U.S. patent application number 14/755938 was filed with the patent office on 2015-10-22 for pvc membrane with reduced plasticizer migration.
The applicant listed for this patent is SIKA TECHNOLOGY AG. Invention is credited to Norman BLANK, Elyes JENDOUBI.
Application Number | 20150300023 14/755938 |
Document ID | / |
Family ID | 43845962 |
Filed Date | 2015-10-22 |
United States Patent
Application |
20150300023 |
Kind Code |
A1 |
JENDOUBI; Elyes ; et
al. |
October 22, 2015 |
PVC MEMBRANE WITH REDUCED PLASTICIZER MIGRATION
Abstract
The invention relates to a membrane including a partition layer,
wherein the partition layer contains at least 50 wt % of PVC, and a
barrier layer. The barrier layer can be a barrier layer, wherein
the barrier layer has a polyamide layer containing more than 50 wt
% of copolymer, wherein said polyamide layer is connected to the
partition layer by a polyurethane layer, wherein the polyurethane
layer contains more than 10 wt % of polyurethane. Alternatively,
the barrier layer can be a barrier layer, wherein the barrier layer
is made of a composition containing 5-50 wt % of polyurethane and
50-95 wt % of copolymer. The membranes according to the invention
have significantly lower plasticizer migration compared to the
membranes of the prior art and are characterized by improved aging
resistance, in particular with regard to the adhesion of the
barrier layer to the partition layer, and impermeability to
moisture.
Inventors: |
JENDOUBI; Elyes; (Zurich,
CH) ; BLANK; Norman; (Ruschlikon, CH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SIKA TECHNOLOGY AG |
Baar |
|
CH |
|
|
Family ID: |
43845962 |
Appl. No.: |
14/755938 |
Filed: |
June 30, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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13882916 |
May 1, 2013 |
9097018 |
|
|
PCT/EP2011/072796 |
Dec 14, 2011 |
|
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14755938 |
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Current U.S.
Class: |
427/393.5 |
Current CPC
Class: |
B32B 27/34 20130101;
E04D 5/06 20130101; B05D 7/04 20130101; E04D 5/10 20130101; B32B
27/30 20130101; Y10T 428/3158 20150401; B32B 27/40 20130101; B32B
27/08 20130101; B05D 3/0406 20130101; E04B 1/665 20130101 |
International
Class: |
E04D 5/06 20060101
E04D005/06; B05D 7/04 20060101 B05D007/04; E04B 1/66 20060101
E04B001/66; B05D 3/04 20060101 B05D003/04 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 17, 2010 |
EP |
10195776.9 |
Claims
1. A method for producing a membrane, comprising a sealing layer,
wherein the sealing layer consists more than 50% by weight of PVC,
relative to the total weight of the sealing layer, and a barrier
layer S2, wherein the barrier layer S2 consists of a composition
comprising 5-50% by weight polyurethane PUR and 50-95% by weight
copolymer PA, comprising the steps: (i) applying a composition Z1
comprising polyurethane PUR, copolymer PA and solvent onto a
sealing layer; and (ii) flashing off the composition Z1 while
forming a barrier layer S2, wherein the copolymer PUR has at least
one nucleophilic functional group, which is selected from the group
consisting of hydroxyl group, carboxyl group, sulfonate group and
phosphate group, and wherein the copolymer PA is a copolymer of
aliphatic diamine with 4-10 C atoms, dicarboxylic acid with 4-10 C
atoms, cycloaliphatic diamine with 6-20 C atoms, and a compound
selected from the group consisting of aliphatic lactam with 4-10 C
atoms and alpha, omega-amino carboxylic acids with 2-20 C
atoms.
2. The method according to claim 1, wherein the application of the
composition Z1 in Step (i) is performed by applying the composition
Z1 in the liquid state.
3. The method according to claim 1, wherein flashing-off of the
composition Z1 in Step (ii) is performed for 1-5 minutes at
100-170.degree. C.
4. The method according to claim 1, wherein the proportion of the
sum of polyurethane PUR together with copolymer PA is 1-30% by
weight, relative to the total weight of the composition Z1.
Description
[0001] This application is a divisional application of U.S. patent
application Ser. No. 13/882,916, filed May 1, 2013, which is a U.S.
National Phase of Application No. PCT/EP2011/072796, filed Dec. 14,
2011, which in turn claims priority to European Application
10195776.9, filed Dec. 17, 2010. The disclosures of these prior
applications are hereby incorporated by reference.
TECHNICAL FIELD
[0002] The invention relates to the field of sealing in the civil
construction sector, in particular roof covering.
[0003] 1. Prior Art
[0004] PVC as a component of flexible sheeting for waterproofing
plays an important part for sealing in the civil construction
field, in particular for roof covering. Plasticizers have been used
for a long time to control the processability of PVC. These
plasticizers have the big disadvantage, however, that they migrate.
