Note: Descriptions are shown in the official language in which they were submitted.
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FIRE RETARDANT LAMINATE
TECHNICAL FIELD AND INDUSTRIAL APPLICABILITY OF THE
INVENTION
This invention relates generally to fire retardant, high pressure laminates
and
more particularly to a high pressure laminate complying with prEN 13823 and
having
a caloric value of lower than 3.0 MJ/kg when tested in accordance with ISO
1716.
BACKGROUND OF THE INVENTION
High pressure laminates (HPL) are well known in the art and HPL panels are
used, for example, as wall linings, for furniture, facade cladding, bench tops
and the
like.
One of the most important parameters of HPL panels, especially in the
building industry, is fire performance. Since 2003, all building materials in
Europe
must comply with prEN 13823 (reaction to fire tests for building products).
This
norm describes the Single Burning Item (SBI) test. Al and A2 classification of
additional caloric value measurement according to ISO 1716 is required.
State of the art HPL panels are made fire retardant by using fire retardant
kraft
paper or by using a fire retardant phenol-formaldehyde resin. State of the art
FR-HPL
products have achieved an SBI classification of as high as B (above 3.0 MJ/kg
when
tested under ISO 1716).
HPL manufacturers have a strong desire for an SBI A2 classified HPL panel.
Such a classification would allow the manufacturers to expand the application
range
for their products and thereby penetrate additional markets. To date, this
hasn't been
achieved because no one has been able to meet the caloric value requirement
and still
achieve the desired mechanical properties and fire propagation
characteristics. The
present invention relates to the first HPL panel meeting all these
requirements
including those for A2 classification (below 3.0 MJ/kg when tested under ISO
1716).
The present invention relates to a novel laminate characterized by improved
fire and impact resistance.
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SUMMARY OF THE INVENTION
The high pressure laminate of the present invention comprises a first layer of
resin impregnated paper and at least one layer of fiber reinforced veil. Each
layer of
fiber reinforced veil includes both a secondary binder and a filler. The high
pressure
laminate is characterized by having a caloric value of lower than about 3.0
MJ/kg
when tested in accordance with ISO 1716.
The laminate may further include a second layer of resin impregnated paper.
In such an embodiment the layer or layers of fiber reinforced veil are
sandwiched
between the first and second layers of resin impregnated paper.
In any of the possible embodiments the secondary binder is a heat curable
resin. Suitable binders include but are not limited to self-crosslinkable
polyacrylates,
polyamide-amine epichlorohydrin resin (PAE), polyvinyl alcohol, acrylates,
styrene
acrylates, melamine-formaldehyde, urea-formaldehyde, phenol-formaldehyde,
epoxy
resin, unsaturated polyesters, crosslinkable acrylic resin, polyurethane
resin,
epichlorohydrin-polyaminopolyamide resins, epichlorohydrin-polyamine resins,
epichlorohydrin-polyamide resins and mixtures thereof.
The filler is typically selected from a group consisting of metal hydroxides,
metal carbonates, titanium dioxide, calcined clay, barium sulfate, magnesium
sulfate,
aluminum sulfate, zinc oxide, kaolin clay, chlorite, diatomite, feldspar,
mica,
nepheline syenite, pyrophyllite (aluminum silicate), silica, talc,
wollastonite,
montmorillonite (bentonite), hectorite, saponite, calcium carbonate, magnesium
carbonate, aluminum oxide, iron oxide, magnesium hydroxide, glass micro beads
and
mixtures thereof.
In one embodiment, the filler is selected from the group of of metal
hydroxides, metal carbonates and mixtures thereof. A mixture of calcium
carbonate
and aluminum hydroxide is a particularly useful filler for the present
invention. This
is particularly true when the binder is melamine-formaldehyde.
Other fillers include aluminum trihydrate, magnesium hydroxide, melamine
cyanurate, halogenated additive, antimony trioxide, metal hydroxide, metal
carbonate,
titanium dioxide, calcined clay, barium sulfate, magnesium sulfate, aluminum
sulfate,
zinc oxide, kaolin clay, chlorite, diatomite, felspar, mica, nepheline
syenite,
pyrophyllite, silica, ta1c, wollastonite, montmorillonite, hectorite,
saponite,
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magnesium carbonate, aluminum oxide, iron oxide, glass microbeads,
ethylenediaminephosphate, guanidinephosphates, melamine borate, melamine
(mono,
pyro, poly) phosphate, ammonium (mono, pyro, poly) phosphate, dicyandiamide
condensates, general intumescent systems (systems which foam during fire and
therefore generate in situ an insulating layer) and mixtures thereof.
In one possible embodiment each layer of fiber reinforced veil includes
between about 1 and about 95 weight percent reinforcement fibers about 5 and
about
50 weight percent melamine-formaldehyde, between about 10 and about 80 weight
percent calcium carbonate and about 20 and about 90 weight percent aluminum
hydroxide.
