U.S. patent application number 13/040642 was filed with the patent office on 2012-04-12 for non-pvc film and non-pvc film laminate.
This patent application is currently assigned to AVERY DENNISON CORPORATION. Invention is credited to Sujith CHACKO, Chad Cummings, Frank Y. SHIH.
Application Number | 20120088054 13/040642 |
Document ID | / |
Family ID | 44247939 |
Filed Date | 2012-04-12 |
United States Patent
Application |
20120088054 |
Kind Code |
A1 |
CHACKO; Sujith ; et
al. |
April 12, 2012 |
Non-PVC Film and Non-PVC Film Laminate
Abstract
The present invention relates to a non-PVC film and film
laminate for use in marketing, advertising campaigns, particularly
outdoor or other environment impacted promotions and safety
applications. The film is in one exemplary embodiment includes two
layers, a top layer and a bottom layer. The top layer is a
urethane-acrylic hybrid polymer and the bottom layer is a non-PVC
based polymer. The film may be transparent, translucent, clear or
have other desirable optical properties.
Inventors: |
CHACKO; Sujith; (Alhambra,
CA) ; SHIH; Frank Y.; (Arcadia, CA) ;
Cummings; Chad; (Reminderville, OH) |
Assignee: |
AVERY DENNISON CORPORATION
Pasadena
CA
|
Family ID: |
44247939 |
Appl. No.: |
13/040642 |
Filed: |
March 4, 2011 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
61310378 |
Mar 4, 2010 |
|
|
|
Current U.S.
Class: |
428/41.8 ;
428/195.1; 428/423.1 |
Current CPC
Class: |
B44F 1/066 20130101;
B32B 2451/00 20130101; B32B 27/308 20130101; B32B 2307/75 20130101;
Y10T 428/24802 20150115; B32B 2307/732 20130101; B32B 2307/584
20130101; B32B 27/40 20130101; B32B 2307/414 20130101; B32B 2553/00
20130101; G09F 3/10 20130101; B32B 2307/406 20130101; B32B 2307/50
20130101; Y10T 428/31551 20150401; B32B 2270/00 20130101; B32B
2413/00 20130101; B32B 2519/00 20130101; B32B 27/08 20130101; B32B
2307/71 20130101; B32B 2457/00 20130101; Y10T 428/2848 20150115;
B32B 27/00 20130101; B32B 2307/54 20130101; B32B 2307/546 20130101;
B32B 2307/712 20130101; B32B 2605/00 20130101; Y10T 428/1476
20150115; B32B 7/12 20130101; B32B 2307/412 20130101 |
Class at
Publication: |
428/41.8 ;
428/423.1; 428/195.1 |
International
Class: |
C09J 7/02 20060101
C09J007/02; B32B 3/00 20060101 B32B003/00; B32B 7/06 20060101
B32B007/06; B32B 27/40 20060101 B32B027/40; B32B 27/18 20060101
B32B027/18 |
Claims
1. An optically transparent protective film comprising: a top
layer; and a bottom layer substantially coextensive with the top
layer, and wherein the top layer is selected from the group
consisting of polyurethane, polyurethane-acrylic copolymer,
polyurethane-acrylic blend and urethane-acrylic hybrid polymer; and
the bottom layer is comprised of a non-PVC based polymer.
2. The film as recited in claim 1, wherein the non-PVC based
polymer is selected from the group consisting of an emulsion based
polymer, a solvent based polymer, and an extruded polymer.
3. The film as recited in claim 1, wherein the non-PVC based
polymer is an acrylic polymer.
4. The film as recited in claim 1, further comprising: an adhesive
layer, and wherein the adhesive layer is in contact with the bottom
layer.
5. The film as recited in claim 1, further including at least one
additive in at least one of the top and bottom layers of the
film.
6. A film as recited in claim 5 wherein the at least one additive
is selected from the group consisting of UV stabilizing agents,
free-radical scavengers, cross-linking agents, thickeners, flow and
leveling agents, rheology modifiers, surfactants, defoamers,
dispersants, wetting agents, dyes, pigments, co-solvents, water,
isopropyl alcohol and combinations thereof.
7. A film laminate comprising: a top layer; a bottom layer; an
intermediate layer; a substrate layer, and wherein the top layer is
selected from the group consisting of polyurethane,
polyurethane-acrylic copolymer, polyurethane-acrylic blend and
urethane-acrylic hybrid polymer; the bottom layer includes a
non-PVC based polymer; and the substrate layer having printed or
image indicia thereon.
8. The film laminate as recited in claim 7, wherein the
intermediate layer is selected from a group including an adhesive
layer, a tie coating layer and an adhesive promotion layer.
9. The film laminate as recited in claim 7, further including at
least one additive in at least one of the top, intermediate and
bottom layers of the film.
10. The film laminate as recited in claim 9 wherein the at least
one additive is selected from the group consisting of UV
stabilizing agents, free-radical scavengers, cross-linking agents,
thickeners, flow and leveling agents, rheology modifiers,
surfactants, defoamers, dispersants, wetting agents, dyes,
pigments, co-solvents, water, isopropyl alcohol and combinations
thereof.
11. An advertising or informational graphic, comprising: a surface
having promotional indicia provided thereon; a film having front
and back faces, with the back face in contact with the surface; the
film including a first layer and a second layer substantially
beneath the first layer, and an adhesive layer beneath the second
layer opposite the first layer; and wherein the first layer
includes a urethane-acrylic hybrid polymer and the second layer
includes non-PVC based polymer.
12. An advertising or informational graphic, comprising: a surface;
an adhesive layer; a printable substrate having front and back
faces, with the back face facing the surface and in contact with
the adhesive layer and the front face having promotional indicia
provided thereon; a transparent film having a top layer and a
bottom layer, with the bottom layer facing the front face of the
printable substrate; and wherein the top layer is selected from the
group consisting of polyurethane, polyurethane-acrylic copolymer,
polyurethane-acrylic blend and urethane-acrylic hybrid polymer; and
the bottom layer includes non-PVC based polymer.
