STONE JAMES W (US)
SCHAEFER DONALD P (DE)
REITZEL LUTZ H (DE)
LIU WEN-FENG (US)
STONE JAMES W (US)
SCHAEFER DONALD P (DE)
REITZEL LUTZ H (DE)
WO1998056866A1 | 1998-12-17 | |||
WO2005016663A1 | 2005-02-24 | |||
WO1994000526A1 | 1994-01-06 |
US3701711A | 1972-10-31 |
1. | An adhesivecoated laminate substrate, comprising: a laminate substrate; and an adhesive layer coating a surface of the substrate; the adhesive layer comprising a physically setting, solventfree adhesive material which includes an acrylic polymer, wherein the adhesive layer is selfadhesive at room temperature. |
2. | The adhesivecoated laminate substrate according to Claim 1, wherein the laminate substrate has a peelingoff force of at least about 0.2 N/mm2 after application on a carrier substrate at room temperature. |
3. | The adhesivecoated laminate substrate according to Claim 1, wherein the laminate has a peelingoff force of about 0.5 to about 1.5 N/mm2 after application on a earner substrate. |
4. | The adhesivecoated laminate substrate according to Claim 1, wherein a peeling of the laminate from a earner does not appear up to a temperature load of at least about 8O0C over at least about 2 hours. |
5. | The adhesivecoated laminate substrate according to Claim 1, wherein the adhesive layer has an addon level of about 10 to about 300 g/m2. |
6. | The adhesivecoated laminate substrate according to Claim 1, wherein the adhesive layer has an addon level of about 75 to about 100 g/m2. |
7. | The adhesivecoated laminate substrate according to Claim 1, wherein the adhesive layer further comprises at least one of an additional thermoplastic elastomer, a block copolymer, a hydrocarbon resin, and a plasticizer. |
8. | The adhesivecoated laminate substrate according to Claim 1, wherein the acrylic polymer comprises a terpolymer of vinyl acetateethylene and acrylic. |
9. | The adhesivecoated laminate substrate according to Claim 1, wherein the laminate substrate comprises a highpressure laminate (HPL) or a continuously produced laminate (CPL). |
10. | The adhesivecoated laminate substrate according to Claim I5 further comprising a release layer, wherein the adhesive layer is disposed between the laminate substrate and the release layer. |
11. | The adhesivecoated laminate substrate according to Claim 10, wherein the release layer comprises a siliconized release paper or film. |
12. | The adhesivecoated laminate substrate according to Claim I5 further comprising a nonpressure sensitive adhesive layer. |
13. | The adhesivecoated laminate substrate according to Claim 12, wherein the nonpressure sensitive adhesive layer is disposed between the laminate substrate and the selfadhesive layer. |
14. | The adhesivecoated laminate substrate according to Claim 13, wherein the nonpressure sensitive adhesive layer comprises a second adhesive material having a glass transition temperature of about 2O0C or greater. |
15. | The adhesivecoated laminate substrate according to Claim 14, wherein the nonpressure sensitive adhesive layer has an addon level of about 10 to about 30 g/m2. |
16. | The adhesivecoated laminate substrate according to Claim 1, wherein the adhesive layer is applied to the substrate by a roller coater. |
17. | A composite material, comprising an adhesivecoated laminate substrate according to Claim 1 applied to a carrier. |
18. | The composite material according to Claim 17, wherein the carrier is selected from the group consisting of an uncoated particle board, an uncoated wood material, a metal, a ceramic, a glass, a coated wood material, a coated particle board, and combinations thereof. |
19. | A method for the production of the adhesivecoated laminate substrate of Claim 1, comprising: heating an adhesive material to a temperature of about 15O0C to about 19O0C; applying the adhesive material to the laminate substrate; and cooling the adhesive material to form the adhesive layer. |
20. | The method according to Claim 19, wherein the adhesive material is applied using a roller coater. |
21. | A laminate, comprising: a laminate substrate; a nonpressure sensitive adhesive layer applied to the laminate substrate; and a selfadhesive layer applied to the nonpressure sensitive adhesive layer, the selfadhesive layer including a physically setting, solventfree adhesive material, wherein the selfadhesive layer is selfadhesive at room temperature. |
22. | The laminate according to Claim 21, additionally comprising a release layer disposed over the selfadhesive layer. |
23. | The laminate according to Claim 21, wherein the nonpressure sensitive adhesive layer comprises an adhesive material having a glass transition temperature of about 2O0C or greater. |
24. | The laminate according to Claim 21, wherein the nonpressure sensitive adhesive layer comprises an addon level of about 10 to about 30 g/m2, and the selfadhesive layer comprises an addon level of about 75 to about 100 g/m2. |
25. | The laminate according to Claim 21, wherein the selfadhesive layer comprises an adhesive material including an acrylic polymer. |
26. | The laminate according to Claim 21, wherein the selfadhesive layer comprises a terpolymer of vinyl acetateethylene and acrylic. |
27. | The laminate according to Claim 26, wherein the nonpressure sensitive layer comprises polyvinyl acetate. |
28. | A method of coating a laminate substrate with an adhesive, comprising the steps of: providing a release layer coated with a layer of physically setting, solventfree adhesive comprising an acrylic polymer; applying the adhesive to a surface of the laminate substrate by overlaying the adhesivecoated release layer on the laminate substrate; and applying pressure to the release layer to press the adhesive onto the surface of the laminate substrate; wherein the release layer is manually peelable to expose the adhesive on the laminate substrate. |
29. | The method of Claim 28, wherein the laminate substrate comprises a high pressure laminate of cellulose strips. |
30. | The method of Claim 28, wherein the adhesive is applied to the surface of the laminate substrate without first sanding the surface of the laminate substrate. |
31. | The method of Claim 28, further comprising the step of priming the surface of the laminate substrate to create a primed surface, wherein the adhesive is applied to the primed surface. |
32. | The method of Claim 31, further comprising the step of sanding the surface of the laminate substrate before priming it. |
33. | The method of Claim 28, wherein the pressure is applied by passing the adhesivecoated release layer and the laminate substrate between a pair of nip rolls. |
34. | The method of Claim 28, wherein the release layer comprises a siliconecoated paper. |
35. | The method of Claim 28, wherein the layer of physically setting, solvent free adhesive is provided by applying an aqueous acrylicbased adhesive to the release layer and drying the adhesive on the release layer. |
36. | The method of Claim 28, wherein the layer of physically setting, solventfree adhesive has a thickness of about 50500 microns. |
37. | The method of Claim 28, wherein the layer of physically setting, solventfree adhesive has a thickness of about 100300 microns. |
38. | The method of Claim 28, further comprising the step of heating at least one of the adhesive and the laminate substrate before applying the pressure to the release layer. |
39. | The method of Claim 31, wherein the primed surface comprises an acrylicbased primer. |
40. | The method of Claim 39, wherein the primer has a dry thickness of about 1050 microns. |
41. | The method of Claim 38, wherein the heating step comprises heating at least one of the adhesive and the laminate substrate to a temperature of about 30120° C. |
CROSS REFERENCE TO RELATED APPLICATION
The subject matter of this application is related to Provisional Patent
Application 60/652,257, filed on 11 February 2005, and International Patent
Application PCT/EP2004/009001, filed 12 August 2004. International Patent
Application PCT/EP2004/009001 in turns claims priority based on German Patent
Application DE 2003 103 7351 , filed 14 August 2003. The disclosure of these
related patent applications are hereby incorporated by reference herein in their
entirety and made a part hereof, including but not limited to those portions that
specifically appear hereinafter.