Which means that the plasticizers over time migrate towards the
surface, on the one hand, were they produce stickiness of the
surface, or they migrate into the carrier that joins them to a
substrate. Experience has shown that migration is even reinforced
by high temperatures, such as those caused by exposure to sunlight,
for example. The migration moreover causes plasticizer depletion of
the PVC layer, which reduces its elasticity significantly over
time, so that the layers become brittle, which produces cracks
sooner or later. The migration of the plasticizer thus results in
that the properties which are important for a PVC layer, that is
the sealing against moisture, flexibility and aging stability, are
lost.
[0005] 2. Representation of the Invention
[0006] It is therefore an objective of the present invention to
provide sealing membranes which do not have the above-mentioned
disadvantages. Surprisingly it was found that a membrane pursuant
to claim 1 solves this problem.
[0007] The core of the invention is therefore a membrane 1,
comprising a sealing layer 2, wherein the sealing layer consists
more than 50% by weight of PVC, relative to the total weight of the
sealing layer, and a barrier layer 3. The barrier layer 3 can
either be a barrier layer S1 31 or a barrier layer S2 32.
[0008] In case of a barrier layer S1 31, this involves a barrier
layer which has a polyamide layer 4 which has more than 50% by
weight of copolymer PA, relative to the total weight of the
polyamide layer 4, which is connected with the sealing layer 2 by a
polyurethane layer 5, wherein the polyurethane layer 5 contains
more than 10% by weight of polyurethane PUR, relative to the total
weight of the polyurethane layer 5.
[0009] In the case of a barrier layer S2 32, this is a barrier
layer consisting of a composition comprising 5-50% by weight of
polyurethane PUR and 50-95% by weight of copolymer PA.
[0010] The polyurethane PUR contains at least one nucleophilic
functional group, which is selected from the group consisting of
hydroxyl group, carboxyl group, sulfonate group and phosphate
group. The copolymer PA is a copolymer of aliphatic diamine with
4-10 C atoms, dicarboxylic acid with 4-10 C atoms, cycloaliphatic
diamine with 6-20 C atoms, and a compound selected from the group
consisting of aliphatic lactam with 4-10 C atoms and alpha,
omega-amino carboxylic acids with 2-20 C atoms.
[0011] The membranes according to the invention comprise a
significantly deeper plasticizer migration compared to the
membranes from the prior art and distinguish themselves by an
improved aging stability, particularly relative to the adhesion of
the barrier layer 3 on the sealing layer 2, and impermeability
against moisture.
[0012] Further aspects of the invention are among other things
methods for producing the previously mentioned membranes and are
the subject of further independent claims. Particularly preferred
embodiments of the invention are the subject of the dependent
claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The invention is described more detailed in the following
with reference to the figures below, wherein it is pointed out that
only the elements are shown which are significant for understanding
the invention clearly. Identical elements in the different figures
are marked with the same reference symbols. It is pointed out
moreover that the FIGS. 1 and 2 that are shown here are merely
schematic representations without references to dimensions.
[0014] FIG. 1 shows a cross-section through a membrane according to
the invention.
[0015] FIG. 2 shows a cross-section through a further possible
membrane according to the invention.
[0016] FIG. 3 illustrates a delamination of a polyamide layer from
a PVC layer, following anti-aging treatment.
[0017] FIG. 4 shows a polyamide layer on top of the PVC layer that
shows no delamination following anti-aging treatment.
MEANS OF IMPLEMENTING THE INVENTION
[0018] The present invention relates to a membrane 1 comprising a
sealing layer 2, wherein the sealing layer consists of PVC more
than 50% by weight relative to the total weight of the sealing
layer, as well as a barrier layer 3.
[0019] The sealing layer 2 consists more than 50% by weight of PVC
relative to the total weight of the sealing layer. The sealing
layer consists preferably more than 70% by weight of PVC relative
to the total weight of the sealing layer.
[0020] To be optionally suited as a sealing layer, such layer
should be waterproof, if possible, and even if subjected to water
or moisture for extended periods should not decompose or be damaged
mechanically. Films that are particularly suited as a sealing layer
are those which are already in use for sealing applications in
structural and civil engineering in the prior art. The sealing
layer should advantageously have at least a low degree of
elasticity to be able to bridge differences in expansion between
the sealing membrane and the substrate caused by temperature, for
example, or stresses caused by cracks in the substrate, without
damaging the sealing layer or causing it to tear and which would
impair the sealing function of the sealing layer.