13. The advertising graphic as recited in claim 12, wherein the
surface is selected from the group consisting of architectural,
transportational, artistic, aesthetic, safety devices, road signs,
automotive exterior and interior, military, safety devices road
signs, exterior automotive and combinations thereof.
14. The advertising graphic as recited in claim 12, wherein the
adhesive layer includes an adhesive selected from the group
consisting of a permanent adhesive, a removable adhesive, a
repositionable adhesive, and combinations thereof.
15. The advertising graphic as recited in claim 12, wherein the
promotional indicia is selected from the group consisting of alpha
and/or numeric characters, images and combinations thereof.
16. The advertising graphic as recited in claim 12, wherein a
substrate layer is provided over one of the first and second
layers.
17. The advertising graphic as recited in claim 16, wherein the
substrate layer includes an ink layer.
18. The advertising graphic as recited in claim 12, further
including at least one additive in at least one of the top and
bottom layers of the film.
19. The advertising graphic as recited in claim 18, wherein the at
least one additive is selected from the group consisting of UV
stabilizing agents, free-radical scavengers, cross-linking agents,
thickeners, flow and leveling agents, rheology modifiers,
surfactants, defoamers, dispersants, wetting agents, dyes,
pigments, co-solvents, water, isopropyl alcohol and combinations
thereof.
20. A roll or sheet of graphic advertising film, comprising; a film
having at least first and second layers, the first layer includes a
urethane-acrylic hybrid polymer and the second layer includes
non-PVC emulsion based polymer; and one of the first and second
layers provided in operative association with advertising
indicia.
21. The roll or sheet of graphic advertising film as recited in
claim 20, wherein the film further includes an adhesive layer
provided on one of the first and second layers.
22. The roll or sheet of graphic advertising film as recited in
claim 21, wherein a release layer is provided over the adhesive
layer.
23. The roll or sheet of graphic advertising film as recited in
claim 20, wherein the film further includes a substrate layer
provided over one of the first and second layers.
24. The roll or sheet of graphic advertising film as recited in
claim 23, wherein the substrate layer includes a print layer.
25. The roll or sheet of graphic advertising film as recited in
claim 20, further including at least one additive in at least one
of the first and second layers of the film.
26. The roll or sheet of graphic advertising film as recited in
claim 25 wherein the at least one additive is selected from the
group consisting of UV stabilizing agents, free-radical scavengers,
cross-linking agents, thickeners, flow and leveling agents,
rheology modifiers, surfactants, defoamers, dispersants, wetting
agents, dyes, pigments, co-solvents and combinations thereof.
27. A transparent film for use in outdoor environment, comprising
polymers selected from the group consisting of polyurethane,
polyurethane-acrylic copolymer, polyurethane-acrylic blend and
urethane-acrylic hybrid polymer.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application claims priority from U.S.
Provisional Patent Application No. 61/310,378 filed Mar. 4, 2010,
which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention is in the field of non-PVC films and
non-PVC film laminates for use with small format, and large format
graphic films and presentations, advertising media, promotional
media, static visual communications, vehicle and product wraps and
other commercial applications. The film may be clear, transparent,
translucent or have other desirable optical properties.
BACKGROUND OF THE INVENTION
[0003] Polyvinyl chloride (PVC) films have been used widely in a
number of promotional and advertising campaigns, such as outdoor
graphics applications in the past. Such applications include signs,
banners, fleet marketing graphics, architectural and wall covering,
consumer product labeling and other pressure sensitive products.
However, there is an increasing awareness on the environmental and
health impacts and effects of using PVC based products, which has
increased significantly in recent years. Currently, there is a
movement to reduce or even eliminate PVC-based products from the
consumer marketing, promotional and advertising product
streams.
[0004] Films for outdoor marketing and graphics applications
ideally should have at least some of the following properties:
printability, durability, color retention, and scratch resistance.
Conformability and proper mechanical properties such as tensile
elongation and tensile strength are also preferable for the
application process. A non-conformable film, i.e. a film which does
not have sufficient elongation or flexibility may not follow the
contour of the subject or surface to which it is applied, creating
bubbles or gaps between the surface and the film. Insufficient
elongation properties may make the film hard to apply over a
surface, e.g. those surfaces that have curves, angles, ridges and
other non-planar configurations, but too much elongation may deform
the film and potentially causing a distortion of the printed
indicia. Films with a low tensile strength may cause the film to
break easily when being stretched such as when the film is being
applied to a non-planar surface.
[0005] As new PVC replacement films are being developed, some of
the films have superior performance in one area, such as
printability, but lack adequate functionality with respect to the
other properties such as the outdoor durability to make the films
acceptable for the demanding advertising and promotional market.
One possible way to resolve the foregoing problem is to use a
multi-layer film laminate with each layer providing one or more of
the desired properties so that the laminate has all the desired
properties that are needed.
[0006] When used as the outermost protective layer in a film
laminate, or simply used as a protective film for a given surface,
good outdoor durability and in many cases optical transparency is
also required so the indicia on an underneath printable layer can
be visible.
[0007] Therefore, there is a need for non-PVC-based transparent
films and non-PVC film laminates for use with outdoor graphics and
other marketing and consumer use applications.
BRIEF SUMMARY OF THE INVENTION
[0008] The embodiments of the present invention described below are
not intended to be exhaustive or to limit the invention to the
precise forms disclosed in the following detailed description.
Rather, the embodiments are chosen and described so that others
skilled in the art may appreciate and understand the principles and
practices of the present invention.
[0009] The invention is directed to a non-PVC based film product
having similar properties to those of conventional PVC offerings
that is suitable for use in connection with marketing promotions,
graphics, branding campaigns and other printed or imaged
communication based initiatives.
