. A transparent vapor-deposited film
according to 1. or 2. above, wherein the bonding
strength between the plastic film and the vapordeposited
film is at least 3 N/15 mm based on
5 measurement of the lamination strength after hot water
treatment at 121°C, 60 min.
5. A transparent vapor-deposited film
according to any one of 1. to 4. above, wherein the
abundance of Al-C covalent bonds is between 0.3% and
0 30% of the total bonds that include C, based on
measurement by X-ray photoelectron spectroscopy
(measuring conditions: X-ray source: AlKa, X-ray
output: 120W), and the Al/O ratio of the inorganic
oxide vapor-deposited film that is composed mainly of
5 aluminum oxide from the interface between the plastic
substrate and the vapor-deposited film up to 3 nm
toward the surface of the vapor-deposited film is no
24
greater than 1.0.
6. A transparent vapor-deposited film
according to any one of 1. to 5. above, wherein the
vapor-deposited film containing Al-C covalent bonds is
formed by holding the surface of the plastic substrate
in a voltage-applied state between the plasma
preprocessing roller and the plasma supply means for
plasma preprocessing, and then continuously forming an
inorganic oxide vapor-deposited film that is composed
mainly of aluminum oxide.
7. A transparent vapor-deposited film
according to 6. above, wherein the plasma
preprocessing is plasma preprocessing using a rollertype
continuous vapor-deposited film forming device
comprising a preprocessing chamber in which the
surface of a plastic substrate to be provided with a
vapor-deposited film is subjected to plasma processing
and a film-forming chamber in which the vapordeposited
film is formed, which are provided in a
continuous manner, the plasma preprocessing having a
construction in which there are situated a
preprocessing roller, and plasma supply means and
magnetism forming means facing the preprocessing
roller, the supplied plasma source gas is introduced
as plasma near the substrate surface, with a gap being
formed that traps the plasma, and plasma processing is
carried out while holding in a voltage-applied state
25
between the plasma preprocessing roller and the plasma
supply means.
8. A transparent vapor-deposited film
according to 6. or 7. above, wherein the preprocessing
5 by plasma is processing in which the surface of the
plastic substrate on which the vapor-deposited film is
to be provided is processed using a roller-type
continuous vapor-deposited film forming device having
a separated plasma preprocessing chamber and vapor-
0 deposited film-forming chamber, under conditions with
a plasma strength per unit area of 100-8000W - sec/m2.
9. A transparent vapor-deposited film
according to any one of 6. to 8. above, wherein the
plasma source gas is argon alone, and/or a mixed gas
5 with one or more from among oxygen, nitrogen and
carbon dioxide gas.
10. A transparent vapor-deposited film
according to 9. above, wherein the preprocessing with
plasma is carried out using a plasma source gas
0 comprising a mixed gas of argon and one or more from
among oxygen, nitrogen and carbon dioxide gas.
11. A transparent vapor-deposited film
according to any one of 1. to 10. above, wherein the
means for forming the vapor-deposited film is physical
5 vapor deposition.
12. A transparent vapor-deposited film
according to any one of 1. to 11., wherein the
26
inorganic compound is an inorganic oxide composed
mainly of aluminum oxide, or a mixture thereof.
13. A transparent vapor-deposited film
according to 12. above, wherein the inorganic oxide is
5 an inorganic oxide mixture of aluminum oxide with one
or more selected from among silicon oxide, magnesium
oxide, tin oxide and zinc oxide.
14. A transparent vapor-deposited film
according to any one of 1. to 13., wherein an aluminum
10 oxide vapor deposition layer is formed to a thickness
of 5-10 0 nm on at least one surface of the plastic
substrate.
15. A packaging material according to any one
of 1. to 14. above, wherein a heat-sealable
15 thermoplastic resin is layered as an innermost layer
via an adhesive layer.
16. A packaging material according to any one
of 2. to 14. above, wherein after forming a printed
layer on the gas barrier coating film, a heat-sealable
20 thermoplastic resin is layered as an innermost layer
via an adhesive layer.
17. A packaging material according to 15. or
16., wherein the heat-sealable thermoplastic resin is
a heat-sealable thermoplastic resin with a light-
25 shielding property.
18.. A packaging material according to any one
of 1. to 17. above, wherein the packaging material is
27
to be used in a package for boiling or retort
sterilization.
19. A packaging material according to any one
of 1. to 17., wherein the packaging material is to be
5 used in a daily commodity such as a shampoo, rinse or
rinse-in-shampoo, or in a cosmetic package or liquid
soup package.
Advantageous Effects of Invention
[0041] The highly adhesive transparent vapor-
0 deposited film of the invention allows formation of
Al-C covalent bonds that could not be formed by
conventional plasma processing, and is an inorganic
oxide vapor-deposited film that is composed mainly of
aluminum oxide, formed on a plastic substrate by
5 laminar bonding that includes Al-C covalent bonds, or
further having a coating film with hot water
resistance and a gas barrier property on the formed
vapor-deposited film, and it is therefore possible to
obtain a highly adhesive transparent vapor-deposited
0 film having vastly reinforced adhesiveness, waterresistant
adhesiveness and moist heat-resistant
adhesiveness between the plastic substrate and the
vapor-deposited film, compared to the prior art, and
excellent transparency.
5 The vapor-deposited film of the invention is
a moist heat-resistant, transparent vapor-deposited
film having a bonding strength of at least 3.0 N/15 mm
28
between the plastic substrate and the vapor-deposited
film, based on measurement of the lamination strength
after storage for 500 hours in an environment of 60 °C
* 90% RH, vastly reinforced moist heat-resistant
adhesiveness over the prior art, and also excellent
transparency.
The vapor-deposited film of the invention is
also a water-resistant adhesive transparent vapordeposited
film having a bonding strength of at least
3.0 N/15 mm between the plastic substrate and the
vapor-deposited film, based on measurement of the
lamination strength after hot water treatment at 121°C,
60 rain, vastly reinforced water-resistant adhesiveness
over the prior art, and also excellent transparency.
[0042] According to the invention, during formation
of a layer of an inorganic oxide vapor-deposited film
that is composed mainly of aluminum oxide, a voltage
is applied to the surface of the plastic substrate
that passes through a limited gap formed by a
preprocessing roll, plasma supply means and magnetism
forming means, while supplying inert argon plasma and
active gas plasma with increased activity, from the
plasma supply means during preprocessing. This forms
plasma on the plastic substrate surface in a
concentrated manner, conducting plasma processing
using a specific plasma preprocessing device that can
perform plasma preprocessing of the substrate surface
29
in an effective manner at a desired plasma strength,
and can accomplish plasma processing and form a vapordeposited
film on the plastic substrate in a
continuous manner using a roller-type continuous
5 vapor-deposited film forming device that comprises a
plasma preprocessing device and a vapor-deposited film
forming device, the device being a roll-to-roll type
having a preprocessing roll and film-forming roll
provided in series, thereby forming a bonded structure
0 at the interface between the plastic substrate and the
vapor-deposited film, so that Al-C covalent bonds
capable of maintaining and reinforcing adhesiveness
even under high temperature, high humidity
environments are reliably created in the inorganic
5 oxide vapor-deposited film.
Furthermore, the abundance of the Al-C
covalent bonds can be controlled to between 0.3% and
30% of the total bonds that include C, based on
measurement by X-ray photoelectron spectroscopy. In
0 addition, the plasma ion implantation effect on the
substrate can be modified to form a vapor-deposited
film on the plastic substrate with reduced damage to
the substrate.
As a result, the adhesiveness between the
5 plastic substrate and vapor-deposited film is
reinforced compared to the prior art and it is
possible to minimize the characteristic tint of the
30
inorganic oxide vapor-deposited film, to obtain a
highly adhesive transparent vapor-deposited film
having an excellent balance between vapor-deposited
film bonding strength and transparency.
5 [0043] The present invention employs a roll-to-roll
type continuous vapor-deposited film forming device
comprising a specific plasma preprocessing device for
formation of a vapor-deposited film, whereby a
preprocessed surface is obtained to allow reliable
0 formation of Al-C covalent bonds that reinforce
adhesiveness at the interface between the plastic
substrate and the inorganic oxide vapor-deposited film
that is composed mainly of aluminum oxide, while an
inorganic oxide vapor-deposited film is continuously
5 formed on the preprocessed surface and a coating film
with hot water resistance and a gas barrier property
is continuously layered on the formed vapor-deposited
film, thereby allowing formation of an adhesive vapordeposited
film containing Al-C covalent bonds at the
0 interface between the plastic substrate and the vapordeposited
film, forming a vapor-deposited film with
more reliably reinforced adhesiveness than the prior
art in a high-speed and stable manner that has not
been achievable by prior art processing, to allow
5 production of a highly adhesive transparent vapordeposited
film with excellent adhesiveness, excellent
productivity and resistance to moist heat.
31
The packaging material of the invention can
exhibit satisfactory performance even when storing
various contents such as water, curry or soy sauce.
Brief Description of Drawings
5 [0044] Fig. 1 is a cross-sectional view showing an
example of a highly adhesive transparent vapordeposited
film of the invention.
Fig. 2 is a cross-sectional view showing
another example of a highly adhesive transparent
10 vapor-deposited film of the invention.
Fig. 3 is a diagram of a continuous vapordeposited
film forming device which forms a vapordeposited
film as a highly adhesive transparent vapordeposited
film of the invention.
15 Description of Embodiments
[0045] A vapor-deposited film according to an
embodiment of the invention, and a film forming device
for formation of the vapor-deposited film, will now be
described in detail with reference to the accompanying
20 drawings. This example is merely for illustration and
is not intended to limit the invention in any way.
Fig. 1 and Fig. 2 are cross-sectional views
showing examples of a highly adhesive transparent
vapor-deposited film as a vapor-deposited film formed
25 according to the invention, and Fig. 3 is a diagram
schematically showing the construction of a rollertype
continuous vapor-deposited film forming device
32
that forms a vapor-deposited film as a highly adhesive
transparent vapor-deposited film of the invention.
The gas barrier coating applicator, for formation of a
highly adhesive transparent vapor-deposited film
5 coated with a layer of a coating film with resistance
to moist heat and a gas barrier property, is situated
in a continuous manner with the vapor-deposited film
forming device, but because it is a publicly known
roller coating applicator that is provided, it is not
0 shown here.
[0046] As shown in Fig. 1, the transparent vapordepo
si ted film A of the invention is a transparent
vapor-deposited film having a basic laminar structure
wherein, by forming an inorganic oxide vapor-deposited
5 film that is composed mainly of aluminum oxide 2 on
the surface of a plastic substrate 1 which is a
biaxially stretched plastic substrate, one side of
which has been subj ected to plasma preprocessing using
a roller-type continuous vapor-deposited film forming
0 device utilizing plasma as shown in Fig. 3, an
inorganic oxide vapor-deposited film containing Al-C
covalent bonds based on measurement by X-ray
photoelectron spectroscopy (hereunder abbreviated as
"XPS measurement") is formed at the interface between
5 the surface of a plastic substrate and the inorganic
oxide vapor-deposited film.
[004 7] The materials used in the transparent vapor33
deposited film of the invention, the method for
producing the highly adhesive transparent vapordeposited
film of the invention, and the apparatus
used therefor, will now be described as examples of
5 the invention.
[0048] The plastic substrate to be used in the
transparent vapor-deposited film of the invention is
not particularly restricted, and a publicly known
plastic film or sheet may be used.
0 Examples of films or sheets include films or
sheets of polyester-based resins such as polyethylene
terephthalate (PET) and polyethylene naphthalate (PEN),
polyamide-based resins such as polyamide resin 6,
polyamide resin 66, polyamide resin 610, polyamide
5 resin 612, polyamide resin 11 and polyamide resin 12,
and polyolefin-based resins such as a-olefin polymers
including polyethylene and polypropylene.
[0049] According to the invention, the plastic
substrate film or sheet of the resin may employ one or
0 more of these resins, and it may be produced using an
extrusion method, cast molding method, T-die method,
cutting method, inflation method or other film-forming
method, or one or two or more different resins may be
used for co-extrusion of a multilayer in the film-
5 forming method, or two or more different resins may be
used as a mixture prior to film formation, as the
film-forming method.
34
In addition, it may be stretched in the
uniaxial or biaxial direction using a tenter system or
tubular system.
[ 0 05 0] When one or more resins are used for film
5 formation, various plastic mixtures or additives may
also be added for the purpose of, for example,
improving or modifying the workability, heat
resistance, weather resistance, mechanical properties,
dimensional stability, oxidation resistance,
0 slidability, releasability, flame retardance, mold
resistance, electrical properties, strength or other
properties of the film, in which case they may be
added as desired, from very trace amounts to several
tens of percent, according to the purpose.
5 [0051] Examples of common additives to be used
include lubricants, crosslinking agents, antioxidants,
ultraviolet absorbers, light stabilizers, fillers,
reinforcing agents, antistatic agents, pigments and
the like, as well as modifier resins.
0 [0052] There are no particular restrictions on the
thickness of the plastic substrate film or sheet of
the invention, and it may be sufficient so as to allow
preprocessing or film-forming processing during
formation of the vapor-deposited film by the roller-
5 type continuous vapor-deposited film forming device of
the invention, although it is preferably 6 to 400 urn
and more preferably 12 to 200 um from the viewpoint of
35
flexibility and form retention.
If the thickness of the substrate is within
this range, it will be easily bendable and manageable
with the continuous vapor-deposited film forming
5 device of the invention, without tearing during
conveyance.
[ 005 3] An inorganic oxide vapor-deposited film layer
used to compose a highly adhesive transparent vapordeposited
film according to the invention will now be
0 described.
[0054] According to the invention, during formation
of the inorganic oxide vapor-deposited film layer, the
surface of the plastic substrate film or sheet must be
subjected to preprocessing with the plasma processing
5 device using plasma, as preprocessing, in order to
improve adhesiveness with the inorganic oxide vapordeposited
film layer.
According to the invention, the plasma
preprocessing is carried out as a method for
0 reinforcing and improving adhesiveness between the
film or sheet of different resins and the inorganic
oxide vapor-deposited film, over the prior art.
[0055] As shown in Fig. 3, the roller-type
continuous vapor-deposited film forming device 1 of
5 the invention has partitions 35a~35c formed in a
pressure reduction chamber 12. The partitions 35a-3 5c
form a- substrate conveying chamber 12A, a plasma
36
preprocessing chamber 12B and a film-forming chamber
12C, and particularly they form a plasma preprocessing
chamber 12B and a film-forming chamber 12C as spaces
surrounded by the partitions 35a-35c, with each
5 chamber having an exhaust chamber formed therein if
necessary.
[0056] In the plasma preprocessing chamber 12B, the
substrate S to be preprocessed is conveyed, with the
plasma processable section of the plasma preprocessing
10 roller 2 0 being exposed into the substrate conveying
chamber 12A, and the substrate S is taken up while
being transferred from the substrate conveying chamber
12A into the plasma preprocessing chamber 12B.
[0057] The plasma preprocessing chamber 12B and
15 film-forming chamber 12C are provided in contact with
the substrate conveying chamber 12A, so that the
substrate S can be transferred without contacting air.
The preprocessing chamber 12B and the substrate
conveying chamber 12A are connected by a rectangular
20 hole, a section of the plasma preprocessing roller 2 0
protruding outward through the rectangular hole toward
the substrate conveying chamber 12A side, and a gap is
opened between the walls of the conveying chamber and
the preprocessing roller 20, the substrate S being
25 transferable from the substrate conveying chamber 12A
to the film-forming chamber 12C through the gap. The
same structure is provided between the substrate
37
conveying chamber 12A and the film-forming chamber 12C,
allowing the substrate S to be transferred without
contacting air.
[ 005 8] The substrate conveying chamber 12A is
provided with a take-up roller as take-up means for
taking up into a roll form the substrate S on which
the vapor-deposited film has been formed on one side
and that has been transferred back into the substrate
conveying chamber 12A by the film-forming roller 25,
and this allows the vapor-deposited film-formed
substrate S to be taken up.
[0059] In the pressure reduction chamber 12 there is
provided a vacuum pump via a pressure-adjusting valve,
and it can reduce the pressure throughout the entire
substrate conveying chamber 12A, plasma preprocessing
chamber 12B and film-forming chamber 12C that are
divided by the partitions 35a-3 5c.
[00 60] During production of the transparent vapordeposited
film of the invention, the plasma
preprocessing chamber divides the plasma-generated
space into another region and allows efficient
evacuation of the opposing space, thereby easily
controlling the plasma gas concentration and improving
productivity. The preprocessing pressure resulting
from pressure reduction is preferably set and
maintained at about 0.1 Pa to 100 Pa.
[00 61] A plasma preprocessing roller 20 is situated
38
straddling the substrate conveying chamber 12A and the
plasma preprocessing chamber 12B, and guide rolls 14a,
14b are provided between the wind-out roll 13 and the
plasma preprocessing roller 20.
5 Also, a film-forming roller 25 is situated in
the film-forming chamber 12C, and guide rolls 14c, 14d
are provided between the plasma preprocessing roller
20 and the film-forming roller 2 5 and between the
film-forming roller 25 and the take-up roller, forming
0 a substrate film formation conveying pathway by the
group of rollers.
[ 0062] The substrate conveying speed is not
particularly restricted, but from the viewpoint of
allowing high-speed film-forming processing and
5 increasing production efficiency, it is at least 200
m/rnin and preferably from 48 0 m/min to 100 0 m/min
according to the invention.
[0063] In the plasma preprocessing chamber 12B there
is provided a plasma preprocessing device comprising a
0 preprocessing roller 2 0 for plasma preprocessing of
the conveyed substrate S, and plasma preprocessing
means for preprocessing of the substrate S on the
preprocessing roller.
[00 64] The plasma preprocessing roller 2 0 serves to
5 prevent shrinkage or damage of the plastic substrate S
by heat during plasma processing by the plasma
preprocessing means, and to apply the plasma P to the
39
substrate S in a uniform manner across a wide region.
The preprocessing roller 2 0 is preferably
adjustable to a constant temperature between -20°C and
100°C by adjusting the temperature of the temperatureadjusting
medium circulating in the preprocessing
roller. Electrical insulators are provided on both
sides of the center section of the roller main body
and around the rotating shaft, and the substrate S is
taken up at the center section of the roller main body
[0065] The preprocessing roller 20 is installed at
an electrical ground level. In this case, a metal
conducting material can be used for the roller main
body, rotating shaft, bearing or roller support.
[00 66] Also, the preprocessing roller 2 0 may be set
at an electrical floating level, i.e. an insulating
potential. If the potential of the preprocessing
roller 20 is at a floating level, it will be possible
to prevent leakage of electric power, the input power
for plasma preprocessing can be increased, and
utilization efficiency for preprocessing will be high,
[00 67] The plasma preprocessing means comprises
plasma supply means and magnetism forming means. The
plasma preprocessing means cooperates with the plasma
preprocessing roller 2 0 to enclose the plasma P near
the surface of the substrate S, and by changing the
shape of the surface of the substrate, the chemical
bonded state and functional groups, it is possible to
40
alter the chemical properties and increase
adhesiveness between the substrate and the vapor
deposited film formed on the substrate during film
formation in subseguent steps.
5 [0068] The plasma preprocessing means is provided
covering a portion of the preprocessing roller 20.
Specifically, the plasma supply means and magnetism
forming means composing the plasma preprocessing means
are placed along the surface near the outer periphery
0 of the preprocessing roller 20, and are placed so that
a sandwiched gap is formed by the plasma supply means
a preprocessing roller 2 0 and plasma supply
s 22a, 22b that supply plasma source gas and
se electrodes that generate plasma P, and the
ism forming means having a magnet 21 to promote
tion of plasma P.
Thus, the plasma supply nozzles 22a, 22b open
he space of the gap to create a plasma-forming
and form regions with high plasma density near
rface of the preprocessing roller 2 0 and plastic
ate S, thereby forming a plasma processing
e on one side of the substrate.
The plasma supply means of the plasma
cessing means comprises a starting material
lizing and supply apparatus 18 connected to a
supply nozzle provided on the exterior of the
re reduction chamber 12, and source gas-supply
having
nozzle
compri
5 magnet
genera
into t
region
0 the su
substr
surfac
[0069]
prepro
5 volati
plasma
pressu
41
nozzles 19a~19d that supply a source gas from the
apparatus. The supplied plasma source gas is an inert
gas alone such as argon, or a mixed gas with oxygen,
nitrogen, carbon dioxide gas or one or more of these
5 gases, supplied from a gas reservoir at a gas flow
rate measured by a flow rate controller.
[0070] The supplied gases are mixed in a prescribed
proportion as necessary, to form a plasma source gas
alone or a mixed gas for plasma formation, and
10 supplied to the plasma supply means. The single or
mixed gas is supplied to the plasma supply nozzles 22a,
22b of the plasma supply means, the supply ports of
the plasma supply nozzles 22a, 22b being supplied near
the outer periphery of the preprocessing roller 20
15 where the supply port is open.
The nozzle opening is directed toward the
substrate S on the preprocessing roller 20 allowing
plasma P to be uniformly diffused and supplied on the
plastic substrate surface, so that homogeneous plasma
20 preprocessing can be accomplished on a large-area
section of the substrate.
[007 1] The plasma supply nozzles 22a, 22b are
designed to have electrode functions, functioning as
counter electrodes against the ground electrode of the
2 5 preprocessing roller 20, and by the potential
difference produced by high-frequency voltage or the
like supplied between them and the preprocessing
42
roller 20, the supplied plasma source gas is brought
to an excited state and plasma P is generated and
supplied.
[0072] The plasma preprocessing device must have a
5 mechanism for producing a desired direct current
potential between the plasma preprocessing roller and
the plasma preprocessing means, to strengthen or
weaken the implantation effect of the plasma P on the
substrate S. In order to strengthen the plasma
0 implantation effect, it is preferred to impart a
negative potential to the substrate S, and in order to
weaken the plasma implantation effect it is preferred
to impart a positive potential to the substrate S.
By performing such adjustment of the plasma
5 strength, the plasma implantation effect into the
substrate S can be adjusted, damage to the plastic
substrate S can be reduced, and conversely the
adhesion rate of film onto the plastic substrate S can
be reinforced.
0 [0073] Specifically, the plasma supply means of the
plasma preprocessing means is provided with a power
source 32 that can apply a desired voltage to the
plasma preprocessing roller 20, and that can apply a
bias voltage for conversion to a positive potential of
5 the plasma P that is capable of physical or chemical
modification of properties of the surface of the
substrate.
43
Such plasma supply means is capable of
supplying the plasma P near the outer periphery of the
preprocessing roller 2 0 to the desired density, and it
can increase the power efficiency of the plasma
preprocessing.
[0074] The plasma strength per unit area used for
the invention is between 100 and 8000 W • sec/m2, there
being no effect of plasma preprocessing at 50 W-sec/m2
or lower, while at 4000 W-sec/m2 or higher the
substrate will tend to undergo degradation by plasma,
such as ablation, breakage, coloration or burning.
[0075] The plasma preprocessing means also has
magnetism forming means. The magnetism forming means
has an insulating spacer and base plate provided in a
magnet case, with a magnet 21 in the base plate. An
insulating shield plate is provided in the magnet case,
with an electrode being attached to the insulating
shield plate.
Therefore, even when the magnet case and
electrode are electrically insulated and the magnet
case is placed and anchored in the pressure reduction
chamber 12, the electrode can be at an electrical
floating level.
[0076] Power supply wiring 31 is connected to the
electrode, the power supply wiring 31 also being
connected to the power source 32. A temperatureadjusting
medium tube is also provided inside the
44
electrode to cool the electrode and magnet 21.
[0077] The magnet 21 is provided to concentrate and
apply the plasma P from the plasma supply nozzles 22a,
22b serving as electrode/plasma supply means, on the
5 substrate S. By providing the magnet 21, it is
possible to increase reactivity near the substrate
surface and to rapidly form a satisfactory plasma
preprocessing surface.
[007 8] The magnet 21 has a flux density of between
0 10 gauss and 10,000 gauss at the location of the
surface of the substrate S. If the flux density at
the substrate surface is at least 10 gauss it will be
possible to adequately increase the reactivity near