[0021] The sealing layer 2 can furthermore contain materials which
are suitable as processing aids for PVC. Such materials are
typically selected from the group consisting of polyethylene with
high density (HDPE), polyethylene with medium density (MDPE),
polyethylene with low density (LDPE), polyethylene (PE),
polypropylene (PP), polyethylene terephthalate (PET), polystyrene
(PS), ethylene vinyl acetate (EVA), chloro-sulfonated polyethylene,
thermoplastic polyolefins (TPO), ethylene propylene diene monomer
(EPDM) and polyisobutylene (PIB) as well as mixtures thereof. The
sealing layer 2 will preferably consist less than 5% by weight,
preferably less than 1% by weight, particularly preferably less
than 0.5% by weight of the above-mentioned materials which are
suitable processing aids for PVC, relative to the total weight of
the sealing layer.
[0022] The sealing layer preferably has a percentage of plasticizer
between 20-45% by weight, particularly preferably 30-40% by weight,
relative to the total weight of the sealing layer.
[0023] The plasticizers used are typically esters of organic
carboxylic acids or their anhydrides, such as phthalates, for
example dioctyl phthalate, diisononyl phthalate, adipates, for
example dioctyl adipate, azelates and sebacates, polyols, for
example polyoxyalkylene polyols and polyester polyols, organic
phosphoric acid esters and sulfonic acid esters or polybutenes.
[0024] The sealing layer preferably has a layer thickness in the
millimeter range, typically between 0.2 and 15 mm, preferably
between 0.5 and 4 mm.
[0025] The barrier layer 3 can either be a barrier layer S1 31 or a
barrier layer S2 32.
[0026] FIG. 1 illustrates a cross-section through a potential
membrane according to the invention, which has a barrier layer S1
31.
[0027] The barrier layer S1 31, has a polyamide layer 4, comprising
more than 50% by weight of copolymer PA, relative to the total
weight of the polyamide layer 4, which is connected with the
sealing layer 2 by a polyurethane layer 5, wherein the polyurethane
layer 5 consists more than 10% by weight of polyurethane PUR,
relative to the total weight of the polyurethane layer 5.
[0028] The polyamide layer 4 comprises more than 50% by weight of
copolymer PA, relative to the total weight of the polyamide layer
4.
[0029] The copolymer PA is a copolymer of aliphatic diamine with
4-10 C atoms, dicarboxylic acid with 4-10 C atoms, cycloaliphatic
diamine with 6-20 C atoms, and a compound selected from the group
consisting of aliphatic lactam with 4-10 C atoms and alpha,
omega-amino carboxylic acids with 2-20 C atoms.
[0030] The aliphatic diamine with 4-10 C atoms is a propane-1,
4-diamine, pentane-1, 5-diamine, hexane-1,6-diamine, heptane-1,
7-diamine, octane-1,8 diamine, nonan-1,9 diamine, decane-1,
10-diamine, for example. The aliphatic diamine with 4-10 C atoms is
preferably hexane-1,6-diamine.
[0031] The dicarboxylic acid is 4-10 C atoms is preferably
butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic
acid or its derivatives such as its salts or its anhydrides, for
example. The dicarboxylic acid with 4-10 C atoms is preferably
hexanedioic acid.
[0032] The cycloaliphatic diamine with 6-20 C atoms is preferably a
cycloaliphatic diamine, whose cycloaliphatic ring/s comprise/s no
heteroatoms. The cycloaliphatic diamine with 6-20 C atoms is
preferably a cycloaliphatic diamine, which comprises at least one
cyclohexane ring. The cycloaliphatic diamine with 6-20 C atoms is
particularly preferably a cycloaliphatic diamine which has at least
one cyclohexane ring and on which at least one ring and/or on a
centrally located methylene group between two rings, at least one
ring is substituted by monosubstituted or poly-substituted methyl,
ethyl or propyl groups.
[0033] The cycloaliphatic diamine with 6-20 C atoms is preferably
methylene-bis(4-cyclohexyl amine),
[0034] The compound selected from the group consisting of aliphatic
lactam with 4-10 C atoms and alpha, omega-amino carboxylic acids is
2-20 C atoms is preferably an aliphatic lactam with 4-10 C
atoms.
[0035] The aliphatic lactam with 4-10 C atoms is preferably
enantholactam, undecanolactam, dodecanolatcam or
.epsilon.-caprolactam, particularly .epsilon.-caprolactam.
[0036] The alpha, omega-amino carboxylic acid with 2-20 C atoms is
preferably an alpha, omega-amino carboxylic acid with 3-18 C atoms,
in particular 6-aminohexanoic acid and 11-aminohexanoic acid. The
alpha, omega-amino carboxylic acid with 2-20 C atoms can moreover
be its dimers, trimers, tetramers, pentamers or hexamers; as well
as its salts, its acid amides or its esters.