[0010] In one exemplary embodiment of the presently described
invention, a non-PVC film, which may be clear, transparent,
translucent or have other desirable optical properties, is made of
polyurethane, polyurethane-acrylic copolymer, polyurethane-acrylic
blend, or urethane-acrylic hybrid polymer.
[0011] In another exemplary embodiment of the presently described
invention, a non-PVC transparent film includes a top layer and a
bottom layer. The top layer includes a polyurethane,
polyurethane-acrylic copolymer, polyurethane-acrylic blend, or
urethane-acrylic hybrid polymer. The bottom layer includes an
emulsion based, solvent-based, or extruded non-PVC based
polymer.
[0012] In another exemplary embodiment of the presently described
invention, a non-PVC film laminate is provided that includes a top
layer, a bottom layer, an adhesive layer and a substrate. The top
layer includes a urethane-acrylic hybrid polymer. The bottom layer
has a non-PVC emulsion based polymer. The substrate layer bears
printed or imaged indicia or graphics.
[0013] In a further exemplary embodiment of the presently described
invention, an advertising graphic is presented and includes a
surface having promotional indicia provided thereon, a transparent
film having front and back faces, with the back face in contact
with the surface and the front face exposed to an atmosphere (e.g.
air) or non-atmosphere (e.g. ice). The film includes a first layer
and a second layer substantially beneath the first layer, and an
adhesive layer beneath the second layer opposite the first layer.
The first layer of the film includes a urethane-acrylic hybrid
polymer and the second layer includes non-PVC emulsion based
polymer.
[0014] Other features and advantages of the present invention will
become apparent to those skilled in the art from the following
detailed description. It is to be understood, however, that the
detailed description of the various embodiments and specific
examples, while indicating preferred and other embodiments of the
present invention, are given by way of illustration and not
limitation. Many changes and modifications within the scope of the
present invention may be made without departing from the spirit
thereof, and the invention includes all such modifications.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] These, as well as other objects and advantages of this
invention, will be more completely understood and appreciated by
referring to the following more detailed description of the
presently preferred exemplary embodiments of the invention in
conjunction with the accompanying drawings, of which:
[0016] FIG. 1 is a sectional illustration of one exemplary
embodiment of a film according to the present invention;
[0017] FIG. 2 is a block diagram illustrating an exemplary
manufacturing process for making one embodiment of the film
according to the present invention;
[0018] FIG. 3 is a flow chart illustrating another manufacturing
process for making one embodiment of the film according to the
present invention;
[0019] FIG. 4 is a sectional illustration of one exemplary
embodiment of a film according to the present invention;
[0020] FIG. 5 is a sectional illustration of a further exemplary
embodiment of a film laminate according to the present
invention;
[0021] FIG. 6 illustrates the top view of an exemplary embodiment
of an advertising graphic applied on a surface according to the
present invention; and
[0022] FIG. 7 illustrates an exemplary embodiment of a roll of an
advertising graphic according to the present invention.
[0023] Unless otherwise indicated, the illustrations in the above
figures are not necessarily drawn to scale.
DETAILED DESCRIPTION OF THE INVENTION
[0024] The apparatuses and methods disclosed in this document are
described in detail by way of examples and with reference to the
figures. Unless otherwise specified, like numbers in the figures
indicate references to the same, similar, or corresponding elements
throughout the figures. It will be appreciated that modifications
to disclosed and described examples, arrangements, configurations,
components, elements, apparatuses, methods, materials, etc. can be
made and may be desired for a specific application. In this
disclosure, any identification of specific shapes, materials,
techniques, arrangements, etc. are either related to a specific
example presented or are merely a general description of such a
shape, material, technique, arrangement, etc. Identifications of
specific details or examples are not intended to be, and should not
be, construed as mandatory or limiting unless specifically
designated as such. Selected examples of apparatuses and methods
are hereinafter disclosed and described in detail with reference
made to FIGURES.
[0025] The present invention relates to a film and a film laminate
used for outdoor graphics applications, advertising, promotions and
other marketing campaigns. More particularly, the present invention
relates to a non-PVC transparent film and non-PVC film laminate for
use in such applications. The film and film laminate provide
suitable outdoor durability, scratch resistance, gloss,
conformability, tensile elongation and tensile strength.
[0026] In one exemplary embodiment of the invention, a single layer
transparent film with properties suitable for use in the outdoor
graphics applications is made of polyurethane, polyurethane-acrylic
copolymer, polyurethane-acrylic blend or polyurethane-acrylic
hybrid polymer.
[0027] In another exemplary embodiment of the invention, a
multi-layer transparent film provides properties suitable for use
in the outdoor graphics applications. The multi-layer film has at
least two layers. The first layer is made of polyurethane,
polyurethane-acrylic copolymer, polyurethane-acrylic blend or
urethane-acrylic hybrid polymer. The thickness of this first layer
can be from about 0.3 mil (7.6 microns) to about 2 mils (50.8
microns). The other layers provide additional mechanical strength,
improved adhesion, improved conformability and reduced cost to the
overall construction. The number of layers can be determined based
on the final requirement on the product, the cost restriction and
availability of processing equipments. Such other layers can be
made from emulsion polymers, solvent polymers or extruded polymers.
Suitable polymers include, without limitation, acrylic polymers,
styrene acrylic polymers, vinyl acetate ethylene copolymers, and
polyolefins. The thickness of such other layer can vary from about
0 mil to about 2 mils. Examples of emulsion polymers include,
without limitation, JONCRYL 617A JONCRYL 1987, JONCRYL 98, JONCRYL
FLX5000, ACRONAL NX4612X and ACRONAL OPTIVE 410 available from
BASF, Ludwigshafen, Germany; and VINNAPAS EF 811 from Wacker
Chemicals, Munich, Germany or combinations thereof.
[0028] In yet another exemplary embodiment of the invention, a
non-PVC transparent film includes a top layer and a bottom layer.