The fiber reinforced veil may be woven or nonwoven. Where multiple
layers of fiber reinforced veil are provided, they may all be woven, they may
all be
nonwoven or the layers may be a mixture of woven and nonwoven. The fiber
reinforced veil includes fibers selected from a group consisting of glass
fibers, basalt
fibers, metal fibers, inorganic fibers, silica fibers, carbide fibers, nitride
fibers, carbon
fibers and mixtures thereof. Glass fibers utilized for the fiber reinforced
veil may be
selected from a group of materials consisting of boron-free glass, E-glass,
ECR-glass,
C-glass, AR-glass, S2-glass and mixtures thereof.
The high pressure laminate of the present invention may be made more
aesthetically appealing when the first layer of resin impregnated paper is a
melamine
impregnated decor paper. Further, the product may include a radiation cured
paint
film or coating such as a UV cured paint film or an electron beam cured paint
film on
an exposed face of the first layer of resin impregnated paper. In yet another
alternative the product may include a thermally cross-linked urethane acrylate
paint
layer on an exposed face of the first layer of the resin impregnated paper.
In accordance with yet another aspect of the present invention a method is
provided for making a high pressure laminate. That method comprises pressing a
first
layer of resin impregnated paper and at least one layer of fiber reinforced
veil
together at a pressure of between about 525 Nfm' and about 15,750 N/m2 while
simultaneously heating the layers to a temperature of between about 120
degrees C
and about 220 degrees C to form a laminate. In addition the method includes
the step
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WO 2006/111458 4 PCT/EP2006/061194
of using a combination of secondary binder and filler to provide a caloric
value of
lower than 3.0 MJ/kg when the laminate is tested in accordance with ISO 1716.
The method may further include the selecting of the secondary binder from a
group consisting of melamine-formaldehyde, phenol-formaldehyde, urea-
formaldehyde, epoxy resin, unsaturated polyesters, cross-linkable acrylic
resin,
polyurethane resin, an epichlorohydrin-polyaminopolyamide resin, an
epichlorohydrin-polyamine resin, an epichlorohydrin-polyamide resin and
mixtures
thereof. The filler may be selected from a group consisting of metal
hydroxides,
metal carbonates and mixtures thereof. In a particularly useful embodiment the
filler
is selected from a mixture of calcium carbonate and aluminum hydroxide.
In one possible embodiment the method includes the forming of the first layer
of resin impregnated paper from melamine impregnated decor paper. In addition,
the
method may include the painting of an exposed face of the first layer of resin
impregnated paper with a radiation cured paint. In yet another possible
embodiment
the method may include the painting of an exposed face of the first layer of
resin
impregnated paper with a thermally crosslinked urethane acrylate paint.
In another embodiment, the laminate of the present invention comprises a
resin impregnated decorative layer, a fire barrier formed from a fiber
reinforced veil
and a layer of fiberboard.
The layer of fiberboard in the laminate may be generally described as a wood-
based panel. The fiberboard may be constructed from a material selected from
the
group consisting of high density fiberboard, medium density fiberboard,
oriented
strand board, chipboard and mixtures thereof. In addition, the laminate may
include a
layer of resin impregnated overlay paper overlying the resin impregnated
decorative
paper and/or a resin impregnated backing layer underlying the layer of
fiberboard.
Both the resin impregnated decorative layer and the resin impregnated backing
layer
may be made from a decorative paper of a type known in the art.
In this embodiment, the fiber reinforced veil includes between about 5 to
about 95 weight percent reinforcement fibers, about 5 to about 75 weight
percent
binder and about 0 to about 80 weight percent filler. Following impregnation
and
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prior to pressing, the fiber reinforced veil has a weight per unit area of
between about
20 and about 500 g/m2.
The method of making the fiber board laminate comprises pressing a resin
impregnated overlay layer, a resin impregnated decorative layer, a fire
barrier formed
from a fiber reinforced veil, a layer of fiberboard and a resin impregnated
backing
layer together at a pressure of between about 1050 N/m2 and about 5250 N/m2
while
simultaneously heating to a temperature of between about 150 to about 225
degrees C
for a time period of between about 10 to about 50 seconds. That method may be
further described as including a step of providing a binder in the fiber
reinforced veil
selected from a group consisting of polyvinyl alcohol, acrylates, styrene
acrylates,
melamine-formaldehyde, urea-formaldehyde, phenol-formaldehyde, epoxy resin,
unsaturated polyesters, crosslinkable acrylic resin, polyurethane resin,
polyamide-
amine epichlorohydrin resin and mixtures thereof.
The laminate may be used in a laminate flooring application wherein the
laminate is formed from boards having a wood basis such as chipboard,
fiberboard
including high and medium density fiberboard, and oriented strand board.