[0037] The copolymer PA is most preferably a copolymer of
1,6-hexane diamine, adipinic acid, methane-bis-4-(cyclohexylamine)
and .epsilon.-caprolactam.
[0038] A preferred copolymer PA is commercially available under the
name of Ultramid.RTM. 1C from BASF SE, Germany, for example.
[0039] For inhibiting the migration of plasticizers, it is
furthermore advantageous, if the copolymer PA comprises a molar
ratio of aliphatic diamine with 4-10 C atoms: dicarboxylic acid
with 4-10 C atoms: cycloaliphatic diamine with 6-20 C atoms: a
compound selected from the group consisting of aliphatic lactam
with 4-10 C atoms, and alpha, omega-amino carboxylic acids with
2-20 C atoms from 0.5-2:0.5-4:0.5-2:0.5-2.
[0040] The barrier layer S1 consists preferably more than 80% by
weight, particularly preferably more than 95% by weight of
copolymer PA, relative to the total weight of the barrier layer
S1.
[0041] The barrier layer S1 preferably comprises a layer thickness
in the micrometer range, typically between 100 and 1 .mu.m,
preferably between 10 and 2 .mu.m.
[0042] The polyamide layer 4 of the barrier layer S1 31 is
connected by a polyurethane layer 5 to the sealing layer 2. The
polyurethane layer 5 consists more than 10% by weight of
polyurethane PUR, relative to the total weight of the polyurethane
layer 5, in particular more than 20% by weight, particularly
preferably more than 40% by weight.
[0043] Names of substances beginning with "poly," such as polyol or
polyisocyanate in the present document indicate substances, which
formally contain two or more of the functional groups per molecule
which occur in their name.
[0044] In the present document, the term "polymer" on the one hand
comprises a collective of chemically uniform macromolecules that
was produced by a polyreaction (polymerization, polyaddition,
polycondensation), but which differ however with reference to the
degree of polymerization, molar mass and chain length. But on the
other hand, this term comprises also derivatives of such collective
of macromolecules from polyreactions, that is compounds which were
obtained by conversions such as additions or substitutions of
functional groups with specified macromolecules, and which can be
chemically uniform or chemically non-uniform. This term moreover
comprises also so-called prepolymers, i.e. reactive oligomeric
prepolymers, whose functional groups participate in building-up
macromolecules.
[0045] The term "polyurethane polymer "includes all polymers which
are produced according to the so-called diisocyanate polyaddition
method. This even includes such polymers which are almost or
completely free of urethane groups. Examples for polyurethane
polymers are polyether polyurethanes, polyester polyurethanes,
polyether polyureas, polyureas, polyester polyureas,
polyisocyanurates and polycarbodiimides.
[0046] The polyurethane PUR is preferably a polyester polyurethane
or a poly-(meth)-acrylate PAC.
[0047] Polyurethanes PUR, which include at least one nucleophilic
group, can particularly be produced from at least one
polyisocyanate and at least one polyol as well as at least one
monomer M1, which comprises at least one isocyanate group or a
group which reacts with isocyanate groups and which moreover
comprises at least one nucleophilic functional group.
[0048] Suitable polyisocyanates that can be used are normal
commercial aliphatic, cycloaliphatic or aromatic polyisocyanates,
in particular diisocyanates.
[0049] Suitable polyols are particularly polyester or polyether
polyols, preferably polyester or polyether diols. Further suitable
polyols are low-molecular divalent or multivalent alcohols, such as
1,2-ethane diol, 1,3- and 1,4-butane diol, 1,2- and 1,3- propane
diol, neopentyl glycol, diethylene glycol, triethylene glycol, the
isomeric dipropylene glycols and tripropylene glycols, the isomeric
pentane diols, hexane diols, heptane diols, octane diols, nonane
dials, decane diols, undecane diols, 1,3- and 1,4-cyclohexane
dimethanol, hydrated bisphenol A, dimeric fatty alcohols,
1,1,1-trimethylolethane, 1,1,1-trimethylol propane, glycerin,
pentaerythrol, sugar alcohols like xylitol, sorbitol or mannitol,
sugar like sucrose, other higher-valent alcohols, as well as
mixtures of the above.
[0050] Suitable monomers M1 have preferably at least one carboxyl
group and/or one sulfonate group. The monomer M1 will preferably be
an amino carboxylic acid, in particular a dihydroxy alkyl
carboxylic acid, such as dimethylol proprionic acid or a similar
structured diol carboxylic acid, or a sulfonic acid comprising NCO
controlled reactive groups, such as a dihydroxy sulfonic acid, for
example. Preferred is the monomer M1, which comprises a sulfonate
group, the sodium salt of the N-(2-aminoethyl)-2-aminoethane
sulfonic acid.
