U.S. patent application number 10/457806 was filed with the patent office on 2004-08-19 for extrusion method of making a dry paint transfer laminate.
Invention is credited to Conti, Norman A., Enlow, Howard, Fahlsing, Roger A., Truog, Keith L..
Application Number | 20040159969 10/457806 |
Document ID | / |
Family ID | 32850013 |
Filed Date | 2004-08-19 |
United States Patent
Application |
20040159969 |
Kind Code |
A1 |
Truog, Keith L. ; et
al. |
August 19, 2004 |
Extrusion method of making a dry paint transfer laminate
Abstract
This disclosed invention relates to a method of making a dry
paint transfer laminate, comprising: extruding a paint film layer
over a release liner; and extruding a pressure sensitive adhesive
layer over the paint film layer.
Inventors: |
Truog, Keith L.; (Crown
Point, IN) ; Enlow, Howard; (Munster, IN) ;
Conti, Norman A.; (Painesville, OH) ; Fahlsing, Roger
A.; (Hobart, IN) |
Correspondence
Address: |
Neil A. DuChez
Renner, Otto, Boisselle & Sklar, LLP
1621 Euclid Avenue, Nineteenth Floor
Cleveland
OH
44115
US
|
Family ID: |
32850013 |
Appl. No.: |
10/457806 |
Filed: |
June 9, 2003 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10457806 |
Jun 9, 2003 |
|
|
|
10367611 |
Feb 14, 2003 |
|
|
|
Current U.S.
Class: |
264/132 ;
264/171.13; 264/173.12; 264/173.16 |
Current CPC
Class: |
B44C 1/1737 20130101;
Y10T 428/14 20150115; Y10T 428/1462 20150115; B32B 37/153 20130101;
Y10T 156/1168 20150115; Y10T 428/1476 20150115; Y10T 428/1481
20150115; B32B 7/06 20130101; B44C 1/1716 20130101; B32B 27/20
20130101; B32B 2309/105 20130101; Y10T 428/2486 20150115; Y10T
428/1467 20150115; Y10T 428/1405 20150115; Y10T 428/1452 20150115;
Y10T 428/2848 20150115; B32B 2307/402 20130101; Y10T 428/1486
20150115; Y10T 428/24876 20150115; B44C 7/00 20130101; Y10S 428/906
20130101; Y10T 428/24355 20150115; C09J 7/22 20180101 |
Class at
Publication: |
264/132 ;
264/171.13; 264/173.12; 264/173.16 |
International
Class: |
B29C 047/06; B32B
031/30 |
Claims
1. A method of making a dry paint transfer laminate, comprising:
extruding a paint film layer over a release liner; and extruding a
pressure sensitive adhesive layer over the paint film layer
2. The method of claim 1 wherein the release liner comprises: a
backing liner which has an upper surface and a lower surface; a
first release coating layer overlying the upper surface of the
backing liner; and a second release coating layer overlying the
lower surface of the backing liner; the first release coating layer
contacting the lower surface of the paint film layer.
3. The method of claim 1 wherein a transparent film layer is
applied over the release liner prior to applying the paint film
layer, the paint film layer being applied over the transparent film
layer.
4. The method of claim 1 wherein a printed decorative layer is
applied over the release liner prior to applying the paint film
layer, the paint film layer being applied over the printed
decorative layer.
5. The method of claim 4 wherein a transparent film layer is
applied over the release liner prior to applying the printed
decorative layer, the printed decorative layer being applied over
the transparent film layer.
6. The method of claim 4 wherein a second printed decorative layer
is applied over the release liner prior to applying the printed
decorative layer, the printed decorative layer being applied over
the second decorative layer.
7. The method of claim 6 wherein a transparent film layer is
applied over the release liner prior to applying the second printed
decorative layer, the second decorative layer being applied over
the transparent film layer.
8. The method of claim 1 wherein another release liner is adhered
to the adhesive layer.
9. The method of claim 1 wherein the binder comprises a
thermoplastic thermosetting resin.
10. The method of claim 1 wherein the binder comprises one or more
acrylic resins, vinyl resins, polyester resins, alkyd resins,
butadiene resins, styrene resins, phthalic acid or anhydride
resins, urethane resins or epoxy resins.
11. The method of claim 1 wherein the binder comprises one or more
vinyl or vinylidene polymers or copolymers containing units of
vinyl acetate, vinyl chloride or vinylidene chloride.
12. The method of claim 1 wherein the binder comprises a copolymer
of vinyl chloride and vinyl acetate.
13. The method of claim 1 wherein the binder comprises one or more
polymers or copolymers containing ethylene or proplene units and
oxygenated or halogenated derivatives of ether, butadiene,
oxygenated butadiene, isoprene, oxygenated isoprene,
butadiene-styrene, butadiene-vinyl toluene, or
isoprene-styrene.
14. The method of claim 1 wherein the binder comprises one or more
polymers or copolymers containing units of acrylic acid,
methacrylic acid, esters of acrylic acid, esters of methacrylic
acid, or acrylonitrile.
15. The method of claim 1 wherein the binder comprises the reaction
product of maleic acid or anhydride with styrene.
16. The method of claim 1 wherein the binder comprises one or more
of diphenylmethane diisocyanate, methylene diethyl diisocyanate,
isocyanurate, ureaformaldehyde, phenolformaldehyde, phenolic glue,
animal hide glue, fluorine resin, silicone resin, or fibrin
resin.
17. The method of claim 1 wherein the pigment comprises one or more
of titanium dioxide, zinc oxide, carbon black, yellow oxide, brown
oxide, tan oxide, raw or burnt sienna or umber, chromium oxide
green, phthalocyanine green, phthalocyanine blue, ultramarine blue,
cadmium pigment, chromium pigment, azo red, quinacridone red,
perylene red, diarylide yellow or a mixed metal oxide.
18. The method of claim 1 wherein the pigment comprises one or more
of clay, silica, talc, mica, woloastonite wood flour, barium
sulfate, calcium carbonate or aluminum silicate.
19. The method of claim 1 wherein the paint film layer is derived,
from a liquid composition containing water or a water-alcohol
mixture.
20. The method of claim 1 wherein the paint film layer is derived
from a liquid composition containing an organic solvent.
21. The method of claim 20 wherein the organic solvent comprises
one or more of toluene, methylethyl ketone, methylisobutyl ketone,
benzene, ethyl acetate, white spirit, an alkane, a cycloalkane, or
an isoparaffin solvent.
22. The method of claim 1 wherein the paint film layer is derived
from a liquid composition containing one or more wetting agents,
plasticizers, suspension aids, thixotropic agents, water repellant
additives, fire retardant additives, biocides, defoamers or flow
agents.
23. The method of claim 1 wherein the paint film layer is derived
from a liquid composition having a pigment volume ratio of about 5
to about 35%.
24. The method of claim 1 wherein the adhesive is a pressure
sensitive adhesive.
25. The method of claim 1 wherein the adhesive is a moisture
activatable adhesive.
26. The method of claim 1 wherein the adhesive is a heat
activatable adhesive.
27. The method of claim 1 wherein the adhesive comprises a rubber
based adhesive, acrylic adhesive, vinyl ether adhesive, silicone
adhesive, or mixture of two or more thereof.
28. The method of claim 1 wherein the adhesive layer is derived
from a hot melt adhesive, solvent based adhesive or water based
adhesive.
29. The method of claim 1 wherein the adhesive layer comprises an
acrylic polymer; a block copolymer; a natural, reclaimed or
styrene-butadiene rubber; a tackified natural or synthetic rubber;
a copolymer of ethylene and vinyl acetate; an
ethylene-vinyl-acrylic terpolymer; a polyisobutylene; or a poly
vinyl ether.
30. The method of claim 1 wherein the adhesive layer is
pigmented.
31. The method of claim 2 wherein the backing liner comprises
paper, polymer film, or a combination thereof.
32. The method of claim 2 wherein the first release coating layer
comprises an alkyd resin and/or a vinyl resin cross linked with a
melamine resin.
33. The method of claim 2 wherein the first release coating
comprises one or more solid particulates.
34. The method of claim 2 wherein the second release coating layer
comprises a silicone coating.
35. The method of claim 3 wherein the transparent film layer
comprises polyvinyl chloride or a copolymer of vinyl chloride and
acrylic or methacrylic acid.
36. The method of claim 4 wherein the paint film layer comprises a
continuous layer, and the printed decorative layer comprises a
pattern or design.
37. The method of claim 6 wherein the paint film layer comprises a
continuous layer; and the printed decorative layer and the second
printed decorative layer independently comprise patterns or
designs.
38. The method of claim 1 wherein a support layer is applied over
the one side of the release layer prior to applying the paint film
layer, the paint film layer being applied over the support
layer.
39. The method of claim 38 wherein the support layer comprises a
polymeric film.
40. The method of claim 38 wherein the support layer is made of a
material comprising a polyolefin, a polyamide, a polystyrene, a
polyurethane, a polyester, an acrylate polymer or copolymer, an
ionomer, a polycarbonate, polyvinyl alcohol, polyethylene vinyl
alcohol, polyvinyl acetate, or a mixture of two or more
thereof.
41. The method of claim 1 wherein a barrier layer is applied over
the upper surface of the paint film layer prior to applying the
adhesive, the adhesive being applied over the barrier layer.
42. The method of claim 41 wherein the barrier layer comprises an
acrylate containing polymer or copolymer, polyvinyl alcohol, a
copolymer of ethylene and vinyl acetate, a copolymer derived from
ethylene, vinyl acetate and polyvinyl alcohol, or a polymer blend
derived from polyvinyl alcohol and urethane.
43. The method of claim 1 wherein the paint film layer has a
thickness of about 0.5 to about 1.5 mils.
44. The method of claim 1 wherein the adhesive layer has a
thickness of about 0.4 to about 1 mil.
45. The method of claim 38 wherein the combined thickness of the
paint film layer and the support layer is in the range of about 0.5
to about 1.5 mils.
46. The method of claim 2 wherein the first release coating layer
comprises a resin and solid particulates, the weight ratio of
particulates to resin being in the range of up to about 1.1:1.
47. The method of claim 1 wherein the binder comprises a
polystyrene, polyolefin, polyamide, polyester, polycarbonate,
polyvinyl alcohol, polyethylene vinyl alcohol, polyurethane,
polyacrylate, polyvinyl acetate, an ionomer, or a mixture of two or
more thereof.
48. A method of making a dry paint transfer laminate, comprising:
coextruding a paint film layer and a pressure sensitive adhesive
layer over a release liner, the paint film layer overlying the
release liner and the pressure sensitive adhesive layer overlying
the paint film layer.
49. A method of making a dry paint transfer laminate, comprising:
extruding a transparent film layer over a release liner; applying a
paint film layer over the transparent film layer; and extruding a
pressure sensitive adhesive layer over the paint film layer.
50. The method of claim 49 wherein a support layer is extruded over
the paint film layer prior to extruding the pressure sensitive
adhesive layer, the pressure sensitive adhesive layer being
extruded over the support layer.
51. A method of making a dry paint transfer laminate, comprising:
extruding a transparent film layer over a release liner; and
coextruding a paint film layer and a pressure sensitive adhesive
layer over the transparent film layer, the paint film layer
overlying the transparent film layer and the pressure sensitive
adhesive layer overlying the paint film layer.
52. A method of making a dry paint transfer laminate, comprising:
extruding a transparent film layer over a release liner; applying a
paint film layer over the transparent film layer; and coextruding a
pressure sensitive adhesive layer and a support layer over the
paint film layer, the support layer overlying the paint film layer
and the pressure sensitive adhesive layer overlying the support
layer.
Description
[0001] This application is a continuation-in-part of U.S.
application Ser. No. 10/367,611, filed Feb. 14, 2003, which is
incorporated herein by reference in its entirety.
TECHNICAL FIELD
[0002] This invention relates to an extrusion method of making a
dry paint transfer laminate. These laminates comprise a dry paint
film layer, an adhesive layer overlying one side of the dry paint
film layer, and a release liner overlying the other side of the dry
paint film layer.
BACKGROUND OF THE INVENTION
[0003] Conventional painting using liquid paint requires set up
steps involving masking off areas not to be painted and the
spreading of drop cloths. Conventional painting also requires messy
clean up of brushes, rollers, and the like, the problem of spills,
exposure to fumes, and delays while the paint dries. When special
effects such as faux finishes are desired, additional time and
effort is required to apply additional coats.
[0004] The present invention provides a solution to these problems.
With the present invention it is not necessary to mask off areas
that are not to be painted and it is not necessary to use drop
cloths. The messy clean up of brushes, rollers, and the like is
avoided. Spills and exposure to fumes are avoided. Delays waiting
for paint to dry are avoided. Special effects such as faux finishes
can be accomplished with a single application.
SUMMARY OF THE INVENTION
[0005] This invention relates to a method of making a dry paint
transfer laminate, comprising:
[0006] extruding a paint film layer over a release liner; and
[0007] extruding a pressure sensitive adhesive layer over the paint
film layer.
[0008] In one embodiment, the release liner comprises: a backing
liner which has an upper surface and a lower surface; a first
release coating layer overlying the upper surface of the backing
liner; and a second release coating layer overlying the lower
surface of the backing liner; the first release coating layer
contacting the lower surface of the paint film layer.
[0009] In one embodiment, a transparent film layer is applied over
the release liner prior to applying the paint film layer, the paint
film layer being applied over the printed transparent film
layer.
[0010] In one embodiment, a printed decorative layer is applied
over the release liner prior to applying the paint film layer, the
paint film layer being applied over the decorative layer. In one
embodiment, a transparent film layer is applied over the release
liner prior to applying the printed decorative layer, the printed
decorative layer being applied over the transparent film layer. In
one embodiment, a second printed decorative layer is applied over
the release liner prior to applying the printed decorative layer,
the printed decorative layer being applied over the second
decorative layer. In one embodiment, a transparent film layer is
applied over the release liner prior to applying the second printed
decorative layer, the second decorative layer being applied over
the transparent film layer.