FIELD OF THE INVENTION
This invention relates to a decorative laminate substrate that is coated
with a self-adhesive layer of an adhesive material including an acrylic polymer.
Furthermore, the invention concerns a method for the production of such a laminate.
BACKGROUND OF THE INVENTION
Laminated sheets (otherwise referred to as "laminate substrates' 1 ) are
generally used for decorative puiposes in many areas of daily life. They are used, for
example, in interior construction for the covering or lining of windows, stairs, and
floors, and in the coating of furniture, both in the private as well as in the commercial
sectors.
Laminated sheets often are made of cellulose sheets impregnated with
curable synthetic resins and pressed with heat under high pressure. One or more
sheets on one or two sheet sides exhibit decorative colors or decorations. Such
laminated sheets (known as high pressure laminates or HPL) are sold, for example, by
Resopal GmbH (a Wilsonart International company), under the tradename
RESOPAL®.
The application of the laminated sheets on a carrier substrate such as
chipboard, fireboard, or plywood used for wall, floor or ceiling finishes or other
objects, can be done with an aqueous adhesive. Depending on the type of the
adhesive, various conditions must be precisely maintained, so as to obtain a coating of
good quality and stability. According to known application methods, the laminated
sheets and the carrier are typically joined together after the application of the adhesive,
immediately or after a short waiting time. The joining together is done according to
the previous methods under a pressing pressure of 2 to 5 bar and at a temperature of up
to 12O 0 C.
Furthermore, the adhesive application is typically uniformly distributed
over the laminated sheet and/or earner surface, so as to avoid warp phenomena. This
is particularly true for water-containing adhesive systems, in which the application
quantity is to be kept as low as possible.
With a nonuniform adhesive application and an inexact maintenance of
the pressing pressure, pressing temperature, and/or pressing time, unsatisfactory results
can be obtained during the cementing. Thus, for example, excessively high
temperatures can lead to warping and material damage. Low temperatures or
pressures often result, on the other hand, in an insufficient adhesion. Depending on the
adhesive system, the pressing pressure and the pressing temperature typically must be
maintained between a few minutes and up to several hours. If necessary, one must
wait overnight to obtain a final curing.
Working with solvent-containing contact adliesives generally requires
adherence to work protection and accident prevention regulations. Furthermore, the
use of solvent-containing adhesives is generally classified as problematic from a health
and environmental policy viewpoint. The use of dispersion adhesives on a water basis,
such as casein glue, frequently leads to the partial swelling of the canier surface,
which is frequently the case, for example, when using particleboard as the carrier
material. As a result, a slightly corrugated or nonuniformly plane surface is obtained.
Furthermore, the drying of water- or solvent-containing adhesives may require several
hours.
Reaction adhesive, such as epoxide, polyesters, or polyurethane
adhesives, are also of concern with respect to health and require a precise knowledge
and maintenance of the processing conditions.
The previous adhesives and adhesive methods typically require a high
equipment outlay, such as, for example, for the use of uniform and high pressing
pressures and for the maintenance of the temperature. Depending on the adhesive, the
curing, e.g., until a sufficient adhesive is attained, can require several hours.
The circumstances mentioned above often make the use and the
successful processing of laminated sheets relatively difficult, particularly for the
private sector or in the craftsman's sector. There is a need for an improved, efficient,
safe, and less expensive decorative laminate panel.
SUMMARY OF THE INVENTION
A general object of this invention is to provide an improved adhesive-
coated laminate substrate, particularly for use as a decorative or protective laminate
covering for a material, such as wood, metal or mineral boards.
A more specific objective of this invention is to overcome one or more
of the problems described above. In addition to the needs of the commercial sector,
the needs of the private user with regard to a simple processing or application are
considered and met.
Another object of this invention is to provide a decorative adhesive-
coated laminate substrate, which adheres rapidly and firmly on a carrier substrate
surface, without having to accept the long waiting times.
The rapid and firm adhesion of the laminate on the carrier can be
achieved without the use and precise maintenance of high pressures or high
temperatures during the application.
Another object of this invention is simplifying or eliminating the
handling and application of the adhesive on the carrier. In particular, the difficulty of
obtaining a uniform application of the adhesive on the carrier is avoided by instead
uniformly applying the adhesive to the laminate substrate.
Fuithermore, it is an object of this invention to provide a decorative
laminate substrate that can be cemented without the use of water or solvents, and is as
unobjectionable as possible from a health viewpoint and with regard to safety aspects.
Finally, it is an object of this invention to provide a decorative laminate
substrate, which, after application on a carrier, provides a uniform planar surface.
The general object of the invention can be attained, at least in part,
through an improved decorative laminate substrate coated with an adhesive layer.
The adhesive layer may include a layer of a physically setting, solvent-free adhesive
material including an acrylic polymer. The adhesive layer is self-adhesive at room
temperature.