The top layer is made of polyurethane, polyurethane-acrylic
copolymer, polyurethane-acrylic blend or polyurethane-acrylic
hybrid polymer. The bottom layer includes a non-PVC emulsion based
polymer. Generally, the non-PVC based polymer can be an emulsion
based polymer, a solvent based polymer, and/or an extruded polymer.
In certain embodiments, the non-PVC based polymer is an acrylic
polymer.
[0029] As used herein the term "graphic" or "graphics" refers to a
visually perceptible presentation on some surface that is intended
to brand, illustrate, entertain, inform, advertise, announce and
market a product, service, event or the like.
[0030] Reference is now directed to the FIGURES in which FIG. 1
provides a sectional view of an exemplary film prepared in
accordance with the presently described invention. The film 100 has
two layers. The film may be transparent, translucent, clear or have
other desirable optical properties. The top layer 102 is, in one
exemplary embodiment, a urethane-acrylic hybrid polymer. Bottom
layer 104 is in the presently described embodiment a strengthening
polymer layer.
[0031] In addition, the film layers may have at least one additive
added to either one or both, or two additives added to one or both
of the layers. If an intermediate layer is included (see FIG. 4)
the additive may also be present in the intermediate layer. The
additives are selected from a group including UV stabilizing
agents, free-radical scavengers, cross-linking agents, thickeners,
flow and leveling agents, rheology modifiers, surfactants,
defoamers, dispersants, wetting agents, dyes, pigments, co-solvents
or combinations thereof.
[0032] The urethane-acrylic hybrid polymer of the top layer 102 is
a combination of urethane polymer and acrylic polymer mixed at the
molecular level. In order to be environmentally friendly, the top
layer 102 is preferred to be created from waterborne dispersions,
although other methods for producing the urethane-acrylic hybrid
polymer may also be used. Typically, there are two methods to make
such hybrid polymer dispersions. In a first method, a polyurethane
dispersion is prepared. Acrylic monomers are then added to the
polyurethane dispersion. The acrylic polymer is formed in the
presence of the polyurethane dispersion. In a second method, a
polyurethane prepolymer is formed. The acrylic monomers are then
added to the prepolymer. The urethane and acrylic polymerizations
are completed concurrently. There are numerous publications on
these methods. For example, U.S. Pat. No. 3,684,758 to Honig; U.S.
Pat. No. 4,198,330 to Kaizerman; U.S. Pat. No. 4,644,030 to
Loewrigkeit; and U.S. Pat. No. 5,594,065 to Tien describe the
foregoing methods in detail. Publications, patents and patent
applications are referred to throughout this disclosure. All
references cited herein are hereby incorporated by reference.
[0033] The urethane-acrylic hybrid polymer dispersions prepared
according to the above described methods have been found to show
better mechanical properties when compared to a simple blend of the
two polymers due to the molecular level mixing which occurs through
use of the foregoing processes. In order to make the formulation
even more environmentally friendly, that is to reduce the
environmental impact over other preparations, the urethane-acrylic
hybrid polymer dispersions can be further improved to be free of
N-methylpyrrolidone (NMP), a component typically used as a
processing solvent in other applications.
[0034] Suitable urethane-acrylic hybrid polymer dispersions for use
in the compositions of the present invention are those with
aliphatic acrylic monomers and aliphatic polyurethane components.
As the film products produced will be used in an outdoor
environment, the films will be exposed to moisture, such as dew,
rain or snow; temperature deviations; light and other conditions
which may impact the film performance. For example, moisture may
cause components of the film or images thereon to bleach out or
fade, and the film itself to whiten. Therefore, maintaining a
proper balance of hydrophilic monomers and other components is
required in order for this film to achieve the required resistance
when exposed to such conditions. The monomers and other components
should also be selected so as to be balanced to achieve the
required tensile properties, block resistance, scratch resistance,
transparency, and gloss. For example, the amount of acrylic present
in the urethane-acrylic hybrid polymer controls the tensile
properties of this top layer.
[0035] Suitable urethane-acrylic hybrid dispersions for use in the
present invention are available under the trade name HYBRIDUR from
Air Products, Allentown, Pa., including HYBRIDUR 870; HYBRIDUR 570;
HYBRIDUR 580; HYBRIDUR 878; and NEOPAC R9000 from DSM NeoResins, of
Waalwijk, The Netherlands.
[0036] UV blocking agents and free radical scavengers can be added
to the top layer to improve the outdoor durability. UV blocking
agents suitable for this application are typically benzotrizole
based compounds, or other compounds capable of absorbing UV energy
in the required region. Commercially available UV absorbing agents
include, without limitation, TINUVIN 400 DW, TINUVIN 292 from BASF,
Ludwigshafen, Germany; and HOSTAVIN 3310 from Clariant; Muttenz,
Switzerland. The amount of UV blocking agent can range from about
0% to about 5%.
[0037] Free radical scavengers may also be added to the top layer
of the film to improve the weather durability of the top layer.
Suitable free radical scavengers include but are not limited to
TINUVIN 1130, TINUVIN 123 DW from BASF, Ludwigshafen, Germany; and
HOSTAVIN 3065 from Clariant, Muttenz, Switzerland. The amount of
free radical scavengers can range from about 0% to about 5%.
[0038] Other UV blocking systems can also be used for improving
weathering durability of this film. These include nano sized zinc
oxide and cerium oxide or combinations thereof which may be used to
achieve the UV resistance required for the film. Suitable nano
metal oxides include but are not limited to NANOBYK 3840, NANOBYK
3810 from BYK Additives, of Altana, Wesel, Germany. The total
amount of additives may range from about 0% to about 10%.
[0039] Continuing with a discussion of the laminate provided in
FIG. 1, the bottom layer 104 has a polymer layer that improves
tensile properties of the overall film 100 which may also reduce
the cost of the overall film. Examples of such strengthening
polymer layer include, without limitation, emulsion based polymers,
solvent based polymers, and extruded polymers. Suitable polymers
include, without limitation, acrylic polymers, styrene acrylic
polymers, vinyl acetate ethylene copolymers, and polyolefins. UV
stabilizers and free radical scavengers can also be added to the
bottom layer. The additives together can range from about 0% to
about 5% of the total formulation.