[0011] In one embodiment, another release liner is adhered to the
adhesive layer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] In the annexed drawings, like references indicate like parts
or features.
[0013] FIG. 1 is a schematic illustration of the side view of a dry
paint transfer laminate embodying the present invention in a
particular form.
[0014] FIG. 2 is a schematic illustration of the dry paint transfer
laminate illustrated in FIG. 1, the laminate being partially wound
into a roll.
[0015] FIG. 3 is a schematic illustration of the side view of
another embodiment of the dry paint transfer laminate of the
present invention.
[0016] FIG. 4 is a schematic illustration of the side view of still
another embodiment of the dry paint transfer laminate of the
present invention.
[0017] FIG. 5 is a schematic illustration of the side view of still
another embodiment of the dry paint transfer laminate of the
present invention.
[0018] FIG. 6 is a schematic illustration of the side view of still
another embodiment of the dry paint transfer laminate of the
present invention.
[0019] FIG. 7 is a schematic illustration of the side view of still
another embodiment of the dry paint transfer laminate of the
present invention.
[0020] FIG. 8 is a schematic illustration of the side view of still
another embodiment of the dry paint transfer laminate of the
present invention.
[0021] FIG. 9 is a schematic illustration of the side view of still
another embodiment of the dry paint transfer laminate of the
present invention.
[0022] FIG. 10 is a schematic illustration of the side view of
still another embodiment of the dry paint transfer laminate of the
present invention.
[0023] FIG. 11 is a schematic illustration of a process for
coextruding the support layer and the adhesive layer used in one
embodiment of the inventive laminate.
[0024] FIG. 12 is a schematic illustration of another embodiment of
a process for coextruding the support layer and the adhesive layer
used in one embodiment of the inventive laminate.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0025] The terms "over" and "overlies" and cognate terms such as
"overlying" and the like, when referring to the relationship of one
or a first layer relative to another or a second layer, refers to
the fact that the first layer partially or completely lies over the
second layer. The first layer overlying the second layer may or may
not be in contact with the second layer. For example, one or more
additional layers may be positioned between the first layer and the
second layer. The terms "under" and "underlies" and cognate terms
such as "underlying" and the like have similar meanings except that
the first layer partially or completely lies under, rather than
over, the second layer.
[0026] The term "dry paint" refers to a paint composition which has
been applied to a substrate and has dried or cured sufficiently so
that it does not smear or smudge when touched or handled by the
user. The dry paint composition may be derived from a liquid (i.e.,
solvent based or water based) coating or film forming composition
or a hot melt coating or film forming composition. In one
embodiment, the dry paint composition may be derived from a
composition containing one or more volatile components (e.g.,
organic solvent, water, etc.) wherein the paint composition is
applied to a substrate and allowed to dry to the extent that the
volatile components are removed completely or sufficiently to
permit the paint to adhere to the substrate and not smear or smudge
when touched by the user. The term "volatile" is used herein to
refer to materials that are volatile at the drying temperature and
atmospheric pressure.
[0027] The term "transparent" when referring to the transparent
film layer overlying one or more of the dry paint film layers of
the inventive dry paint transfer laminate means that the one or
more dry paint film layers can be seen through the transparent film
layer. The transparent film layer may be translucent.
[0028] Referring to FIG. 1, the inventive dry paint transfer
laminate, in one of its illustrated embodiments, is generally
indicated by the reference numeral 100, and comprises: a dry paint
film layer 110 which has an upper surface 112 and a lower surface
114; an adhesive layer 120 overlying and adhered to upper surface
112; and a release liner 130 overlying and adhered to the lower
surface 114. The release liner 130 comprises: a backing liner 132
which has an upper surface 133 and a lower surface 134; a first
release coating layer 135 overlying and adhered to the upper
surface 133; and a second release coating layer 136 overlying and
adhered to the lower surface 134. The first release layer 135 is
positioned between the upper surface 133 of backing liner 132 and
the lower surface 114 of dry paint film layer 110, and
preferentially adheres to the upper surface 133 of backing liner
132. Thus, when the release liner 130 is peeled away from the dry
paint film layer 110, the release coating layer 135 separates from
the dry paint film layer 110 and remains adhered to the backing
liner 132. The lower surface 137 of release layer 136 is adapted
for contacting the upper surface 122 of adhesive layer 120 when the
laminate 100 is wound into roll form as illustrated in FIG. 2.
[0029] Referring to FIG. 2, the dry paint transfer laminate 100 is
wound into roll form with the lower surface 137 of release coating
layer 136 in contact with the upper surface 122 of adhesive layer
120. The release coating layer 136 preferentially adheres to
backing liner 132. Thus, when the dry paint transfer laminate 100
illustrated in FIG. 2 is unwound, the release coating layer 136
separates from adhesive layer 120 and remains adhered to backing
liner 132.
[0030] The dry paint transfer laminate 100A illustrated in FIG. 3
is identical to the dry paint transfer laminate 100 illustrated in
FIG. 1 except that transparent film layer 140 is positioned between
dry paint film layer 110 and release coating layer 135. The release
coating layer 135 is adhered to transparent film layer 140 on one
side and to backing liner 132 on the other side, and is
preferentially adhered to backing liner 132. Thus, when the release
liner 130 is peeled away from the transparent film layer 140, the
release coating layer 135 separates from the transparent film layer
140 and remains adhered to the backing liner 132.
[0031] The dry paint transfer laminate 100B illustrated in FIG. 4
is identical to the dry paint transfer laminate 100A illustrated in
FIG. 3 except that printed decorative layer 150 is positioned
between dry paint film layer 110 and transparent film layer
140.
[0032] The dry paint transfer laminate 100C illustrated in FIG. 5
is identical to the dry paint transfer laminate 100B illustrated in
FIG. 4 except that second printed decorative layer 160 is
positioned between printed decorative layer 150 and transparent
film layer 140.
[0033] Additional printed decorative layers beyond layers 150 and
160 may be used. For example, the inventive laminates may contain
up to about 5 or more, and in one embodiment about 3 or about 4,
printed decorative layers overlying one another. The printed
decorative layers may provide a desired print or design and may be
applied using conventional printing methods such as gravure,
flexography, silk screen ink jet, etc.
[0034] The dry paint transfer laminate 100D illustrated in FIG. 6
is identical to the laminate 100 illustrated in FIG. 1 except that
release coating layer 136 is not present, and additional release
liner 170 has been added to overlie adhesive layer 120. Release
liner 170 comprises: a backing liner 172 which has an upper surface
173 and a lower surface 174; and a release coating layer 176
overlying and adhered to the lower surface 174. The release layer
176 is positioned between the lower surface 174 of backing liner
172 and the upper surface 122 of adhesive layer 120, and
preferentially adheres to the lower surface 174 of backing liner
172. Thus, when the release liner 170 is peeled away from the
adhesive layer 120, the release coating layer 176 separates from
the adhesive layer 120 and remains adhered to the backing liner
172.
[0035] The dry paint transfer laminate 100E illustrated in FIG. 7
is identical to the laminate 100 illustrated in FIG. 1 except that
the laminate 100E includes support layer 180 positioned between dry
paint film layer 110 and adhesive layer 120.
[0036] The dry paint transfer laminate 100F illustrated in FIG. 8
is identical to the laminate 100 illustrated in FIG. 1 except that
the laminate 100F includes barrier layer 190 positioned between the
dry paint film layer 110 and the adhesive layer 120.
[0037] The dry paint transfer laminate 100G illustrated in FIG. 9
is identical to the laminate 100 illustrated in FIG. 1 except that
the laminate 100G includes support layer 180 positioned between the
dry paint film layer 110 and the adhesive layer 120. Also, the
laminate 100G includes printed decorative layers 150, 160 and 165
positioned between the dry paint film layer 110 and the first
release coating layer 135.
[0038] The dry paint transfer laminate 100H illustrated in FIG. 10
is identical to the dry paint transfer laminate 100C illustrated in
FIG. 5 except that the release liner 130 in laminate 100C is not
present, and release liner 170 overlies adhesive layer 120 and
release layer 176 is positioned between release liner 170 and
adhesive layer 120.
[0039] The dry paint film layer 110 may have a thickness of about
0.5 to about 1.5 mils, and in one embodiment about 0.5 to about 1.2
mils, and in one embodiment about 0.5 to about 0.9 mil, and in one
embodiment about 0.7 mil. The thickness of the adhesive layer 120
may range from about 0.4 to about 1 mil, and in one embodiment
about 0.4 to about 0.8 mil, and in one embodiment about 0.4 to
about 0.6 mil. The thickness of the backing liner 132 may range
from about 0.5 to about 2 mils, and in one embodiment about 0.5 to
about 1.5 mils, and in one embodiment about 0.85 to about 1.05
mils. The thickness of the first release coating layer 135 may
range from about 0.05 to about 0.3 mil, and in one embodiment about
0.1 to about 0.2 mil. The thickness of the second release coating
layer 136 may range from about 0.04 to about 0.2 mil, and in one
embodiment about 0.04 to about 0.15 mil, and in one embodiment
about 0.04 to about 0.08 mil. The thickness of the transparent film
layer 140 may range from about 0.05 to about 0.4 mil, and in one
embodiment about 0.05 to about 0.3 mil, and in one embodiment about
0.2 mil. The thickness of the printed decorative layer 150 may
range from about 0.02 to about 0.15 mil, and in one embodiment
about 0.02 to about 0.08 mils. The thickness of the second printed
decorative layer 160 may range from about 0.02 to about 0.15 mil,
and in one embodiment about 0.02 to about 0.1 mil. The thickness of
the backing liner 172 may range from about 0.5 to about 2 mils, and
in one embodiment about 0.5 to about 1.5 mils, and in one
embodiment about 0.85 to about 1.05 mils.
[0040] The thickness of the release coating layer 176 may range
from about 0.04 to about 0.2 mil, and in one embodiment about 0.04
to about 0.15 ml, and in one embodiment about 0.04 to about 0.08
mil. The support layer 180 may have a thickness of about 0.3 to
about 1.4 mils, and in one embodiment about 0.3 to about 1.1 mils,
and in one embodiment about 0.3 to about 0.8 mil, and in one
embodiment about 0.3 to about 0.5 mil. When the support layer 180
is used, the overall thickness of the combination of the dry paint
film layer 110 and support layer 180 may be in the range of about
0.5 to about 1.5 mils, and in one embodiment about 0.5 to about 1.2
mils, and in one embodiment about 0.5 to about 0.9 mil, and in one
embodiment about 0.7 mil. The barrier layer 190 may have a
thickness in the range of about 0.01 to about 0.1 mil, and in one
embodiment about 0.05 to about 0.1 ml, and in one embodiment about
0.01 to about 0.02 mil. Each of the foregoing thicknesses are dry
film thicknesses. The laminates 100 through 100H may have any width
and length that is suitable for facilitated use by the user. For
example, the width may range from about 1 to about 200 cm, and in
one embodiment 10 to 100 cm, and in one embodiment about 30 to
about 40 cm. The length may range from about 10 to about 6500
meters, and in one embodiment about 15 to about 1000 meters. In one
embodiment, the length may range from about 19 to about 6500
meters. In one embodiment, the length may range from about 17 to
about 20 meters. In one embodiment, the laminate may have a width
of about 10 to about 20 cm, and a length of about 10 to about 30
cm. The laminates may be provided in the form of flat sheets or in
roll form as illustrated in FIG. 2.
[0041] The layers 110, 150, 160 and 165 may comprise independently
one or more binders or resins, and one or more pigments. The
support layer 180 may comprise one or more binders or resins, and
optionally one or more pigments. The transparent film layer 140 may
comprise one or more binders or resins. These layers may be made
from liquid coating or paint compositions comprising the one or
more binders or resins, the one or more pigments (if used), water
or one or more organic solvents, and optionally one or more
additional additives for controlling properties such as rheological
properties and the like. The layers 110, 140 and 180 may each
comprise independently one or more extruded film layers.
[0042] The binder or resin may comprise any binder or resin
conventionally used in coating or paint formulations. The binder
may comprise a thermoplastic or a thermosetting resin. The binder
or resin may be a synthetic resin or a natural resin. The binder or
resin may comprise a film forming material, which in one embodiment
may be an extrudable film forming material. Examples of useful
binders or resins include acrylic resins, vinyl resins, polyester
resins, alkyd resins, butadiene resins, styrene resins, phthalic
acid or anhydride resins, urethane resins, epoxy resins, and the
like. The binder or resin may comprise vinyl and vinylidene
polymers or copolymers containing units such as vinyl acetate,
vinyl chloride, vinylidene chloride, and the like; hydrocarbon
polymers and copolymers containing ethylene or proplene units and
oxygenated or halogenated derivatives of ether, butadiene,
oxygenated butadiene, isoprene, oxygenated isoprene,
butadiene-styrene, butadiene vinyl toluene, isoprene-styrene and
the like; polymers or copolymers containing units of acrylic acid,
methacrylic acid, their esters, or acrylonitrile; vinylic
hydrocarbon monomers reacted with unsaturated materials such as the
reaction product of maleic acid or anhydride with styrene; and,
broadly, various other resinous rubber-like elastomeric latex
polymers and copolymers of ethylenically unsaturated monomers and
polymers obtainable in stable aqueous latex form. The binder or
resin may comprise a copolymer of vinyl chloride and vinyl acetate.
The binder or resin may comprise diphenylmethane diisocyanate,
methylene diethyl diisocyanate, isocyanurate, urea-formaldehyde,
phenolformaldehyde, phenolic glue, animal hide glues, and the like.
Other examples of binders or resins which may be used include
fluorine resins, silicone resins, and fibrin resins.
