U.S. patent application number 13/714785 was filed with the patent office on 2013-06-20 for binder-consolidated textile fabric, method for producing it, and use thereof.
This patent application is currently assigned to JOHNS MANVILLE. The applicant listed for this patent is JOHNS MANVILLE. Invention is credited to Agnes Frick, Werner Groh, Hermann Weizenegger.
Application Number | 20130157030 13/714785 |
Document ID | / |
Family ID | 47471457 |
Filed Date | 2013-06-20 |
United States Patent
Application |
20130157030 |
Kind Code |
A1 |
Frick; Agnes ; et
al. |
June 20, 2013 |
BINDER-CONSOLIDATED TEXTILE FABRIC, METHOD FOR PRODUCING IT, AND
USE THEREOF
Abstract
The invention relates to a novel binder system and its use for
bonding textile fabrics as well as products containing such bonded
textile fabrics. The materials of the invention are suitable for
the manufacture of lining materials which can be used in the
manufacture of sarking membranes, roofing sheets and water-proof
sheetings, in particular of coated sarking membranes, roofing
sheets and water-proof sheetings, or in the manufacture of carpets
and PVC floorings as a textile backing or as a textile
reinforcement.
Inventors: |
Frick; Agnes; (Bobingen,
DE) ; Weizenegger; Hermann; (Schwabmuenchen, DE)
; Groh; Werner; (Schwabmuenchen, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
JOHNS MANVILLE; |
Denver |
CO |
US |
|
|
Assignee: |
JOHNS MANVILLE
Denver
CO
|
Family ID: |
47471457 |
Appl. No.: |
13/714785 |
Filed: |
December 14, 2012 |
Current U.S.
Class: |
428/219 ;
428/221; 428/340; 442/152; 442/164; 442/174; 442/180; 442/59;
524/53 |
Current CPC
Class: |
D04H 1/64 20130101; D06M
17/00 20130101; Y10T 442/2861 20150401; Y10T 428/27 20150115; D21H
17/67 20130101; D06N 5/00 20130101; D04H 3/12 20130101; Y10T
428/249921 20150401; D04H 13/00 20130101; C09D 131/04 20130101;
D04H 3/004 20130101; Y10T 442/2762 20150401; C08L 31/04 20130101;
D04H 1/587 20130101; D06N 3/0002 20130101; D21H 17/36 20130101;
Y10T 442/2992 20150401; D04H 3/011 20130101; D06N 7/0081 20130101;
D21H 17/37 20130101; Y10T 442/20 20150401; D06N 5/003 20130101;
D21H 21/18 20130101; C08K 3/00 20130101; C08L 3/02 20130101; D04H
3/005 20130101; D06M 15/00 20130101; D04H 1/4209 20130101; C08K
3/00 20130101; D04H 3/16 20130101; Y10T 442/2943 20150401; C08L
3/02 20130101; C08L 31/04 20130101; D06N 3/00 20130101; D06N 7/006
20130101; E04B 1/665 20130101; D04H 1/4218 20130101; C08L 3/02
20130101; C08K 3/00 20130101; C08L 3/02 20130101; C08L 31/04
20130101 |
Class at
Publication: |
428/219 ; 524/53;
442/59; 442/152; 442/164; 442/174; 442/180; 428/221; 428/340 |
International
Class: |
D06M 15/00 20060101
D06M015/00; D06N 3/00 20060101 D06N003/00; D04H 13/00 20060101
D04H013/00; D06N 5/00 20060101 D06N005/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 20, 2011 |
DE |
10 2011 121 589.5 |
Claims
1. A binder system, comprising: a) 10 to 90% by weight, preferably
30 to 70% by weight of at least one polyvinyl acetate and b) 90 to
10% by weight, preferably 70 to 30% by weight of one or more
starches and c) 0 to 60% by weight of at least one additive
selected from the group of amphoteric hydroxides, salts of the
first and second main groups of the periodic table, mineral
additives which are of synthetic or natural origin, kaolin, carbon
blacks or mixtures thereof and d) 0 to 10% by weight of additives,
the information on the proportions by weight referring to the dry
mass of the binder system, i.e. without water and the sum of the
constituents a) to d) giving 100% by weight.