[0040] When acrylic polymers are used in the bottom layer 104, the
acrylic polymers can be the same or different from those used in
the top layer 102. Both aliphatic and aromatic acrylics can be
suitable for inclusion in the bottom layer. Suitable acrylic
polymers include acrylic emulsions that have superior block
resistance, tensile properties and clarity, such as JONCRYL 617A
available from BASF, Ludwigshafen, Germany.
[0041] The thickness of the top layer 102 can range from about 0.5
mil to about 5 mils. The thickness of the bottom layer 104 can
range from about 0.5 mil (12.7 microns) to about 5 mils (127
microns). When the thickness of the top layer 102 is too thin, the
chemical resistance, scratch resistance and outdoor durability of
the film may suffer. When the thickness of the bottom layer 104 is
too thin, the tensile properties of the whole film may not be
sufficient. Contrary to the above, when the top and bottom layers
102, 104 respectively, are too thick, the thickness of the
construction may also impact the conformability of the film.
[0042] The film 100 can be generated using any process suitable for
such purpose. In one embodiment, the film compositions were first
deposited onto a removable support or carrier layer by techniques
well known to those skilled in the art. Examples of such techniques
include die coating, knife coating, curtain coating and reverse
roll coating. The removable support can be separated after the
compositions have been dried. An exemplary removable support can be
selected from a group including a siliconized belt, a release
paper, and a release film such as PET or other suitable
materials.
[0043] An exemplary method of making a film according to the
present invention is illustrated in the block diagram 200 of FIG.
2. After starting the process at step 205, the next step 210 is to
provide the top layer components and a removable support. Next, at
step 215, the top layer components are blended to form a top layer
composition. The top layer composition includes polyurethane,
polyurethane-acrylic copolymer, polyurethane-acrylic blend, or
urethane-acrylic hybrid dispersions and at least one of free
radical scavenger and UV blocking agent. Next, at step 220, the
removable support is coated with the top layer composition, such as
by slot die coating, curtain coating or other acceptable methods.
At step 225, the top layer composition is dried. Drying may occur
by using a heated or ambient air environment, curing or by other
suitable methods. At step 230, the bottom layer components are
provided. At step 235, the bottom layer components are blended to
form a bottom layer composition. The bottom layer composition
includes emulsion polymer or solvent polymer and at least one of a
free radical scavenger and a UV blocking agent. The bottom layer
composition is coated over the top layer at step 240, such as by
slot die coating. At step 245, the bottom layer composition is
dried. Alternatively, the film is further laminated with a pressure
sensitive adhesive (PSA) coated release liner before proceeding to
the next step. At step 250, the removable support is removed or
separated from the dried two layer film. The separation or removal
can be accomplished by using a peel blade or knife which serves to
separate the film from the carrier or support layer. Alternatively,
the film can be separated by the carrier at a sharp angle so that
the film can be easily picked up from the carrier or support. The
film is rolled up and ready for use. Alternatively, the film can be
cut and separated into sheets or sections of equivalent sizes or of
varying lengths. The method ends at step 255.
[0044] The top layer and the bottom layer are substantially
coextensive with one another, that is the edges and/or sides are
aligned and in juxtaposition. It is of course possible, that the
top layer could be applied in a pattern over the bottom layer so
that the layers are not completely juxtaposed on one another.
[0045] In another embodiment of the invention, the compositions of
the top layer and the bottom layer can be coated onto a removable
support simultaneously. Flowchart 300 in FIG. 3 illustrates such an
exemplary process. After starting at step 305, the next step 310 is
to provide the top layer components, the bottom layer components
and a removable support. Next, at step 315, the top layer
components are blended to form a top layer composition.
Substantially, simultaneously, the bottom layer components are
blended to form a bottom layer composition. Next, at step 320, the
top layer composition and the bottom layer composition are coated
simultaneously using a dual die with the top layer composition
contacting the removable support and the bottom layer composition
contacting the top layer composition. Additionally, the top layer
and bottom layer can be formed separately and then extruded or
coated on to the support or carrier through a common apparatus. At
step 325, the coated compositions are dried. Alternatively, the
film is further laminated with a PSA coated release liner before
proceeding to the next step. After drying of the compositions, the
removable support or carrier layer can be removed from the dried
two layer film in step 330. The film can be rolled up and ready for
use or sheeted depending on the requirements of the particular
application. The film may then be printed or imaged by conventional
methods such as by ink jet and electrostatic printing technologies
or alternatively, the film can be applied over another substrate
which may have been printed or imaged previously. The method ends
at step 335.
[0046] In addition to the foregoing, the film can be further
overcoated with a varnish or other material to provide a glossy
appearance. This step may occur during the film forming process,
after printing or after collection of the material after the
production process has been completed.
[0047] The film of the present invention can be used in operative
association with a graphic or other message. As used herein,
operative association includes applying the film over the graphic
or message, including the graphic or message as part of the film
either as an additional layer, such as a printing layer or
previously printed layer, or applying a graphic or message over the
film.
[0048] The film can be used as a printable media for outdoor
applications, architectural and transportation type advertising
campaigns and the like. The film can also be used as a protective
film to be laminated over a subject, such as a protective laminate
for electronic appliances, architectural, artistic or aesthetic
elements, a retro-reflective license plate, a retro-reflective
signage film, a name plate, a label, automotive exterior and
interior parts, and the like. Additional exemplary uses may include
safety signs, a graphic display, governmental mandated displays,
military applications or a surface that needs protection in the
outdoor environment.