the substrate surface, and to rapidly form a
5 satisfactory preprocessed surface.
[0079] According to the invention, the configuration
and shape of the electrode magnet 21 is such that,
since the ions and electrons formed during plasma
preprocessing move according to the configuration and
0 shape, the electrons, -ions or substrate decomposition
product evenly diffuse across the entire electrode
surface even when plasma preprocessing is carried out
on a plastic substrate with a large area of 1 m2 or
greater, to allow homogeneous and stable preprocessing
5 at the desired plasma strength, even when the plastic
substrate S has a large area.
[0080] The plastic substrate S, having a plasma
45
processed surface formed on one side by the plasma
preprocessing roller 20, then moves from the substrate
conveying chamber 12 A to the film-forming chamber 12C
by guide rolls 14a-14d that guide it to the film-
5 forming chamber 12C, and an inorganic oxide vapordeposited
film is formed in the film-forming chamber.
[0081]
(Vapor-deposited film-forming method)
The inorganic oxide vapor-deposited film
0 layer of the invention is a thin-film having gas
barrier performance that blocks or shields permeation
of oxygen gas, water vapor and the like, and it may be
produced, for example, by a method of forming an
aluminum oxide layer using a chemical vapor deposition
5 method.
[0 082] The inorganic oxide layer used to form the
vapor-deposited film is an inorganic oxide layer
composed primarily of aluminum oxide, and it is a
layer composed mainly of an aluminum compound,
0 containing at least a 1uminum oxide or its nitride or
carbide, either alone or as a mixture.
In addition, the inorganic oxide vapordeposited
film layer may be a layer composed of a
mixture of inorganic oxides, containing the aluminum
5 compound as the maj or component, and containing Al-C
covalent bonds, and also comprising a metal oxide such
as silicon oxide, silicon nitride, silicon oxynitride,
46
silicon carbide, magnesium oxide, titanium oxide, tin
oxide, indium oxide, zinc oxide or zirconium oxide, or
a metal nitride or carbide or mixture thereof.
[0083] The inorganic oxide vapor-deposited film
5 layer of the invention is a layer wherein the presence
of Al-C covalent bonds is indicated by a peak as
measured by ion etching in the depthwise direction
using an X-ray photoelectron spectrometer (measuring
conditions: X-ray source: AlKa, X-ray output: 12OW),
0 and having transparency as well as a gas barrier
property to prevent permeation of oxygen, water vapor
and the like.
[0084] Furthermore, in the inorganic oxide vapordeposited
film layer of the invention, the abundance
5 of Al-C covalent bonds among all of the bonds that
include C based on measurement by X-ray photoelectron
spectroscopy is preferably between 0.3% and 30%, in
terms of reinforced adhesiveness between the inorganic
oxide vapor-deposited film and the plastic substrate,
0 excellent transparency, and well-balanced performance
as a vapor-deposited film with a gas barrier property.
[0085] If the abundance ratio of Al-C covalent bonds
is less than 0.3%, improvement in the adhesiveness of
the formed inorganic oxide vapor-deposited film will
5 be insufficient and it will be difficult to stably
maintain the barrier property, while if it is greater
than 30%, the problems of surface treatment, such as
47
loss of improvement in the adhesiveness and reduction
in transparency due to decomposition of the surface of
the plastic substrate by the plasma processing,
surface roughening and adhesion of decomposition
components, will be greater than the improvement in
adhesiveness by the plasma preprocessing, thereby
reducing the effect of the preprocessing.
[008 6] Also, the Al/O ratio of the inorganic oxide
vapor-deposited film that is composed mainly of
aluminum oxide is preferably no greater than 1.0 from
the interface between the plastic substrate and vapordeposited
film up to 3 nm toward the vapor-deposited
film surface.
If the Al/O ratio exceeds 1.0 from the
interface between the inorganic oxide vapor-deposited
film and plastic substrate toward the vapor-deposited
film surface, the adhesiveness between the plasmatreated
surface of the plastic substrate and the
aluminum oxide vapor-deposited film will be
insufficient, the proportion of aluminum will increase,
and the transparency of the inorganic oxide vapordeposited
film will be reduced.
[0087] The thickness of a vapor deposited inorganic
oxide film formed by a single film forming device is
preferably 10 to 200 nm and more preferably 10 to 50
nm.
[0088] In the film-forming chamber 12C there is
48
provided a vapor-deposited film forming device
comprising a film-forming roller 25 and vapordeposited
film-forming means 24. The film-forming
means of the vapor-deposited film forming device forms
5 a vapor-deposited film on the plasma preprocessing
surface of the plastic substrate that has been
preprocessed by the plasma preprocessing means.
[008 9] The vapor-deposited film forming device of
the invention is disposed so as to form a vapor-
0 deposited film on the plasma-preprocessed plastic
substrate surface, and the method of vapor deposition
for film formation of the vapor-deposited film may be
any of various vapor deposition methods such as
physical vapor deposition or chemical vapor deposition.
5 The physical vapor deposition method may be
selected from the group consisting of vapor deposition,
sputtering, ion plating, ion beam assist and cluster
ion beam methods, or it may be selected from the group
consisting of plasma CVD, plasma polymerization,
0 thermal CVD and catalyst reactive CVD methods.
[0090] The film forming device comprises a filmforming
roller that is set in a reduced pressure filmforming
chamber and takes up and conveys a substrate
that has been preprocessed with a plasma preprocessing
5 device, with the processed side of the substrate
facing outward, and performs film-forming processing,
and also comprises vapor-deposited film-forming means
49
such as a vapor-deposited film forming device,
sputtering film forming device, ion plating film
forming device, ion beam assist film forming device,
cluster ion beam film forming device, plasma CVD film
5 forming device, plasma polymerization film forming
device, thermal CVD film forming device or catalyst
reactive CVD film forming device, that vaporizes a
film formation source target set opposite the filmforming
roller to form a vapor-deposited film on the
0 substrate surface.
[00 91] The film forming device of the invention may
employ various physical vapor deposition apparatuses
by exchanging the vaporizing means for the film
formation source target, or it may also have a
5 construction allowing film formation by a chemical
vapor deposition apparatus, and various film-forming
methods may be used.
[0092] The vapor-deposited film-forming means 24
used may be a physical vapor deposition apparatus such
0 as a resistance heating vacuum film forming device,
sputtering apparatus, ion plating film forming device,
ion beam assist film forming device, cluster ion beam
film forming device or the like, or a chemical vapor
deposition apparatus such as a plasma CVD film forming
5 device, plasma polymerization film forming device,
thermal CVD film forming device or catalyst reactive
CVD film forming device, for formation of an inorganic
50
oxide layer.
[0093] When a vacuum film forming device is used as
the vapor-deposited film-forming means 2 4 of the
invention, it may be one having a target metal
5 material composed mainly of aluminum filled into a
crucible as the vaporization source, either as a
single type or different types, and heated to high
temperature to generate aluminum metal-containing
metal vapor, the metal vapor being oxidized by
0 introduction of oxygen gas supplied from gas supply
means to the aluminum metal vapor, to form a film of a
metal oxide containing an aluminum oxide on the
substrate surface.
[ 00 94] When resistance heating is employed, a metal
5 wire such as aluminum may be used for oxidation of the
aluminum metal vapor in the same manner while forming
a film on the substrate surface. The vaporization
source for film formation may be a sputter
vaporization source, arc vaporization source or a
0 plasma CVD film formation mechanism such as a plasma
generation electrode or source gas-supplying means.
[0095] During the film formation, depending on the
composition of the vapor-deposited film to be formed,
the metal material of the target may be separately
5 vaporized so that aluminum oxide is the maj or
component, according to the ease of vaporization of
the aluminum and the other metal, or a mixture of the
51
metal material for the desired proportion may be
vaporized.
The film-forming means may be a single film
forming device, or two or more of the same or
different film forming devices' in combination,
depending on the vapor-deposited film to be formed in
the film-forming chamber.
[0096] When a thin-film is to be formed to a high
thickness with a single film forming device, the thinfilm
becomes fragile due to stress and cracking is
generated, notably lowering the gas barrier property
or causing detachment of the thin-film during
conveyance or during take-up. A plurality of film
forming devices may therefore be provided to obtain a
thick layer of the gas barrier thin-film, for multiple
formation of thin-films of the same substance.
Furthermore, the invention forms a coating
film with moist heat resistance and a gas barrier
property on the vapor-deposited film formed having
reinforced adhesiveness, using a known roller-type
coating applicator provided in a continuous manner
(not shown). A plurality of film forming devices may
be used to form thin-films of different materials, in
which case it is possible to obtain a multilayer,
multifunctional film imparted with not only a gas
barrier property but also various other functions.
[0097] A plurality of film forming devices may be
52
used to form thin-films of different materials, in
which case it is possible to obtain a multilayer film
imparted with not only a gas barrier property but also
various other functions.
[ 00 98] In a vapor-deposited film forming device it
is particularly preferred for the preset temperature
to be set to a constant temperature of between -20°C
and 100°C, from the viewpoint of heat resistance
restrictions on the related mechanical parts and for
general purpose use.
In various film forming methods, the filmforming
pressure of the film-forming chamber in which
vapor-deposited film formation is continuously carried
out is preferably set and maintained at about 0.1 Pa
to 100 Pa in order to form a vapor-deposited film
having sufficient denseness of the vapor-deposited
film and adhesiveness with the substrate.
[0099]
(Coating film layer with moist heat resistance and gas
barrier property)
The coating film layer with moist heat
resistance and a gas barrier property will now be
described.
The coating film layer is a coating film that
retains its gas barrier property in high temperature,
high humidity environments, and it contains at least
one type of metal alkoxide represented by the general
53
formula R1ni-i(OR2)m (where R1 and R2 represent Cl-8
organic groups, M represents a metal atom, n
represents an integer of 0 or greater, m represents an
integer of 1 or greater and n + m is the valence of M ),
5 and a water-soluble polymer, and it is also a coated
film comprising a gas barrier composition obtained by
polycondensation by a sol-gel method in the presence
of a sol-gel method catalyst, an acid, water and an
organic solvent.
0 The composition is applied onto the vapordeposited
film on the vapor-deposited film to form a
coated film, and subj ected to heat drying treatment
for 10 seconds to 10 minutes at a temperature of 20 °C
to 180°C, and no higher than the melting point of the
5 vapor-deposited film.
[0100] The gas barrier composition may also be
applied onto the vapor-deposited film on the base film
and two or more coated films layered and subj ected to
heat drying treatment for 10 seconds to 10 minutes at
0 20°C to 180°C and no higher than the melting point of
the base film, to form a compound polymer layer having
two or more layered gas barrier coating films.
The metal atom represented by M in the
general formula R1
nM (OR2)ra for the metal alkoxide may be,
5 for example, silicon, zirconium, titanium, aluminum or
the like.
[0101] According to the invention, two or more of
54
the aforementioned alkoxides may also be used together
For example, when a mixture of an alkoxysilane and a
zirconium alkoxide is used, the toughness and heat
resistance of the obtained gas barrier laminated film
can be improved, and reduction in retort resistance of
the film during stretching can be avoided. When an
alkoxysilane and a titanium alkoxide are used in
admixture, the thermal conductivity of the obtained
gas barrier coating film is lowered and the heat
resistance is notably increased.
[0102] The water-soluble polymer used for the
invention may be a polyvinyl alcohol-based resin or an
ethylene-vinyl alcohol copolymer, used alone, or a
polyvinyl alcohol-based resin and an ethylene/vinyl
alcohol copolymer may be used in combination.
According to the invention, a polyvinyl alcohol-based
resin and/or ethylene-vinyl alcohol copolymer may be
used to notably improve the physical properties
including the gas barrier property, water resistance
and weather resistance,
[0103] As polyvinyl alcohol-based resins there may
generally be used those obtained by saponification of
polyvinyl acetate. Polyvinyl alcohol-based resins are
not particularly restricted, and may be partially
saponified polyvinyl alcohol-based resins with several
tens of percent of acetic acid group residues, or
totally saponified polyvinyl alcohols without acetic
55
acid group residues, or modified polyvinyl alcoholbased
resins modified with OH groups.
[0104] The ethylene-vinyl alcohol copolymer used may
be a saponification product of a copolymer of ethylene
5 and vinyl acetate, i.e. one obtained by saponification
of an ethylene-vinyl acetate random copolymer.
There are no particular restrictions for
these, and they include, for example, partial
saponification products having several tens of mol% of
0 residual acetic acid groups, and complete
saponification products having only a few mol% of
residual acetic acid groups or having absolutely no
residual acetic acid groups. However, from the
viewpoint of the gas barrier property the
5 saponification degree is preferably 8 0 mol% or greater,
more preferably 90 mol% or greater and even more
preferably 95 mol% or greater.
It is preferred to use one wherein the
content of ethylene-derived repeating units in the
0 ethylene-vinyl alcohol copolymer (hereunder also
referred to as "ethylene content") is generally 0 to
50 mol% and preferably 20 to 45 mol%.
[ 0105] According to the invention, the gas barrier
laminated film may be produced by the following method.
5 First, the metal alkoxide, silane coupling
agent, water-soluble polymer, sol-gel method catalyst,
acid, water and organic solvent are mixed to prepare a
56
gas barrier composition.
[0106] Next, the gas barrier composition is coated
onto the vapor-deposited film on the vapor-deposited
film by a common method, and dried. The drying step
5 further promotes polycondensation of the metal
alkoxide, silane coupling agent and polyvinyl alcoholbased
resin and/or ethylene-vinyl alcohol copolymer,
forming a coated film. This coating procedure may be
repeated on the first coated film to form several
0 coating films composed of two or more layers.
[0107] Next, the base film on which the gas barrier
composition has been coated is subj ected to heat
treatment for 10 seconds to 10 minutes at a
temperature of 20°C to 18 0 °C and no higher than the
5 melting point of the vapor-deposited film, and
preferably in the range of 50°C to 160°C. This allows
production of a barrier property film having one, two
or more gas barrier coated films formed from the gas
barrier composition on the vapor-deposited film.
0 [0108] The method for coating the gas barrier
composition of the invention may be, for example,
coating once or several times using coating means such
as roll coating with a gravure roll coater, spray
coating, spin coating, dipping, brushing, bar coating
5 or applicator coating, allowing formation of a coated
film with a dry film thickness of 0.01 to 30 um and
preferably 0.1 to 10 um, and then heating and drying
57
in an ordinary environment at a temperature of 50°C to
300°C and preferably 70°C to 200°C, for 0.005 to 60
minutes and preferably 0.01 to 10 minutes, resulting
in condensation to form a gas barrier coated film
according to the invention.
(Heat-sealable innermost layer)
According to the invention, a heat-sealable
thermoplastic resin or the like can be layered as an
innermost layer via an adhesive layer, or without
using one, to impart heat sealability.
The heat seal layer used for this may be a
resin layer or film or sheet that can melt and be
fused together by heat, and for example, it may be a
low-density polyethylene, medium-density polyethylene,
high-density polyethylene or linear low-density resin
film or sheet.
Also, it is preferred to use, for example, a
sheet comprising one or more resins such as lowdensity
polyethylene, medium-density polyethylene,
high-density polyethylene, linear low-density
polyethylene, polypropylene, polymethylpentene,
polystyrene, ethylene-vinyl acetate copolymer, cede
fin copolymer, ionomer resin, ethylene-acrylic acid
copolymer, ethylene-ethyl acrylate copolymer,
ethylene-methyl methacrylate copolymer, ethylenepropylene
copolymer, an elastomer or the like, or
films thereof, among which there are more preferred
58
sheets comprising one or more olefin-based resins such
as polyethylene or polypropylene, or films thereof,
which have excellent hygienic properties, heat
resistance, chemical resistance and aroma retention,
5 since the layer will be in contact with contents such
as food.
Also, the thickness is preferably about 13 to
100 um and more preferably about 15 to 7 0 um.
The heat seal layer may also have a light-
0 shielding property. According to the invention, a
heat seal layer with a light-shielding property may be
a material having a property of shielding external
light.
Specifically, the material used for a light-
5 shielding heat seal layer may be a vapor-deposited
film formed by vacuum vapor deposition or sputtering
of a metal such as aluminum on a heat sealable film.
A light-shielding property can also be
imparted by using an opaque film as the film, or using
0 a film having a light-shielding ink layer formed
thereon.
It is preferred to form a metal vapordeposited
film of aluminum or the like in order to
impart a light-shielding property and barrier property
5 as a packaging material.
Specifically, the material for the barrier
layer will usually be a vapor-deposited film formed by
59
vacuum vapor deposition of a metal such as aluminum on
a plastic film, but aluminum foil may be used instead.
The metal to be formed in the metal vapordeposited
film is preferably a metal such as aluminum
5 (Al), chromium (Cr), silver (Ag), copper (Cu), tin
(Sn) or the like, with aluminum (Al) being preferred
for use.
An aluminum foil preferably has a thickness
of about 5 to 30 urn, and a metal vapor-deposited film
10 preferably has a thickness of about 50-3000 angstrom
and more preferably 100-1000 angstrom.
Such a light-shielding ink may be,
specifically, ink containing a pigment with a lightshielding
property, such as aluminum paste.
15 The film thickness of the ink layer is
preferably about 1 to 8 urn and more preferably about 2
to 5 urn.
A white film may be used, that contains a
white pigment composed mainly of a polyolefin resin
2 0 that imparts a light-shielding property.
The white pigment used in the white film may
be, specifically, titanium oxide, zinc oxide, the
extender pigment aluminum hydroxide, magnesium
carbonate, calcium carbonate, settling barium sulfate,
25 silica, talc or the like.
The white pigment content is preferably about
10% to 40%.
60
The method of forming the metal vapordeposited
film according to the invention will now be
explained^ where the method may be, for example, a
physical vapor deposition method (PVD) such as vacuum
5 vapor deposition, sputtering or ion plating, or a
chemical vapor deposition method (CVD) such as plasma
chemical vapor deposition, thermochemical vapor
deposition or photochemical vapor deposition.
As an explanation of the method of forming
0 the metal vapor-deposited film according to the
invention, the vapor-deposited film may be formed
using a vacuum vapor deposition method in which the
aforementioned metal is used as starting material and
heated for vapor deposition on a flexible film, an
5 oxidation reaction vapor deposition method in which a
metal is used as starting material and oxygen gas or
the like is introduced for oxidation to cause vapor
deposition on a flexible film, or a plasma-assisted
oxidation reaction vapor deposition method in which
0 the oxidation reaction is further assisted with plasma.
[0109] The following is an explanation of a method
for producing a highly adhesive transparent vapordeposited
film by employing a continuous vapordeposited
film forming device having separately
5 provided a preprocessing chamber with a plasma
preprocessing device of the invention, and a filmforming
chamber.
61
A roll-shaped substrate S supply roll is set
on the wind-out roller 13 in a substrate conveying
chamber 12A, and a vacuum pump is used to reduce the
pressure in the substrate conveying chamber 12A and in
5 the plasma preprocessing chamber and film-forming
chamber 12C.
[0110] After the pressure has been reduced to the
prescribed pressure, the substrate S is wound out from
the substrate S supply roll by the wind-out roller 13,
0 the substrate S is directed to the plasma
preprocessing device via the guide roller 14a, and the
substrate S is taken up onto the preprocessing roller
20 for plasma preprocessing, whereby the substrate S
is transferred from the substrate conveying chamber
5 12A to the preprocessing chamber 12B.
Also, plasma is introduced between the plasma
supply means and the preprocessing roller in a state
that produces an applied potential, and plasma
preprocessing is carried out so that the substrate S
0 taken up on the preprocessing roller 20 has a plasmapreprocessed
surface formed on one side by the plasma
preprocessing means.
[0111] The substrate S with the plasma-preprocessed
surface formed on one side is conveyed back to the
5 substrate conveying chamber 12A by being wound around
the guide roller 14b from the preprocessing roller 20.
It is then transferred from the guide rolls
62
14b, 14c into the substrate conveying chamber 12A, and
taken up onto the film-forming roller 25 with the
plasma-treated surface facing outward, thereby being
conveyed into the film-forming chamber 12C. A vapor-
5 deposited film is formed by vapor-deposited filmforming
means 2 4 on the preprocessed surface of the
substrate S in the film-forming chamber 12C.
[0112] The substrate S with the vapor-deposited film
formed in this manner is conveyed back to the
10 substrate conveying chamber 12A from the film-forming
roller 25, and taken up as a roll by a take-up roller
via the guide roller 14d.
[ 0113] According to an embodiment of the roller-type
continuous vapor-deposited film forming device of the
15 invention, the plastic substrate S prior to formation
of the vapor-deposited film is passed through a gap
formed by the preprocessing roller 2 0 and the plasma
supply means and magnetism forming means 21, during
which time plasma P is introduced from the plasma
20 supply nozzles 22a, 22b, together with supply of
plasma source gas, toward the substrate S in the gap
near the outer periphery of the preprocessing roller
20, and a positive voltage is applied between the
plasma P and the preprocessing roller 20 for plasma
25 preprocessing, whereby the atmosphere in the plasma
preprocessing means is improved.
Thus, a homogeneous and high-quality plasma63
preprocessed surface is obtained on the plastic
substrate, after which an inorganic oxide vapordeposited
film is formed by the vapor-deposited filmforming
means 2 4 to obtain a substrate having a
5 homogeneous vapor-deposited film with excellent
adhesiveness.
It is also possible to obtain a plastic
substrate with a homogeneous vapor-deposited film
having adhesiveness even after hot water treatment at
0 121°C, 60 min and excellent water-resistant
adhesiveness.
In addition, it is possible to obtain a
substrate having a homogeneous vapor-deposited film
with excellent moist heat-resistant adhesiveness,
5 exhibiting adhesiveness even in a high temperature,
high humidity environment, such as when stored for 50 0
hours in an environment of 60°C x 90% RH.
[0114] The substrate conveying chamber 12A has a
different pressure than the plasma preprocessing
0 chamber in which the electrode resides, by being
partitioned with the partition 3 5a (zone seal). By
forming spaces in the substrate conveying chamber 12A
and preprocessing chamber 12B with different pressures,
this eliminates plasma discharge of the preprocessing
5 chamber 12B from becoming unstable due to leakage of
the plasma P in the preprocessing chamber into the
substrate conveying chamber 12A, or damage to the
64
members of the substrate conveying chamber 12A, and
electrical damage to the electrical circuits that
serve to control the substrate conveying mechanism,
which can lead to control failures, and as a result
5 stable film formation and conveying of the substrate
can be accomplished.
[0115] Specifically, the plasma processing pressure
of the additional preprocessing chamber 12B is between
0.1 Pa and 100 Pa. By conducting preprocessing at
0 such a preprocessing pressure it is possible to form
stabilized plasma P.
[0116] The plasma preprocessing of the invention can
prevent increase in impedance of plasma discharge,
allowing easier formation of plasma P and allowing
5 stabilized discharge and plasma processing for
prolonged periods.
[0117] In addition, since the discharge impedance of
the plasma P does not increase, it is possible to
accomplish plasma processing with a greater processing
0 speed, reduced film stress, and less damage to the
substrate (minimized electrical charge-up, reduced
substrate etching and reduced substrate coloration).
Thus, it is possible to optimize the
discharge impedance, and to adjust the ion
5 implantation effect onto the substrate and increase
adhesiveness of the vapor-deposited film formed on the
preprocessed surface, while reducing damage to the
65
substrate and forming a satisfactory preprocessed
surface.
[0118] The above explanation was set forth for a
preferred embodiment of a highly adhesive transparent
vapor-deposited film having Al-C covalent bonds at the
interface between the plastic film and the inorganic
oxide vapor-deposited film that is composed mainly of
aluminum oxide, using a continuous vapor-deposited
film forming device comprising a plasma preprocessing
device according to the invention, with reference to
accompanying drawings, but the invention is not
limited to this example.
The invention may of course incorporate
various modifications and alterations by a person
skilled in the art within the scope of the technical
concept disclosed in the present application, and
these are naturally within the technical scope of the
film forming device of the invention.
Examples
[0119] The invention will now be explained through
examples and comparative examples.
A. Examples 1 to 4, Comparative Examples 1 to 3 and
their evaluation