2. The binder system according to claim 1, characterized in that it
does not contain any polymers based on polyacrylates.
3. The binder system according to claim 1 or 2, characterized in
that the polyvinyl acetate is homopolymers of vinyl acetate and co-
or terpolymerizates of vinyl acetate.
4. The binder system according to claim 3, characterized in that
the homopolymers of the polyvinyl acetate contain up to 5 mole %
further constituents which derive from other monomers than vinyl
acetate.
5. The binder system according to claims 1 to 4, characterized in
that it is a polyvinly acetate having a glass temperature of 18 to
45.degree. C.
6. The binder system according to claims 1 to 5, characterized in
that it is a polyvinyl acetate having a degree of polymerization of
between 100 and 5000.
7. The binder system according to claims 1 to 6, characterized in
that it is a polyvinyl acetate whose molecular weight (weight
average) is between 10000 and 1500000 g/mol.
8. A binder system, comprising: a) 10 to 90% by weight, preferably
30 to 70% by weight of polymerizates based on carboxylic acid
derivatives and b) 90 to 10% by weight, preferably 70 to 30% by
weight of one or more starches and c) 0 to 60% by weight of at
least one additive selected from the group of amphoteric
hydroxides, salts of the first and second main groups of the
periodic table, mineral additives which are of synthetic or natural
origin, kaolin, carbon blacks or mixtures thereof and d) 0 to 10%
by weight of additives, the information on the proportions by
weight referring to the dry mass of the binder system, i.e. without
water and the sum of the constituents a) to d) giving 100% by
weight, and the polymerizates based on carboxylic acid derivatives
having been obtained by means of polymerization of monomeric
carboxylic acid derivatives which have at least one terminal double
bond.
9. The binder system according to claim 8, characterized in that
the polymerizates based on carboxylic acid derivatives and
polycarboxylic acids still have unsaturated constituents and/or are
used as a mixture with unsaturated monomeric carboxylic acid
derivatives.
10. The binder system according to claim 8 or 9, characterized in
that the monomeric carboxylic acid derivatives, which have at least
one terminal double bond, are unsaturated carboxylic acid esters,
preferably unsaturated acrylates and/or methacrylates which have
been esterified by converting the basic acids and/or mono- or
polyvalent, branched or linear C.sub.1 to C.sub.4 alcohol.
11. The binder system according to claim 10, characterized in that
the C.sub.1 to C.sub.4 alcohol is methanol, ethanol, propanol,
iso-propanol, butanol, 1-butanol, 2-butanol or tert-butanol.
12. The binder system according to claims 8 to 10, characterized in
that the unsaturated carboxylic acid is acrylic acid and/or
methacrylic acid.
13. The binder system according to claims 1 to 12, characterized in
that the starch is a natural or modified starch or starch
derivates.
14. The binder system according to claims 1 to 13, characterized in
that the starch is a starch from vegetable raw material, in
particular from tubers, seeds, fruit, and/or from pith.
15. The binder system according to claims 1 to 14, characterized in
that the starch is of native vegetable origin or is chemically
modified, enzymatically extracted, of recombinant origin or is
manufactured by biotransformation (biocatalysis).
16. The binder system according to claims 1 to 15, characterized in
that, in addition to the starch, this has at least two constituents
selected from the group of amphoteric hydroxides, salts of the
first and second main groups of the periodic table, mineral
additives which are of synthetic or natural origin, kaolin, carbon
blacks, and the ratio is preferably 1:10 to 10:1 (proportions by
weight).
17. The binder system according to claims 1 to 16, characterized in
that it is a dispersion and that the polymer solids content of the
dispersion, in particular the polymer solids content of the
dispersions, is between 10 and 40% by weight, in particular between
10 and 30% by weight, particularly preferably 15 to 25% by
weight.