The invention further comprehends a laminate including a laminate
substrate, a non-pressure sensitive adhesive layer applied to the laminate substrate,
and a self-adhesive layer applied to the non-pressure sensitive adhesive layer. The
non-pressure sensitive adhesive layer serves as a barrier layer (e.g. "primer") to
prevent penetration of the self-adhesive layer into the laminate substrate, and to
provide the laminate substrate with a primed surface. The self-adhesive layer
includes a layer of a physically setting, solvent- free adhesive material comprising an
acrylic polymer. The self-adhesive layer is self-adhesive at room temperature,
meaning it does not require heat for activation, and may be manually activated upon
contact with a earner with or without pressure, or with light manual pressure.
The present invention also includes a method for the production of the
laminate of this invention.
Furthermore, a composite material of a carrier and the adhesive-coated
laminate substrate and the use of the adhesive-coated laminate substrate for the coating
of earners are provided.
A decorative laminate with an adhesive layer is made available, which is
characterized in that the adhesive layer is a layer of a physically setting, solvent-free
adhesive, which is self-adhesive at room temperature, wherein the laminated sheet has
a peeling-off force of at least 0.2 N/mn after the application on a carrier at room
temperature. It is possible, in a manner which was not readily predictable, to make
available a laminate, which quickly and firmly adheres on a carrier, without having to
accept long waiting times.
Furthermore, the following advantages are attained by this invention.
The application of the adhesive-coated laminate substrate on the carrier can be done
without the use of high pressures and increased temperatures. A simple short pressing
pressure, for example, manually, on the adhesive-coated laminate substrate is
generally sufficient for immediate adhesion to the carrier. In addition, the adhesive-
coated laminate substrate adheres stably on a carrier. Thus, one obtains, for example,
a very high peeling-off force of the adhesive-coated laminate substrate from the
carrier. Furthermore, a high peel resistance and a high static shearing strength are
attained. Also with a temperature load of the composite of the adhesive-coated
laminate substrate and earner over a longer time, the adhesion remains stable and no
peeling of the decorative adhesive-coated laminate substrate from the carrier appears.
The adhesion characteristics, such as the peeling force, the shearing strength, and the
peel resistance also are essentially retained with a temperature load. The previously
mentioned characteristics are already attained with a small application quantity or
layer thickness of the adhesive so that it can be used in a manner which saves material.
Another advantage is to be found in that the adhesive application need not be
undertaken by the end user himself. The reverse of the laminate substrate is already
provided with the adhesive and can be immediately processed-that is, be applied on
the earner, without processing conditions of the adhesive, a uniform application, etc.,
having to be observed. The laminate substrate already provided with adhesive, in
accordance with the invention, can be stored over a relatively long time. It is not
necessary to apply the laminate substrate to the carrier immediately after application of
the adhesive, as is typically the case with previous adhesive systems. The adhesive-
coated laminate substrate of this invention provides a particularly uniform and planar
surface after application on a carrier. In addition, the use of solvents and dispersants
during the cementing of the plate, in accordance with the invention, can be dispensed
with, which is particularly advantageous with regard to environmental and health
aspects. Finally, the adhesive used, in accordance with the invention, contains only
not very volatile plasticizers with a relatively low evaporation.
The previously mentioned advantages provide a relatively simple and
easy to install adhesive-coated laminate substrate for the private user and the craftsman
without mechanical equipment. The processing can be undertaken directly on site,
without machines or special apparatuses having to be used for the processing. By the
simple and rapid possibility of the application, the adhesive-coated laminate substrate
in accordance with the invention is suitable, in particular, also, for the home user, to
upgrade and cover furniture, door surfaces, walls, etc.
Other objects and advantages will be apparent to those skilled in the
art from the following detailed description taken in conjunction with the appended
claims.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 schematically illustrates a process for preparing an adhesive-
coated laminate substrate of the invention.
Fig. 2 schematically illustrates an alternative process for preparing an
adhesive-coated substrate laminate of the invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a decorative laminate substrate having
a self-adhesive layer applied, either directly or indirectly, to one side of the laminate
substrate. In one embodiment of this invention, the self-adhesive layer, at room
temperature, includes a physically applied, solvent- free adhesive material including
an acrylic polymer. The adhesive-coated laminate substrate of this invention
provides improved bond strength or adhesion, temperature and humidity resistance,
and adequate shear or creep resistance when bonded to a carrier. The adhesive-
coated laminate substrate is relatively easily applied by the end user, as compared to
typical known adhesive systems.
In accordance with the invention, "laminate substrate" includes
materials such as, for example, glass fiber fabrics, paper, wood, textiles, plastic films,
paper base laminates, laminated fabrics, laminated wood, which are produced by a
buildup (the so-called laminating) of paper or fabric strips or glass fiber mats, soaked
or coated with synthetic resins, such as epoxy, melamine resins, thermoplastics,
phenoplastics, urea-formaldehyde resins, and by using pressure and heat. They are
designated, in the state of the art, as "laminates" also, and are used in diverse
embodiments, such as plates, round rods, tubes, long and construction molded articles,
for many different uses, such as printed circuits, for aircraft, motor vehicle, boat
construction, weather-resistant covers, sports gear (for example, skiers) and decorative
purposes.
In one embodiment of this invention, the use of a high-pressure laminate
("HPL") as the laminate substrate has proved to be very particularly advantageous.
The HPLs have layers of fibrous strips, preferably, paper, impregnated with curable
resins, and optionally, one or more decorative layers, wherein the decorative layers are
provided with decorative colors and/or patterns and preferably, are impregnated with
resins on a melamine basis. The strips are bonded together under heat and high
pressure of about 5 mPa or greater. In accordance with the invention, a continuously
produced laminate (CPL) can also be used as the laminate substrate.
As will be appreciated by one skilled in the art following the teachings
herein provided, various and alternative types, shapes, configurations of laminate
substrates are available for use in the laminate of this invention. Such alternatives and
details regarding the above materials can be found, for example, in the current
technical literature, for example, "Ullmann's Encyclopedia of Industrial Chemistry,"
4th Edition, Vol. 15, p. 326, and the norms DIN EN 438, Part 1 to Part 6, ISO 4586-1
and ISO 4586-2, each herein incorporated by reference in its entirety.
In one embodiment of this invention, the laminate substrate is a
decorative high-pressure laminate preferably produced by a method in which fibrous
strips are impregnated with at least a curable resin and then are pressed by the
simultaneous use of heat, advantageously at a temperature in the range of about 12O 0 C
to about 15O 0 C, and at a pressure of at least 7 mPa, so that the resins initially flow and
subsequently harden. A homogeneously closed material with an increased density,
advantageously about 1.35 g/cm 3 , and the desired surface characteristics is desirably
obtained. Within the scope of this method, discontinuous multi-stage presses are used.