On the side of a 12 urn-thick PET (PET-F,
product of Unitika, Ltd.) substrate to be provided
with a vapor deposition layer, plasma was introduced
66
using a continuous vapor-deposited film forming device
having a separated preprocessing chamber provided with
a plasma preprocessing device of the invention, and a
film-forming chamber, from a plasma supply nozzle in
5 the preprocessing chamber under the following plasma
conditions, and after conducting plasma preprocessing
at a transport speed of 480 m/min, an aluminum oxide
vapor deposition layer was formed to a thickness of 8
nm on the plasma-treated surface under the following
0 conditions being continuously transported in the filmforming
chamber, using a reactive resistance heating
system as the heating means of the vacuum vapor
deposition method.
(Plasma preprocessing conditions)
5 High-frequency power source output: 4 kW
Plasma strength: 550 W-sec/m2
Plasma-forming gas: Oxygen 100 {seem), argon 1000
(seem)
magnetism forming means: 10 00 gauss permanent magnet
0 Appl "iod voltage between preprocessing drum and plasma
supply nozzles: 420 V
Degree of vacuum of preprocessing chamber: 2.0 * 10_1
Pa
(Aluminum oxide film-forming conditions)
5 Degree of vacuum: 2.1 * 10~2 Pa
Light transmittance at wavelength of 366 nm: 88 %
[0120]
67