[0043] The binder or resin may include one or more polystyrenes,
polyolefins, polyamides, polyesters, polycarbonates, polyvinyl
alcohol, polyethylene vinyl alcohol, polyurethanes, polyacrylates,
polyvinyl acetates, ionomers and mixtures thereof. The polyolefins
may be characterized as having a melt index or melt flow rate of
less than about 30, and in one embodiment less than about 20, and
in one embodiment less than about 10 as determined by ASTM Test
Method 1238.
[0044] The polyolefins include polymers and copolymers of ethylene,
propylene, 1-butene, etc., or blends of mixtures of such polymers
and copolymers. The polyolefins may comprise polymers and
copolymers of ethylene and propylene. The polyolefins may comprise
propylene homopolymers, and copolymers such as propylene-ethylene
and propylene-1-butene copolymers. Blends of polypropylene and
polyethylene with each other, or blends of either or both of them
with a polypropylene-polyethylene copolymer may be used. The
polyolefin film forming materials may have a high propylenic
content, either polypropylene homopolymer or propylene-ethylene
copolymers or blends of polypropylene and polyethylene with low
ethylene content, or propylene-1-butene copolymers or blend of
polypropylene and poly-1-butene with low butene content.
[0045] Various polyethylenes may be used including low, medium, and
high density polyethylenes. The low density range for the
polyethylenes may be from about 0.910 to about 0.925 g/cm.sup.3,
the medium density range may be from about 0.925 to about 0.940
g/cm.sup.3, and the high density range may be from about 0.940 to
about 0.965 g/cm.sup.3. An example of a useful low density
polyethylene (LDPE) is Rexene 1017 available from Huntsman.
[0046] The propylene homopolymers which may be used either alone or
in combination with a propylene copolymer include a variety of
propylene homopolymers such as those having melt flow rates (MFR)
from about 0.5 to about 20 as determined by ASTM Test D 1238,
condition L. In one embodiment, propylene homopolymers having MFR's
of less than about 10, and in one embodiment from about 4 to about
10 may be used. The propylene homopolymers may be characterized as
having densities in the range of from about 0.88 to about 0.92
g/cm.sup.3. A number of useful propylene homopolymers are available
commercially from a variety of sources, and some useful polymers
include: 5A97, available from Union Carbide and having a melt flow
of 12.0 g/l 0 min and a density of 0.90 g/cm.sup.3; DX5E66, also
available from Union Carbide and having an MFI of 8.8 g/l 0 min and
a density of 0.90 g/cm.sup.3; and WRD5-1057 from Union Carbide
having an MFI of 3.9 g/l 0 min and a density of 0.90 g/cm.sup.3.
Useful commercial propylene homopolymers are also available from
Fina and Montel.
[0047] The polyamide resins include resins available from EMS
American Grilon Inc., Sumter, S.C. under the general tradename
Grivory such as CF6S, CR-9, XE3303 and G-21. Grivory G-21 is an
amorphous nylon copolymer having a glass transition temperature of
125.degree. C., a melt flow index (DIN 53735) of 90 ml/10 min and
an elongation at break (ASTM D638) of 15. Grivory CF65 is a nylon
6/12 film grade resin having a melting point of 135.degree. C., a
melt flow index of 50 ml/10 min, and an elongation at break in
excess of 350%. Grilon CR9 is another nylon 6/12 film grade resin
having a melting point of 200.degree. C., a melt flow index of 200
ml/10 min, and an elongation at break at 250%. Grilon XE 3303 is a
nylon 6.6/6.10 film grade resin having a melting point of
200.degree. C., a melt flow index of 60 ml/10 min, and an
elongation at break of 100%. The polyamide resins include those
available from, for example, Union Camp of Wayne, N.J. under the
Uni-Rez product line, and dimer-based polyamide resins available
from Bostik, Emery, Fuller, Henkel (under the Versamid product
line). The polyamides include those produced by condensing
dimerized vegetable acids with hexamethylene diamine. Examples of
polyamides available from Union Camp include Uni-Rez 2665; Uni-Rez
2620; Uni-Rez 2623; and Uni-Rez 2695.
[0048] The polystyrenes include homopolymers as well as copolymers
of styrene and substituted styrene such as alpha-methyl styrene.
Examples of styrene copolymers and terpolymers include:
acrylonitrile-butene-styrene (ABS); styrene-acrylonitrile
copolymers (SAN); styrene butadiene (SB); styrene-maleic anhydride
(SMA); and styrene-methyl methacrylate (SMMA); etc.
[0049] The polyurethanes include aliphatic as well as aromatic
polyurethanes.
[0050] The polyesters may be prepared from various glycols or
polyols and one or more aliphatic or aromatic carboxylic acids.
Polyethylene terephthalate (PET) and PETG (PET modified with
cyclohexanedimethanol) are useful film forming materials which are
available from a variety of commercial sources including Eastman.
For example, Kodar 6763 is a PETG available from Eastman Chemical.
Another useful polyester from DuPont is Selar PT-8307 which is
polyethylene terephthalate.
[0051] Acrylate polymers and copolymers and alkylene vinyl acetate
resins (e.g., EVA polymers) may be used. Examples include Escorene
UL-7520 (Exxon), a copolymer of ethylene with 19.3% vinyl acetate;
Nucrell 699 (DuPont), an ethylene copolymer containing 11% of
methacrylic acid, etc.
[0052] Ionomers (polyolefins containing ionic bonding of molecular
chains) may be used. Examples of ionomers include ionomeric
ethylene copolymers such as Surlyn 1706 (DuPont) which is believed
to contain interchain ionic bonds based on a zinc salt of ethylene
methacrylic acid copolymer. Surlyn 1702 from DuPont is an ionomer
that may be used.
[0053] Polycarbonates also are useful, and these are available from
the Dow Chemical Co. (Calibre) G.E. Plastics (Lexan) and Bayer
(Makrolon). These polycarbonates may be obtained by the reaction of
bisphenol A and carbonyl chloride in an interfacial process.
Molecular weights may vary from about 22,000 to about 35,000, and
the melt flow rates may be in the range of from about 4 to about 22
g/10 min.
[0054] The pigment may be any pigment used in making decorative
coatings. These include opacifying pigments, such as titanium
dioxide and zinc oxide, as well as tinting pigments such as carbon
black, yellow oxides, brown oxides, tan oxides, raw and burnt
sienna or umber, chromium oxide green, phthalocyanine green,
phthalocyanine blue, ultramarine blue, cadmium pigments, chromium
pigments, and the like. The pigments include organic reds such as
azo reds, quinacridone red and perylene red as well as organic
yellows such as diarylide yellow. Mixed metal oxide pigments may be
used. Filler pigments such as clay, silica, talc, mica,
woloastonite wood flour, barium sulfate, calcium carbonate,
aluminum silicate, and the like can be added as well in
conventional amounts traditionally used in coating and paint
formulations.
[0055] The solvent may be an organic-based solvent, such as a
ketone, ester, aliphatic compound, aromatic compound, alcohol,
glycol, glycol ether, etc. These include methylethyl ketone,
methylisobutyl ketone, ethyl acetate, white spirits, alkanes,
cycloalkanes, benzene, hydrocarbon substituted aromatic compounds
(e.g., toluene, the xylenes, etc.), isoparaffinic solvents, and
combinations of two or more thereof. Alternatively, water or a
water-based solution may be used to form an emulsion with the
binder or resin. Water-based solutions include water-alcohol
mixtures, and the like. The solvent or water is sufficiently
volatile so that when applied to a substrate, the solvent
evaporates leaving behind the binder or resin, pigment (if used)
and any other additional non-volatile ingredients.
[0056] Additional ingredients that may be used include wetting
agents; plasticizers; suspension aids; thixotropic agents such as
silica; water repellant additives such as polysiloxane compounds;
fire retardant additives; biocides; defoamers; flow agents; and the
like.
[0057] The pigment concentration for the liquid paint or coating
composition used to provide the layers 110, 150,160 and 165 may
range from about 10 to about 30% by weight, and in one embodiment
about 13 to about 27% by weight. The binder or resin concentration
may range from about 20 to about 40% by weight, and in one
embodiment about 22 to about 37% by weight. The water or organic
solvent concentration may range from about 30 to about 70% by
weight, and in one embodiment about 40 to about 60% by weight. The
additional ingredients such as wetting agents, suspension agents,
etc., may be provided at concentrations known in the art, for
example, up to about 5% by weight, and in one embodiment from about
0.1 to about 5% by weight. The coating or paint compositions used
in making the layers 110, 150, 160 and 165 may have a pigment
volume concentration (PVC) in the range of about 5 to about 35%,
and in one embodiment 10 to about 30%. The liquid paint or coating
compositions used for making the film layers 110, 150, 160, 165 and
180 may be mixed using known techniques.
[0058] The dry paint film layer 110 may comprise a single coat or
multiple coats of paint and is in the form of a continuous layer,
while the printed decorative layers 150, 160 and 165 may
independently be in the form of continuous or discontinuous layers.
When multiple coats for the layer 110 are used, each coat may have
the same or a different formulation. The layers 150, 160 and/or 165
may have the same color or a different color than the layer 110.
The layers 150, 160 and/or 165 may have the same color, or they may
have colors that are different from each other. The layer 110 may
be used to provide background color while the layers 150, 160
and/or 165 may be used to provide a pattern or design. For example,
the layers 150, 160 and/or 165 may be used to provide a faux finish
or a "ragging" or "sponging" look. The layers 150, 160 and/or 165
may be used to provide a desired print or design image (e.g., a
flowered design) having one or multiple colors. The designs may be
in the form of repeat designs or random non-repeat designs.
[0059] The transparent film layer 140 may comprise a single coating
layer or multiple coats, and may comprise any of the resin
materials described above. When multiple coats are used, each coat
may have the same or a different formulation. The transparent film
layer 140 may be extruded. Specific examples of the resins that may
be used include polyvinyl chloride, and copolymers of vinyl
chloride and acrylic or methacrylic acid. The transparent film
layer 140 is primarily distinguishable from the dry paint film
layer 110 by the fact that it is transparent or translucent. The
transparent film layer 140, in one embodiment, provides enhanced
scuff resistance, stain resistance and/or recoatability to the dry
paint film layer or layers underlying it. Enhanced recoatability
refers to the fact that the presence of the transparent film layer
140 facilitates the subsequent application of another dry paint
film layer or printed decorative layer over it, or the application
of conventional paint or wall coverings (e.g., wall paper) over
it.
[0060] The support layer 180 may be formed from any of the binder
or resin materials described above. The support layer may be formed
from a solution or an emulsion and applied using any of the coating
techniques described below. The support layer 180 may be extruded.
The support layer 180 may contain one or more of the
above-indicated pigments. In one embodiment, the support layer 180
contains sufficient pigment to provide it with a neutral color such
as gray, light blue, light red, etc. The concentration of pigment
in the support layer 180, when used, may range up to about 10% by
weight, and in one embodiment about 6 to about 10% by weight.
[0061] The layers 110, 140 and 180 independently may contain
inorganic fillers or other organic or inorganic additives to
provide desired properties such as appearance properties (clear,
opaque or colored films), durability and processing
characteristics. Examples of useful materials include calcium
carbonate, titanium dioxide, metal particles, fibers, flame
retardants, antioxidant compounds, heat stabilizers, light
stabilizers, ultraviolet light stabilizers, antiblocking agents,
processing aids, acid acceptors, etc.
[0062] Nucleating agents may be added to one or more of the layers
110, 140 or 180 to increase crystallinity and thereby increase
stiffness. The nucleating agents which may be used include mineral
nucleating agents and organic nucleating agents. Examples of
mineral nucleating agents include carbon black, silica, kaolin and
talc. Examples of organic nucleating agents include salts of
aliphatic mono-basic or di-basic acids or aryalkyl acids such as
sodium succinate, sodium glutarate, sodium caproate, sodium
4-methylvalerate, aluminum phenyl acetate, and sodium cinnamate.
Alkali metal and aluminum salts of aromatic and alicyclic
carboxylic acids such as aluminum benzoate, sodium or potassium
benzoate, sodium betanaphtholate, lithium benzoate and aluminum
tertiary-butyl benzoate also are useful organic nucleating agents.
Substituted sorbitol derivatives such as bis (benzylidene) and bis
(alkylbenzilidine) sorbitols wherein the alkyl groups contain from
about 2 to about 18 carbon atoms are useful nucleating agents.
Sorbitol derivatives such as 1,3,2,4-dibenzylidene sorbitol,
1,3,2,4-di-para-methylbenzylidene sorbitol, and
1,3,2,4-di-para-methylbenzylidene sorbitol may be used. The amounts
of nucleating agent incorporated into the film forming formulations
may range from about 100 to about 6000 ppm of the film. In one
embodiment, the amount of nucleating agent may range from about
1000 to about 5000 ppm.
[0063] One or more of the layers 110, 140 or 180 may contain a
minor amount of an adhesive resin to enhance the adhesion of the
layer 110 to the layer 140 and/or 180. Also, or alternatively, tie
layers of an adhesive resin can be positioned between the layers
110 and 140 or the layers 110 and 180. The adhesive resin can be an
ethylene/vinyl acetate copolymer such as those available from
DuPont under the tradename Elvax. The adhesive resins available
from DuPont under the tradename Bynel may be used.
[0064] In one embodiment, the layers 110, 140 and/or 180 are
non-stretchable and non-elastic at room temperature.