In another embodiment of this invention, a laminate substrate in which
the fibrous snips are impregnated with heat-curable resins and then are continuously
pressed on double-band presses at a high temperature, preferably, in the range of about
140 to about 200 0 C, has proved particularly advantageous. Such a method is
5 particularly useful in producing continuously produced laminates (CPLs) .
In another embodiment of this invention, a plastic laminate, in
particular, polyester laminates made of paper strips, which are impregnated with at
least one polyester resin, is used as a laminate substrate. One or both laminate sides
thereby advantageously have a decorative paper, impregnated with polyester resin.
i o The production of these polyester laminates advantageously takes place continuously.
The thickness of the laminate substrate of this invention can be selected
freely, in principle, according to the field of application; it is generally in the range of
0.2 mm to 20 mm or 0.3 to 15 mm. More desirably, the thickness can also be in the
range of 0.5 mm to 3.0 mm or in the range of 0.6 to 2.5 mm. In one embodiment, the
15 thickness 0.6 to 1.6 mm is particularly desirable and 0.6 to 1.2 mm is even more
desirable.
In one particularly preferred embodiment of this invention, a physically
setting, solvent-free adhesive material is used to form a self-adhesive layer on at least
one side of the laminate substrate. As used herein, "solvent-free" refers to an applied
20 adhesive layer that contains no water and no organic liquids, which act as solvents or
dispersants. In one embodiment, the self-adhesive layer is formed at least in part of an
adhesive material including an acrylic polymer or copolymer.
In one particularly preferred embodiment of this invention, the adhesive
includes a terpolymer of vinyl acetate-ethylene and acrylic. An example of such a
terpolymer is available from Air Products and Chemicals, Inc., Allentown,
Pennsylvania, and sold under the tradename FLEXBOND 153. Other FLEXBOND
adhesives, such as, for example, FLEXBOND AF75 and FLEXBOND EAF60 are
useful in fonning laminates of this invention.
In one embodiment of this invention, the self-adhesive layer includes at
least one elastomer, at least one not very volatile plasticizer, and at least one
hydrocarbon resin. Additional component(s) of the adhesive layer can be a
elastomeric components selected from the natural rubbers, polyisobutylene rubber,
ethylene-propylene rubber (EPR), styrene-butadiene rubber, ethylene-propylene-diene-
terpolymer rubber (EPDM), butyl rubber, ethylene-vinyl acetate copolymer, ethylene-
(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer, ethylene-
(meth)acrylic acid-(methy)acrylate terpolymer, and acrylate rubbers. The elastomer
can also be a block copolymer as described below. The elastomeric component(s) can
be combined with the acrylic polymer, i.e. a polymer which includes an acrylic and/or
acrylate group, e.g. the vinyl acetate-ethylene-acrylic terpolymer described above.
Other elastomers may be combined with the acrylic polymer.
In one preferred embodiment of this invention, an additional
elastomer is a high molecular weight polyisobutylene rubber with a number-average
molecular weight of about 300,000-3,500,000 g/mol, desirably about 400,000-
1,500,000 g/mol, and more desirably about 800,000 g/mol (according to GPC). The
polyisobutylene rubber can be copolymerized with one or more comonomers, which
are selected from styrene, ring-substituted styrenes, divinylbenzene, isoprene, indene,
1,3-butadiene, cyclopentadiene. The fraction of isobutene in the polyisobutylene
rubber is desirably about 90%.
In one embodiment of this invention, the total weight fraction of the
elastomer is about 10 to about 70 wt%, relative to the dry weight of the adhesive, and
preferably about 30 to about 60 wt%. Of this amount, the acrylic polymer (e.g. the
vinyl acetate-ethylene-acrylic terpolymer) should constitute at least about 10% by
weight of the adhesive composition, and may constitute up to about 70% by weight
depending on whether or not other elastomers are also present. The balance of the
adhesive composition includes about 15 - 40% by weight of the plasticizer, about 15 -
30% by weight of the hydrocarbon resin, and about 0.01 - 2% by weight antioxidant.
The plasticizer can be a low-molecular weight polyisobutylene with a
molecular weight of about 800 to about 5000 g/rαol. The weight fraction of the low-
molecular weight polyisobutylene can be about 18 to about 25 wt%, relative to the
total weight of the adhesive.
In accordance with one embodiment of this invention, isobutylene
polymers which can be used in the adhesive can be obtained from Bayer AG, under
the tradenames BAYER BUTYL (a copolymer of isobutylene and isoprene) and
POLYSAR BUTYL XL (a copolymer of isobutylene, isoprene, and divinylbenzene).
In accordance with one embodiment of this invention, block copolymers
can be used as the elastomer which have at least two end blocks of a vinyl-aromatic
monomer (block A) and at least one middle block (block B), which contains either a
conjugated diene or is formed from an ethylene-butylene copolymer or an ethylene-
propylene copolymer. The configuration can be linear, grafted, or star-shaped,
depending on the method of production.
Typical block copolymers with the simplest conformation have the
structure polystyrene-polybutadiene-polystyrene (SBS) or polystyrene-polyisoprene-
polystyrene (SIS), or polystyrene-polyethylene/polybutylene-polystyrene. A typical
radial or star polymer comprises one in which the B-block has three or four branches
(radial) or more branches (star).
The end blocks A of the copolymer are formed from one or more vinyl-
aromatic monomers, which are advantageously selected from styrene, ring- alkylated
styrenes, such as alpha-methylstyrene and vinyltoluene, and polycyclic vinyl-aromatic
compounds, such as vinylnaphthalene. Styrene and alpha-methylstyrene are preferred.
Styrene is especially preferred. A block which is built as the end block A, can also be
present, once or several times, in the middle of the polymer chain, in addition to being
at the ends.
If the middle block B of the block copolymer contains a conjugated
diene, it can be a homopolymer of a conjugated diene, a copolymer from several
conjugated dienes, or a copolymer from a conjugated diene and a vinyl-aromatic
compound, such as styrene or alpha-metfiylstyrene, as long as the conjugated diene
predominates. The conjugated diene is preferably selected from a compound with 4-8
carbon atoms, such as butadiene, isoprene, 2,3-dimethyl-l,3-butadiene and piperylene,
wherein butadiene and isoprene are preferred.