[0049] The film can also include an adhesive layer. The adhesive
can be a pressure sensitive adhesive, glue, and any other type of
adhesives that are optically transparent, and when used to contact
the printed indicia, would not affect the printed indicia. The
adhesive may be pattern coated, and may be selected for particular
properties such as permanent, removable or repositionable and the
like. The adhesive can be random copolymer adhesives or block
copolymer adhesives. Random copolymer adhesives include those based
upon acrylic and/or methacrylic copolymers, a-olefin copolymers,
silicone copolymers, chloroprene/acrylonitrile copolymers, and the
like. Block copolymer adhesives including those based upon linear
block copolymers (i.e., A-B and A-B-A type), branched block
copolymers, star block copolymers, grafted or radial block
copolymers, and the like, and natural and synthetic rubber
adhesives. A description of useful pressure sensitive adhesives can
be found in Encyclopedia of Polymer Science and Engineering, Vol.
13. Wiley-Interscience Publishers (New York, 1988). Additional
descriptions of useful pressure sensitive adhesives can be found in
Encyclopedia of Polymer Science and Technology, Vol. 1,
Interscience Publishers (New York, 1964).
[0050] When pressure sensitive adhesives are used, a release liner
can be used to protect the adhesive from inadvertent contact with
unintended surfaces. Any release liner suitable for the chosen
adhesive can be used. For pressure sensitive adhesives, release
liners can be coated papers or films, and super calendared paper,
for example. Coating materials suitable for release liners include,
for example, silicone-based and fluorine-based materials, or any
other material that has the desired releasing properties, for
example, waxes and carbamates.
[0051] FIG. 4 illustrates one embodiment of the current invention.
The film 400 has a top layer 402, a bottom layer 404, an
intermediate layer 406 and a release liner 408. Upon application,
the release liner can be peeled off to expose the adhesive surface.
The film can be attached to the surface to be protected through the
adhesive layer. The intermediate layer may include an adhesive
layer, a tie coating layer or an adhesion promoting layer.
[0052] The film can also be used as part of a larger film laminate.
FIG. 5 illustrates a cross-sectional view of one embodiment of a
film laminate. The film laminate 500 is comprised of a top layer
502, a bottom layer 504, an adhesive layer 506, an ink layer 510,
and an underlying substrate layer 512. Though referred to as an ink
layer, the ink may not necessarily form a continuous layer. Various
printable materials can be used as the underlying substrate layer.
A non-PVC based printable material is preferred to make the whole
film laminate non-PVC based. International patent application
PCT/US08/84812 describes various films created using non-PVC
compositions and is incorporated herein by reference in its
entirety. Ink or toner anchor coatings, such as polyvinyl alcohol
can be added to increase the anchorage of the printing to the
laminate.
[0053] FIG. 6 illustrates a top view of an exemplary embodiment of
an advertising graphic film applied to a surface according to the
present invention. The film laminate bearing advertising graphic
614 is posted on a surface 616 through the use of an adhesive.
[0054] FIG. 7 illustrates an exemplary embodiment of a roll of the
film laminate 700 according to the present invention.
[0055] Additional components, such as thickeners, flow and leveling
agents, and rheology modifiers can be added to each of the top and
bottom formulations to achieve desired coating quality. Examples of
suitable thickeners include, without limitation, ACRYSOL RM-2020
NPR, TM8W, and UCAR POLYPHOBE 115 TR from Dow Chemicals, Midland,
Mich. Examples of suitable flow and leveling agents include without
limitation, ZONYL FS300 from Dupont; Polyfox PF-156A from Omnova
Solutions; and Masurf from Mason Chemical Company and others with
similar chemistry. The percent incorporation can vary from 0% to
10% in both layers. Additional viscosity modifiers can be included
in the formulation to modify the viscosity to a desired level
and/or to impart desirable flow characteristics. These can be
urethane based alkali swellable associative thickeners. Products
like UCAR polyphobe 102 from Arkema Emulsion Systems or Rheolate
350 from Element is are typical examples that can be used in the
formulations. The percent incorporation can vary from between 0% to
10% in both layers. Other components, such as water or isopropyl
alcohol (IPA) can also be added to the formulation at about 0% to
about 10%.
[0056] Cross-linking agents can be added to the top layer
formulations to improve the mechanical properties of that film
layer. Examples of suitable cross-linking agents include, without
limitation, polyaziridine based CX-100 from DSM Neo Resins,
Waalwijk, The Netherlands; UCARLINK XL-255E, ERL-4221, ERL-4234
from Dow Chemicals, Midland, Mich.; and COATOSIL 1770, SILQUEST
A-187 from Momentive Performance Materials Inc., Waterford,
N.Y.
[0057] Without limitation, other additives, for example,
surfactants, defoamers, dispersants, wetting agents, dyes, pigments
and co-solvents known to those skilled in the art can be added to
the composition of each of the top layer and bottom layer.
[0058] Test Methods
[0059] Thickness
[0060] Film thickness is measured using TMI Model 49-70 Precision
Micrometer available from Testing Machines Inc. in Ronkonkoma, N.Y.
The specimen is placed between an upper and a lower anvil. The
upper anvil rests on top of the specimen and the thickness is
measured and displayed on the digital readout.
[0061] CIE L*a*b* Color Space
[0062] This test is used to describe the color of a sample. This
3-dimensional color space system was developed by the International
Commission on Illumination (CIE), and defines L* as representing
the lightness of the color, ranging from 0 (black) to 100 (white).
In this system, a* represents the color's position along the red
(magenta)/green axis, in which negative values represent green and
positive values represent red or magenta, and b* represents the
color's position along the blue/yellow axis, in which negative
values represent blue and positive values represent yellow. The
test is conducted using a COLOR I 5 Benchtop Spectrophotometer
available from X-Rite, Inc., Grand Rapids, Mich. The test method is
TAPPI T524 om-94.
[0063] Accelerated Weathering
[0064] Accelerated weathering test simulates the damaging effects
of long term outdoor exposure of materials by exposing test samples
to light, moisture and temperature extremes. Sample is tested and
observed for light fastness (fading of colors), and weatherability
(cracking, chalking, curling, shrinkage, etc. . . . ). An Atlas
CI65A Xenon Arc Weather-Ometer from Atlas Material Testing
Technology LLC in Chicago, Ill. is used for this test.