18. The binder system according to claims 1 to 17, characterized in
that it is a dispersion and the viscosity of the dispersion is
preferably 1 to 3000 mPa*s, in particular 2 to 2500 mPa*s,
particularly preferably 5 to 2000 mPa*s.
19. Use of the binder system according to one or more of claims 1
to 18 for the consolidation of textile fabrics.
20. A textile fabric which has been consolidated by means of a
binder system according to one or more of claims 1 to 7 and 13 to
18 and comprises a) 10 to 90% by weight, preferably 30 to 70% by
weight of at least one polyvinyl acetate and b) 90 to 10% by
weight, preferably 70 to 30% by weight of one or more starches and
c) 0 to 60% by weight of at least one additive selected from the
group of amphoteric hydroxides, salts of the first and second main
groups of the periodic table, mineral additives which are of
synthetic or natural origin, kaolin, carbon blacks or mixtures
thereof and d) 0 to 10% by weight of additives, the information on
the proportions by weight referring to the dry mass of the binder
system, i.e. without water and the sum of the constituents a) to d)
giving 100% by weight.
21. A textile fabric which has been consolidated by means of a
binder system according to one or more of claims 8 to 18 and
comprises a) 10 to 90% by weight, preferably 30 to 70% by weight of
polymerizates based on carboxylic acid derivatives and b) 90 to 10%
by weight, preferably 70 to 30% by weight of one or more starches
and c) 0 to 60% by weight of at least one additive selected from
the group of amphoteric hydroxides, salts of the first and second
main groups of the periodic table, mineral additives which are of
synthetic or natural origin, kaolin, carbon blacks or mixtures
thereof and d) 0 to 10% by weight of additives, the information on
the proportions by weight referring to the dry mass of the binder
system, i.e. without water and the sum of the constituents a) to d)
giving 100% by weight, and the polymerizates based on carboxylic
acid derivatives having been obtained by means of polymerization of
monomeric carboxylic acid derivatives which have at least one
terminal double bond.
22. The textile fabric according to claim 20 or 21, characterized
in that the applied quantity of the binder system is between 5 and
35 wt % of dry binder in relation to the total weight of the raw
textile fabric.
23. The textile fabric according to claims 20 to 22, characterized
in that said textile fabric is any structure composed of fibers
which has been manufactured according to a surface forming
method.
24. The textile fabric according to claims 20 to 23, characterized
in that it is a textile fabric on the basis of natural fibers,
fibers composed of synthetic products and/or fibers composed of
synthesized polymers.
25. The textile fabric according to claims 20 to 24, characterized
in that said textile fabric is a woven fabric, a yarn sheet, a
knitted fabric and/or a non-woven fabric.
26. The textile fabric according to claims 20 to 25, characterized
in that the textile fabrics are non-wovens made of synthetic
polymer fibers, preferably a spinbonded non-woven.
27. A textile fabric according to claims 20 to 26, characterized in
that said textile fabric is a non-woven fabric made of fibers of
glass fibers and/or mineral fibers.
28. The textile fabric according to claim 27, characterized in that
the textile fabric has a weight per unit area of 20 and 500
g/m.sup.2.
29. Use of the textile fabric according to one or more of claims 20
to 28 as a lining material, optionally in combination with at least
one further textile fabric, for coated sarking membranes, roofing
sheets and water-proof sheetings as well as a textile backing or a
textile reinforcement in floorings, in particular in carpets and
PVC floorings.
30. A lining material for sarking membranes, roofing sheets and
water-proof sheetings, textile backings or textile reinforcements
in floorings, in particular in carpets and PVC floorings,
comprising at least one textile fabric according to one or more of
claims 20 to 28.
31. The lining material according to claim 30, characterized in
that it has at least one additional reinforcement.
32. A lining material according to claim 30 or 31, characterized in
that it has at least one further textile fabric besides the textile
fabric according to one or more of claims 20 to 28 which differ
from each other.