If block B contains a conjugated diene, it can be partially or completely
hydrogenated. In addition, the A-blocks can also be partially or completely
hydrogenated.
The average molecular weight of an A-block is about 5000-125,000
g/mol, and preferably about 6000-60,000 g/mol (weight average according to GPC).
The average molecular weight of a B-block is about 10,000-300,000 g/mol and
preferably about 30,000-150,000 g/mol (weight average according to GPC). The total
weight of the block copolymer is desirably about 25,000 to about 350,000 g/mol, more
desirably about 35,000-300,000 g/mol (weight average according to GPC).
Advantageously, the fraction of the A-block is about 5-65 wt%, and more desirably
about 35-50 wt%, relative to the block copolymer. Another advantageous range is
about 5-30 wt%.
Details of the production of the aforementioned block copolymer can be
found, for example, in the documents EP 0 537 115 Al and US Patents 3,239,478;
3,427,269; 3,700,633; 3,753,936; and 3,932,327, the disclosure of each being herein
incorporated by reference in its entirety.
The aforementioned polymers can be used individually or in
combination with one another.
When used as an additional thermoplastic elastomer, the weight fraction
of the block copolymer is desirably about 5-50 wt%, and more desirably about 10-40
wt%, relative to the total weight of the adhesive. A more desirable range of the weight
fraction of the block copolymer is about 12-25 wt%, and more desirably about 15-20
wt%. Another advantageous range for some applications is about 30-40 wt%.
Exemplary block copolymers which can be used within the scope of one
embodiment of this invention, without limitation, can be obtained, under the
tradenames KRATON G1650, G1651, G1652, G1657, G4309 (linear styrene-
ethylene/butylene-ethylene block copolymers of different block lengths), KRATON
RP-6906, KRATON DXl 122, AND KRATON D1118X. These polymers are
available from Kraton Polymers, LLC.
To build up the pronounced long-term tackiness, the adhesive, in one
advantageous embodiment, contains synthetic plasticizers with a low volatility
(evaporation loss or migration) at high temperatures (greater than about 12O 0 C).
The plasticizers contained in the adhesive are desirably synthetic
plasticizers with a high boiling point and vapor pressure, which are not very volatile
and exhibit an only slight evaporation from the adhesive.
Plasticizers are advantageously selected from mineral oils, paraffin oils,
olefin oligomers, and polymers with lower molecular weights. As oligomers, one can
use, for example, polypropylenes, polybutenes (e.g. the low molecular weight
polyisobutylene described above), hydrogenated polyisoprenes, hydrogenated
butadienes, etc., wherein the molecular weight is advantageously about 350 to about
10,000 g/mol.
The weight fraction of plasticizers is desirably about 0-40 wt%, and
more desirably about 15-40 wt%, or about 15-30 wt%, relative to the total weight of
the adhesive.
Furthermore, hydrocarbon resins can optionally be added to the
adhesive, in order to attain a pronounced surface tackiness. The surface tackiness
(tack) makes possible a pronounced tackiness in connection with low pressing forces
during the assembly.
A group of the hydrocarbon resins (tackifiers), contained in the
adhesive, desirably include natural and modified resins, such as, for example, gum
resin, wood resin, tallow oil resin, distillate resin, and rosin, hydrogenated resin,
dimerized resin, and polymerized resin.
Likewise, glycerol and pentaerythritol esters of natural and modified
resins, such as the aforementioned, can be used.
Other resins which can be used in the adhesive as tackifiers are
polyterpene resins, hydrogenated polyterpene resins, copolymers and terpolymers of
natural terpenes, such as styrene/terpene, alpha-methylstyrene/terpene, and
vinyltoluene/terpene. Also usable are phenol-modified terpene resins, which can be
obtained, for example, by the condensation of a teipene and a phenol. Finally,
aliphatic, cycloaliphatic, aromatic and aliphatic/aromatic resins based on petroleum
can also be used as the hydrocarbon resin. Other resins which can be used in
accordance with the invention and are known to the specialist are mentioned in the
document EP 0 537 15 Al, the disclosure of which is herein incorporated by reference
in its entirety.
The weight fraction of the hydrocarbon resin can be about 0-80 wt%,
relative to the total weight of the adhesive, more desirably about 10-50 wt%, and even
more desirably about 15-30 wt%.
In one embodiment of this invention, the self-adhesive layer and/or
adhesive material can, optionally, contain common stabilizers, antioxidants, and other
auxiliaries, fillers, and/or additives, known and available to those skilled in the art.
Antioxidants can advantageously be selected from the hindered phenols and
multifunctional phenols, such as sulfur- and phosphorous-containing phenols. An
overview of such stabilizers and additives is given in the documents US 6,143,818,
and EP 0 537 115 Al, the disclosures of which are each incorporated by reference
herein in their entirety. The weight fraction of stabilizers is desirably about 0.1-2 wt%,
relative to the total weight of the adhesive, and preferably about 0.1-1 wt%.
The self-adhesive laminate of this invention desirably has a high
tackiness, a strong immediate adhesion (tack), and also a high cohesion and good shear
or creep resistance. As a result of the latter characteristics, the applied adhesive layer
or the applied laminate can be loaded mechanically. Advantageously, in one
embodiment of this invention, the applied adhesives are also resistant to water, weak
acids, and alkalis. Using adhesive materials that are free of water or other solvents or
dispersants means that with a carrier substrate having an absorbing capacity, they do
not produce any swelling of the material due to the liquid. In one embodiment of this
invention, the adhesives used are swell-free.
In one embodiment of this invention, those previously described
adhesives are used, which have a solids content of about 100%, a density of about 1
g/cm 3 (at 2O 0 C), a viscosity at 16O 0 C of about 15,000-65,000 mPas, a processing
temperature of 150-190 0 C, a softening point of about 90-135 0 C (DIN 52011), a static
shearing resistance at room temperature of about 5-15 kg (based on DIN EN 1943), a
peeling-off resistance of about 35-65 N/25 mm (based on DIN EN 1939), and a
shearing strength loss temperature (measurement method, see examples below), of
about 6O 0 C to about 105 0 C, and more desirably about 65 0 C to about 97 0 C.