[0065] The adhesive layer 120 may comprise a pressure sensitive
adhesive (PSA) layer, a moisture activatable adhesive layer or a
heat activatable adhesive layer. The adhesive may comprise any
pressure sensitive, moisture activatable or heat activatable
adhesive known in the art for use with film substrates. The
adhesive layer 120 may be in the form of a continuous or
discontinuous layer, and may comprise one or a mixture of two or
more adhesives. The adhesive layer may be in the form of a
patterned adhesive layer with a relatively strong adhesive in some
areas and a relatively weak adhesive in other areas. In one
embodiment, the adhesive layer provides initial tack and allows
slight movement of the laminate to allow positioning adjustments
prior to forming a permanent bond. In one embodiment, the adhesive
permits facilitated stripping of the dry paint film layer from a
substrate when use of the paint film layer is no longer desired. In
one embodiment, the adhesive layer is characterized by producing
only a limited amount of ooze beyond the borders of the laminate
when the laminate is applied to a substrate. In one embodiment, no
ooze is produced. The adhesive may comprise a rubber based
adhesive, acrylic adhesive, vinyl ether adhesive, silicone
adhesive, or mixture of two or more thereof. The adhesive may be
applied as a hot melt, solvent-based or water based adhesive. The
adhesive materials that are useful may contain as a major
constituent an adhesive polymer such as an acrylic-type polymer;
block copolymer; natural, reclaimed, or styrene-butadiene rubber;
tackified natural or synthetic rubber; a copolymer of ethylene and
vinyl acetate; an ethylene-vinyl-acrylic terpolymer;
polyisobutylene; poly (vinyl ether); etc. Other materials may be
included in the adhesive such as tackifying resins, plasticizers,
antioxidants, fillers, waxes, etc.
[0066] The adhesives may be classified into the following
categories: random copolymer adhesives such as those based upon
acrylate and/or methacrylate copolymers, .alpha.-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 may
be found in Encyclopedia of Polymer Science and Engineering, Vol.
13. Wiley-Interscience Publishers (New York, 1988). Additional
description of useful pressure-sensitive adhesives may be found in
Encyclopedia of Polymer Science and Technology, Vol. 1,
Interscience Publishers (New York, 1964).
[0067] Pressure-sensitive adhesives that may be used include the
hot melt pressure-sensitive adhesives available from H.B. Fuller
Company, St. Paul, Minn. as HM-1597, HL-2207-X, HL-2115-X,
HL-2193-X. Other useful pressure-sensitive adhesives include those
available from Century Adhesives Corporation, Columbus, Ohio.
[0068] Conventional PSAs, including silicone-based PSAs,
rubber-based PSAs, and acrylic-based PSAs are useful. Another
commercial example of a hot melt adhesive is H2187-01, sold by Ato
Findley, Inc., of Wauwatusa, Wis. In addition, rubber based block
copolymer PSAs described in U.S. Pat. No. 3,239,478 (Harlan) also
can be used, and this patent is hereby incorporated by a reference
for its disclosure of such hot melt adhesives.
[0069] In one embodiment, the pressure sensitive adhesives comprise
rubber based elastomer materials such as linear, branched, graft or
radial block copolymers represented by the diblock structures A-B,
the triblock A-B-A, the radial or coupled structures (A-B).sub.n,
and combinations of these where A represents a hard thermoplastic
phase or block which is non-rubbery or glassy or crystalline at
room temperature but fluid at higher temperatures, and B represents
a soft block which is rubbery or elastomeric at service or room
temperature. These thermoplastic elastomers may comprise from about
75% to about 95% by weight of rubbery segments and from about 5% to
about 25% by weight of non-rubbery segments.
[0070] The non-rubbery segments or hard blocks comprise polymers of
mono- and polycyclic aromatic hydrocarbons, and more particularly
vinyl-substituted aromatic hydrocarbons which may be monocyclic or
bicyclic in nature. The rubbery blocks or segments are typically
polymer blocks of homopolymers or copolymers of aliphatic
conjugated dienes. Rubbery materials such as polyisoprene,
polybutadiene, and styrene butadiene rubbers may be used to form
the rubbery block or segment. The rubbery segments include
polydienes and saturated olefin rubbers of ethylene/butylene or
ethylene/propylene copolymers. The latter rubbers may be obtained
from the corresponding unsaturated polyalkylene moieties such as
polybutadiene and polyisoprene by hydrogenation thereof.
[0071] The block copolymers of vinyl aromatic hydrocarbons and
conjugated dienes which may be utilized include any of those which
exhibit elastomeric properties. The block copolymers may be
diblock, triblock, multiblock, starblock, polyblock or graftblock
copolymers. Throughout this specification and claims, the terms
diblock, triblock, multiblock, polyblock, and graft or
grafted-block with respect to the structural features of block
copolymers are to be given their normal meaning as defined in the
literature such as in the Encyclopedia of Polymer Science and
Engineering, Vol. 2, (1985) John Wiley & Sons, Inc., New York,
pp. 325-326, and by J. E. McGrath in Block Copolymers, Science
Technology, Dale J. Meier, Ed., Harwood Academic Publishers, 1979,
at pages 1-5.
[0072] Such block copolymers may contain various ratios of
conjugated dienes to vinyl aromatic hydrocarbons including those
containing up to about 40% by weight of vinyl aromatic hydrocarbon.
Accordingly, multi-block copolymers may be utilized which are
linear or radial symmetric or asymmetric and which have structures
represented by the formulae A-B, A-B-A, A-B-A-B, B-A-B,
(AB).sub.0,1,2 . . . BA, etc., wherein A is a polymer block of a
vinyl aromatic hydrocarbon or a conjugated diene/vinyl aromatic
hydrocarbon tapered copolymer block, and B is a rubbery polymer
block of a conjugated diene.
[0073] The block copolymers may be prepared by any of the
well-known block polymerization or copolymerization procedures
including sequential addition of monomer, incremental addition of
monomer, or coupling techniques as illustrated in, for example,
U.S. Pat. Nos. 3,251,905; 3,390,207; 3,598,887; and 4,219,627. As
is well known, tapered copolymer blocks can be incorporated in the
multi-block copolymers by copolymerizing a mixture of conjugated
diene and vinyl aromatic hydrocarbon monomers utilizing the
difference in their copolymerization reactivity rates. Various
patents describe the preparation of multi-block copolymers
containing tapered copolymer blocks including U.S. Pat. Nos.
3,251,905; 3,639,521; and 4,208,356, the disclosures of which are
hereby incorporated by reference.
[0074] Conjugated dienes which may be utilized to prepare the
polymers and copolymers are those containing from 4 to about 10
carbon atoms and more generally, from 4 to 6 carbon atoms. Examples
include from 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene),
2,3-dimethyl-1,3-butadiene, chloroprene, 1,3-pentadiene,
1,3-hexadiene, etc. Mixtures of these conjugated dienes also may be
used. The preferred conjugated dienes are isoprene and
1,3-butadiene.
[0075] Examples of vinyl aromatic hydrocarbons which may be
utilized to prepare the copolymers include styrene and the various
substituted styrenes such as o-methylstyrene, p-methylstyrene,
p-tert-butylstyrene, 1,3-dimethylstyrene, alpha-methylstyrene,
beta-methylstyrene, p-isopropylstyrene, 2,3-dimethylstyrene,
o-chlorostyrene, p-chlorostyrene, o-bromostyrene,
2-chloro-4-methylstyrene, etc. The preferred vinyl aromatic
hydrocarbon is styrene.
[0076] Many of the above-described copolymers of conjugated dienes
and vinyl aromatic compounds are commercially available. The number
average molecular weight of the block copolymers, prior to
hydrogenation, is from about 20,000 to about 500,000, preferably
from about 40,000 to about 300,000.
[0077] The average molecular weights of the individual blocks
within the copolymers may vary within certain limits. In most
instances, the vinyl aromatic block will have a number average
molecular weight in the order of about 2000 to about 125,000, and
preferably between about 4000 and 60,000. The conjugated diene
blocks either before or after hydrogenation will have number
average molecular weights in the order of about 10,000 to about
450,000 and more preferably from about 35,000 to 150,000.
[0078] Also, prior to hydrogenation, the vinyl content of the
conjugated diene portion generally is from about 10% to about 80%,
and the vinyl content is preferably from about 25% to about 65%,
particularly 35% to 55% when it is desired that the modified block
copolymer exhibit rubbery elasticity. The vinyl content of the
block copolymer can be measured by means of nuclear magnetic
resonance.
[0079] Specific examples of diblock copolymers include
styrene-butadiene (SB), styrene-isoprene (SI), and the hydrogenated
derivatives thereof. Examples of triblock polymers include
styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS),
alpha-methylstyrene-butadiene-alpha-methy- lstyrene, and
alpha-methylstyrene-isoprene alpha-methylstyrene. Examples of
commercially available block copolymers useful as the adhesives in
the present invention include those available from Shell Chemical
Company and listed in the following Table II.
1 TABLE II Styrene/Rubber Melt Kraton Type Ratio (w) Index D1101
Linear SBS 31/69 <1 D1107P Linear SIS 15/85 11 D1111 Linear SIS
22/78 3 D1112P Linear SIS 15/85 23 D1113P Linear SIS 16/84 24
D1117P Linear SIS 17/83 33 D1320X Multi-arm (SI).sub.n 10/90 NA
[0080] Vector 4111 is an SIS block copolymer available from Dexco
of Houston Tex.
[0081] Upon hydrogenation of the SBS copolymers comprising a
rubbery segment of a mixture of 1,4 and 1,2 isomers, a
styrene-ethylene-butylene styrene (SEBS) block copolymer is
obtained. Similarly, hydrogenation of an SIS polymer yields a
styrene-ethylene propylene-styrene (SEPS) block copolymer.
[0082] The selective hydrogenation of the block copolymers may be
carried out by a variety of well known processes including
hydrogenation in the presence of such catalysts as Raney nickel,
noble metals such as platinum, palladium, etc., and soluble
transition metal catalysts. Suitable hydrogenation processes which
can be used are those wherein the diene-containing polymer or
copolymer is dissolved in an inert hydrocarbon diluent such as
cyclohexane and hydrogenated by reaction with hydrogen in the
presence of a soluble hydrogenation catalyst. Such procedures are
described in U.S. Pat. Nos. 3,113,986 and 4,226,952, the
disclosures of which are incorporated herein by reference. Such
hydrogenation of the block copolymers which are carried out in a
manner and to extent as to produce selectively hydrogenated
copolymers having a residual unsaturation content in the polydiene
block of from about 0.5% to about 20% of their original
unsaturation content prior to hydrogenation.
[0083] In one embodiment, the conjugated diene portion of the block
copolymer is at least 90% saturated and more often at least 95%
saturated while the vinyl aromatic portion is not significantly
hydrogenated. Useful hydrogenated block copolymers include
hydrogenated products of the block copolymers of
styrene-isoprene-styrene such as a
styrene-(ethylene/propylene)-styrene block polymer. When a
polystyrene-polybutadiene-polystyrene block copolymer is
hydrogenated, it is desirable that the 1,2-polybutadiene to
1,4-polybutadiene ratio in the polymer is from about 30:70 to about
70:30. When such a block copolymer is hydrogenated, the resulting
product resembles a regular copolymer block of ethylene and
1-butene (EB). When the conjugated diene employed as isoprene, the
resulting hydrogenated product resembles a regular copolymer block
of ethylene and propylene (EP).
[0084] A number of selectively hydrogenated block copolymers are
available commercially from Shell Chemical Company under the
general trade designation "Kraton G." One example is Kraton G1652
which is a hydrogenated SBS triblock comprising about 30% by weight
of styrene end blocks and a midblock which is a copolymer of
ethylene and 1-butene (EB). A lower molecular weight version of
G1652 is available from Shell under the designation Kraton G1650.
Kraton G1651 is another SEBS block copolymer which contains about
33% by weight of styrene. Kraton G1657 is an SEBS diblock copolymer
which contains about 13% w styrene. This styrene content is lower
than the styrene content in Kraton G1650 and Kraton G1652.
[0085] In another embodiment, the selectively hydrogenated block
copolymer is of the formula
B.sub.n(AB).sub.oA.sub.p
[0086] wherein: n=0 or 1; o is 1 to 100; p is 0 or 1; each B prior
to hydrogenation is predominantly a polymerized conjugated diene
hydrocarbon block having a number average molecular weight of about
20,000 to about 450,000; and each A is predominantly a polymerized
vinyl aromatic hydrocarbon block having a number average molecular
weight of from about 2000 to about 115,000; the blocks of A
constituting about 5% to about 95% by weight of the copolymer; and
the unsaturation of the block B is less than about 10% of the
original unsaturation. In other embodiments, the unsaturation of
block B is reduced upon hydrogenation to less than 5% of its
original value, and the average unsaturation of the hydrogenated
block copolymer is reduced to less than 20% of its original
value.
[0087] The block copolymers may also include functionalized
polymers such as may be obtained by reacting an alpha,
beta-olefinically unsaturated monocarboxylic or dicarboxylic acid
reagent onto selectively hydrogenated block copolymers of vinyl
aromatic hydrocarbons and conjugated dienes as described above. The
reaction between the carboxylic acid reagent in the graft block
copolymer can be effected in solutions or by a melt process in the
presence of a free radical initiator.
[0088] The preparation of various selectively hydrogenated block
copolymers of conjugated dienes and vinyl aromatic hydrocarbons
which have been grafted with a carboxylic acid reagent is described
in a number of patents including U.S. Pat. Nos. 4,578,429;
4,657,970; and 4,795,782, and the disclosures of these patents
relating to grafted selectively hydrogenated block copolymers of
conjugated dienes and vinyl aromatic compounds, and the preparation
of such compounds are hereby incorporated by reference. U.S. Pat.
No. 4,795,782 describes and gives examples of the preparation of
the grafted block copolymers by the solution process and the melt
process. U.S. Pat. No. 4,578,429 contains an example of grafting of
Kraton G1652 (SEBS) polymer with maleic anhydride with
2,5-dimethyl-2,5-di(t-butylperoxy) hexane by a melt reaction in a
twin screw extruder.
[0089] Examples of commercially available maleated selectively
hydrogenated copolymers of styrene and butadiene include Kraton
FG1901X, FG1921X, and FG1924X from Shell, often referred to as
maleated selectively hydrogenated SEBS copolymers. FG1901X contains
about 1.7% w bound functionality as succinic anhydride and about
28% w of styrene. FG1921X contains about 1% w of bound
functionality as succinic anhydride and 29% w of styrene. FG1924X
contains about 13% styrene and about 1% bound functionality as
succinic anhydride.