On the side of a 12 urn-thick PET (PET-F,
product of Unitika, Ltd.) substrate to be provided
with a vapor deposition layer, plasma was introduced
5 from a plasma supply nozzle under the same conditions
an Example 1, except that the plasma strength was 12
kW in the preprocessing chamber of the continuous
vapor-deposited film forming device having a separated
preprocessing chamber provided with a plasma
10 preprocessing device of the invention, and a filmforming
chamber, and after conducting plasma
preprocessing at a transport speed of 4 80 m/min, an
aluminum oxide vapor deposition layer was formed to a
thickness of 8 nm on the plasma-treated surface under
15 the same conditions as Example 1, being continuously
transported in the film-forming chamber, using a
reactive resistance heating system.
[0121]

20 On the side of a 12 um-thick PET (PET-F,
product of Unitika, Ltd.) substrate to be provided
with a vapor deposition layer, plasma was introduced
from a plasma supply nozzle under the same conditions
an Example 1, except that the plasma strength was 12
25 kW in the preprocessing chamber of the continuous
vapor-deposited film forming device having a separated
preprocessing chamber, provided with a plasma
68
preprocessing device of the invention, and a filmforming
chamber, and the oxygen plasma-forming gas was
changed to nitrogen, and after conducting plasma
preprocessing at a transport speed of 480 m/min, an
5 aluminum oxide vapor deposition layer was formed to a
thickness of 8 nm on the plasma-treated surface under
the same conditions as Example 1 while being
continuously transported in the film-forming chamber,
using a reactive resistance heating system.
0 [0122]