[0051] It has been shown that particularly suitable polyurethanes
are those described as "polymer (PII)" in DE 100 00 656 A1 or WO
01/34559 A1, or as "polyurethane" in DE 195 21 500 A1, for
example.
[0052] Poly (meth) acrylates PAC, which comprise at least one
nucleophilic group, can in particular be manufactured from at least
one (meth) acrylate monomer and at least one monomer M2, which can
be polymerized with the (meth) acrylate monomer and moreover
comprises at least one nucleophilic functional group. For example,
such poly (meth) acrylates are copolymers from at least one (meth)
acrylate monomer and at least one unsaturated carboxylic acid, in
particular (meth) acrylic acid, maleic acid, fumaric acid, crotonic
acid or the like, a (meth) acrylamide or a (meth) acrylic acid
ester, comprising a hydroxyl group, in particular hydroxy alkyl
(meth) acrylate such as hydroxy butyl acrylate (HBA), hydroxybutyl
methacrylate (HBMA), hydroxypropyl acrylate (HPA), hydroxypropyl
methacrylate (HPMA), hydroxy ethylacrylate (HEA) or hydroxy ethyl
methacrylate (HEMA), or a partial ester of a polyol, preferably
glycerin or trimethylolpropane, with (meth) acrylic acid.
[0053] This will preferably be polyurethane PUR with a molecular
weight of 10,000-500,000 g/mol.
[0054] The polyurethane layer 5 preferably has a layer thickness in
the micrometer range, typically between 10 in 0.1 .mu.m, preferably
between 5 and 0.2 .mu.m, particularly preferably between 4 and 0.5
.mu.m.
[0055] FIG. 2 illustrates a cross-section through a potential
membrane according to the invention, which has a barrier layer S2
32.
[0056] In the case of a barrier layer S2 32, this will be a barrier
layer consisting of a composition comprising 5-50% by weight,
preferably 5-20% by weight, polyurethane PUR and 50-95% by weight,
preferably 80-95% by weight, copolymer PA.
[0057] The polyurethane PUR and the copolymer PA are polyurethane
PUR and copolymer PA, as they were described previously. The
polyurethane PUR and copolymer PA are moreover preferably those
that were previously mentioned as preferred polyurethane PUR and
copolymer PA.
[0058] The barrier layer S2 32 comprises preferably a layer
thickness in the micrometer range, typically between 100 and 1
.mu.m, preferably between 10 and 2 .mu.m.
[0059] The barrier layer S2 32 consists preferably more than 90% by
weight, particularly preferably more than 98% by weight of the sum
of copolymer PA together with polyurethane PUR, relative to the
total weight of the barrier layer S2.
[0060] It is furthermore advantageous, if membrane 1 is a flexible
membrane, in particular a flexible sheet. This can be easily rolled
up and can therefore be stored or transported easily. It is
therefore uncomplicated to bring the membrane to the construction
site, where it can be unrolled and be cut to the required
dimensions.
[0061] A further aspect of the invention is that it also comprises
a method for producing a membrane 1 comprising a sealing layer 2,
wherein the sealing layer consists more than 50% by weight of PVC,
relative to the total weight of the sealing layer. The membrane
further includes a barrier layer S1 31, wherein the barrier layer
is a polyamide layer 4 consisting more than 50% by weight of
copolymer PA, relative to the total weight of the polyamide layer
4, which is connected by a polyurethane layer 5 to the sealing
layer 2. The polyurethane layer 5 consists more than 10% by weight
of polyurethane PUR, relative to the total weight of the
polyurethane layer 5. The method includes the following steps;
[0062] (i) applying a polyurethane dispersion composition PD onto a
sealing layer 2; [0063] (ii) flashing off the polyurethane
dispersion composition PD while forming a polyurethane layer 5;
[0064] (iii) forming a polyamide layer 4 on the polyurethane layer
5.
[0065] The steps are preferably performed in the chronological
sequence of Step (i), followed by Step (ii), followed by Step
(iii).
[0066] The polyurethane PUR, the copolymer PA, the sealing layer 2,
the barrier layer S1 31, the polyamide layer 4 and the polyurethane
layer 5 were already described previously. The layers which are
suitable and preferred are polyurethane PUR, copolymer PA, sealing
layer 2, barrier layer S1 31, polyamide layer 4 and polyurethane
layer 5, are those which were previously mentioned as being
suitable and preferred polyurethane PUR, copolymer PA, sealing
layer 2, barrier layer S1 31, polyamide layer 4 and polyurethane
layer 5.
[0067] "Flashing off" is to be understood in the entire document as
drying a liquid composition following its application, wherein the
solvent, respectively the liquid phase, is evaporated either
entirely or at least to the extent possible. The flashing off can
be performed by evaporation to air with or without flash off means.