[0090] Useful block copolymers also are available from Nippon Zeon
Co., 2-1, Marunochi, Chiyoda-ku, Tokyo, Japan. For example, Quintac
3530 is available from Nippon Zeon and is believed to be a linear
styrene-isoprene-styrene block copolymer.
[0091] The adhesive compositions may contain at least one solid
tackifier resin component. A solid tackifier is defined herein as
one having a softening point above 80.degree. C. When the solid
tackifier resin component is present, the adhesive compositions may
comprise from about 40 to about 80% by weight of a thermoplastic
elastomer component and from about 20% to about 60% by weight, and
in one embodiment from about 55 to about 65% by weight of a solid
tackifier resin component. The solid tackifier reduces the modulus
of the mixture sufficiently to build tack or adhesion. Also, solid
tackifiers (particularly the higher molecular weight solid
tackifiers (e.g., Mw greater than about 2000) and those having a
lower dispersity (Mw/Mn=less than about 3)) may be less sensitive
to migration into the polymer film layer, and this is desirable,
since migration of tackifier into the film layer 110 or 180 may
cause dimensional instability.
[0092] The solid tackifier resins include hydrocarbon resins,
rosin, hydrogenated rosin, rosin esters, polyterpene resins, and
other resins which exhibit the proper balance of properties. A
variety of useful solid tackifier resins are available commercially
such as terpene resins which are sold under the trademark Zonatac
by Arizona Chemical Company, and petroleum hydrocarbons resins such
as the resins sold under the trademark Escorez by Exxon Chemical
Company. One particular example of a useful solid tackifier is
Escorez 2596 which is a C.sub.5-Cg (aromatic modified aliphatic)
synthetic tackifier having an Mw of 2100 and a dispersity (Mw/Mn)
of 2.69. Another useful solid tackifier is Escorez 1310LC,
identified as an aliphatic hydrocarbon resin having an Mw of 1350
and a dispersity of 1.8. Wingtack 95 is a synthetic tackifier resin
available from Goodyear, Akron, Ohio consisting predominantly of
polymerized structure derived from piperylene and isoprene.
[0093] The modulus of the adhesive mixtures to be coextruded also
may be lowered by the incorporation of liquid rubbers, i.e., liquid
at room temperature. The liquid rubbers generally will have an Mw
of at least 5,000 and more often at least 20,000. Incorporation of
liquid rubbers in amounts of less than 10%, and even less than 5%
by weight based on the overall weight of the adhesive formulation
results in adhesives which is coextrudable with the polymeric film
materials. The incorporation of a liquid rubber may produce an
adhesive having increased tack and adhesion. Liquid block
copolymers such as liquid styrene-isoprene block copolymers may be
used. Examples include Kraton LVSI-101, available from the Shell
Chemical Company. Another example is a liquid polyisoprene obtained
by depolymerization of high molecular weight polyisoprene. An
example of a commercially available depolymerized high molecular
weight polyisoprene is Isolene D-400 from Elementis Performance
Polymers, Belleville, N.J., and this liquid rubber has an Mw of
about 20,000. Other liquid rubbers which may be incorporated into
the adhesive mixture include liquid styrene-butadiene rubbers,
liquid butadiene rubbers, ethylene-propylene rubbers, etc.
[0094] The adhesive layer 120 may contain one or more pigments to
enhance the opacity of the paint film layers overlying it and
permit the use of thinner paint film layers to achieve desired
levels of opacity. Any of the pigments identified above may be
used. Specific examples include titanium dioxide and carbon black.
The pigment volume concentration may range up to about 10%, and in
one embodiment from about 5 to about 10%, and in one embodiment
about 2 to about 8%.
[0095] The adhesive compositions also may include other materials
such as antioxidants, heat and light stabilizers, ultraviolet light
absorbers, fillers, colorants, antiblocking agents, reinforcing
agents, processing aids, etc. Hindered phenolic and amine
antioxidant compounds may be included in the adhesive compositions,
and a wide variety of such antioxidant compounds are known in the
art. A variety of antioxidants are available from Ciba-Geigy under
the general trade designations "Irganox" and "Irgafos". For
example, the hindered phenolic antioxidant n-octadecyl
3-(3,5-di-t-butyl-4-hydroxyphenol)-proprionate is available under
the general trade designation "Irganox 1076". Irganox 1010, is
identified as Tetrakis (methylene
3-(3',5'-di-tert-butyl-4'-hydroxyphenol) proprionate) methane.
Irgafos 168 is another useful antioxidant from Ciba-Geigy.
Hydroquinone-based antioxidants also may be utilized, and one
example of such an antioxidant is
2,5-di-tertiary-amyl-hydroquinone. Light stabilizers, heat
stabilizers, and UV absorbers also may be included in the adhesive
compositions. Ultraviolet absorbers include benzo-triazol
derivatives, hydroxy benzyl phenones, esters of benzoic acids,
oxalic acid, diamides, etc. Light stabilizers include hindered
amine light stabilizers, and the heat stabilizers include
dithiocarbamate compositions such as zinc dibutyl
dithiocarbamate.
[0096] The adhesive compositions may contain inorganic fillers and
other organic and inorganic additives to provide desired
properties. Examples of useful fillers include calcium carbonate,
titanium dioxide, metal particles, fibers, etc. An example of a
useful end-block reinforcing agent is Cumar LX509 from Neville
Resins.
[0097] The barrier layer 190 may comprise any of the acrylate
polymers or copolymers described above, polyvinyl alcohol,
copolymers derived from ethylene and vinyl acetate, and copolymers
derived from ethylene, vinyl acetate and polyvinyl alcohol. The
barrier layer may comprise a polymer blend derived from polyvinyl
alcohol, urethane, Cymel 385 (a product of Cytec identified as a
melamine formaldehyde resin) and a polyaziridine (e.g, NeoCryl
CX100 which is identified as trimethol-tris N (methyl aziridinyl)
proprionate and is available from Avecia Resins), the weight ratio
of polyvinyl alcohol to urethane in one embodiment being about
20:80. The barrier layer may be provided to inhibit or reduce the
migration of dyes or pigments and other materials from the
substrate to which the inventive laminate is applied into the dry
paint film layer 110. The following examples illustrate specific
coating compositions which may be used in forming the barrier layer
190:
2 Percent by weight Barrier Layer No. 1 Elvacite 2042 (product of
Ineos 20 identified as an ethyl methacrylate copolymer) Toluene 48
Methyl ethyl ketone 32 Barrier Layer No. 2 Adcote 61WG178 (product
of Rohm 0.10 and Haas identified as a solution of acrylic polymer)
Syloid 234 (product of Grace Davidson identified as synthetic
amorphous silica) N-propanol 44.35 Barrier Layer No. 3 Adcote
61WG178 74.07 N-propanol 25.83 Syloid 234 0.10 Barrier Layer No. 4
Adcote 61WG178 55.55 N-propanol 44.35 Syloid 234 0.10 Desmodur CB
75N (product of 0.44 Bayer identified as an oligomeric toluene
diisocyanate) Barrier Layer No. 5 Adcote 61WG178 74.07 N-propanol
25.83 Syloid 234 0.10 Desmodur CB 75N 0.44 Barrier Layer No. 6
Adcote 61WG178 58.0 R-900 TiO.sub.2 (product of DuPont 15.00
identified as rutile titanium dioxide) N-propanol 24.0 Isobutanol
3.00 Barrier Layer No. 7 Adcote 61WG178 58.00 R-900 TiO.sub.2 15.00
N-propanol 24.00 Isobutanol 3.00 Desmodur CB 75N 0.88 Barrier Layer
No. 8 Air Vol 523 (product of Air Products 5.0 identified as
polyvinyl alcohol) Water 47.5 Isopropanol 47.5
[0098] The backing liners 132 and 172 may independently comprise
paper, polymer film, or a combination thereof. These backing
liners, in one embodiment, are thermally stable, non-elastomeric
and non-stretchable at room temperature. Paper liners are useful
because of the wide variety of applications in which they can be
employed. Paper is also relatively inexpensive and has desirable
properties such as antiblocking, antistatic, dimensional stability,
and can potentially be recycled. Any type of paper having
sufficient tensile strength to be handled in conventional paper
coating and treating apparatus can be employed as the backing
liner. Thus, any type of paper can be used depending upon the end
use and particular personal preferences. Included among the types
of paper which can be used are clay coated paper, glassine, polymer
coated paper, hemp, and similar cellulose materials prepared by
such processes as the soda, sulfite or sulfate (Kraft) processes,
the neutral sulfide cooking process, alkali-chlorine processes,
nitric acid processes, semi-chemical processes, etc. Although paper
of any weight may be employed as a backing liner, paper having
weights in the range of from about 30 to about 120 pounds per ream
are useful, and papers having weights in the range of from about 60
to about 100 pounds per ream may be used. The term "ream" as used
herein equals 3000 square feet.
[0099] Alternatively, the backing liners 132 and 172 may
independently comprise a polymer film, and examples of polymer
films include polyolefin, polyester, and combinations thereof. The
polyolefin films may comprise polymer and copolymers of monoolefins
having from 2 to about 12 carbon atoms, and in one embodiment from
2 to about 8 carbon atoms, and in one embodiment 2 to about 4
carbon atoms per molecule. Examples of such homopolymers include
polyethylene, polypropylene, poly-1-butene, etc. Films prepared
from blends of copolymers or blends of copolymers with homopolymers
may be used. The films may be extruded in mono or multilayers.
[0100] Another type of material which may be used as the backing
liners 132 and 172 is a polycoated kraft liner which is basically
comprised of a kraft liner that is coated on either one or both
sides with a polymer coating. The polymer coating, which can be
comprised of high, medium, or low density polyethylene, propylene,
polyester, or other similar polymerfilms, is coated onto the
substrate surface to add strength and/or dimensional stability to
the liner. The weight of these types of liners ranges from about 30
to about 100 pounds per ream, with about 94 to about 100 pounds per
ream being useful. In total, the final backing liner 132 may
comprise from about 10% to about 40% polymer and from about 60% to
about 90% paper. For two sided coatings, the quantity of polymer
may be approximately evenly divided between the top and bottom
surface of the paper.
[0101] The backing liners 132 and 172, in one embodiment, provide
structural integrity to the laminate until they are removed upon
application of the laminate to a substrate. As a result of the use
of either or both of these liners, it is not necessary to employ a
semi-rigid or reinforcing backing sheet with the inventive
laminates.
[0102] The release coating layer 135 may comprise a single coat of
release coating material or multiple coats. When multiple coats are
used, each coat may have the same formulation, or different
formulations may be used. The release coating layer 135 may
comprise any of the above indicated binders or resins which provide
sufficient tack or adherence between the release coating layer 135
and either the dry paint film layer 110 (FIG. 1 or 6-8),
transparent film layer 140 (FIGS. 3-5) or printed decorative layer
165 (FIG. 9) to prevent separation of the release coating layer 135
from film layer 110, 140 or 165 during the making of the dry paint
transfer laminate and normal handling of such laminate, and yet
have sufficient release properties to provide for facilitated
separation between the release coating layer 135 and the layers
110, 140 or 165 when using the laminate. The release coating layer
135 may comprise an alkyd resin and/or a vinyl resin cross linked
with a melamine resin. The alkyd resins include resins formed by
the condensation of one or more polyhydric alcohols with one or
more polybasic acids or anhydrides. The polyhydric alcohols include
glycerol and the polybasic acids or anhydrides include phthalic
anhydride. Modified alkyds wherein the polybasic acid is
substituted in part by a monobasic acid such as acrylic acid or a
vegetable oil fatty acid may be used. The vinyl resins that may be
used include polyvinyl chloride, polyvinyl acetate, copolymers of
vinyl chloride and vinyl acetate, acrylic resins, methacrylic
resins, polystyrene resins, and the like. The melamine resins
include amino resins made by the condensation of melamine with
formaldehyde or a compound capable of providing methylene bridges.
The cross linking of the alkyd and/or vinyl resin with the melamine
resin typically occurs when the release coating 135 is applied to
the backing liner and dried or cured. In one embodiment, the
release coating comprises on a solids basis from zero to about 80%
by weight, and in one embodiment about 10 to about 30% by weight
alkyd resin; from zero to about 80% by weight, and in one
embodiment about 10 to about 30% by weight vinyl resin; and from
about 10 to about 30% by weight, and in one embodiment about 20 to
about 25% by weight melamine resin.
[0103] Release coating layer 135 may contain one or more solid
particulates that project into the surface 114 of dry paint film
layer 110, the surface 141 of transparent film layer 140 or the
printed decorative layer 165 to provide the layers 110, 140 or 165
with a matte or flat finish. When particulates are present, the
release coating layer 135 may be referred to as a matte release
coat or matte release coating layer. The particulates that may be
used may be any of the filler pigments described above for use in
the paint film layers. Specific examples include talc and aluminum
silicate. Particulates with irregular shapes (e.g., platelet
shapes) may be used. By controlling the use of these particulates
the surface finish of the dry paint film layer, transparent film
layer or printed decorative layer may be controlled. For example,
by using these particulates, the dry paint film layer, transparent
film layer or printed decorative layer may be provided with a flat
or semi-gloss finish. The paint film layer, transparent film layer
or printed decorative layer may be provided with a glossy finish by
not using or minimizing the use of these particulates. The weight
ratio of particulates to resin or binder may range up to about
1.1:1, and in one embodiment about 0.7:1 to about 1.1:1, and in one
embodiment from about 0.7:1 to about 0.9:1, and in one embodiment
about 0.9:1 to about 1.1:1.