On the side of a 12 um-thick PET (PET-F,
product of Unitika, Ltd.) substrate to be provided
with a vapor deposition layer, plasma was introduced
5 from a plasma supply nozzle under the same conditions
an Example 1, except that the plasma strength was 12
kW in the preprocessing chamber of the continuous
vapor-deposited film forming device having a separated
preprocessing chamber provided with a plasma
0 preprocessing device of the invention, and a filmforming
chamber, and after conducting plasma
preprocessing at a transport speed of 480 m/min, an
aluminum oxide vapor deposition layer was formed to a
thickness of 8 nm on the plasma-treated surface under
5 the following conditions, while being continuously
transported in the film-forming chamber, using a
reactive resistance heating system.
69
(Aluminum oxide film-forming conditions)
Degree of vacuum: 2.5 x 10"2 Pa
Light transmittance at wavelength of 3 66 nm: 82%
[0123]

The side of a 12 urn-thick PET (PET-F, product
of Unitika, Ltd.) substrate to be provided with a
vapor deposition layer was subj ected to plasma
preprocessing at a transport speed of 480 m/min under
the following plasma processing conditions using a
continuous vapor-deposited film forming device
equipped with a parallel flat plate-type direct
current-type plasma generating device, and then an
aluminum oxide vapor deposition layer was formed to a
thickness of 8 nm on the plasma-treated surface under
the conditions of Example 1 while being continuously
transported, using a reactive resistance heating
system.
(Plasma preprocessing conditions)
Plasma strength: 550 W-sec/m2
Plasma-forming gas: Oxygen 100 (seem), argon 1000
(seem)
Degree of vacuum of preprocessing chamber: 2.0 x 10"1
Pa
(Aluminum oxide film-forming conditions)
Degree of vacuum: 2.1 x 10~2 Pa
Light transmittance at wavelength of 366 nm: 88 %
70
[0124]

The side of a 12 vim-thick PET (PET-F, product
of Unitika, Ltd.) substrate to be provided with a
5 vapor deposition layer was subjected to plasma
preprocessing at a transport speed of 480 m/min under
the same plasma processing conditions as Comparative
Example 1 using a continuous vapor-deposited film
forming device eguipped with a parallel flat plate-
0 type direct current-type plasma generating device, and
then an aluminum oxide vapor deposition layer was
formed to a thickness of 8 nra on the plasma-treated
surface under the following conditions while being
continuously transported, using a reactive resistance
5 heating system.
(Aluminum oxide film-forming conditions)
Degree of vacuum: 2.2 * 10~2 Pa
Light transmittance at 3 66 nm: 7 5%
[0125]
0
On the corona side of 12 um-thick PET (PET-F,
product of Unitika, Ltd.) there was formed an aluminum
oxide vapor deposition layer to a thickness of 8 nm
using a reactive resistance heating system, under the
5 conditions of Example 1.
[0126]
(Evaluation)
71
The vapor-deposited films produced under the
conditions of Examples 1 to 4 and Comparative Examples
1 to 3, described in the examples and comparative
examples, were used as samples for X-ray photoelectron
5 spectroscopy, measurement of the oxygen permeability,
measurement of the hydrogen permeability and
measurement of the bonding strength between the films
and vapor-deposited films.
The measuring samples were used for the
10 following measurements, by X-ray photoelectron
spectroscopy and measurement of the oxygen
permeability, water vapor permeability and lamination
strength (peel strength).
[0127]
15
1. X-ray photoelectron spectroscopy
An X-ray photoelectron spectrometer {Quantum
2000) by PHI was used for analysis of the bonded state
at the interface between the vapor-deposited film,
2 0 such as aluminum oxide, and the film substrate, such
as a PET substrate, using AlKa (1486.6 eV) as the Xray
source, with an output of 120W, and measurement
was conducted for each of the bond types between the
vapor-deposited film and film, including bonds of
2 5 283.5 +0.5 eV (CIS bond energy) arising from carbonaluminum
bonding (Al-C covalent bonds) .
Also, the Al/0 ratio was calculated from the
72
relative content ratio of Al and 0, as obtained from
the X-ray photoelectron spectroscope.
[0128]
2. Gas barrier property (oxygen/water vapor)
5
Using an oxygen permeability meter ([device
name: OX-TRAN 2/21] by Modan Control (MOCON)), the
test sample was set with the film side as the
humidification side, and measurement was carried out
0 according to JIS K 7126 B with the measuring
conditions being an environment of 23°C, 100% RH.
[0129]

Using a water vapor permeability meter
5 ([device name: PERMATRAN 3/33] by Modan Control
(MOCON)), the test sample was set with the barrier
coat layer side as the humidification side, and
measurement was carried out according to JIS K 7126 B
with the measuring conditions being an environment of
0 37.8°C, 100% RH.
[0130]
Bonding strength between plastic substrate and
aluminum oxide vapor deposition layer

5 Thevapor deposition surface side of the
vapor-deposited film was coated with a two-pack
curable polyurethane-based adhesive and dried, and
73
this was dry laminated with an unstretched
polypropylene film with a thickness of 30 um that had
been coated with a two-pack curable polyurethane-based
adhesive and dried, to form a layered composite film
for use as a bonding strength measuring sample.
The layered composite film was subj ected to
aging treatment for 48 hours, and then with the sample
cut into 15 mm-wide strips, a tensile tester {device
name: TENSILON General-Purpose Material Tester by
Orientech Co., Ltd.) was used according to JIS K6854-2
for measurement of the bonding strength at the bonding
interface between the vapor-deposited film and the
unstretched polypropylene film, by 180° peeling at a
peel rate of 50 mm/min (T-peel method).