33. Use of the lining material according to one or more of claims
30 to 32 for the manufacture of lining materials for sarking
membranes, roofing sheets and water-proof sheetings, in particular
for the manufacture of coated sarking membranes, roofing sheets and
water-proof sheetings, for the manufacture of textile backings or
as a textile reinforcement in floorings, in particular in carpets
and PVC floorings.
34. A coated sarking membrane, roofing sheet and water-proof
sheeting, comprising at least one coating compound and at least one
textile fabric according to one or more of claims 20 to 28 or a
lining material according to one or more of claims 30 to 32.
35. A flooring, in particular a carpet or a PVC flooring,
comprising a textile backing or a textile reinforcement comprising
at least one textile fabric according to one or more of claims 20
to 28 or a lining material according to one or more of claims 30 to
32.
Description
BACKGROUND OF THE INVENTION
[0001] The invention relates to novel binder systems for
consolidating textile fabrics, textile fabrics consolidated
therewith, their manufacture as well as products containing the
binder system or a textile surface fitted therewith.
[0002] Textile fabrics, in particular those which are used as
inserts for the manufacture of coated materials, have to meet
various requirements. Examples of the use of such inserts are,
among others, textile backings for carpets, textile reinforcements
in PVC floorings or roofing sheets.
[0003] When used in the manufacture of roofing sheets, the used
inserts or lining materials must have a sufficient mechanical
stability, such as good perforation strength and good tensile
strength, which appear, for example, during further processing,
such as bituminization or laying. In addition, there is a need for
high resistance to thermal stress, for example during
bituminization, or to radiant heat and spreading fire.
[0004] When used in the manufacture of coated floorings, such as
PVC floorings, additional demands are made on such inserts. In this
field of application, said inserts not only have to meet the
mechanical/thermal requirements but they have to avoid the
formation of gaseous substances, since otherwise blistering can be
observed during manufacture, for example by the formation of water
vapor. Such blistering is very problematic and leads to yield loss
and/or poor quality.
[0005] In addition to the aforementioned technical requirements,
the environmental compatibility and/or new legal regulations
account for the need to replace existing, to partly already
well-functioning systems by new compliant systems. Examples thereof
are new industrial standards, such as the DIN EN 14041, or legal
changes, such as the REACH regulation.
[0006] The binder systems used so far for consolidating textile
fabrics are based on thermoplastic and/or thermosetting binder
systems. Examples thereof are aminoplasts and binders on the basis
of acrylates.
[0007] There is hence a great need to provide novel binder systems
for consolidating textile fabrics to be used as inserts which, on
the one hand, meet the technical requirements and the legal
regulations, and on the other hand, are available under economic
aspects.
[0008] Binder systems based on starch are known from EP-A-2199333,
EP-A-2192153 and EP-A-2231917. The systems are already very
well-suited for the consolidation of textile fabrics. Nonetheless,
there is a further requirement for binder systems which on the one
hand satisfy legal requirements and on the other hand are available
in terms of economics.
[0009] It was therefore the object of the present invention to
provide novel binder systems for consolidating textile fabrics
which, on the one hand, meet the technical requirements and the
legal regulations, and on the other hand, are available under
economic aspects. Another object is the processability of the
binder systems by means of the known and established procedures so
that investments can be kept at a low level. The binder systems
must optimize a multiplicity of parameters at the same time,
satisfactory strength, tear resistance, elongation and
thermostability being important, in order to be suitable as a
binder for the consolidation of industrial textile fabrics. The
parameter tear resistance in particular is important for many
industrial applications. Here, there is a particular requirement
for improvement which the invention fulfills.