Additional
applications for the laminate include, but are not limited to, wall linings,
ceilings,
interior shop fittings, and decoration panels such as those found in ships,
trains, and
buildings.
In the following description there is shown and described one possible
embodiment of the invention simply by way of illustration of one of the modes
best
suited to carry out the invention. As it will be realized, the invention is
capable of
other different embodiments and its several details are capable of
modification in
various, obvious aspects all without departing from the invention.
Accordingly, the
drawings and descriptions will be regarded as illustrative in nature and not
as
restrictive.
BRIEF DESCRIPTION OF THE DiZ.AWEN GS
The accompanying drawing incorporated in and forming a part of this
specification, illustrates several aspects of the present invention, and
together with the
description serves to explain certain principles of the invention. In the
drawing:
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WO 2006/111458 6 PCT/EP2006/061194
Figure 1 is a side elevational view of one possible embodiment of the present
invention.
Figure 2 is a side elevational view of a first alternative embodiment of the
present invention.
Figure 3 is a side elevational view of yet another possible embodiment of the
present invention.
Figure 4a is a total heat release graph comparing two representative examples
of the present invention with two representative state of the art products.
Figure 4b is a heat release rate graph comparing the same two representative
examples of the present invention with two representative state of the art
products.
Figure 5 is a side elevational view of one possible embodiment of the present
invention.
Fig. 6 shows the impact classification ratings using both the small ball
impact
test and the large ball impact test.
Reference will now be made in detail to the present preferred embodiment of
the invention, an example of which is illustrated in the accompanying
drawings.
DETAILED DESCRIPTION OF THE INVENTION
Three embodiments of the high pressure laminate 10 of the present invention
are illustrated in Figures 1-3. The high pressure laminate 10 may be generally
described as comprising a first layer of resin impregnated paper and at least
one layer
of fiber reinforced veil,
Each layer of fiber reinforced veil further includes a secondary binder and
filler so that the high pressure laminate is characterized by having a caloric
value of
lower than 3.0 MJ/kg when tested in accordance with ISO 1716. The term
"secondary binder" is defined as a binder which is applied in a second
processing step
which is discussed in more detail below.
As illustrated in the Figure 1 embodiment, the high pressure laminate 10
includes a first layer 12 of resin impregnated paper, such as melamine
impregnated
decor paper. In addition, the laminate 10 includes two layers 14, 16 of fiber
reinforced veil.
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WO 2006/111458 7 PCT/EP2006/061194
Each layer 14, 16 of fiber reinforced veil is impregnated with a secondary
binder and filler composition. The secondary binder is a heat curable resin.
Typically, the secondary binder is selected from a group consisting of
melamine-
formaldehyde, phenol-formaldehyde, urea-formaldehyde, epoxy resin, unsaturated
polyesters, cross-linkable acrylic resin, polyurethane resin, an
epichlorohydrin-
polyaminopolyamide resin, an epichlorohydrin-polyamine resin, an
epichlorohydrin-
polyamide resin and mixtures thereof.
The filler is selected from a group consisting of metal hydroxides, metal
carbonates, titanium dioxide, calcined clay, barium sulfate, magnesium
sulfate,
aluminum sulfate, zinc oxide, kaolin clay, chlorite, diatomite, feldspar,
mica,
nepheline syenite, pyrophyllite (aluminum silicate), silica, talc,
wollastonite,
montmorillonite (bentonite), hectorite, saponite, calcium carbonate, magnesium
carbonate, aluminum oxide, iron oxide, magnesium hydroxide, glass micro beads
and
mixtures thereof. Typically the filler is selected from a group consisting of
metal
hydroxides, metal carbonates and mixtures thereof. A mixture of calcium
carbonate
and aluminum hydroxide is particularly useful in the present invention. This
is
particularly true when used in conjunction with a melamine-formaldehyde
binder.
The particle size of the fillers typically ranges from about 0.3 m to about
150 m,
more preferably between about 1 m to about 75 gm, and most preferably between
about 4 p.m to about 50 m.
The fiber reinforced veil includes reinforcing fibers selected from a group
consisting of glass fibers, basalt fibers, inorganic fibers (carbide, nitride,
etc.) and
mixtures thereof. Glass fibers particularly useful in the present invention
include E-
glass (such as Advantex glass), ECR-glass, AR-glass, C-glass, M-glass, D-
glass, S-
glass, S2-glass and mixtures thereof. The fibers are typically chopped in
lengths of
between about 0.1 mm and 100 mm and may be in the forms of chopped strands,
chopped rovings or chopped individual fibers or mixtures thereof. Where
individual
fibers are utilized, the diameter of those fibers is typically between about 3
and about
50 microns.
The fiber reinforced veils, prior to impregnation of the secondary binder and
fillers, contain up to about 95 weight percent glass fibers, preferably
between about
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75 to about 95 weight percent glass fibers, more preferably between about 78
to about
93 weight percent glass fibers, and most preferably between about 80 to about
92.5
weight percent glass fibers. Preferably, the fiber reinforced veil layer
includes E-
glass fibers.