The vapor deposition surface side of the
vapor-deposited film was coated with a two-pack
curable polyurethane-based adhesive and dried, and
this was dry laminated with an unstretched
polypropylene film with a thickness of 30 urn that had
been coated with a two-pack curable polyurethane-based
adhesive and dried, to form a layered composite film,
and after completing aging, it was used as a bonding
strength measuring sample.
The layered composite film was used to form a
four-sided pouch prepared to size B5, 100 mL of water
was poured in and hot water retort treatment was
74
carried out at 121°C, 60 min, and after removing the
water, a sample cut into 15 mm-wide strip from the
four-sided pouch was used for measurement of the
bonding strength at the bonding interface between the
5 vapor-deposited film and the unstretched polypropylene
film, with a tensile tester (device name: TENSILON
General-Purpose Material Tester by Orientech Co.,
Ltd.) according to JIS K6854-2, by 180° peeling at a
peel rate of 50 mm/min {T-peel method).
0
The vapor deposition surface side of the
vapor-deposited film was coated with a two-pack
curable polyurethane-based adhesive and dried, and
this was dry laminated with an unstretched
5 polypropylene film with a thickness of 30 urn that had
been coated with a tv/o-pack curable polyurethane-based
adhesive and dried, to form a layered composite film,
and after completing aging, it was used as a bonding
strength measuring sample.
0 A sheet prepared to size B5 using the layered
composite film was stored for 500 hours in a thermohygrostat
at 60°C, 90% RH, and then with the sample
cut into 15 mm-wide strips, a tensile tester (device
name: TENSILON General-Purpose Material Tester by
5 Orientech Co., Ltd.) was used according to JIS K6854-2
for measurement of the bonding strength at the bonding
interface between the vapor-deposited film and the
75
unstretched polypropylene film, by 180° peeling at a
peel rate of 50 mm/min {T-peel method).
[0131]

The results for evaluation of the performance
of testing samples for bonding strength measurement
(1) are shown in Table 1.
[Table 1]
Example
Example
1
Example
2
Example
3
Example
4
Comp.
Ex. 1
Comp.
Ex. 2
Comp .
Ex . 3
Al-C bond
abundance
ratio (%)
17
21
20
22
Below
detection
limit
Below
detection
limit
Below
detection
limit
Al/O
ratio
up to
3 nm
0. 83
0. 79
0. 82
0. 91
0. 85
1 . 44
0 . 87
Surface
roughness
Ra [nm]
8
8
8
8
12
11
8
Oxygen
permeability
[ cc/m2- day]
1. 3
1.3
1. 4
1. 6
1. 4
1. 8
1. 8
Water vapor
permeability
[g/m2- day]
1.2
1. 8
1.7
2 . 1
1. 5
2 . 4
2 . 6
Bonding
strength
[N/15
mm]
5. 8
7.4
6. 9
7.7
2.5
2 . 1
2 . 7
[0132] As shown in Table 1, a clear difference was
seen between the vapor-deposited films produced using
the plasma preprocessing device of the invention, and
15 those of the prior art.
5
10
76
[ 0133] In plasma preprocessing by a continuous
vapor-deposited film forming device separately
comprising a preprocessing chamber provided with a
plasma preprocessing device of the invention, and a
5 film-forming chamber, the surface roughness is Ra = 8
nm, while the surface roughness is still Ra = 8 nm on
the plastic substrate without plasma preprocessing in
Comparative Example 3, whereas with conventional
plasma preprocessing, the surface roughness is large
0 at Ra = 11 to 13 nm, and with plasma RIE, the plasma
etching is such that the surface is ion-etched to
sputter off the impurities and produce a smooth
surface {Ra = 4 nm), causing the surface condition to
be altered, and therefore the plasma preprocessing of
5 the invention clearly differs in a technical sense
from conventional plasma processing.
The surface roughness Ra is measured at 20
different locations in a visual field range of 0.11 mm
x 0.11 mm using a non-contact three-dimensional
0 surface roughness meter (NewView TM7000 by Zygo), and
the arithmetic mean roughness (Ra) is calculated from
the average value.
[0134] Furthermore, it is notable that with the
plasma preprocessing of the invention, the abundance
5 ratio of Al-C covalent bonds was 17% to 22%, while
being absent below the detection limit (not generated)
by conventional plasma preprocessing, as shown in
77
Table 1, and therefore Al-C covalent bonds were
produced in a high proportion during vapor-deposited
film formation.
As seen by the bonding strengths in the
examples and comparative examples, the bonding
strength was 5.8 to 7.7 by the plasma preprocessing of
the invention, while the bonding strength was 2.1 to
2.7 by the conventional plasma preprocessing, and thus
generation of Al-C covalent bonds can increase the
adhesiveness by about 3-fold.
[0135] Moreover, the expression of such bonding
strength is assumed to be due to the Al-C covalent
bonds, allowing a vapor-deposited film to be obtained
with stable bonding strength, unlike with layering of
a plastic substrate and a vapor-deposited film by
functional groups via oxygen as in the prior art.
[0136] A vapor-deposited film obtained by plasma
preprocessing using a continuous vapor-deposited film
forming device separately comprising a preprocessing
chamber provided with a plasma preprocessing device of
the invention, and a film-forming chamber, can be
produced as a vapor-deposited film with low water
vapor permeability and oxygen permeability and stable
performance, as is clear by comparison between
Examples 1 to 4 and Comparative Examples 1 to 3, and
it has become possible to form a high-quality,
homogeneous vapor-deposited film with significantly
78
reinforced adhesiveness between the plastic substrate
and the vapor-deposited film.

The results for evaluation of the performance
of testing samples for lamination strength measurement
(2) are shown in Table 2.
[Table 2]
l v ,
[0137] As shown in Table 2, a clear difference was
seen between the vapor-deposited films produced using
the plasma preprocessing device of the invention, and
those obtained by prior art preprocessing technology,
15 based on comparison between the examples and
comparative examples.
79
[0138] It is notable that with the plasma
preprocessing of the invention, the abundance ratio of
Al-C covalent bonds was 17% to 22%, while being absent
below the detection limit (not generated) by
conventional plasma preprocessing, as shown in Table 2
and therefore Al-C covalent bonds were produced during
vapor-deposited film formation. As seen by the
bonding strengths in the examples and comparative
examples, the bonding strength based on the lamination
strength between the plastic film and the vapor
deposition layer after hot water treatment at 121°C,
60 min was 4.0 to 4.8 with plasma preprocessing
according to the invention, whereas the bonding
strength based on measurement of the lamination
strength with conventional plasma preprocessing was
0.1 to 0.4, and thus generation of Al-C covalent bonds
can increase the water-resistant adhesive of the
water-resistant adhesive transparent vapor-deposited
film of the invention by about 10- to 40-fold or
greater.
[0139] Moreover, the expression of such bonding
strength is assumed to be due to the Al-C covalent
bonds, allowing a vapor-deposited film to be obtained
with stable water-resistant adhesiveness, unlike with
layering of a plastic substrate and a vapor-deposited
film by functional groups via oxygen as in the prior
art.
80
[0140] A vapor-deposited film obtained by plasma
preprocessing using a continuous vapor-deposited film
forming device separately comprising a preprocessing
chamber provided with a plasma preprocessing device of
5 the invention, and a film-forming chamber, can be
produced as a vapor-deposited film with low water
vapor permeability and oxygen permeability and stable
performance, as is clear by comparison between
Examples 1 to 4 and Comparative Examples 1 to 3, and
10 it has become possible to form a high-quality,
homogeneous vapor-deposited film with maintained
adhesiveness between the plastic substrate and the
vapor-deposited film even after hot water treatment,
and significantly reinforced water-resistant
15 adhesiveness.

The results for evaluation of the performance
of testing samples for bonding strength measurement
20 (3) are shown in Table 3.
[Table 3]
81
[0141] As shown in Table 3, a clear difference was
5 seen between the vapor-deposited films produced using
the plasma preprocessing device of the invention, and
those obtained by prior art technology, based on
comparison between the examples and comparative
examples.
10 [0142] It is notable that with the plasma
preprocessing of the invention, the abundance ratio of
Al-C covalent bonds was 17% to 22%, while being absent
below the detection limit (i.e. not generated) by
conventional plasma preprocessing, as shown in Table 3,
15 and therefore Al-C covalent bonds were produced at a
82
high proportion during vapor-deposited film formation.
As seen by the bonding strengths in the
examples and comparative examples, the bonding
strength based on the lamination strength after
5 storage for 500 hours at 60°C x 90% RH was 3.3 to 3.9
with plasma preprocessing according to the invention,
whereas the bonding strength based on the lamination
strength with conventional plasma preprocessing was
0.1 or lower, and thus generation of Al-C covalent
0 bonds can increase the moist heat-resistant
adhesiveness of the moist heat-resistant transparent
vapor-deposited film of the invention by about 35-fold
or greater compared to the prior art, even under high
temperature, high humidity environments, without
5 reduction in the gas barrier property.
[0143] Moreover, the expression of such bonding
strength is assumed to be due to the Al-C covalent
bonds, allowing a vapor-deposited film to be obtained
with stable moist heat-resistant adhesiveness, unlike
0 with layering of a plastic substrate and a vapordeposited
film by functional groups via oxygen as in
the prior art.
[0144] A vapor-deposited film obtained by plasma
preprocessing using a continuous vapor-deposited film
5 forming device separately comprising a preprocessing
chamber provided with a plasma preprocessing device of
the invention, and a film-forming chamber, can be
83
produced as a vapor-deposited film that maintains
water vapor permeability and oxygen permeability and
exhibits stable performance, as is clear by comparison
between Examples 1 to 4 and the comparative examples,
5 and it has become possible to form a high-quality,
homogeneous vapor-deposited film with maintained
adhesiveness between the plastic substrate and the
vapor-deposited film even in high temperature, high
humidity environments, and significantly reinforced
0 moist heat-resistant adhesiveness.
B. Examples 5 to 9, Comparative Examples 4 to 7 and
their evaluation