A blower, in particular an air blower, can serve as flash off
means. Preferably, a flash off means will be used. The flash off
can be done at room temperature or at an elevated temperature.
Flashing off the polyurethane dispersion composition PD in Step
(ii) is preferably performed for 1-5 minutes at 100-170.degree.
C.
[0068] The polyurethane dispersion composition PD is typically a
dispersion of polyurethane PUR in a liquid phase, wherein the
polyurethane PUR is present as a solid. The liquid phase is
preferably water.
[0069] The polyurethane dispersion composition PD in Step (ii)
preferably comprises a disperse phase consisting of polyurethane
PUR as well as a liquid phase, in particular water. It is
furthermore advantageous, if the polyurethane PUR of the disperse
phase is a non-reactive polyurethane. The percentage of the
disperse phase is typically 0.1-90% by weight, relative to the
total weight of the polyurethane dispersion composition PD. The
percentage of the disperse phase is preferably 30-60% by weight,
relative to the total weight of the polyurethane dispersion
composition PD.
[0070] The polyurethane dispersion composition PD is preferably an
aqueous polyurethane dispersion, wherein the polyurethane PUR is
present as a solid and the percentage of the polyurethane PUR is
preferably 15 to 55% by weight, in particular 25 to 50% by weight,
particularly preferably 35 to 45% by weight, relative to the total
weight of the polyurethane dispersion composition PD.
[0071] The polyamide layer 4 in Step (iii) is preferably formed by
applying a composition Z2 in the liquid state, consisting of
copolymer PA and a solvent, onto the polyurethane layer 5.
[0072] The solvent is typically selected from the group consisting
of water, ethanol, methanol, ethanol, 1-propanol, 1-butanol,
2-propanol, 2-butanol, 1, 2-ethane diol, 1, 2-propanediol, 1,
3-propanediol, 1, 2-butanediol, 1, 3- butanediol, 1, 4-butanediol,
2, 3-butanediol, 1, 5-pentanediol and prop-2-en-1-ol. The solvent
will preferably be a 1-propanol/water mixture, preferably the ratio
of the weight of 1-propanol:water is from 99:1 to 1:99,
particularly preferably from 5:1 to 3:1. It is moreover
advantageous, following the application of the composition Z2 in
the liquid state, if the applied composition Z2 is heated for 1-5
minutes at 100-170.degree. C. This is an advantage to the effect
that this is beneficial for forming a homogenous, continuous
barrier layer S1.
[0073] It is furthermore advantageous for inhibiting plasticizer
migration, if the composition Z2 has a percentage of 1-25% by
weight copolymer PA, in particular preferably 15-20% by weight,
relative to the total weight of the composition Z2.
[0074] The ratio of the weight of copolymer PA to solvent in the
composition Z2 is preferably from 1:100 to 1:4, in particular from
1:10 to 1:5.
[0075] In a further aspect, the invention also comprises a further
method for producing a membrane 1 comprising a sealing layer 2,
wherein the sealing layer consists more than 50% by weight of PVC,
relative to the total weight of the sealing layer.
[0076] The membrane furthermore comprises a barrier layer S2 32,
wherein the barrier layer S2 32 consists of a composition
comprising 5-50% by weight, preferably 5-20% by weight,
polyurethane PUR and 50-95% by weight, preferably 80-95% by weight
copolymer PA, including the steps; [0077] (i') applying a
composition Z1 comprising polyurethane PUR, copolymer PA and
solvent onto a sealing layer 2; [0078] (ii') flashing off the
composition Z1 while forming a barrier layer S2 32.
[0079] The steps are performed preferably in the chronological
sequence of Step (i'), followed by Step (ii').
[0080] The polyurethane PUR, the copolymer PA, the sealing layer 2,
and the barrier layer S2 32 were already described previously. The
layers which are suitable and preferred as polyurethane PUR,
copolymer PA, sealing layer 2 and barrier layer S1 32 are those
which are previously mentioned as being suitable and preferred
polyurethane PUR, copolymer PA, sealing layer 2 and barrier layer
S2 32.
[0081] It is furthermore advantageous, if the application of the Z1
composition in Step (i') is performed by applying the Z1
composition in the liquid state. The viscosity of the Z1
composition at 25.degree. C. is preferably 500-30,000 mPas
(measured according to DIN EN ISO 3219/A.3).
[0082] It is furthermore advantageous, if the Z1 composition in
Step (ii') is flashed off at 100-170.degree. C. for 1-5
minutes.
[0083] The solvent of the Z1 composition is typically selected from
the group consisting of water, ethanol, methanol, ethanol,
1-propanol, 1-butanol, 2-propanol, 2-butanol, 1, 2-ethane diol, 1,
2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3- butanediol,
1, 4-butanediol, 2, 3-butanediol, 1, 5-pentanediol and
prop-2-en-1-ol.