The fiber reinforced veil, prior to impregnation of the secondary binder
composition and fillers, may include a binder, as mentioned above, preferably
the
binder is a polyvinyl alcohol. Preferably, the binder is present in the veil
at a content
of about 5 to about 25 percent by weight.
In the embodiment illustrated in Figure 1, the laminate 10 incorporates two
layers 14, 16 of veil. Each veil layer 14, 16 may be woven or nonwoven. In the
embodiment illustrated in Figure 1, both veil layers 14, 16 may be woven, both
may
be nonwoven or one may be woven while the other is nonwoven.
A particularly useful embodiment of the present invention incorporates one or
more veil layers 14, 16 including between about 1 and about 95 weight percent
reinforcement fibers, preferably between about 75 weight percent to about 95
weight
percent reinforcement fibers, more preferably between about 78 to about 93
weight
percent reinforcement fibers, most preferably between about 80 to about 92.5
weight
percent reinforcement fibers, prior to impregnation of the secondary binder
composition and fillers. The veil layers also contain between about 2 to about
50
weight percent, preferably between about 5 to about 25 weight percent melamine-
formaldehyde secondary binder and at least one filler in the amount of between
about
10 and about 80 weight percent, preferably between about 17.5 to about 65
weight
percent calcium carbonate and about 20 to about 90 weight percent, preferably
about
35 to about 70 weight percent aluminum hydroxide.
As further illustrated in Figure 1, the laminate 10 may be made more
aesthetically pleasing by including a radiation curable paint such as an
electron beam
cured or UV cured paint film 18 on an otherwise exposed face of the first
layer of
resin impregnated paper 12. Alternatively, the layer 18 may comprise a
thermally
cross-linked urethane acrylate paint.
An alternative embodiment of the present invention is illustrated in Figure 2.
In this embodiment, the high pressure laminate 10 includes a single fiber
reinforced
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veil layer 20 sandwiched between first and second layers 22, 24 of resin
impregnated
paper. The laminate 10 of Figure 2 may also include a layer 26 of radiation
cured
paint such as an electron beam cured or UV cured paint film or a thermally
cross-
linked urethane acrylate paint. The layer 26 is, however, optional.
In still another embodiment illustrated in Figure 3, the laminate 10 may
include a first layer 28 of resin impregnated paper, six intermediate layers
30, 32, 34,
36, 38, 40 of fiber reinforced veil and a second layer 42 of resin impregnated
paper.
The Figure 3 embodiment may also include an optional layer 44 comprising a
radiation cured paint such as an electron beam or UV cured paint film or a
thermally
cross-linked urethane acrylate paint layer for enhanced aesthetic appearance.
It should be appreciated that the resin impregnated paper layers 22, 24, 28
and
42 of the embodiments illustrated in Figures 2 and 3 are similar or identical
to the
resin impregnated paper layer 12 of the first embodiment illustrated in Figure
1.
Similarly, the fiber reinforced veil layers 20, 30, 32, 34, 36, 38, 40 of the
embodiments illustrated in Figures 2 and 3 are also identical or similar to
the veil
layers 14, 16 of the Figure 1 embodiment. As illustrated, the laminate 10 of
the
present invention may include any number of fiber reinforced veil layers while
still
meeting the fire propagation, caloric value and mechanical properties of any
particular end product application.
Typically, each fiber reinforced veil layer is a prepreg or ready-to-mold
sheet
of woven or nonwoven reinforcement fibers impregnated with a resin binder and
stored for subsequent use such as the final construction of the laminate
product by a
manufacturer.
Any water-based, wet strength binder known in the art could be used. Useful
binders include but are not limited to the following polyvinyl alcohol,
(partially
hydrolyzed) polyvinyl acetate, acrylic polymers and copolymers, crosslinkable
acrylic
polymers and copolymers, polymerizable polyfunctional N-methylol compounds,
notably N-methylol ureas such as dimethylol urea and N-methylol melamine type
resins, melamine formaldehyde, phenol formaldehyde, furfuryl formaldehyde,
resorcinol formaldehyde, styrene butadiene copolymer latices, cationic
polyamideepichlorohydrin, aminoresins, epoxyresins, polystyrene emulsion
binder,
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WO 2006/111458 10 PCT/EP2006/061194
polycarboxylic acid based binders, other latices and/or acrylic polymers or
copolymers like acrylamide, ethylene vinyl acetate/vinyl chloride, alkyl
acrylate
polymer,styrene-butadiene rubber, acrylonitrile polymer, polyurethane resins,
polyvinyl chloride, polyvinylidene chloride, copolymers of vinylidene chloride
with
other monomers, polyvinyl acetate, polyvinyl pyrrolidone, polyester resins,
acrylate
emulsion resin, styrene acrylate. More preferably, the binder is polyvinyl
alcohol.