On the side of a 12 um-thick PET (PET-F,
5 product of Unitika, Ltd.) substrate to be provided
with a vapor deposition layer, plasma was introduced
using a continuous vapor-deposited film forming device
having a separated preprocessing chamber provided with
a plasma preprocessing device of the invention, and a
0 film-forming chamber, from a plasma supply nozzle in
the preprocessing chamber under the foliowing plasma
conditions, and after conducting plasma preprocessing
at a transport speed of 480 m/min, an aluminum oxide
vapor deposition layer was formed to a thickness of 8
5 nm on the plasma-treated surface under the following
conditions in the continuously transporting filmforming
chamber, using a reactive resistance heating
84
system as the heating means of the vacuum vapor
deposition method.
{Plasma preprocessing conditions)
High-frequency power source output: 4 kW
Plasma strength: 550 W'sec/m2
Plasma-forming gas: Oxygen 100 (seem), argon 10 0 0
(seem)
magnetism forming means: 100 0 gauss permanent magnet
Applied voltage between preprocessing drum and plasma
supply nozzles: 420 V
Degree of vacuum of preprocessing chamber: 2.0 * 10"1
Pa
(Aluminum oxide film-forming conditions)
Degree of vacuum: 2.1 x 10 Pa
Light transmittance at wavelength of 366 nm: 88%

A 0.3 urn gas barrier coating film was formed
on the aluminum oxide vapor deposition layer of a film
having an aluminum oxide vapor deposition layer, by
the same method as in Example 5, to produce an
adhesiveness-reinforced transparent vapor-deposited
film.
Here, the gas barrier coating film was a gas
barrier coating film of a gas barrier composition,
obtained by first obtaining a colorless transparent
gas barrier coating film-forming composition by adding
a prepared hydrolysate with a solid content of 4 wt%,
85
comprising tetraethoxysilane {ethyl silicate 40),
hydrochloric acid, isopropyl alcohol, acetylacetone
aluminum and ion-exchanged water to an EVOH solution
comprising EVOH (ethylene copolymerization ratio: 2 9%)
5 and a mixed solvent of isopropyl alcohol and ionexchanged
water, stirring the mixture and further
adding a prepared liquid mixture comprising a
polyvinyl alcohol aqueous solution, acetic acid,
isopropyl alcohol and ion-exchanged water and stirring
0 the mixture, and then coating this gas barrier coating
film-forming composition onto an aluminum oxide vapor
deposition layer by gravure roll coating and
subsequently subj ecting the composition to
polycondensation by a sol-gel method with heating at
5 150°C for 60 seconds.

On the side of a 12 um-thick PET (PET-F,
product of Unitika, Ltd.) substrate to be provided
with a vapor deposition layer, plasma was introduced
0 from a plasma supply nozzle under the same conditions
an Example 5, except that the plasma strength was 12
kW in the preprocessing chamber of the continuous
vapor-deposited film forming device having a separated
preprocessing chamber provided with a plasma
5 preprocessing device of the invention, and a filmforming
chamber, and after conducting plasma
preprocessing at a transport speed of 480 m/min, an
86
aluminum oxide vapor deposition layer was formed to a
thickness of 8 nm on the plasma-treated surface under
the same conditions as Example 5 in the continuously
transporting film-forming chamber, using a reactive
resistance heating system.
Next, the same procedure was carried out as
in Example 5 to form a 0.3 um gas barrier coating film
on the aluminum oxide vapor deposition layer, to
produce an adhesiveness-reinforced transparent vapordeposited
film.

On the side of a 12 um-thick PET (PET-F,
product of Unitika, Ltd.) substrate to be provided
with a vapor deposition layer, plasma was introduced
from a plasma supply nozzle under the same conditions
an Example 5, except that the plasma strength was 12
kW in the preprocessing chamber of the continuous
vapor-deposited film forming device having a separated
preprocessing chamber provided with a plasma
preprocessing device of the invention, and a filmforming
chamber, and the oxygen plasma-forming gas was
changed to nitrogen, and after conducting plasma
preprocessing at a transport speed of 480 m/min, an
aluminum oxide vapor deposition layer was formed to a
thickness of 8 nm on the plasma-treated surface under
the same conditions as Example 5 in the continuously
transporting film-forming chamber, using a reactive
87
resistance heating system.
Next, the same procedure was carried out as
in Example 5 to form a 0.3 urn gas barrier coating film
on the aluminum oxide vapor deposition layer, to
5 produce an adhesiveness-reinforced transparent vapordeposited
film.

On the side of a 12 um-thick PET {PET-F,
product of Unitika, Ltd.) substrate to be provided
0 with a vapor deposition layer, plasma was introduced
from a plasma supply nozzle under the same conditions
an Example 5, except that the plasma strength was 12
kW in the preprocessing chamber of the continuous
vapor-deposited film forming device having a separated
5 preprocessing chamber provided with a plasma
preprocessing device of the invention, and a filmforming
chamber, and after conducting plasma
preprocessing at a transport speed of 480 m/min, an
aluminum oxide vapor deposition layer was formed to a
0 thickness of 8 nm on the plasma-treated surface under
the following conditions in the continuously
transporting film-forming chamber, using a reactive
resistance heating system.
(Aluminum oxide film-forming conditions)
5 Degree of vacuum: 2.5 x 10 Pa
Light transmittance at wavelength of 366 nm: 82%
Next, the same procedure was carried out as
88
in Example 5 to form a 0.3 urn gas barrier coating film
on the aluminum oxide vapor deposition layer, to
produce an adhesiveness-reinforced transparent vapordeposited
film.
5
The side of a 12 um-thick PET (PET-F, product
of Unitika, Ltd.) substrate to be provided with a
vapor deposition layer was subjected to plasma
preprocessing at a transport speed of 480 m/min under
0 the following plasma processing conditions using a
continuous vapor-deposited film forming device
equipped with a parallel flat plate-type direct
current-type plasma generating device, and then an
aluminum oxide vapor deposition layer was formed to a
5 thickness of 8 nm on the plasma-processed surface
under the conditions of Example 5 while being
continuously transported, using a reactive resistance
heating system.
(Plasma preprocessing conditions)
0 Plasma strength: 550 W'sec/m2
Plasma-forming gas: Oxygen 100 (seem), argon 1000
{seem)
Degree of vacuum of preprocessing chamber: 2.0 x 10"1
Pa
5 (Aluminum oxide film-forming conditions)
Degree of vacuum: 2.1 x 10-2 Pa
Light transmittance at wavelength of 366 nm: 88%
89

A 0.3 urn gas barrier coating film was formed
on the aluminum oxide vapor deposition layer of a film
having an aluminum oxide vapor deposition layer, by
5 the same method as in Comparative Example 4 , to
produce an adhesiveness-reinforced transparent vapordeposited
film.

The side of a 12 um-thick PET (PET-F, product
0 of Unitika, Ltd.) substrate to be provided with a
vapor deposition layer was subj ected to plasma
preprocessing at a transport speed of 4 80 m/min under
the same plasma processing conditions as Comparative
Example 4 using a continuous vapor-deposited film
5 forming device equipped with a parallel flat platetype
direct current-type plasma generating device, and
then an aluminum oxide vapor deposition layer was
formed to a thickness of 8 nm on the plasma-treated
surface under the following conditions while being
0 continuously transported, using a reactive resistance
heating system.
(Aluminum oxide film-forming conditions)
Degree of vacuum: 2.2 x 10"2 Pa
Light transmittance at 366 nm: 75%
5 Next,the same procedure was carried out as
in Example 5 to form a 0.3 urn gas barrier coating film
on the aluminum oxide vapor deposition layer, to
90
produce an adhesiveness-reinforced transparent vapordeposited
film.

On the corona side of 12 um-thick PET (PET-F,
5 product of Unitika, Ltd.) there was formed an aluminum
oxide vapor deposition layer to a thickness of 8 nm
using a reactive resistance heating system/ under the
conditions of Example 5.
Next, the same procedure was carried out as
0 in Example 5 to form a 0.3 um gas barrier coating film
on the aluminum oxide vapor deposition layer, to
produce an adhesiveness-reinforced transparent vapordeposited
film.
(Evaluation)
5 The vapor-deposited films produced under the
conditions of Examples 5 to 9 and Comparative Examples
4 to 7, or the vapor-deposited films having the gas
barrier coating films formed on the vapor-deposited
films, were used as samples for X-ray photoelectron
0 spectroscopy, measurement of the oxygen permeability,
measurement of the hydrogen permeability and
measurement of the bonding strength between the films
and vapor-deposited films.
The measuring samples were used for
5 measurement by X-ray photoelectron spectroscopy and
measurement of the oxygen permeability, water vapor
permeability and bonding strength.
91

1. Measurement was performed in the same
manner as Example 1 for X-ray photoelectron
spectroscopy, and for the oxygen permeability and
5 water vapor permeability as gas barrier properties.
2. Bonding strength between plastic substrate
and aluminum oxide vapor deposition layer

The coating film side, where the gas barrier
0 coating film had been formed on the vapor deposited
surface side of the vapor-deposited film, was coated
with a two-pack curable polyurethane-based adhesive
and dried, and this was dry laminated with an
unstretched polypropylene film with a thickness of 60
5 urn that had been coated with a two-pack curable
polyurethane-based adhesive and dried, to form a
layered composite film, and after completing aging, it
was used as a bonding strength measuring sample.
The layered composite film was used to
0 prepare a size B5 four-sided pouch i nto whi ch 100 mL
of water was poured, and hot water retort treatment
was carried out at 121°C for 60 minutes. After retort
treatment, and cutting out a sample into a 15 mm-wide
strip from the four-sided pouch after removal of the
5 water contents, a tensile tester (device name:
TENSILON General-Purpose Material Tester by Orientech
Co., Ltd.) was used according to JIS K6854-2 for
92
measurement of the bonding strength at the bonding
interface between the vapor-deposited film and the
unstretched polypropylene film, by 180° peeling at a
peel rate of 50 mm/min (T-peel method).

The coating film side, where the gas barrier
coating film had been formed on the vapor deposition
surface side of the vapor-deposited film, was coated
with a two-pack curable polyurethane-based adhesive
and dried, and this was dry laminated with an
unstretched polypropylene film with a thickness of 30
um that had been coated with a two-pack curable
polyurethane-based adhesive and dried, to form a
layered composite film, and after completing aging, it
was used as a bonding strength measuring sample.
A sheet prepared to size B5 using the layered
composite film was stored for 500 hours in a thermohygrostat
at 60°C, 90% RH, and then with the sample
cut into 15 mm-wide strips, a tensile tester (device
name: TENSILON General-Purpose Material Tester by
Orientech Co., Ltd.) was used according to JIS K6854-2
for measurement of the bonding strength at the bonding
interface between the vapor-deposited film and the
unstretched polypropylene film, by 180° peeling at a
peel rate of 50 mm/min (T-peel method).