[0065] A printing pattern with white, yellow, magenta, cyan and
black stripes is first printed on a printable substrate. The film
of the current invention, which may be transparent, translucent,
clear or have other desirable optical properties, is then laminated
over the print layer to make a film laminate through the use of a
pressure sensitive adhesive. The sample is first tested for CIE
L*a*b* Color Space before placed in the Weather-Ometer. The sample
is allowed to age in the Weather-Ometer for a designated amount of
time. The sample is taken out of the Weather-Ometer for CIE L*a*b*
Color Space reading and observation for any changes in shrinkage,
chalking, cracking etc. . . . If there is no visible change after
2000 hours, and the changes in L*, a* and b* together, represented
by .DELTA.E, is less than 10, the sample is given a pass grade.
.DELTA.E value is calculated using the following formula:
.DELTA.E= {square root over
((.DELTA.L.sup.2+.DELTA.a.sup.2+.DELTA.b.sup.2))}.
[0066] Gloss
[0067] Gloss is measured using a BYK Gardner Micro-TRI-Gloss Gloss
Meter from BYK Gardner USA in Columbia, Md. The universal
measurement angle 60.degree. is used for the measurement. Typically
the acceptable gloss reading is 80 or higher.
[0068] Tensile Strength and Tensile Elongation
[0069] The tensile elongation and tensile strength of the film is
tested using Instron Model 5542 from Instron Co. in Canton, Mass. A
modified ASTM D882 was used to determine the tensile strength and
percentage elongation of the films of the present invention. The
procedure is as follows: [0070] 1. A 1 inch.times.4 inch (25.4
mm.times.101.6 mm) specimen was cut out in the machine direction.
[0071] 2. Grip the film 1 inch (25.4 mm) from the end at both the
ends, so the separation between the grips is 2 inches (50.8 mm).
[0072] 3. Set the crosshead speed at 12 inches per minute ("ipm")
(304.8 mm per minute). [0073] 4. Obtain the tensile strength, which
is the product of tensile stress times, the thickness of the film.
The tensile strength at break is the maximum stress that occurs at
break times the thickness of the film. [0074] 5. The % elongation
is reported by the machine.
[0075] The standard requires a minimum ultimate elongation of 180%
and a minimum tensile strength of 0.5 pound per square inch ("psi")
(6,895 N/m.sup.2). The presence or absence of pressure sensitive
adhesive (PSA) on the film does not appreciably alter the strength
and/or elongation of the film. As such, wherever the film in the
examples below includes PSA, the tensile elongation test was
performed using the same film but without the layer of PSA.
[0076] Rivet Testing
[0077] Test samples approximately 2.5 inch (63.5 mm).times.2.5 inch
(63.5 mm) are applied over painted 4 inch (101.6 mm).times.12 inch
(304.8 mm) aluminum panels from Frontier Tank Center in Richfield,
Ohio. Brazier rivet heads which are 11.4 mm (diameter).times.3.3 mm
(height).times.7.62 mm (shaft diameter) (0.45''
(diameter).times.0.13'' (height).times.0.3'' (shaft diameter)) are
uniformly distributed over the aluminum panel. Application is done
so as to minimize forming any wrinkles especially around these
rivet heads. Entrapped air is released with the use of pin pricks
while a brush with hard bristles and plastic squeegee is used to
get the best conformation of the film around the rivet. The sample
is dwelled for 24 hours at ambient condition. The diameter of the
lifted portion of the film around the rivet is measured and
recorded. The sample is then placed in Atlas Ci5000 Xenon Arc
Weather-Ometer from Atlas Electric Devices Co. in Chicago, Ill.,
using a UVB 313 bulb for 1000 hours. The sample is then taken out
and the diameter of the film lifted around the rivets is measured
again. When the change in diameter is less than 0.0625 inch (1.58
mm), the sample is given a pass grade.
[0078] Shrinkage Test
[0079] Test sample is coated with a pressure sensitive adhesive
under the trade name S8072 from Avery Dennison Corporation in
Pasadena, Calif. at about 30 gram per square meter (gsm) coat
weight. The sample is then attached to a clean aluminum panel from
0-Lab Corporation of Cleveland, Ohio. The sample is dwelled at
ambient condition for 24 hours. A 5 inch (127 mm) cross hatch in
both machine direction (MD) and cross-machine direction (CD) are
made on the film. The sample is then aged at 160.degree. F.
(71.degree. C.) for 48 hours. The dimension change in the MD and CD
are measured. If the shrinkage is less than 0.33% in both
directions, the sample is given a pass grade.
EXAMPLES
[0080] The chemicals used in the following examples are listed in
Table 1 with information on the function, manufacture and location
of each.
TABLE-US-00001 TABLE 1 Name of the Manufacturing Chemical Function
Company Location HYBRIDUR 870 Top layer Air Products Allentown,
component Pennsylvania JONCRYL 617 A Bottom layer BASF
Ludwigshafen, component Germany TINUVIN 123 DW Free radical BASF
Ludwigshafen, scavenger Germany TINUVIN 400 DW UV blocking BASF
Ludwigshafen, agent Germany TINUVIN 292 UV blocking BASF
Ludwigshafen, agent Germany TINUVIN 1130 Free radical BASF
Ludwigshafen, scavenger Germany TEXANOL ESTER Solvent Eastman
Kingsport, SOLVENT Chemical Tennessee DOWANOL DPNB Solvent Dow
Midland, Chemicals Michigan VINNAPS EF 811 Component for Wacker
Munich, additional layers Chemicals Germany ZONYL FS300 Flow and
Dupont Wilmington, leveling agent DE UCAR Viscosity Arkema Cary, NC
POLYPHOBE 102 modifier Emulsion Systems ARCRONAL Bottom layer BASF
Ludwigshafen, NX4612X component Germany JONCRYL 1987 Bottom layer
BASF Ludwigshafen, component Germany
[0081] Table 2 lists five examples of formulations used to create
the top layer.