The prepreg is impregnated with the secondary binder and filler composition.
The secondary binder and filler composition preferably includes between about
2 to
about 30 weight percent glass, in addition to the glass already present in the
prepreg,
more preferably between about 3 to about 25 weight percent glass, and most
preferably between about 4 to about 20 weight percent glass. The prepreg also
contains between about 5 to about 25 weight percent secondary binder,
preferably
between about 7 to about 20 weight percent secondary binder, most preferably
between about 8 to about 18 weight percent secondary binder. The prepreg also
contains between about 50 to about 93 weight percent fillers, more preferably
between about 55 to about 90 weight percent fillers and most preferably
between
about 60 to about 88 weight percent total fillers.
Typically the filler is a mixture of metal hydroxide and metal carbonate at a
ratio of between about 1:0.01 and about 1:100. Preferably, the metal hydroxide
aluminum hydroxide and is present in the prepreg the amount of between about
20 to
about 90 weight percent, more preferably between about 30 to about 80 weight
percent, and most preferably between about 35 to about 70 weight percent. The
preferred metal carbonate is calcium carbonate and is present in the prepreg
in the
amount of about 10 to about 80 weight percent, more preferably about 15 to
about 70
weight percent and most preferably between about 17.5 to about 65 weight
percent.
The particle size of the fillers typically ranges from about 0.3 pm to about
150
m, more preferably between about t[tm to about 75 m, and most preferably
between about 4~tm. to about 50 m.
Following impregnation, and before pressing, a typical fiber reinforced veil
prepreg will have a total weight per unit area of between about 250 g/m2 and
about
2000 g/m', a density of between about 500 kgl m3 and about 2000 kg,/m3
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The high pressure laminate 10 is constructed by pressing a first layer of
resin
impregnated paper and at least one layer of fiber reinforced veil together at
a pressure
of between about 525 N/m2 and about 15,750 N/m2 (about 5 and about 150 bar)
while
simultaneously heating the layers to a temperature of between about 120
degrees C
and about 220 degrees C to form the laminate. In addition the method includes
the
step of using a combination of binder and filler to provide a caloric value of
lower
than 3.0 MJ/kg when the laminate is tested in accordance with ISO 1716. This
allows
one to produce an HPL panel or product with an SBI A2 classification.
In order to achieve this end, the secondary binder is selected from a group
consisting of melamine-formaldehyde, phenol-formaldehyde, urea-formaldehyde,
epoxy resin, unsaturated polyesters, cross-linkable acrylic resin,
polyurethane resin,
an epichlorohydrin-polyaminopolyamide resin, an epichlorohydrin-polyamine
resin,
an epichlorohydrin-polyamide resin and mixtures thereof. The filler is
selected from
a group of materials consisting of metal hydroxides, metal carbonates,
titanium
dioxide, calcined clay, barium sulfate, magnesium sulfate, aluminum sulfate,
zinc
oxide, kaolin clay, chlorite, diatomite, feldspar, mica, nepheline syenite,
pyrophyllite
(aluminum silicate), silica, talc, wollastonite, montmorillonite (bentonite),
hectorite,
saponite, calcium carbonate, magnesium carbonate, aluminum oxide, iron oxide,
magnesium hydroxide, glass micro beads and mixtures thereof.
Typically, the filler is selected from a group consisting of metal hydroxides,
metal carbonates and mixtures thereof. Calcium carbonate and aluminum
hydroxide
are particularly useful in this method.
In order to further enhance the aesthetic appeal of the product, the method
may also include forming the first layer of resin impregnated paper from
melamine
impregnated decor paper. Further, the method may include painting an exposed
face
of the first layer of resin impregnated paper with electron beam cured paint.
Alternatively the method may include painting an exposed face of the first
layer of
resin impregnated paper with a thermally crosslinked urethane acrylate paint.
Example 1
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WO 2006/111458 12 PCT/EP2006/061194
Five samples of a high pressure laminate of the present invention were
prepared. In the first (Example 1), five fiber reinforced glass veils were
sandwiched
between two layers of melamine formaldehyde impregnated decorative paper.
The glass fiber utilized in the glass veils was E-glass having a fiber
diameter
of 11 microns and a length of 10 mm. The glass veils each had a weight per
unit area
of 100 g/m2. The glass veils included a poly vinyl alcohol binder at a content
of 16
weight percent.
The decorative paper layers each had a weight per unit area of 160 g/m2
including 80 g/m' base weight paper and 80 g/m2 melamine formaldehyde resin.
The stacked layers of glass veil were then impregnated with a secondary
binder and filler formulation including 21 weight percent phenol formaldehyde,
26
weight percent calcium carbonate and 53 weight percent aluminum hydroxide. The
final glass veil weight was 1000 g/m2.