[0084] The solvent will preferably be a 1-propanol/water mixture,
preferably the ratio of the weight of 1-propanol:water is from 99:1
to 1:99, particularly preferably from 5:1 to 3:1.
[0085] It is further advantageous, if the percentage of the sum of
polyurethane PUR together with copolymer PA totals 1-30% by weight,
in particular 15-25% by weight, relative to the total weight of the
composition Z1.
[0086] The membrane 1 produced according to one of the previously
described methods can now be cut to size, cut off, rolled up, or be
directly processed further, as required. The rolls with the
membrane can now be stored or transported to other locations, as
needed.
[0087] A further aspect of the present invention relates to the use
of the sealing membrane 1 for sealing substrates, which was
described in detail previously. The membrane 1 is typically used as
prefabricated sheet. In this case, the membrane is preferably
produced in a foil facility and is used on the construction site
preferably in the form of a membrane from a roll. But the membrane
can also be used in the form of strips with a typical width of 1-20
cm, however, to seal connection joints between two roofing
membranes. The membrane can furthermore also be available and used
in the form of flat objects for the repair of defective positions
in seals, for example roofing membranes. A preferred use of the
membrane 1 is therefore the use for sealing buildings against
moisture in structural and civil engineering, in particular roofs
and floors.
[0088] A further aspect of the present invention relates to a
molding, the surface of which has a membrane 1, wherein the
membrane is preferably arranged on the molding with its side facing
away from the sealing layer 2. The molding is typically an entity
from the structural and civil engineering sector. The term
"molding" describes a three-dimensional object.
Examples
Producing the Za-Ze Compositions
[0089] Ultramid.RTM. 1C, which is commercially available from the
BASF SE Company in Germany, was used as the copolymer PA component
of the Za-Ze compositions. Water, [n]-propanol, ethanol,
isopropanol, respectively tetrahydrofuran (TI-IF) was used as the
solvent component. The two components were mixed together to form
the Za-Ze compositions in the quantities and in the weight
percentages listed in Table 1.
TABLE-US-00001 TABLE 1 Za-Ze Compositions. Za Zb Zc Zd Ze Ultramid
1C 10 16 20 20 20.2 Water 18 16.8 16 16 16 n-propanol 72 67.2 64 --
49 Ethanol -- -- -- 64 -- Isopropanol -- -- -- -- 12.3 THF -- -- --
-- 2.5 Sum of 100 100 100 100 100 weight percentages
Producing the Polyurethane Dispersion Compositions (PD)
[0090] The compositions listed in Table 2 were mixed together at
the percentages listed in Table 2 for producing the polyurethane
dispersion compositions PDI-PD3. The following materials were used
as polyurethane PUR: Incorez.RTM. W830/092 and Incorez.RTM. W2400
(both INCOREZ LTD, Great Britain) as well as Bayhydrol.RTM. UH 2606
(Bayer Material Science, Germany). The film forming additive is a
tripropylene glycol n-butyl ether, the liquid phase is water, a
siloxane compound was used as wetting agent, and hydrophobic
pyrogenic silicic acid was used as thixotropic agent.
TABLE-US-00002 TABLE 2 Polyurethane dispersion compositions
PD1-PD3, PD1 PD2 PD3 PUR Incorez W830/092 94.3*** -- -- Incorez
W2400 -- 71.4** -- Bayhydroll XP 2606 -- -- 94.3* Film forming
additive 1 10 0.5 Water 2.7 16.6 3.7 Wetting agent -- 2 1.5
Thixotroping agent 2 -- -- Sum of the weight 100 100 100
percentages *the 94.3 parts by weight relate to a 35% dispersion of
polyurethane PUR in water, **the 71.4 parts by weight relate to a
40% dispersion of polyurethane PUR in water, ***the 94.3 parts by
weight relate to a 35% dispersion of polyurethane PUR in water.
Fabrication of the Sealing Layer
[0091] A composition consisting of:
[0092] PVC (55% by weight relative to the total weight of the
composition),
[0093] plasticizer, di-iso-nonyl phthalate from Sigma-Aldrich,
Switzerland (39% by weight, relative to the total weight of the
composition),
[0094] stabilizer, tin stabilizer dibutyl tin diacetate from
Sigma-Aldrich, Switzerland (1% by weight, relative to the total
weight of the composition),
[0095] CaCO.sub.3 from Sigma-Aldrich, Switzerland (5% by weight,
relative to the total weight of the composition),
[0096] was formed into a 1.5 mm thick film by extrusion with a
sheet-die nozzle.