TABLE-US-00002 TABLE 2 HYBRIDUR TINUVIN TINUVIN Example H 870 123
DW 400 DW TEXANOL DpNB Total No. % % % % % % 1 95.25 1.90 2.85 0.00
0.00 100.00 2 96.78 1.27 1.95 0.00 0.00 100.00 3 93.45 1.87 2.80
0.94 0.94 100.00 4 92.60 1.85 2.77 1.39 1.39 100.00 5 94.95 1.25
1.90 0.95 0.95 100.00
Examples 1 to 5
Top Layer Compositions
[0082] Table 3 lists two examples of formulations used to create
the bottom layer.
Examples 6 to 7
Bottom Layer Compositions
TABLE-US-00003 [0083] TABLE 3 Example JONCRYL 617 A TINUVIN 292
TINUVIN 1130 Total No. % % % % 6 99.0 0.50 0.50 100 7 98.65 0.675
0.675 100
[0084] Table 4 lists five examples of the film created using
Example 5 as the top layer, Example 7 as the bottom layer at
various thickness of each layer.
Examples 8 to 12
Films
TABLE-US-00004 [0085] TABLE 4 Example Thickness of Top Thickness of
Bottom No. layer (mil) Layer (mil) 8 0.75 0.75 9 1 0.5 10 1 1 11
1.33 0.66 12 2 0.5
Example 13
Control
[0086] HYBRIDUR 870 by itself was made into a film. When the film
thickness is about 1.7 mils (43 microns), the tensile elongation is
80%. When the film thickness is about 2.4 mils (61 microns), the
tensile elongation is around 150%. When subject to weather-o-meter
test, the films show heavy shrinking.
[0087] Examples 8 to 12 have been tested for various properties.
The films have been tested for film thickness, gloss at 60 degrees,
and tensile elongation. For scratch resistance and shrinkage test,
each sample is coated with about 30 gsm of a pressure sensitive
adhesive under the trade name 58072 from Avery Dennison Corporation
in Pasadena, Calif. For accelerated weathering and rivet testing,
the adhesive coated sample is further laminated onto a printable
film. The printable film is Example No. 29B in the PCT application
PCT/US08/84812, which has been incorporated by reference herein in
its entirety.
[0088] Table 5 lists the properties measured for each of the
samples. All examples have passed the accelerated weathering test,
have a gloss at 60 degree higher than 90, and tensile elongation
higher than 200. All of the samples have passed the scratch
resistance test, rivet testing, and shrinkage test.
TABLE-US-00005 TABLE 5 Example Total Accelerated Gloss @ Tensile
Rivet Shrinkage No. Thickness Weathering 60 Elongation Testing Test
8 1.5 mils Pass >80 <200 Pass Pass 9 1.5 mils Pass >80
<200 Pass Pass 10 1.5 mils Pass >80 <200 Pass Pass 11 2.0
mils Pass >80 <200 Pass Pass 12 2.0 mils Pass >80 <200
Pass Pass
Example 13
Three-Layer Film
[0089] A three-layer film was created using HYBRIDUR 870 as the top
layer, JONCRYL 617 A as the middle layer, and VINNAPAAS EF 811 as
the third layer. Each layer can be from about 0.5 mil (12.7
microns) to about 2 mils (50.8 microns) thick.
Examples 14-17
[0090] Table 6 lists four additional examples of formulations used
to create the top layer.
TABLE-US-00006 TABLE 6 UCAR Example Hybridur Tinuvin Tinuvin Zonyl
DI Polyphobe Rheolate No. 870 400 DW 123 DW Texanol DPnB FS300
Water 102 350 14 89.56% 0.91% 0.73% 1.41% 1.41% 0.28% 4.70% 0.99%
15 86.25% 0.88% 0.70% 1.36% 1.36% 9.27% 0.18% 16 85.56% 0.87% 0.69%
1.35% 1.35% 9.6% 0.18% 0.40% 17 85.56% 0.87% 0.69% 1.35% 1.35%
9.59% 0.58%
Examples 18-22
[0091] Table 7 lists five additional examples of formulations used
to create the bottom layer.
TABLE-US-00007 TABLE 7 UCAR Example Joncryl Tinuvin Tinuvin
Polyphobe DI Zonyl Acronal No. 1987 292 1130 102 Water FS300
Texanol NX4612X 18 98.85% 0.45% 0.45% 0.05% 0.05% 0.15% 0.0 0.0 19
99.05% 0.45% 0.45% 0.025% 0.025% 0.0 0.0 0.0 20 0.0 0.50% 0.50%
0.10% 0.10% 0.0 2.88% 95.93% 21 49.53% 0.42% 0.42% 0.05% 0.05% 0.0
0.0 49.53% 22 74.30% 0.42% 0.42% 0.05% 0.05% 0.0 0.0 24.77
[0092] All patents, published applications, and articles noted
herein are hereby incorporated by reference in their entirety.
[0093] All of the features disclosed in the specification,
including the claims, abstract, and drawings, and all of the steps
in any method or process disclosed, may be combined in any
combination, except combinations where at least some of such
features and/or steps are mutually exclusive. Each feature
disclosed in the specification, including the claims, abstract, and
drawings, can be replaced by alternative features serving the same,
equivalent, or similar purpose, unless expressly stated otherwise.
Thus, unless expressly stated otherwise, each feature disclosed is
one example only of a generic series of equivalent or similar
features.
[0094] The foregoing detailed description of the present invention
is provided for purposes of illustration, and it is not intended to
be exhaustive or to limit the invention to the particular
embodiments disclosed. The embodiments may provide different
capabilities and benefits, depending on the configuration used to
implement the key features of the invention. Accordingly, the scope
of the invention is defined only by the following claims.
* * * * *