The stacked layers were pressed together at a pressure of 100 kg/em'' at a
temperature of 150 degrees C for 20 minutes to produce a 2.96 mm thick
laminate.
In the second (Example 2), five fiber reinforced glass veils
were sandwiched between a layer of melamine formaldehyde decorative paper and
a
layer of phenol formaldehyde impregnated kraft paper.
The glass fibers utilized in the Example 2 product were E-glass having a fiber
diameter of 13 microns and a length of 11 mm. The glass veils each had a
weight per
unit area of 50 g/m2 and included a poly vinyl alcohol binder at a content of
14
weight percent.
The stacked layers of glass veil were impregnated with a secondary binder and
filler formulation of 15 weight percent melamine formaldehyde, 20 weight
percent
calcium carbonate and 65 weight percent aluminum hydroxide. The final glass
veil
weight was 900 g/m2.
The stacked layers of the Example 2 product were pressed together at a
pressure of 50 kg/cm2 at a temperature of 145 degrees C for 20 minutes in
order to
produce a 3 mm thick laminate.
Additional Examples 3, 4 and 5 of the present invention are presented in Table
1 below along with Examples 1 and 2. Additionally, the Table includes
corresponding measurements for representative state of the art HPL (std HPL)
and
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WO 2006/111458 13 PCT/EP2006/061194
state of the art FR-HPL (fire retardant HPL) products for purposes of
comparison.
Test results for each of these Examples 1-5 and the state of the art products
std HPL
and FR-HPL are presented (where available) in Table 2. Relevant total heat
release
(THR) and heat release rate (HRR) curves are illustrated respectively in
Figures 4a
and 4b.
20
CA 02605155 2007-10-16
WO 2006/111458 14 PCT/EP2006/061194
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CA 02605155 2007-10-16
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~ ., ~ .. =~ N N N N y 'U'i N M fC p
fit X sc c a0
N 'Z) 2
~ t -' tu E E u ci J
CA 02605155 2007-10-16
WO 2006/111458 16 PCT/EP2006/061194
Reference is now made to Figure 5 illustrating one possible embodiment of
the laminate 46 of the present invention. As illustrated the laminate 46
includes a
resin impregnated overlay paper 48 overlying a resin impregnated decorative
layer
50. The decorative layer 50 overlies a first fire barrier formed from a fiber
reinforced
veil 52. The veil 52 overlies a layer of fiberboard 54. Finally, a backing
layer 56
underlies the fiberboard 54. The laminate 46 may also include a second fire
barrier,
formed from a fiber reinforced veil 58, between the fiberboard 54 and the
backing
layer 56. This second veil 58 further enhances the fire retardant properties
of the
laminate 46 and insures that heat is transferred at about the same rate from
the top or
the bottom.
The fiber reinforced veil 52 may include fibers selected from a group
consisting of glass fibers, basalt fibers, metal fibers, inorganic fibers,
silica fibers,
carbide fibers, nitride fibers, carbon fibers and mixtures thereof. Where
glass fibers
are utilized in the fiber reinforced veil, they may, for example, be selected
from a
group of fibers including boron-free glass, E-glass, ECR-glass, C-glass, AR-
glass,
S2-glass and mixtures thereof. Advantext glass fibers, commercially available
from
Owens Corning (Toledo, OH), may be used.
The fiber reinforced veils 52 and 58 following resin impregnation includes
between about 5 to about 95 weight percent reinforcement fibers, about 5 to
about 75
weight percent resinibinder and 0 to about 80 weight percent filler. The
binder
utilized may be a B-stageable resin which may be reactivated during the
pressing step
to reach its final properties. The binder may be selected from a group of
resins
consisting of polyvinyl alcohol, acrylates, styrene acrylates, melamine-
formaldehyde,
urea-formaldehyde, phenol-formaldehyde, epoxy resin, unsaturated polyesters,
crosslinkable acrylic resin, polyurethane resin, polyamide-amine
epichlorohydrin
resin and mixtures thereof. The filler utilized in the fiber reinforced veil
16 may be
selected from a group consisting of aluminum trihydrate, magnesium hydroxide,
melamine cyanurate, halogenated additive, antimony trioxide, metal hydroxide,
metal
carbonate, titanium dioxide, calcined clay, barium sulfate, magnesium sulfate,
aluminum sulfate, zinc oxide, kaolin clay, chlorite, diatomite, felspar, mica,
nepheline
syenite, pyrophyllite, silica, talc, wollastonite, montmorillonite, hectorite,
saponite,
CA 02605155 2007-10-16
WO 2006/111458 17 PCT/EP2006/061194
calcium carbonate, magnesium carbonate, aluminum oxide, iron oxide, glass
microbeads, ethylenediarninephosphate, guanidinephosphates, melamine borate,
melamine (mono, pyro, poly) phosphate, ammonium (mono, pyro, poly) phosphate,
dicyandiamide condensates, general intumescent systems (systems which foam
during fire and therefore generate in situ an insulating layer) and mixtures
thereof.