In a particularly preferred embodiment of this invention, the adhesive
layer applied on the laminated sheet is covered, for protection, with a release layer,
which preferably is made, for example, of a siliconized paper or film. In this state, the
sheet can be stored for a long time, desirably up to 12 months, without losing its
adhesive characteristics or undergoing some appreciable decline.
The application quantity, or add-on level, of the previously described
adhesive on the laminate substrate is generally about 80 to about 300 g/m 2 , desirably
about 140 to about 240 g/m 2 , and more desirably about 150 to about 200 g/m 2 . In one
embodiment of the invention, the add-on level of the adhesive layer is from about 75
to about 150 g/m 2 .
The layer thickness of the self-adhesive layer on the laminate substrate
is generally about 0.05 to about 0.50 mm, or about 0.08 to about 0.30 mm, more
desirably about 0.14 to about 0.24 mm, and particularly about 0.15 to about 0.20 mm.
In one embodiment of the invention, the self-adhesive layer is about 0.175 mm thick.
If both a self-adhesive layer and a non-pressure sensitive adhesive layer are used, each
layer may have a thickness of about 0.125 mm. The adhesive layers can be applied
using a roller coater or other suitable coating device. Each adhesive layer is desirably
applied to the release layer or laminate substrate as a water-based emulsion; however,
the adhesive layer can be applied using organic solvent-based emulsions or hot-melts.
The adhesive layer is desirably applied to the release paper first, and then dried,
although the adhesive layer can also be applied to the laminate substrate first. Upon
application of the adhesive emulsion, the adhesive is dried, such as at 10O 0 C for 5
minutes, to form the applied solvent-free adhesive layer.
The pressing time upon application of the adhesive-coated laminate
substrate is, in accordance with the invention, less than 5 seconds. Advantageously, a
pressing time of 1 to 3 seconds is sufficient for bringing about an adhesion to the
carrier with the mechanical characteristics mentioned in the following.
The necessary pressing pressure in the application of the adhesive-
coated laminate substrate on the carrier surface is, in accordance with one embodiment
of this invention, at most 2 bar. Desirably the needed pressing pressure is from about
0.2-1 bar and more desirably about 0.3-0.6 bar. In general, a light pressure, manually,
is sufficient, in order to attain a complete adhesion. With larger surfaces, a uniform
pressure using a roller is advantageous.
The application of the adhesive-coated laminate substrate of one
embodiment of this invention is preferably carried out in the temperature range of
about 5 0 C to about 35 0 C. Advantageously, the adhesive-coated laminate substrate can
be applied on a carrier at room temperature.
In one embodiment of this invention, the peeling-off force, which is
needed to peel off the adhesive-coated laminate substrate applied on a carrier from the
carrier, is at least about 0.2 N/mm 2 . Desirably the peeling-off force is about 0.2 to
about 2 N/mm 3 , and more desirably about 0.5 to about 1.5 N/mm 2 , and even more
desirably about 0.8 to about 1.2 N/mm 2 . These values of the peeling-off force are
desirably attained when the adhesive-coated laminate substrate is applied at room
temperature with the aforementioned pressing pressures, or by means of a light
pressure, manually or with a roller. The peeling-off force is determined according to
the method described in the European norm EN 311, herein incorporated by reference
in its entirety.
Alternately, the peeling-off force can be increased in that the pressing
pressure is increased above the aforementioned value ranges. This is, however, not
necessary for the invention and can be optionally carried out, if desired.
Likewise, the peeling-off force of the adhesive-coated laminate substrate
from the carrier can be increased in that the laminate substrate and the adhesive layer
are heated shortly before or during the cementing on the carrier. This measure is not
necessary and merely optional. Furthermore, the peeling-off force can be affected if
the surface of the laminate substrate on which the adhesive is applied is roughened
with the usual grinding agents before the application of the adhesive.
Finally, it can be advantageous but not necessary to pretreat the surface
of the laminated substrate on which the adhesive is applied with the usual adhesion
priming agents for adhesives, namely adhesion-imparting, preliminary paints or
primers. Common adhesion priming agents include, for example, ethylene-acrylamide
copolymers, polymeric isocyanates, and reactive silicon-organic compounds.
The adhesive-coated laminate substrate of one embodiment of this
invention is characterized in that up to a temperature load of 8O 0 C over at least 2 hours,
a peeling of the laminate substrate from a earner material, in particular, from a particle
board, does not appear. In particular, a peeling is not observed with a composite of the
laminate, in accordance with the invention, and a carrier after at least a two-hour
temperature load of about 5O 0 C to about 7O 0 C. The adhesive-coated laminate substrate
has been tested by introducing a sample laminate substrate applied on a carrier into a
furnace at room temperature, which is filled with ambient air. This means that the air
in the interior of the furnace has the same temperature and moisture content as the
ambient air. Exemplary conditions are a temperature of about 20-23 0 C and a relative
humidity of 60-65% at the beginning of the test. Subsequently, the furnace is closed
and heated to 8O 0 C, and is maintained at this temperature for at least 2 hours.
The adhesive-coated laminate substrate of this invention can be applied
on different types of earners, wherein the type of carrier is not particularly limited.
Preferred carrier materials are melamine-coated particle boards, carrier plates coated
with laminate, chip board, medium-density fibrous plates, hard fibrous plates, plywood
boards, veneer sheets, solid wood, honeycombs, foams, metal plates, sheet metal,
mineral earners, natural and synthetic rock, tiles, and gypsum plaster board.
This invention further contemplates and includes a composite material,
which comprises one of the previously mentioned carriers and an adhesive-coated
laminate substrate which adheres to the carrier. The laminate substrate can
advantageously be applied both on liquid-absorbing (absorbent) carriers, such as
uncoated particle boards and uncoated wood, as well as on non-liquid- absorbing
(nonabsorbent) carriers, such as metals, ceramic, glass, coated woods, coated particle
boards etc.
The composite of one embodiment of this invention is characterized by
a uniform and planar surface on the sides of the applied laminate substrate. Thus, the
maximum height difference on the sides of the decorative layer is about 0.05-0.5 mm,
and more desirably about 0.05-0.2 mm. The uniformity can easily be determined, in
actual practice, by visual inspection, such as by the undistorted reflection of a light
source (for example, neon tube) on the surface of the laminate substrate applied on the
carrier.
The adhesive-coated laminate substrate applied, in accordance with one
embodiment of this invention, on a carrier generally has a more uniform and more
planar surface, as compared to laminate substrates applied using conventional
methods/adhesives on carriers.