[0104] The release coating layers 136 and 176 may independently
comprise any release coating composition known in the art. Silicone
release coating compositions may be used. The silicone release
coating compositions typically comprise polyorganosiloxanes such as
polydimethylsiloxanes. The silicone release coating composition
used in this invention may be room temperature cured, thermally
cured, or radiation cured. Generally, the room temperature and
thermally curable compositions comprise at least one
polyorganosiloxane and at least one catalyst (or curing agent) for
such polyorganosiloxane(s). These compositions may also contain at
least one cure accelerator and/or adhesivity promoter. As is known
in the art, some materials have the capability of performing both
functions, i.e., the capability of acting as a cure accelerator to
increase the rate, reduce the curing temperature, etc., and also as
an adhesivity promoter to improve bonding of the silicone
composition to the substrate. The use of such dual function
additives where appropriate is within the purview of the
invention.
[0105] In the embodiments illustrated in FIGS. 1-9, the release
force required to separate release coating layer 135 from dry paint
film layer 110, transparent film layer 140, or printed decorative
layer 165 is advantageously greater than the release force required
to separate release coating layer 136 from adhesive layer 120. In
the embodiment illustrated in FIG. 6, the release force required to
separate release coating layer 135 from dry paint film layer 110 is
advantageously greater than the release force required to separate
release coating layer 176 from adhesive layer 20. In one
embodiment, the release force required to separate release coating
layer 135 from dry paint film layer 110, transparent film layer 140
or printed decorative layer 165 may be in the range of about 20 to
about 180 grams per two inches (g/2 in), and in one embodiment 30
to about 150 g/2 in, and in one embodiment 40 to about 120 g/2 in,
and in one embodiment 50 to about 100 g/2 in, and in one embodiment
50 to about 90 g/2 in, and in one embodiment about 70 to about 90
g/2 in, and in one embodiment about 50 to about 65 g/2 in. In one
embodiment, the release force required to separate release coating
layer 136 or 176 from adhesive layer 120 is in the range of 10 to
about 150 g/2 in, and in one embodiment about 20 to about 150 g/2
in, and in one embodiment about 20 to about 90 g/2 in, and in one
embodiment about 30 to about 150 g/2 in, and in one embodiment
about 30 to about 100 g/2 in, and in one embodiment about 30 to
about 70 g/2 in. The test method for determining these release
forces involves measuring the force required to separate a two-inch
wide release coated liner from the layer 110, 140 or 165, or from
an adhesive coated substrate, with the release coated liner
extending at an angle of 90.degree. relative to the layer or
substrate and being pulled at a rate of 300 inches per minute. The
test may be conducted at room temperature.
[0106] Each of the layers 135, 136, 140, 176, 180 and 190 may be
independently applied and dried and/or cured using known
techniques. The application techniques include gravure, reverse
gravure, offset gravure, roll coating, brushing, knife-over roll,
metering rod, reverse roll coating, doctor knife, dipping, die
coating, slot die coating, spraying, curtain coating, slide
coating, slide curtain coating, extrusion, co-extrusion,
flexographic, letter press, rotary screen, flat screen, and the
like. The decorative layers 150, 160 and 165 may be applied using
known printing techniques including gravure, flexographic, silk
screen, ink jet, etc. The applied layers may be dried and/or cured
by exposure to heat or to known forms of ionizing or actinic
non-ionizing radiation. Drying or curing temperatures that may be
used may range from about 115.degree. C. to about 160.degree. C.,
and in one embodiment about 140.degree. C. to about 150.degree. C.
Useful types of radiation include ultraviolet light and electron
beam. The equipment for generating these forms of thermal or
radiation drying and/or curing are well known to those skilled in
the art. The layers 110 and 120, as well as one either of the
layers 140 and 180 may be extruded. The layers 110 and/or 180 may
be coextruded with the adhesive layer 120. In one embodiment, the
support layer 180 may be coextruded with the adhesive layer
120.
[0107] Each of the layers 110, 140 or 180 may independently
comprise a single layer film or a multilayer film of two or more
adjacent coextruded layers. For example, the layer 110, 140 or 180
may comprise one layer of a polyolefin and one layer of a blend of
a polyolefin and a copolymer of ethylene and vinyl acetate (EVA).
In one embodiment, the film layers 110, 140 or 180 may comprise
three layers, a base or core layer of, for example, a polyolefin,
and skin layers in both sides of the base or core layer which may
comprise the same or different polymer blends.
[0108] The dry paint film layer 110 or the support layer 180 may be
coextruded with the adhesive layer 120 using separate extruders as
illustrated in FIG. 11 or a dual die extruder as illustrated in
FIG. 12. Referring to FIG. 11, release liner 200 is uncoiled from
roll 240 and advanced past extrusion die 210 where it is coated
with adhesive layer 120, and then past extrusion die 220 where the
support layer 180 is coated onto the adhesive layer 120. The
resulting coextrudate is collected in roll form as indicated by
collection roll 250. Referring to FIG. 12, release liner 200 is
advanced past dual extrusion die 230 which simultaneously coats
release liner 200 with adhesive layer 120 and support layer 180.
The resulting coextrudate is collected in roll form as indicated by
collection roll 250. When a desired quantity of the coextrudate has
been manufactured, the collection roll 250 is removed from the
process and is stored for subsequent processing (e.g., coating,
printing, etc.) during a separate operation at either the same or
at a different geographic location, thereby providing enhanced
manufacturing flexibility. Alternatively, rather than being
collected, the coextrudate may be routed for coating, printing,
etc., during the same manufacturing operation. The dry paint film
layer 110 may be coextruded with the adhesive layer 120 following
the above procedure. Multi-die application methods useful for
applying both a pressure sensitive adhesive and a film forming
layer to a substrate are further described in Published PCT
International Application Nos. PCT/US95/11807; PCT/US95/11733;
PCT/US95/11734; and PCT/US95/11717, which are herein incorporated
by reference. The polymeric film materials and adhesive
compositions that are coextruded may be neat, or they may be
emulsions or solvent-based. Emulsion and solvent-based acrylic
based PSAs are known and described in, for example, U.S. Pat. No.
5,639,811 and 5,164,444, respectively, and these patents are hereby
incorporated by reference for such disclosures. When emulsions of
the film materials and/or adhesive compositions are used, the water
may be removed in an extruder by using the process described and
claimed in U.S. Pat. No. 5,716,669 (LaRose et al). In one
embodiment, the film materials and adhesives which are coextruded
are compositions substantially free (e.g., less than about 1% by
weight) of water and/or solvents. The presence of water or solvents
during the coextrusion process may result in pinholes and bubbles
in the coextruded film. The presence of voids in the film due to
steam may be referred to as "moisture slits."
[0109] When the polymeric film material and adhesive are
coextruded, the hot melt viscosity of the polymeric-film material
and the adhesive may be within a window or range of viscosities
which may produce a coextrudate of continuous and uniform layers of
the polymeric film material and the adhesive in order to avoid film
defects and intermingling of the polymeric film material and the
adhesive during the coextrusion process. The polymeric film
material may have a hot melt viscosity that is within a factor of
from about 0.07 to about 15 times the hot melt viscosity of the
adhesive at the shear rates incurred during the coextrusion
process. The shear rates may range from about 100 sec-.sup.1 to
about 10,000 sec-.sup.1. The factor may be from about 1 to about
15, and in one embodiment about 1 to about 10. It is also desirable
for the polymeric film material and the adhesive to have relatively
similar melt viscosities at the extrusion temperatures. For
example, when the adhesive is a conventional hot melt adhesive, the
extrusion temperatures of the adhesive may be in the range of from
about 150.degree. C. to about 200.degree. C., and in one embodiment
in the range of from about 175.degree. C. to about 200.degree. C.
The polymeric film material selected for use with the adhesive may
have an extrusion temperature below about 200.degree. C., and in
one embodiment in the range of from about 150.degree. C. to about
180.degree. C.
[0110] The dry paint transfer laminate 100 illustrated in FIG. 1
may be made by applying release coating 136 to lower surface 134 of
backing liner 132 using one of the foregoing application techniques
and then curing the release coating. The coat weight for the
release coating layer 136 may be in the range of about 0.1 to about
1 gram per square meter (gsm), and in one embodiment about 0.25 to
about 0.35 gsm. Release coating layer 135 is then applied to upper
surface 133 of backing liner 132 using one of the above indicated
application techniques (e.g, gravure) and then dried or cured. The
coat weight for the release coating 135 may range from about 2.5 to
about 6.5 gsm, and in one embodiment about 4.5 to about 5.5 gsm.
The liquid paint or coating composition for forming dry paint film
layer 110 is then applied to the surface of release coating layer
135 using one of the above indicated application techniques (e.g.,
reverse roll or slot die) and then dried or cured. The coat weight
for the dry paint film layer 110 may range from about 20 to about
60 gsm, and in one embodiment about 30 to about 40 gsm. One or more
coats may be applied. Pressure sensitive adhesive layer 120 is then
applied to upper surface 112 of dry paint film layer 110 using one
of the above indicated application techniques (e.g., slot die) and
then dried or cured. The pressure sensitive adhesive may be applied
using transfer lamination. The coat weight for the pressure
sensitive adhesive layer 120 may range from about 10 to about 30
gsm, and in one embodiment about 11 to about 17 gsm. The dry paint
transfer laminate 100 may then be wound into roll form as
illustrated in FIG. 2 using known techniques.
[0111] The dry paint transfer laminate 100A illustrated in FIG. 3
may be made using the same procedure used for making the laminate
100 except that transparent film layer 140 is applied to the
surface of release coating layer 135 and then dried or cured prior
to the application of the dry paint film layer 110. The dry paint
film layer 110 is then applied to the surface of the transparent
film layer 140. The transparent film layer 140 may be applied using
one of the foregoing application techniques (e.g., gravure). The
coat weight for the transparent film layer 140 may range from about
1 to about 5 gsm, and in one embodiment about 2.5 to about 3.5 gsm.
One or more coats may be applied. The dry paint transfer laminate
100A may then be wound into a roll as illustrated in FIG. 2 using
known techniques.
[0112] The dry paint transfer laminate 100B illustrated in FIG. 4
may be made using the same procedure used for making the laminate
100A except that the liquid paint composition for forming the
printed decorative layer 150 is applied to the surface of the
transparent film layer 140 and then cured prior to the application
of the dry paint film layer 110. The dry paint film layer 110 is
then applied to the surface of the printed decorative layer 150.
The printed decorative layer 150 may be applied using any of the
foregoing printing techniques (e.g., gravure, flexographic, silk
screen, ink jet, etc.). The coat weight for the printed decorative
layer 150 may range from about 0.3 to about 2 gsm, and in one
embodiment about 0.3 to about 0.7 gsm. The dry paint transfer
laminate 100B may then be wound into a roll as illustrated in FIG.
2 using known techniques.
[0113] The dry paint transfer laminate 100C illustrated in FIG. 5
may be made using the same procedure used for making the laminate
100B except that the liquid paint composition for forming the
second printed decorative layer 160 is applied to the surface of
the transparent film layer 140 and then dried or cured prior to the
application of the printed decorative layer 150. The printed
decorative layer 150 is then applied over the surface of the second
printed decorative layer 160. The second printed decorative layer
160 may be applied using any of the foregoing printing techniques
(e.g., gravure, flexographic, silk screen, ink jet, etc.). The coat
weight for the second printed decorative layer 160 may range from
about 0.3 to about 2 gsm, and in one embodiment about 0.3 to about
0.7 gsm. The dry paint transfer laminate 100C may then be wound
into a roll as illustrated in FIG. 2 using known techniques.
[0114] The dry paint transfer laminate 100D illustrated in FIG. 6
may be made using the same procedure used for making the laminate
100 illustrated in FIG. 1 except that release liner 170 is adhered
to adhesive layer 120 with release coating layer 176 in contact
with adhesive layer 120.
[0115] The dry paint transfer laminate 100E illustrated in FIG. 7
may be made using the same procedure used for making the laminate
100 illustrated in FIG. 1 except that the support layer 180 is
adhered to the dry paint film layer 110. The support layer 180 may
be coextruded with the adhesive layer 120 and then the dry paint
film layer 110 may be coated (e.g., gravure) onto the support layer
180. The dry paint transfer laminate 100E may then be wound into a
roll as illustrated in FIG. 2 using known techniques.
[0116] The dry paint transfer laminate 100F illustrated in FIG. 8
may be made using the same procedure used for making the laminate
100 illustrated in FIG. 1 except tha the barrier layer 190 is
coated on the dry paint transfer film layer 110. The dry paint
transfer laminate 100F may then be wound into a roll as illustrated
in FIG. 2 using known techniques.
[0117] The dry paint transfer laminate 100G illustrated in FIG. 9
may be made using the same procedure used for making the laminate
100 illustrated in FIG. 1 except that support layer 180 is adhered
to dry paint transfer layer 110. The support layer 180 may be
coextruded with the adhesive layer 120. The printed decorative
layers 150, 160 and 165 may be coated sequentially over the dry
paint film layer 110. The dry paint transfer laminate 100G may then
be wound into a roll as illustrated in FIG. 2 using known
techniques.
[0118] The dry paint transfer laminate 100H illustrated in FIG. 10
may be made using the same procedure used for making the laminate
100C illustrated in FIG. 5 except that the release liner used in
the laminate 100C is removed, and the release liner 170 and
accompanying release layer are included. The dry paint film layer
110 and adhesive layer 120 may be coextruded onto the release layer
176 of the release liner 170.
[0119] The inventive dry paint transfer laminate may be made in a
single production line or in multiple production lines or multiple
production facilities. With multiple production lines or
facilities, part of the laminate may be produced as a roll
laminate, dried or cured, rolled up, transferred to the next
production line or facility, unrolled, and further treated with the
application of additional layers. For example, the dry paint film
layer 110 and the adhesive layer 120 may be deposited in multiple
lines, or they may be deposited in sequence in a single line, or
they may be deposited simultaneously such as by coextrusion or
multi-die coating methods. Production in a single production line
may be more efficient by avoiding extra handling, storage, and
transporting steps for what may comprise, at least in one
embodiment, relatively thin and delicate film materials.