93
The results for evaluation of the performance
of testing samples for measurement of the bonding
strength (4) are shown in Table 4.
[0145] As shown in Table 4, a clear difference was
seen between the vapor-deposited films produced using
the plasma preprocessing device of the invention, and
10 those obtained by prior art technology, based on
comparison between the examples and comparative
examples.
[0146] It is notable that with the plasma
preprocessing of the invention, the abundance ratio of
15 Al-C covalent bonds was 17% to 22%, while being absent
below the detection -limit (not generated) by
94
conventional plasma preprocessing, as shown in Table 4
and therefore Al-C covalent bonds were produced at a
high proportion during vapor-deposited film formation.
As seen by the bonding strengths in the
5 examples and comparative examples, the bonding
strength based on the lamination strength after hot
water retort treatment at 121°C for 60 minutes was 5.2
to 6.3 with plasma preprocessing according to the
invention, whereas the bonding strength based on the
0 lamination strength with conventional plasma
preprocessing was 0.5 to 1.3, and thus generation of
Al-C covalent bonds can increase the hot waterresistant
adhesiveness of the transparent vapordeposited
film for retort of the invention by about 4-
5 to 10-fold or greater compared to the prior art even
with hot water retort treatment with high temperature
water, exhibiting hot water resistance while
maintaining excellent gas barrier properties.
[0147] The expression of such bonding strength is
0 assumed to be due to the Al-C covalent bonds, allowing
a vapor-deposited film to be obtained with stable hot
water-resistant adhesiveness, unlike with layering of
a plastic substrate and a vapor-deposited film by
functional groups via oxygen as in the prior art.
5 [0148] A vapor-deposited film obtained by plasma
preprocessing using a continuous vapor-deposited film
forming device separately comprising a preprocessing
95
chamber provided with a plasma preprocessing device of
the invention, and a film-forming chamber, can be
produced as a transparent vapor-deposited film for
retort that maintains excellent water vapor
5 permeability and oxygen permeability and exhibits
stable performance, as is clear by comparison between
Examples 1 to 4 and the comparative examples, and it
has become possible to form a high-quality,
homogeneous transparent vapor-deposited film for
10 retort having adhesiveness maintained between the
plastic substrate and the vapor-deposited film and
having significantly reinforced hot water-resistant
adhesiveness, even after hot water retort treatment at
121°C for 60 minutes.
15
The results for evaluation of the performance
of testing samples for measurement of the bonding
strength (5) are shown in Table 5.
20 [Table 5]
96
Example
Example
5
Example
6
Example
7
Example
8
Example
9
Comp .
Ex. 4
Comp .
Ex. 5
Comp .
Ex. 6
Comp .
Ex. 7
Al-C bond
abundance
ratio [%]
17
21
20
22
22
Below
detection
limit
Below
detection
limit
Below
detection
limit
Below
detection
limit
Surface
roughness
Rz [nm]
8
8
8
8
8
12
11
8
8
Al/O
ratio
up to
3 nm
0. 83
0.79
0.82
0. 91
0. 91
0. 85
1. 44
0.87
0. 87
Oxygen
permeability
[cc/m2, day]
1. 3
0.2
0. 2
0. 3
0.3
0.2
0. 2
0.2
0. 2
Water vapor
permeabilit y
[g/m2- day]
1. 2
0. 6
0. 5
0.3
0. 3
0. 6
0. 7
0.7
0. 7
Bonding
strength
[N/15
mm]
3. 3
6. 0
5.8
6. 3
6.3
0.5
1. 3
0.7
0. 7
10

A packaging material of the invention was
then used to produce a packaging, and in order to
evaluate the performance when holding contents, the
vapor deposition layer or gas barrier coating film
sides of the transparent vapor^deposited films
obtained in Examples 5 to 9 and Comparative Examples •
to 7 were coated with a two-pack curable polyurethanebased
adhesive, a 15 um-thick biaxially stretched
nylon film was attached thereto, a two-pack curable
polyurethane-based adhesive was further coated on the
97
nylon film side and a 70 urn-thick unstretched
polypropylene film was attached thereto, after which
it was aged, to obtain a gas barrier layered composite
film.
5 The same layered composite film was used to
fabricate a 15 cm * 15 cm four-sided pouch as a
packaging bag, and after filling the packaging bag
with water, curry sauce or Chinese soup without
allowing bubbles in, it was subjected to retort
10 sterilization treatment at 121°C for 30 minutes, the
gas barrier property and bonding strength were
measured, and the outer appearance was examined for
the presence of any delamination. The results are
shown in Table 6.
15 [Table 6]
99
The vapor deposition layer or gas barrier
5 coating film sides of the transparent vapor-deposited
films obtained in Examples 5 to 9 and Comparative
Examples 4 to 7 were coated with a two-pack curable
polyurethane-based adhesive, a 3 0 ym-thick highdensity
polyethylene film was attached thereto, and it
10 was aged to obtain a gas barrier layered composite
film.
The same layered composite film was used to
fabricate a 15 cm * 15 cm four-sided pouch as a
packaging bag, and after filling the packaging bag
15 v/ith a rinse-containing shampoo, it was stored for 3
100
months at 4 0 °C, 90% RH, the gas barrier property and
bonding strength were measured, and the outer
appearance was examined for the presence of any
delamination. The results are shown in Table 7.
[0149]
[Table 7]
As explained above, the packaging material o
0 the invention exhibits satisfactory performance even
when holding contents.
Industrial Applicability
[0150] The present invention allows plasma
5 preprocessing to be carried out homogeneously in a
wide range of conditions on a long substrate surface
under reduced pressure, and allows formation of a
101
vapor-deposited film having a highly active surface
and containing Al-C covalent bonds, so that a highly
adhesive transparent vapor-deposited film having a
homogeneous vapor-deposited film with excellent
adhesiveness can be formed at high speed even when
applying physical vapor deposition or chemical vapor
deposition as the film-forming means.
Therefore, it can be applied as a packaging
material for foods, drugs or the like that require
layering materials having vapor-deposited films with
excellent barrier properties that can block permeation
of oxygen gas, water vapor and the like, and excellent
adhesiveness, for example, layering materials that can
withstand the heating of retort treatment or heat
treatment, and as a material in fields with extreme
use environments, such as electrical and electronic
part packages and protective sheets that require
durability and barrier properties, or it can be
applied in the production of such materials.
Explanation of Symbols
[0151]
1, S: Plastic substrates
2: Inorganic oxide vapor-deposited film
3: Gas barrier coating film
P: Plasma
10: Roller-type continuous vapor-deposited film
forming device
102
12: Pressure reduction chamber
12A: Substrate conveying chamber
12B: Plasma preprocessing chamber
12C: Film-forming chamber
13: Take-up roller
14: Guide roller
15: Take-up roller
18: Source gas volatilizing and supply apparatus
19: Source gas-supply nozzle
20: preprocessing roller
21: Magnet
2 2: Plasma supply nozzle
25: Film-forming roller
26: vapor-deposited film-forming means
30: Vacuum pump
31: Power supply wiring
32: Power source
35a-35c: Partitions

CLAIMS
1. A transparent vapor-deposited film having
at least a laminar structure with an inorganic oxide
5 vapor-deposited film that is composed mainly of
aluminum oxide formed on the surface of a plastic
substrate, the transparent vapor-deposited film
containing A1~C covalent bonds at the interface
between the plastic substrate and the inorganic oxide
0 vapor-deposited film that is composed mainly of
aluminum oxide.
2. A transparent vapor-deposited film
according to claim 1, wherein a metal alkoxide
hydrolyzable product and a water-soluble polymer mixed
5 solution are coated onto the vapor-deposited film
surface and heat-dried to produce a gas barrier
coating film.
3. A transparent vapor-deposited film
according to claim 1 or 2 , wherein the bonding
0 strength between the plastic substrate and the vapordeposited
film is at least 3.0 N/15 millimeters based
on measurement of the lamination strength after
storage for 5 00 hours in an environment of 60°C x 90%
RH.
5 4. A transparent vapor-deposited film
according to claim 1 or 2, wherein the bonding
strength between the plastic film and the vapor104
deposited film is at least 3 N/15 mm based on
measurement of the lamination strength after hot water
treatment at 121°C, 60 min.
5. A transparent vapor-deposited film
according to any one of claims 1 to 4, wherein the
abundance of Al-C covalent bonds is between 0.3% and
3 0% of the total bonds that include C, based on
measurement by X-ray photoelectron spectroscopy
(measuring conditions: X-ray source: AlKa, X-ray
output: 12 0W), and the A1/0 ratio of the inorganic
oxide vapor-deposited film that is composed mainly of
aluminum oxide from the interface between the plastic
substrate and the vapor-deposited film up to 3 nm
toward the surface of the vapor-deposited film is no
greater than 1.0.
6. A transparent vapor-deposited film
according to any one of claims 1 to 5, wherein the
vapor-deposited film containing Al-C covalent bonds is
formed by holding the surface of the plastic substrate
in a voltage-applied state between the plasma
preprocessing roller and the plasma supply means for
plasma preprocessing, and then continuously forming an
inorganic oxide vapor-deposited film that is composed
mainly of aluminum oxide.
7. A transparent vapor-deposited film
according to claim 6, wherein the plasma preprocessing
is plasma preprocessing using a roller-type continuous
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vapor-deposited film forming device comprising a
preprocessing chamber, in which the surface of a
plastic substrate to be provided with a vapordeposited
film is subjected to plasma processing, and
5 a film-forming chamber in which the vapor-deposited
film is formed, which are provided in a continuous
manner, the plasma preprocessing being constructed
such that there are situated a preprocessing roller
and plasma supply means and magnetism forming means
0 facing the preprocessing roller, the supplied plasma
source gas is introduced as plasma near the substrate
surface, with a gap being formed that traps the plasma,
and plasma processing is carried out while holding in
a voltage-applied state between the plasma
5 preprocessing roller and the plasma supply means.
8. A transparent vapor-deposited film
according to claim 6 or 7, wherein the preprocessing
by plasma is processing in which the surface of the
plastic substrate on which the vapor-deposited film is
0 to be provided is processing using a roller-type
continuous vapor-deposited film forming device having
a separated plasma preprocessing chamber and vapordeposited
film-forming chamber, under conditions with
a plasma strength per unit area of 100-8000W - sec/m2.
5 9. A transparent vapor-deposited film
according to any one of claims 6 to 8, wherein the
plasma source gas is argon alone, and/or a mixed gas
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with one or more from among oxygen, nitrogen and
carbon dioxide gas.
10. A transparent vapor-deposited film
according to claim 9, wherein the preprocessing with
plasma is carried out using a plasma source gas
comprising a mixed gas of argon and one or more from
among oxygen, nitrogen and carbon dioxide gas.
11. A transparent vapor-deposited film
according to any one of claims 1 to 10, wherein the
means for forming the vapor-deposited film is physical
vapor deposition.
12. A transparent vapor-deposited film
according to any one of claims 1 to 11, wherein the
inorganic compound is an inorganic oxide composed
mainly of aluminum oxide, or a mixture thereof.
13. A transparent vapor-deposited film
according to claim 12, wherein the inorganic oxide is
an inorganic oxide mixture of aluminum oxide with one
or more selected from among silicon oxide, magnesium
oxide, tin oxide and zinc oxide.
14. A transparent vapor-deposited film
according to any one of claims 1 to 13, wherein an
aluminum oxide vapor deposition layer is formed to a
thickness of 5-100 nm on at least one surface of the
plastic substrate.
15. A packaging material according to any one
of claims 1 to 14, wherein a heat-sealable
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thermoplastic resin, is layered as an innermost layer
iria an adhesive layer.
16. A packaging material according to any one
of claims 2 to 14, wherein after forming a printed
layer on the gas barrier coating film, a heat-sealable
thermoplastic resin is layered as an innermost layer
via an adhesive layer.
17 . 7A packaging material according to claim
r
15 or 16, wherein the heat-sealable thermoplastic
resin has a light-shielding property.
18. A packaging material according to any one
of claims 15 to 17, wherein the packaging material is
to >be used in a package for boiling or retort
sterilization.
19. A packaging material according to any one
of claims 15 to 17, wherein the packaging material is
to be used in a daily commodity such as a shampoo,'
rinse or rinse-in-shampoo, or in a cosmetic package or
liguid soup package.