Particularly advantageous, this characteristic manifests itself, if the
adhesive-coated laminate substrate is applied on an absorbent or liquid-absorbing
earner. In this case, the laminate substrate forms a more uniform and more planar
surface than a sheet that was applied with a solvent- or dispersant-containing adhesive.
In another aspect, the invention under consideration concerns the use of
the previously described adhesive-coated laminate substrate for the coating of a carrier
material which is preferably selected from the previously mentioned earner materials.
The used caπier can be both liquid-absorbing (absorbent) and also non-liquid-
absorbing.
Likewise, the invention concerns the use of the composite of the carrier
material and the adhesive-coated laminate substrate in interior and outside
construction, such as for the covering of walls, ceilings, and doors, and for the
production and covering of furniture and pieces of furniture.
Due to the previously described adhesion characteristics of the adhesive-
coated laminate substrate on the carrier material, especially on particle boards, and the
peeling-off resistance with a temperature load, the composite is also suitable for the
production of pieces of furniture which are temporarily exposed to high temperatures,
such as kitchen work plates.
The invention also provides a production method for a decorative
laminate substrate with a self-adhesive layer. The method of one embodiment of this
invention is characterized in mat an adhesive material is applied on a laminate
substrate at a temperature of 150-190 0 C, advantageously on the reverse side opposite
from the decorative side or layer, and is subsequently allowed to cool.
Advantageously, the adhesive is desirably applied on a continuously
advanced laminate with a stationary roller or nozzle. The adhesive application rate on
the laminate is desirably about 1 to 30 m/min.
The adhesive is preferably applied in a quantity of about 80 to about 300
g/m 2 , desirably about 140 to about 240 g/m 2 , and more desirably about 150 to about
200 g/m 2 , on the laminate substrate.
The applied adhesive is advantageously covered with a release layer,
which advantageously is made of a siliconized paper or a siliconized film.
In another embodiment of this invention, the laminate substrate has two
different adhesive layers applied thereon. A non-pressure sensitive adhesive layer is
first applied to one side of the laminate substrate and a self-adhesive layer is applied to
the non-pressure sensitive adhesive layer, and thereby indirectly applied to the
laminate substrate. The self-adhesive layer includes a layer of a physically setting,
solvent-free adhesive material comprising an acrylic polymer. The self-adhesive layer
is desirably self-adhesive at room temperature. A release layer, such as a release paper
or film, is desirably applied over the self-adhesive layer to maintain the adhesive
properties or tackiness until use.
The self-adhesive layer desirably includes a terpolymer of vinyl acetate-
ethylene and acrylic. The non-pressure sensitive adhesive layer comprises an adhesive
material having a glass transition temperature of about 2O 0 C or greater. The non-
pressure sensitive layer desirably functions as a barrier layer or primer separating the
self-adhesive layer from the laminate substrate. The barrier provided by the non-
pressure sensitive adhesive desirably reduces or eliminates penetration of the self-
adhesive into the laminate substrate. In one embodiment of his invention, the non-
pressure sensitive adhesive is, for example, polyvinyl acetate. The non-pressure
sensitive adhesive layer may also be an acrylic primer as described below.
In one embodiment of this invention, the non-pressure sensitive
adhesive layer has an add-on level of about 10 to about 30 g/nϊ " , and the self-
adhesive layer has an add-on level of about 75 to about 100 g/m 2 . The non-pressure
sensitive adhesive is desirably applied to the laminate substrate and subsequently at
least partially cured or dried before the self-adhesive layer is applied over the applied
non-pressure sensitive adhesive. The layer of non-pressure sensitive adhesive
desirably provides improved temperature resistance and extends the shelf life of the
laminate before the final use or application to the carrier. Both the self-adhesive
layer and the non-pressure sensitive adhesive layer can be applied as, for example, a
water-based emulsion, a solvent-based emulsion, or a hot melt.
The adhesive-coated laminate substrate may be prepared by the
following method. First, a release layer is coated with a layer of physically setting,
solvent-free adhesive which includes an acrylic polymer. This may be
accomplished by initially coating the release layer with an aqueous or other solvent-
based acrylic adhesive, suitably containing about 35-75% by weight, or about 45-
65% by weight adhesive solids. The water or other solvent is then removed by
evaporation at about 30-150° C, suitably about 75-120° C for a time of 1-15
minutes, or about 3-8 minutes, sufficient to cause drying. The adhesive layer may
have a dry thickness of about 50-500 microns, or about 80-300 microns, and a wet
thickness perhaps twice as large.
A suitable release layer is a silicone-coated paper, Type 402-6010,
available from Wausau Paper Co. of Rhinelander, WI. Various other plastic-coated
papers and plastic films can also be employed as release layers. The adhesive layer
may be thermoplastic or thermosetting, and is suitably thermoplastic. Suitable
adhesive polymers include without limitation acrylic polymers, copolymers and
terpolymers as described above.
Second, the adhesive can be applied to a surface of the laminate
substrate by overlaying the adhesive-coated release layer on the laminate substrate
with the adhesive side facing the laminate substrate. If the laminate substrate is a
cellulose-based high pressure laminate, or another laminate having a relatively
smooth surface, it may be desirable not to sand the surface or otherwise increase its
roughness prior to applying the adhesive. The solvent-free adhesive is relatively
viscous or solid and will not easily penetrate into the valleys and crevices which are
present in a rough surface. When the laminate substrate surface is relatively
smooth, the adhesive may establish contact over the entire surface, resulting in
better adhesion.
Alternatively, the surface of the laminate substrate may be both
sanded and primed before applying the adhesive. The sanding creates a rough
surface having valleys and crevices which are filled by coating with a suitable
primer. Suitable primers include easy drying, solvent-based primers having
polymer components which are compatible with the adhesive to be applied. For
instance, an acrylic-based primer dries to form an acrylic-based smooth surface
which has excellent affinity to an acrylic-based adhesive layer. One suitable
polyolefin-based primer contains about 50% by weight solids and is sold by Lord
Chemlok under the trade name 459X. The primer coating may have a dry thickness
of about 10-50 microns, or about 15-40 microns, and a wet thickness perhaps twice
as large. Once the primer is dried, the adhesive is applied to the primed surface of
the laminate substrate.