Advantageously, the fire barrier formed from the fiber reinforced veil 16
imparts
improved fire retarding and impact characteristics to the laminate above and
beyond
those achieved with wood based laminates of the prior art not incorporating a
fire
barrier of fiber reinforced veil.
The fiber reinforced veils 52 and 58 are typically constructed from nonwoven
glass fibers or mixed fibers. The veils 52,58 may include directionally
oriented fibers
if desired. Both continuous and chopped fibers may be utilized. The continuous
fibers typically have a diameter of between about 3 and about 30. The chopped
fibers
typically have a length of between about 2 and about 100 mm and a diameter of
between about 3 and about 30 m. The fiber reinforced veil 52 following
impregnation and prior to pressing typically has a weight per unit area of
between
about 20 and about 500 g/m2.
The fiberboard 54 utilized in the present laminate is a wood based panel. The
fiberboard 54 may, for example, be made from materials including high density
fiberboard, medium density fiberboard, oriented strand board, chipboard and
mixtures
thereof.
The decorative layer 50 and backing layer 56 may be made from decorative
paper as is known in the art. The overlay paper 48 may be made from cellulose
as is
also known in the art. The overlay paper 48, the decorative layer 48 and the
backing
layer 56 may all be impregnated with the same resin/binder as the fiber
reinforced
vei146.
The laminate 46 is made by pressing the resin impregnated overlay layer 48,
the resin impregnated decorative layer 50, the first fire barrier formed from
the resin
impregnated, fiber reinforced veil 52, the layer of fiberboard 54, the second
fire
barrier formed from the resin impregnated fiber reinforced veil 58 (if
present) and the
resin impregnated backing layer 56 together at a pressure of between about
1050
N/m'' and about 5250 N/m2 while simultaneously heating to a temperature of
between
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WO 2006/111458 18 PCT/EP2006/061194
about 150 to about 225 degrees C for a time period of between about 10 to
about 50
seconds. Such processing may be completed in-line utilizing equipment that is
presently available in the commercial marketplace.
Example 2
Table 3 shows fifteen samples of glass veil, prior to impregnation with
additional binder and a flame retarder. All samples contain a poly(vinyl
alcohol)
(PVA) binder. The glass fibers in the veil include AdvantexQ glass fibers
manufactured by Owens Coming, Toledo, OH, USA.
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WO 2006/111458 19 PCT/EP2006/061194
TABLE 3 SAMP glass
LE Ni binde
FIBER weigh r perc
TYPE t m2 %
Advantex;
1 11 um-6 mm 47 15
Advantex;
2 11 um-6 mm 46 15
Advantex;
3 11 um-6 mm 47 15
Advantex;
4 11 um-6 mm 47 15
Advantex;
5 11 um-6 mm 46 15
Advantex;
6 11 um-6 mm 46 15
Advantex;
7 11 um-6 mm 47 15
Advantex/si
8 lica (85:15) 33 10
Advantex/si
9 lica (85:15) 54 10
Advantex/si
10 lica (85:15) 76 10
Advantex/si
11 lica (85:15) 48 10
Advantex/si
12 lica (85:15) 47 10
13 silica 100% 81 12
Advantex;
14 11um-6 mm 35 15
Advantex;
15 11um-6 mm 35 15
Table 4 shows samples 1-15 after they have been impregnated with additional
binde, and flame retardant. The "Add on" column shows the amount of fire
ret~brdcr ti11(;r per m2 impregnated into each sample.
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WO 2006/111458 20 PCT/EP2006/061194
TABLE 4
GLASS VEIL IMPREGNATION
Sampl Binde Flame Add on End
e No. r type retarder (gIM2) weight
{ /M2)
1 melamine 26 73
PVA phosphate
2 Melamine 25 71
pyrophosph
PVA ate
3 Melamine 26 73
PVA cyanurate
4 Ammonium 25 72
polyphosph
PVA ate
5 chlorin 25 71
e-
acrylat Aluminum
e trihydrate
6 chlorin 24 70
e-
acrylat
e ATH + APP
7 PVA none 0 47
8 none none 0 33
9 none none 0 54
10 none none 0 76
11 PVA APP 23 71
12 Melamine 24 71
polyphosph
PVA ate
13 none none 0 81
14 PVA ATH 7 42
15 intumescent 7 42
PVA formulation
Table 5 shows the fire properties of samples 1-15 when each of the samples
were exposed to flame. Samples 1-15 were lit above a Bunsen burner where the
flame temperature reached about 950 C. Distance to the flame was fixed, about
20
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WO 2006/111458 21 PCT/EP2006/061194
mm, for all the samples to ensure that the samples were exposed to the same
temperature. Samples were observed for smoke development then the samples were
removed from the flame and observed for self-extinguishing behavior.