Description of the Measuring Methods
Test for Plasticizer Migration
[0097] Test specimens with dimensions of 120 mm.times.120 mm were
produced from the membranes and weighed (weight dO). These test
specimens were thereafter placed onto a body with the dimensions of
120 mm.times.120 mm and a thickness of approximately 40-50 mm of
EPS (expanded polystyrene rigid foam). Furthermore, a glass plate
with the dimensions of 100 mm.times.100 mm and a 2 kg weight on top
was arranged on the test specimen. This configuration was stored
for 28 days at 70.degree. C., 50.+-.5% relative air humidity). The
test specimens were subsequently weighed again (weight d28) and the
difference in weight from the weight dO was determined.
Test for Aging
[0098] Test specimens with the dimensions of 20 cm.times.10 cm were
produced from the membranes. The test specimens were stored for 28
days in an air-circulating oven at a temperature of 70.+-.2
.degree. C. Thereafter, the test specimens were bent 20 times in
the center and were folded together, and subsequently the
detachment of the barrier layer from the membrane was evaluated
visually.
Fabrication and Aging Tests with Comparative Membrane
[0099] To form a polyamide layer, using a knife coater
(K-CONTROL-COATER-System K 202, ERICHSEN, Germany), the respective
Za-Ze composition with a thickness of 24 .mu.m were applied onto a
sealing layer measuring 20 cm.times.30 cm.times.1.5 mm at a
temperature of 30.degree. C., the fabrication of which was
described previously, and were heated in an oven for two minutes at
a temperature of 160.degree. C. The comparative membranes
manufactured in this manner were subjected to the aging test
described previously. All comparative membranes exhibited a heavy
delamination of the polyamide layer. An example of such
delamination of the polyamide layer from the sealing layer is
illustrated in FIG. 3.
Fabrication and Aging Tests with a Membrane According to the
Invention Comprising a Sealing Layer S1
[0100] Using a knife coater (K-CONTROL-COATER-System K 202,
ERICHSEN, Germany), the respective PD1-PD3 polyurethane dispersions
were applied with a 4 .mu.m layer thickness onto a sealing layer of
20 cm.times.30 cm.times.1.5 mm, the fabrication of which was
described previously. The films were heated in an oven for 2
minutes at a temperature of 160.degree. C. Immediately thereafter,
the respective Za-Ze composition was applied onto the sealing layer
by means of the previously mentioned knife coater in order to form
a polyamide layer with a layer thickness of 24 .mu.m at a
temperature of 30.degree. C., and heated in an oven for 2 minutes
at a temperature of 160.degree. C.
[0101] Subsequently, the membranes according to the invention
manufactured in this manner (all combinations of the individual
PD1-PD3 polyurethane dispersions with the individual Za-Ze
composition) were subjected to the previously described aging test.
None of the membranes according to the invention showed a
delamination of the polyamide layer, as can be seen in FIG. 4.
Fabrication and Aging Tests with a Membrane According to the
Invention Comprising a Sealing Layer S2
[0102] 80 parts by weight of the previously described Zc
composition were mixed with 20 parts by weight of the previously
described PD2 polyurethane dispersion and were applied by means of
a knife coater (K-CONTROL-COATER-System K 202, ERICHSEN, Germany)
with a coating thickness of 24 .mu.m (coating thickness immediately
after the application) onto a sealing layer measuring 20
cm.times.30 cm.times.1.5 mm, the fabrication of which was described
previously. The films were heated in an oven for 2 minutes at a
temperature of 160.degree. C. (the layer thickness after heating
was 4-6 .mu.m).
[0103] Subsequently, the membrane manufactured in this way was
subjected to the aging test previously described. The membrane
exhibited no delamination from the sealing layer S2.
Plasticizer Migration Test
[0104] An untreated sealing layer, a first comparative membrane
with a sealing layer S1 with a polyurethane layer of the PD3
polyurethane dispersion, a second comparative membrane the
polyamide layer of the Zc composition, a membrane according to the
invention with a barrier layer S1 with a polyurethane layer of the
PD3 polyurethane dispersion and with a polyamide layer of the Zc
composition, as well as the previously described membrane according
to the invention with a sealing layer S2, were subjected to the
previously described plasticizer migration test.
[0105] The untreated sealing layer exhibited a weight loss of 3.48%
by weight, the first comparative membrane exhibited a weight loss
of 3.19% by weight, the second comparative membrane exhibited a
weight loss of 0.15% by weight, the membrane according to the
invention with a sealing layer S1 exhibited a weight loss of 0.14%
by weight and the membrane according to the invention with a
sealing layer S2 exhibited a weight loss of 0.84% by weight.
LIST OF REFERENCE SYMBOLS
[0106] 1 Membrane [0107] 2 Sealing layer [0108] 3 Barrier layer
[0109] 31 Barrier layer S1 [0110] 32 Barrier layer S2 [0111] 4
Polyamide layer [0112] 5 Polyurethane layer
* * * * *