Third, pressure is applied to the release layer to press the adhesive
onto the surface of the laminate substrate. A suitable pressure is between about 3-
70 N/cm 2 , suitably about 10-50 N/cm 2 . Once the adhesive has been pressed onto the
laminate substrate, the release layer is manually peelable to expose the adhesive.
For instance, the release layer can be manually peeled away and the adhesive layer
can be used to bond the laminate substrate to a wall, floor, counter top, or other
surface.
Fig. 1 schematically illustrates an exemplary process 10 useful for
coating the adhesive layer onto the laminate substrate. An adhesive layer 12,
combined with a release layer 14, are unwound from a roll 16. The foregoing layers
are brought together with laminate substrate 18 in a nip defined by nip rolls 20 and
22, with the adhesive layer 12 facing the surface 17 of laminate substrate 18.
Typically, laminate substrate 18 is positioned so that the surface 17 is its back
surface, i.e. the surface used to bond adhesive-coated laminate substrate 28 to a
wall, floor or object.
Fig. 2 schematically illustrates an alternative process 11 which is
similar to process 10 except for the presence of heaters. The adhesive layer 12 may
be heated using an external infrared heater 24 and/or an internal heater (not shown)
inside roll 20, before the adhesive layer 12 is applied to and pressed onto the surface
17 of laminate substrate 18. Alternatively, or additionally, the laminate substrate 18
may be heated using infrared heater 26 before the adhesive layer l2 is applied. In
either case, the heating may result in a temperature of about 30-120° C, suitably 50-
80° C, which is high enough to soften the adhesive layer 12 and impart a better
adhesive bond to the laminate substrate 18. The release layer 14 can still be
peelably removed to allow bonding of adhesive-coated laminate substrate 28 to an
object.
Examples of embodiments of this invention are described below, which,
in no way, represent a limitation of the inventive idea.
1. Production OfAn Adhesive-Coated Laminate Substrate
AU data refer to the weight.
From a supply container heated to 18O 0 C, an adhesive based on 25%
SIS, 15% SBS, and 60% hydrocarbon resin (with a content of 10% polybutene), was
conducted onto a roller with a width of 60 cm and heated to 18O 0 C. The
thermoplastically liquified adhesive was conveyed via the roller and applied onto an
HPL sheet, which was advanced with the roller at 15 m/min, wherein the gap between
the roller and the HPL sheet was 3 mm, and the adhesive was applied in a quantity of
180 g/m 2 . A siliconized paper was applied for protection to the adhesive layer that
was still warm. Subsequently, the HPL sheet coated with the adhesive was allowed to
cool.
2. Application Of The Adhesive-Coated Laminate Substrate On A Carrier Material
The above adhesive-coated laminate substrate was applied, at room
temperature, on a carrier. The laminate, whose adhesive layer was covered with a
siliconized release paper, is first aligned on the earner. Subsequently, the release
paper was pulled away, partially at an edge, preferably on the narrow edge, and the
adhesive-coated laminate substrate was pressed on the carrier at the edge with the
exposed adhesive layer. Then, the release paper was drawn out, step by step, under the
adhesive-coated laminate substrate and the laminate substrate is pressed, manually, on
the carrier. Advantageously, the adhesive-coated laminate substrate can be pressed
uniformly on the carrier substrate with a hard rubber roller. A subsequent processing
of the edges can be done with the usual doctors, files, cutters, and grinders.
3. Mechanical Characteristics Of The Composite Material
Peeling-off resistance
Measurement values for the peeling-off resistance of a self-adhesive
HPL, in accordance with the invention, on various substrates, are shown below.
The determination of the peeling-off resistance is made according to EN
311. The pressing of the adhesive-coated laminate substrate on the carrier is carried
out by light pressing manually or with a roller.
All measurement values given above are based on roughened HPL
sheets. A smooth HPL surface may result in somewhat higher peel resistance than a
roughened surface if the adhesive is applied to the HPL surface in a dry state from a
release layer, or somewhat lower peel resistance if the adhesive is applied to the HPL
surface in a wet state.
Measurement of the sheet strength loss tempering
A laminate substrate with an adhesive layer according to one
embodiment of this invention was cut to a size of 25 mm in width and 70 mm in
length. The test piece was applied on a carrier in such a way that there was an
overlapping of the adhesive area in the longitudinal direction of 25 mm. On the free,
lower end of the test piece, a weight of 500 g was affixed. Subsequently, the test setup
was introduced into a furnace that was preheated to 4O 0 C and left there at 4O 0 C for 30
min. Then, the furnace was heated at a heating rate of 0.37 0 C per minute until the test
piece detached from the carrier.
Shear resistance loss temperatures between 6O 0 C and 105 0 C were
measured with adhesive-coated laminated sheets, in accordance with the invention.
Further laminate samples (12.7 cm x 20.3 cm) were prepared using: 1)
FLEXBOND 153 to form a self-adhesive layer; and 2) FLEXBOND 153 to form a
self-adhesive layer and polyvinyl acetate to form a non-pressure sensitive adhesive
layer. The laminate samples were applied to a chip board and/or melamine carrier
and subjected to testing. The adhesive layers were applied at about 5 mils (127
microns) and dried at 100 0 C for 5 minutes.
The samples demonstrated temperature resistance upon application to
a earner by maintaining adhesion and laminate integrity to beyond 8O 0 C. The
samples were placed in an oven at 6O 0 C and the temperature was raised ten degrees
every two hours until delamination was observed.
The samples each further demonstrated a desirable long-term shelf life
by maintaining laminate integrity at 75 0 C beyond 1.5 months.
The samples demonstrated humidity resistance by maintaining laminate
integrity for over 14 days at 65 0 C and a 95% humidity level.
The samples further demonstrated desirable shear strength by having a
peeling-off force of over 0.2 N/mrn 2 (e.g., about 0.26 and 0.35 N/mm 2 , respectively).
The determination of the peeling-off resistance was accomplished according to EN
311. The pressing on the substrate is carried out by light pressing manually or with a
roller.
The invention illustratively disclosed herein suitably may be practiced
in the absence of any element, part, step, component, or ingredient which is not
specifically disclosed herein.
While in the foregoing detailed description this invention has been
described in relation to certain preferred embodiments thereof, and many details
have been set forth for purposes of illustration, it will be apparent to those skilled in
the art that the invention is susceptible to additional embodiments and that certain of
the details described herein can be varied considerably without departing from the
basic principles of the invention.