TABLE 5
FIRE PROPERTIES
Sample No. Smoke Self- Burn-
Development* Extinguishing** through
times (s)
1 + +++ 40
2 + +++ 20
3 ++ +++ 3
4 + +++ 159
5 + ++ 3
6 + +++ 130
7 - + 1
8 -- +++ 600
9 -- +++ 170
10 -- +++ 300
11 + +++ 250
12 + +++ 26
13 -- +++ >600
14 + +++ 1
15 ++ +++ 250
*Smoke development: **Self-extinguishing behavior
no smoke development +: poor self-extinguishing properties
hardly any smoke development ++: moderate self-extinguishing properties
+: moderate smoke development +++: significant self-extinguishing properties
++: significant smoke development
The samples were then placed at a fixed distance, about 10 mm, above a
Bunsen burner (F1ame temperature at about 950 C} and the time (in seconds)
was
recorded when the flame burned through the veil samples.
Flooring laminate examples
Specimens 7 and 14 were evaluated as an effective fire barrier in a laminate
flooring panel. An unmodified flooring laminate was taken as a reference. The
laminate flooring panels were evaluated on impact resistance and fire
resistance.
Method of making the laminate flooring_panel:
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WO 2006/111458 22 PCT/EP2006/061194
Specimens 7 and 14 were impregnated with melamine resin to ensure a good
bonding with the decorative paper and with the fiber board. Specimens 7 and 14
were
impregnated to final weights of approximately 150 g/m2.
The melamine-impregnated specimens 7 and 14 were pressed (function as a
fire barrier between the decorative paper and the fiber board) onto the 8 mm
high
density fiber board (pressing conditions: 180 C ; 40 kg/cm2; 20 s) to produce
the
laminate flooring panel. The final laminate flooring panel was subjected to
two
critical tests; impact resistance and fire resistance and tested with a
reference laminate
flooring panel, see Table 6.
TABLE 6
Norm Code A: Code B: Code C:
Unmodified Specimen 7 fire Specimen 14
standard barrier fire barrier
laminate laminate laminate
flooring panel flooring panel flooring panel
Small ball EN 438 <15 16.82 18.84
impact (N)
Large ball EN 438 <1600 >1600 >1600
impact (mm)
Fire resistance NF P 92- M3 M2 M2
501
Impact class IC 1 or IC 2 IC 3 IC 3
(see fig 2)
As shown in Table 6, laminate flooring panels A, B and C were tested using
the small and large ball impact tests described below. In the small ball
impact test,
the panels with their decorative surfaces were subjected to the impact of a 5
mm steel
ball mounted at one end of a spring-loaded bolt. The minimum spring force (N)
needed to cause visible damage was used to measure resistance to impact. In
the
large ball impact test, the laminate flooring panels A, B and C were covered
with a
sheet of carbon paper and subjected to the impact of a large steel ball (324
g; diameter
of 42.8 mm) -vuhich was allowed to fall from a known height. In the large ball
test,
the height is increased in 50 mm intervals until the ball creates an impact
imprint
larger than 10 mm. This height determines the large ball impact resistance in
mm.
Impact resistance is expressed as the maximum drop height (mm) which can be
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WO 2006/111458 23 PCT/EP2006/061194
achieved without incurring visible surface cracking or producing an imprint
greater
than a 10 mm diameter.
Fire resistance
The Epiradiateur test (NF P 92-501) is the national fire test for France and
is
mandatory for many building and construction materials.
The size of the specimens (7 and 14) tested was 300 mm x 400 mm x max 120
mm and the specimens were positioned at an incline of 45 on an 8 mm fixed,
self-
supporting frame. The specimens were ignited, from above and below, using an
electrical radiator (inclined at 45 ) at 500 W. Two butane pilot flames were
used to
ignite the fiber board panels above and below the specimen for 20 minutes.-
Fig. 6 shows the impact classification ratings using both the small ball
impact
test and the large ball impact test.
The foregoing description of a preferred embodiment of the present invention
has been presented for purposes of illustration and description. It is not
intended to be
exhaustive or to limit the invention to the precise form disclosed. Obvious
modifications or variations are possible in light of the above teachings. For
example,
the second fire barrier and the backing layer could be combined into a single
layer if
desired.
The embodiments were chosen and described to provide the best illustration
of the principles of the invention and its practical application to thereby
enable one of
ordinary skill in the art to utilize the invention in various embodiments and
with
various modifications as are suited to the particular use contemplated. All
such
modifications and variations are within the scope of the invention as
determined by
the appended claims when interpreted in accordance with the breadth to which
they
are fairly, legally and equitably entitled. The drawings and preferred
embodiment do
not and are not intended to limit the ordinary meaning of the claims and their
fair and
broad interpretation in any way.