[0120] The dry paint transfer laminate 100 may be used by unrolling
the laminate from the roll illustrated in FIG. 2, and
simultaneously applying the laminate to the substrate (e.g., wall)
to be covered. The substrate may comprise any flat surface. The
flat surface may comprise wall board, plastic sheet, metal sheet,
composites, and the like. The substrate may comprise an interior
(i.e., indoor) surface or an exterior (i.e., outdoor) surface. The
laminate is placed over the substrate with the adhesive layer 120
in contact with the substrate. The release liner 130 is then peeled
off leaving the dry paint film layer 110 adhered to the substrate
by the adhesive layer 120. An advantage of using this laminate, at
least in one embodiment, is that it is possible to overlap part of
the applied dry paint film layer with the next adjacent applied dry
paint film layer due to the fact that the seams substantially
disappear and therefore are not noticeable. This advantage is
provided at least in part due to the fact that the dry paint film
layer 110 is relatively thin. Also, the gloss and opacity of the
dry paint film layer 110 contrubute to this ability to hide
seems.
[0121] The dry paint transfer laminate 100A may be applied to a
substrate in the same manner as the laminate 100. When the release
liner 130 is peeled off, the dry paint film layer 110, transparent
film layer 140, and adhesive layer 120 remain adhered to the
substrate with the adhesive layer 120 in contact with the
substrate.
[0122] The dry paint transfer laminate 100B may be applied to a
substrate in the same manner as the laminate 100. When the release
liner 130 is peeled off, the dry paint film layer 110, printed
decorative layer 150, transparent film layer 140, and adhesive
layer 120 remain adhered to the substrate with the adhesive layer
120 in contact with the substrate.
[0123] The dry paint transfer laminate 100C may be applied to a
substrate in the same manner as the laminate 100. When the release
liner 130 is peeled off, the layers 110, 150 and 160, transparent
film layer 140, and adhesive layer 120 remain adhered to the
substrate with the adhesive layer 120 in contact with the
substrate.
[0124] The dry paint transfer laminate 100D may be applied to a
substrate in the same manner as the laminate 100 except that the
laminate is advantageously provided in the form of a flat sheet
rather than a roll and the release liner 170 is peeled off before
the adhesive layer 120 is adhered to the substrate.
[0125] The dry paint transfer laminate 100E may be applied to a
substrate by adhering the adhesive layer 120 to the substrate, and
then removing the release liner 130.
[0126] The dry paint transfer laminate 100F may be applied to a
substrate by adhering the adhesive layer 120 to the substrate, and
removing the release liner 130.
[0127] The laminate 100G may be applied to a substrate by adhering
the adhesive layer 120 to the substrate, and removing the release
liner 130.
[0128] The laminate 100H may be applied to a substrate by peeling
the peeling the release liner 170 and accompanying release coating
176 from the laminate, and then applying the adhesive layer 120 to
the substrate. The laminate may be applied using a specialized
applicator which winds or coils the release liner 170 and
accompanying release layer 176 as the remainder of the laminate is
applied to the substrate.
EXAMPLES 1 and 2
[0129] A polyethylene terephthalate film backing liner
corresponding to backing liner 132 is coated on one side with a
silicone release coating corresponding to second release coating
layer 136. The thickness of the release coated liner is 0.92
mil.
[0130] A matte release coat corresponding to first release coating
layer 135 is applied to the other side of the backing liner using
gravure at a coat weight of 6.5-7.75 gsm. The formulation for the
matte release coat is as follows: 26% by weight methylisobutyl
ketone, 6% by weight isopropanol, 34.8% by weight Lankyd 13-1425 (a
product supplied by Akzo Resins identified as an acrylic modified
alkyd), 2.6% by weight Elvacite 2042 (a product supplied by Lucite
International identified as a polyethyl methacrylate polymer), 30%
by weight Microtalc MP 15-38 (a product 30 supplied by Barrett's
Minerals identified as a talc extender pigment), 2.5% by weight
Cycat 4040 (a product supplied by Cytec identified as paratoluene
sulfonic acid) and 8.7% by weight Cymel 303 (a product suppled by
Cytec identified as a melamine resin). The matte release coat is
dried using forced hot air at a temperature of 149.degree. C.
[0131] A transparent film layer corresponding to transparent film
layer 140 is applied to the matte release coat using gravure at a
coat weight of 2.7-2.9 gsm and dried using forced hot air at a
temperature of 120.degree. C. The formulation for the transparent
film layer is as follows: 46.7% by weight methyl ethyl ketone,
31.3% by weight toluene, 11% by weight VYNS (a product of Union
Carbide identified as a vinyl chloride/vinyl acetate copolymer
containing 5-20% by weight vinyl acetate), and 11% by weight Vitel
2200B (a product of Bostic identified as a polyester
copolymer).
[0132] The following paint compositions are used to form a dry
paint film layer corresponding to dry paint film layer 110 on the
transparent film layer, one for Example 1 and the other for Example
2. Example 1 has a deep brown tone, while Example 2 has an orange
pastel tone. In the following table, all numerical values are in
parts by weight.
3 Example 1 Example 2 Methylethyl ketone 66.7 66.7 Toluene 33.3
33.3 VYHH (product of Union Carbide 50.05 30.55 identified as a
vinyl chloride/vinyl acetate copolymer) Edinol 9790 (a product of
Cognis 24.65 15.05 identified as a polyester plasticizer) Yellow
pigment 42 (iron oxide) 17.8 2.3 Orange pigment 36 (monoazo 2.5
0.38 benzimidazoline) Black 7 (carbon black) 0.1 0.02 White 6
(titanium dioxide) 4.9 51.7
[0133] The pigment volume ratio for Example 1 is 10%, and for
Example 2 it is 27%. The above paint formulations are applied to
the transparent film layer using a reversed roller coater and dried
at a temperature of 135.degree. C. to drive off the solvents. The
dry film thickness of each of the dry paint film layers is 0.7
mil.
[0134] A pigmented pressure sensitive adhesive is then applied to
the dry paint film layer at a coat weight of 14-20 gsm using
transfer lamination to provide an adhesive layer corresponding to
pressure sensitive adhesive layer 120. The formulation for the
pressure sensitive adhesive is as follows: 70-90% by weight
2-ethylhexal acrylate, 1-10% by weight acrylic acid, 10-20% by
weight methyl acrylate, 3.7% UCD 1106E (a product of Rohm and Haas
identified as a titanium dioxide dispersion concentrate), and 0.3%
by weight of UCD 1507E (a product of Rohm and Haas identified as a
carbon black dispersion concentrate).
EXAMPLE 3
[0135] The procedure used for Examples 1 and 2 is repeated except
that the following liquid paint composition is used to form the dry
paint film layer corresponding to dry paint film layer 110. In the
following table, all numerical values are in parts by weight.
4 Methylethyl ketone 29.6 Toluene 19.5 Vitel 2200 B 11.6 Vitel 2650
(product of Bostic identified 11.5 as a polyester copolymer) R-900
(product of DuPont identified as 27.5 titanium dioxide) 955-39230
(product of Gibraltar Chemical 0.2 Works identified as shading
black) 99-34520 (product of Gibraltar Chemical 0.1 Works identified
as phthalo blue GS) 955-37470 (product of Gibraltar Chemical tint
Works identified as carbazole violet)
[0136] The foregoing paint composition has a light blue color. The
dry film thickness of the dry paint film layer is 0.6-0.8 mil.
EXAMPLE 4
[0137] A polyethylene terphthalate film backing liner corresponding
to backing liner 132 is coated on one side with a silicone release
coating corresponding to second release coating layer 136. The
thickness of the release coated liner is 0.92 mil.
[0138] A matte release coat corresponding to first release coating
layer 135 is applied to the other side of the backing liner using
gravure at a coat weight of 4.4-4.6 gsm. The formulation for the
matte release coat is as follows: 50.54% by weight methylisobutyl
ketone, 7.84% by weight isopropanol, 8.93% by weight Lankyd
13-1425, 10.68% by weight VAGH (product of Union Carbide identified
as hydroxy modified polyvinyl chloride/polyvinyl acetate
copolymer), 22% by weight Microtalc MP 15-38, 2% by weight Cycat
4040, and 6.8% by weight Cymel 303. The matte release coat is dried
using forced hot air at a temperature of 149.degree. C.
[0139] A first coat of a transparent film layer corresponding to
transparent film layer 140 is applied to the matte release coat
using gravure at a coat weight of 1.3-2 gsm and dried using forced
hot air at a temperature of 120.degree. C. The dry film thickness
is 0.05-0.1 mil. The formulation for this first transparent film
layer coat is as follows: 41.5% by weight methyl ethyl ketone,
41.5% by weight methyl isobutyl ketone, and 17% by weight Elvacite
2042 (a product of Lucite International identified as a polymethyl
methacrylate).
[0140] A second coat of a transparent film layer corresponding to
transparent film layer 140 is applied over the first coat of
transparent film layer using gravure at a coat weight of 1.0-1.5
gsm and dried using forced hot air at a temperature of 120.degree.
C. The dry film thickness is 0.03-0.7 mil. The formulation for this
second transparent film layer coat is as follows: 41.5% by weight
methyl ethyl ketone, 41.5% by weight methyl isobutyl ketone, and
17% by weight VYHH (a product of Union Carbide identified as a
vinyl chloride/vinyl acetate copolymer containing 5-20% by weight
vinyl acetate).
[0141] A decorative layer corresponding to second printed
decorative layer 160 is printed over the second coat of the
transparent coating layer at a coat weight of 3.0-3.2 gsm and dried
in hot air at a temperature of 120.degree. C. The paint composition
used for this decorative layer has the following formulation (all
numerical values are in parts by weight):
[0142] Methylethyl Ketone 42.6
5 Methyl isobutyl ketone 38.7 VYHH 15.86 DP 80110 (product of
Gibraltar Chemical 2.1 Works identified as containing methylethyl
ketone, toluene, carbon black and acrylic polymer) DP 36640
(product of Gibraltar Chemical 0.22 Works identified as containing
methyl ethyl ketone, toluene, quinacridone red, and acrylic
polymer) I8977 (product of Gibraltar Chemical 0.10 Works identified
as containing methyl ethyl ketone, toluene, R.S. Phthalo Blue, and
acrylic polymer) I8980 (product of Gibraltar Chemical 0.38 Works
identified as containing methyl ethyl ketone, toluene,
isoindolinone yellow and acrylic polymer)
[0143] A decorative layer corresponding to printed decorative layer
150 is printed over the above indicated decorative layer
corresponding to second printed decorative layer 160 at a coat
weight of 0.8 gsm and dried in hot air at a temperature of
120.degree. C. The paint composition used for this decorative layer
has the following formulation (all numerical values are in parts by
weight):
6 Methylethyl ketone 42.85 Methyl isobutyl ketone 39.1 VYHH 16.0 DP
80110 1.71 DP 36640 0.18 18977 0.18
[0144] The following paint composition is coated over the above
indicated decorative layer corresponding to printed decorative
layer 150 at a coat weight of 30-32 gsm and dried in hot air at a
temperature of 120.degree. C. to provide a dry paint film layer
corresponding to dry paint film layer 110. In the following table,
all numerical values are in parts by weight.
7 Methyl ethyl ketone 34 Toluene 16.7 VYHH 18.3 Edinol 9790 9
AVI-0301-3 Orange (product of Gibraltar 8.9 Chemical Works
identified as containing methyl ethyl ketone, toluene, diarylide
orange, VYHH and Edinol 9790) AVI-0301-5 Magenta (product of
Gibraltar 5.3 Chemical Works identified as containing methyl ethyl
ketone, toluene, Metal Azo Red, VYHH and Edinol 9790) AVI-0301-6
Iron Red (product of Gibraltar 3.7 Chemical Works identified as
containing methyl ethyl ketone, toluene, Iron Oxide Red, VYHH and
Edinol 9790) AVI-0301-1 TiO.sub.2 White (product of Gibraltar 3.52
Chemical Works identified as containing methyl ethyl ketone,
toluene, titanium dioxide, VYHH and Edinol 9790) AVI-0301-2 Carbon
Black (product of 0.03 Gibraltar Chemical Works identified as
containing methyl ethyl ketone, toluene, carbon black, VYHH and
Edinol 9790)
[0145] A pigmented pressure sensitive adhesive is then applied over
the dry paint film layer corresponding to dry paint film layer 110
at a coat weight of 17 gsm using transfer lamination to provide an
adhesive layer corresponding to pressure sensitive adhesive layer
120. The formulation for the pressure sensitive adhesive is as
follows: 96% by weight of a non-tackified acrylic emulsion
containing a crosslinked copolymer of butyl acrylate and ethyl
hexyl acrylate, 3.7% by weight UCD 1106E, and 0.3% by weight UCD
1507E.
EXAMPLE 5
[0146] A polyethylene terphthalate film backing liner corresponding
to backing liner 132 is coated on one side with a silicone release
coating corresponding to second release coating layer 136. The
thickness of the release coated liner is 0.92 mil.
[0147] A matte release coat corresponding to first release coating
layer 135 is applied to the other side of the backing liner using
gravure at a coat weight of 4.4-4.6 gsm. The matte release coat is
dried using forced hot air at a temperature of 149.degree. C. The
formulation for the matte release coat is as follows (all numerical
values are in parts by weight):
8 Methyl isobutyl ketone 52.54 Elvacite 4402 (product of Lucite
20.98 International identified as hydroxy ethyl methacrylate
modified acrylic resin) VYNS 1.35 Microtalc 15-38 22.85 Byk 451
(product supplied by Byk 2.2 Chemie identified as blocked acid
catalyst) Cymel 303 6.38
[0148] A transparent film layer corresponding to transparent film
layer 140 is applied to the matte release coat using a reverse roll
coater at a coat weight of 13 gsm and dried using forced hot air at
a temperature of 120.degree. C. The dry film thickness is 0.4 mil.
The formulation for the transparent film layer coat is as follows
(all numerical values are in parts by weight):
9 Rucothane CO-A-5002L (product 62.5 of Ruco Chemical identified as
polyester urethane) Toluene 18.75 Isopropanol 18.75
[0149] A decorative layer corresponding to printed decorative layer
150 is printed over the above indicated transparent film layer at a
coat weight of 1 gsm and dried in hot air at a temperature of
120.degree. C. The paint composition used for this decorative layer
has the following formulation (all numerical values are in parts by
weight):
10 Methyl ethyl ketone 25.67 Methyl isobutyl ketone 22.0 VYHH 9.17
I8980 3.5 DP 37251 (product of Gibraltar Chemical 0.99 Works
identified as containing perylene red, methyl ethyl ketone, toluene
and acrylic polymer) DP80110 1.0 DP39600 (product of Gibraltar
Chemical 37.47 Works identified as containing TiO.sub.2, methyl
ethyl ketone, toluene and acrylic polymer) I8977 0.20
[0150] The following paint composition is coated over the above
indicated decorative layer corresponding to printed decorative
layer 150 at a coat weight of 66 gsm and dried in hot air at a
temperature of 138.degree. C. to provide a dry paint film layer
corresponding to dry paint film layer 110. In the following table,
all numerical values are in parts by weight:
11 Methyl isobutyl ketone 24.11 Toluene 20.65 VYHH 11.54 R-900 38.4
Acroloid B-72 (product of Rohm and 3.86 Haas identified as an
acrylic resin) I8980 2.6 DP37251 0.21 DP80110 0.40
[0151] A pressure sensitive adhesive is then applied over the dry
paint film layer corresponding to dry paint film layer 110 at a
coat weight of 15-20 gsm using transfer lamination to provide an
adhesive layer corresponding to pressure sensitive adhesive layer
120. The pressure sensitive adhesive is a non-tackified acrylic
emulsion. The formulation for the pressure sensitive adhesive is as
follows: 70-90% by weight 2-ethylhexal acrylate, 1-10% by weight
acrylic acid, and 10-20% by weight methyl acrylate.
EXAMPLE 6
[0152] A polyethylene terphthalate film backing liner corresponding
to backing liner 132 is coated on one side with a silicone release
coating corresponding to second release coating layer 136. The
thickness of the release coated liner is 0.92 mil.
[0153] A matte release coat corresponding to release coating layer
135 is applied to the other side of the backing liner using
gravure. The release coat is dried using forced hot air at a
temperature of 148.9.degree. C. The matte release coat is applied
at a coat weight of 4.0-5.0 gsm. The formulation for the matte
release coat is as follows (all numerical values are in parts by
weight):
12 Methyl isobutyl ketone 42.03 Isopropanol 8.51 Microtalc 15-38
23.87 Cymel 303 7.36 Cycat 4040 1.8 VROH (product supplied by 16.43
Union Carbide identified as a vinyl chloride/vinyl acetate
copolymer with OH functionality)
[0154] A transparent film layer corresponding to transparent film
layer 140 is applied over Matte Release Coat No. 2 using a 2 mil
byrd bar at a coat weight of 30 gsm and dried using hot air at a
temperature of 126.7.degree. C. The formulation for the transparent
film layer is as follows (all numerical values are in party by
weight):
13 Water 7.98 N-methyl pyrrolidone 4.79 Texanol (product of Eastman
4.79 Chemicals identified as an ester alcohol) BYK 333 (product of
Byk Chemie 0.4 identified as a wetting agent) Vycar 351 (product of
Noveon identified 79.81 as a polyvinyl chloride copolymer emulsion)
Antifoam PD-218 (product of Magrabar 0.32 Chemical identified as an
antifoam agent) Rheolate 350 (product of Rheox, Inc. 1.92
identified as a thickener)
[0155] The following paint composition is coated over the above
indicated transparent film at a coat weight of 96 gsm and dried in
hot air at a temperature of 126.7.degree. C. to provide a dry paint
film layer corresponding to dry paint film layer 110. In the
following table, all numerical values are in parts by weight:
14 Water 18.28 Surfynol CT-324 (product of Air 0.98 Products
identified as a surfactant) R-900 32.88 Vycar 460X45 (product of
Noveon identified 34.72 as a vinyl chloride/acrylic copolymer)
Vycar 460X46 (product of Noveon identified 11.57 as a vinyl
chloride/acrylic copolymer) Antifoam PD-218 0.19 Byk 333 0.23
Rheolate 350 1.2
[0156] A pressure sensitive adhesive is then applied over the dry
paint film layer corresponding to dry paint film layer 110 at a
coat weight of 17 gsm using transfer lamination to provide an
adhesive layer corresponding to pressure sensitive adhesive layer
120. The formulation for the pressure sensitive adhesive is as
follows: 96% by weight of a non-tackified emulsion containing a
crosslinked copolymer of butyl acrylate and ethyl hexyl acrylate,
3.7% by weight UCD 1106E, and 0.3% by weight UCD 1507E.
EXAMPLE 7
[0157] A polyethylene terphthalate film backing liner corresponding
to backing liner 132 is coated on one side with a silicone release
coating corresponding to second release coating layer 136. The
thickness of the release coated liner is 0.92 mil.
[0158] A matte release coat corresponding to first release coating
layer 135 is applied to the other side of the backing liner using
gravure at a coat weight of 4.4-4.6 gsm. The formulation for the
matte release coat is as follows: 50.54% by weight methylisobutyl
ketone, 7.84% by weight isopropanol, 8.93% by weight Lankyd
13-1425, 10.68% by weight VAGH (product of Union Carbide identified
as hydroxy modified polyvinyl chloride/polyvinyl acetate
copolymer), 22% by weight Microtalc MP 15-38, 2% by weight Cycat
4040, and 6.8% by weight Cymel 303. The matte release coat is dried
using forced hot air at a temperature of 149.degree. C. A
transparent film layer corresponding to transparent film layer 140
is applied to the matte release coat using gravure at a coat weight
of 12-16 gsm and dried using forced hot air at a temperature of
165.degree. C. The dry film thickness is 0.35-0.5 mil. The
formulation for this transparent film layer is as follows (all
numerical values are in parts by weight)
15 Cyclohexanone 69.3 Elvacite 2042 10.5 Solsperse 17000 (product
of Avecia 0.1 identified as a wetting agent) Tinuvin 234 (product
of Ciba identified 0.6 as a light stabilizer) Kynar 301F (product
of Atofina 27.0 identified as a polyvinyl fluoride homopolymer)
N-methyl-2-pyrrolidone 2.5
[0159] A decorative layer corresponding to second printed
decorative layer 160 is printed over the transparent coating layer
at a coat weight of 0.3-1.2 gsm and dried in hot air at a
temperature of 105.degree. C. The paint composition used for this
decorative layer has the following formulation (all numerical
values are in parts by weight):
16 Methylethyl ketone 36.0 Methyl propyl ketone 35.1 Kynar 7201
(SL) (product of Atofina 10.2 identified as a polyvinyl fluoride
copolymer) Elvacite 2010 (product of Lucite 3.4 International
identified as a polymethyl methacrylate) Tinuvin 234 0.27 DP35740
(product of Gibraltar 0.10 Chemical Works identified as a buff
mixed metal oxide pigment concentrate) DP35820 (product of
Gibraltar 11.7 Chemical Works identified as a brown mixed metal
oxide pigment concentrate) DP39040 (product of Gibraltar 3.3
Chemical Works identified as a black mixed metal oxide pigment
concentrate)
[0160] A decorative layer corresponding to printed decorative layer
150 is printed over the above indicated decorative layer
corresponding to second printed decorative layer 160 at a coat
weight of 0.3-1.2 gsm and dried in hot air at a temperature of
105.degree. C. The paint composition used for this decorative layer
has the following formulation (all numerical values are in parts by
weight):
17 Methylethyl ketone 34.0 Methyl propyl ketone 33.0 Kynar 7201
(SL) 9.6 Elvacite 2010 3.2 Tinuvin 234 0.25 DP35740 14.4 DP35820
5.0 DP39040 3.2
[0161] The following paint composition is coated over the above
indicated decorative layer corresponding to printed decorative
layer 150 at a coat weight of 6-10 gsm and dried in hot air at a
temperature of 105.degree. C. to provide a dry paint film layer
corresponding to dry paint film layer 110. In the following table,
all numerical values are in parts by weight.
18 Methyl ethyl ketone 27.6 Methyl propyl ketone 26.3 Kynar 7201
(SL) 7.4 Elvacite 2010 2.5 Tinuvin 234 0.2 DP35740 4.1 DP35820 7.8
DP39040 0.6 DP39600 (product of Gibralter 23.6 Chemical Works
identified as a white titanium dioxide pigment concentrate)
[0162] A pigmented pressure sensitive adhesive is then applied over
the dry paint film layer corresponding to dry paint film layer 110
at a coat weight of 17 gsm using transfer lamination to provide an
adhesive layer corresponding to pressure sensitive adhesive layer
120. The formulation for the pressure sensitive adhesive is as
follows: 96% by weight of a non-tackified acrylic emulsion
containing a crosslinked copolymer of butyl acrylate and ethyl
hexyl acrylate, 3.7% by weight UCD 1106E, and 0.3% by weight UCD
1507E.
EXAMPLE 8
[0163] A polyethylene terphthalate film backing liner corresponding
to backing liner 132 is coated on one side with a silicone release
coating corresponding to second release coating layer 136. The
thickness of the release coated liner is 0.92 mil.
[0164] A matte release coat corresponding to first release coating
layer 135 is applied to the other side of the backing liner using
gravure at a coat weight of 4.4-4.6 gsm. The formulation for the
matte release coat is as follows: 50.54% by weight methylisobutyl
ketone, 7.84% by weight isopropanol, 8.93% by weight Lankyd
13-1425, 10.68% by weight VAGH (product of Union Carbide identified
as hydroxy modified polyvinyl chloride/polyvinyl acetate
copolymer), 22% by weight Microtalc MP 15-38, 2% by weight Cycat
4040, and 6.8% by weight Cymel 303. The matte release coat is dried
using forced hot air at a temperature of 149.degree. C.
[0165] A decorative layer corresponding to second printed
decorative layer 160 is printed over the matte release coat at a
coat weight of 0.3-1.2 gsm and dried in hot air at a temperature of
105.degree. C. The paint composition used for this decorative layer
has the following formulation (all numerical values are in parts by
weight):
19 Methylethyl ketone 36.0 Methyl propyl ketone 35.1 Kynar 7201
(SL) (product of Atofina 10.2 identified as a polyvinyl fluoride
copolymer) Elvacite 2010 (product of Lucite 3.4 International
identified as a polymethyl methacrylate) Tinuvin 234 0.27 DP35740
(product of Gibraltar 0.10 Chemical Works identified as a buff
mixed metal oxide pigment concentrate) DP35820 (product of
Gibraltar 11.7 Chemical Works identified as a brown mixed metal
oxide pigment concentrate) DP39040 (product of Gibraltar 3.3
Chemical Works identified as a black mixed metal oxide pigment
concentrate)
[0166] A decorative layer corresponding to printed decorative layer
150 is printed over the above indicated decorative layer
corresponding to second printed decorative layer 160 at a coat
weight of 0.3-1.2 gsm and dried in hot air at a temperature of
105.degree. C. The paint composition used for this decorative layer
has the following formulation (all numerical values are in parts by
weight):
20 Methylethyl ketone 34.0 Methyl propyl ketone 33.0 Kynar 7201
(SL) 9.6 Elvacite 2010 3.2 Tinuvin 234 0.25 DP35740 14.4 DP35820
5.0 DP39040 3.2
[0167] The following paint composition is coated using rotogravure
over the above indicated decorative layer corresponding to printed
decorative layer 150 at a coat weight of 5-16 gsm and dried in hot
air at a temperature of 105.degree. C. to provide a dry paint film
layer corresponding to dry paint film layer 110. In the following
table, all numerical values are in parts by weight.
21 Toluene 19.0 Methyl ethyl ketone 23.6 VYHH 5.8 Ednol 9790 2.9
DV39600 (product of Gibraltar 48.6 Chemical identified as iron
oxide red pigment dispersion) DV39420 (product of Gibraltar 0.07
Chemical identified as carbon black pigment dispersion) DV36500
(product of Gibraltar 0.03 Chemical identified as Pigment Red 178
pigment dispersion) DV34130 (product of Gibraltar 0.10 Chemical
identified as Phtalo Blue RS pigment dispersion)
[0168] The following coating composition is coated over the
above-indicated dry paint film layer using roll coating at a coat
weight of 20-30 gsm and dried in hot air at a temperature of
105.degree. C. to provide a support layer corresponding to support
layer 180. In the following table, all numerical values are in
parts by weight.
22 Toluene 14.1 Methyl ethyl ketone 21.1 VYHH 13.2 Ednol 9790 6.6
DV39600 44.96 DV39420 0.04
[0169] A pigmented pressure sensitive adhesive is then applied over
the coated layer corresponding to support layer 180 at a coat
weight of 17 gsm using transfer lamination to provide an adhesive
layer corresponding to pressure sensitive adhesive layer 120. The
formulation for the pressure sensitive adhesive is as follows: 96%
by weight of a non-tackified acrylic emulsion containing a
crosslinked copolymer of butyl acrylate and ethyl hexyl acrylate,
3.7% by weight UCD 1106E, and 0.3% by weight UCD 1507E.
[0170] While the invention has been explained in relation to its
preferred embodiments, it is to be understood that various
modifications thereof will become apparent to those skilled in the
art upon reading the specification. Therefore, it is to be
understood that the invention disclosed herein is intended to cover
such modifications as fall within the scope of the appended
claims.
* * * * *