DETAILED DESCRIPTION OF THE INVENTION
[0010] The subject matter of the present invention is thus a
textile fabric which is consolidated by means of a binder system
comprising: [0011] a) 10 to 90% by weight, preferably 30 to 70% by
weight of at least one polyvinyl acetate and [0012] b) 90 to 10% by
weight, preferably 70 to 30% by weight of one or more starches and
[0013] c) 0 to 60% by weight of at least one additive selected from
the group of amphoteric hydroxides, salts of the first and second
main groups of the periodic table, mineral additives which are of
synthetic or natural origin, kaolin, carbon blacks or mixtures
thereof and [0014] d) 0 to 10% by weight of additives,
[0015] the information on the proportions by weight referring to
the dry mass of the binder system, i.e. without water and the sum
of the constituents a) to d) giving 100% by weight.
[0016] In a preferred embodiment of the invention, the binder
system of polyvinyl acetate and starch used according to the
invention and also the consolidated textile fabric resulting
therefrom does not contain any polymers based on polyacrylates.
[0017] Another subject matter of the present invention is a textile
fabric which is consolidated by means of a binder system
comprising: [0018] a) 10 to 90% by weight, preferably 30 to 70% by
weight of polymerizates based on carboxylic acid derivatives and
[0019] b) 90 to 10% by weight, preferably 70 to 30% by weight of
one or more starches and [0020] c) 0 to 60% by weight of at least
one additive selected from the group of amphoteric hydroxides,
salts of the first and second main groups of the periodic table,
mineral additives which are of synthetic or natural origin, kaolin,
carbon blacks or mixtures thereof and [0021] d) 0 to 10% by weight
of additives,
[0022] the information on the proportions by weight referring to
the dry mass of the binder system, i.e. without water and the sum
of the constituents a) to d) giving 100% by weight, and the
polymerizates based on carboxylic acid derivatives having been
obtained by means of polymerization of monomeric carboxylic acid
derivatives which have at least one terminal double bond.
[0023] Another subject matter of the present invention is the
binder system used according to the invention, comprising: [0024]
a) 10 to 90% by weight, preferably 30 to 70% by weight of at least
one polyvinyl acetate and [0025] b) 90 to 10% by weight, preferably
70 to 30% by weight of one or more starches and [0026] c) 0 to 60%
by weight of at least one additive selected from the group of
amphoteric hydroxides, salts of the first and second main groups of
the periodic table, mineral additives which are of synthetic or
natural origin, kaolin, carbon blacks or mixtures thereof and
[0027] d) 0 to 10% by weight of additives,
[0028] the information on the proportions by weight referring to
the dry mass of the binder system, i.e. without water and the sum
of the constituents a) to d) giving 100% by weight.
[0029] As stated previously, the binder system of polyvinyl acetate
and starch used according to the invention and also the
consolidated textile fabric resulting therefrom does not contain
any polymers based on polyacrylates.
[0030] Another subject matter of the present invention is the
binder system used according to the invention, comprising: [0031]
a) 10 to 90% by weight, preferably 30 to 70% by weight of
polymerizates based on carboxylic acid derivatives and [0032] b) 90
to 10% by weight, preferably 70 to 30% by weight of one or more
starches and [0033] c) 0 to 60% by weight of at least one additive
selected from the group of amphoteric hydroxides, salts of the
first and second main groups of the periodic table, mineral
additives which are of synthetic or natural origin, kaolin, carbon
blacks or mixtures thereof and [0034] d) 0 to 10% by weight of
additives,
[0035] the information on the proportions by weight referring to
the dry mass of the binder system, i.e. without water and the sum
of the constituents a) to d) giving 100% by weight, and the
polymerizates based on carboxylic acid derivatives having been
obtained by means of polymerization of monomeric carboxylic acid
derivatives which have at least one terminal double bond.
[0036] The quantity of the binder system of the invention applied
to the textile fabric is preferably between 5 and 35% by weight dry
binder, in particular 10 and 30% by weight, most preferably 10 and
25% by weight dry binder after drying referring to the total weight
of the untreated textile fabric.
[0037] If the binder system used according to the invention shall
be utilized as an aqueous dispersion or solution, the solids
content is preferably between 10 and 40% by weight, in particular
between 10 and 30% by weight, most preferably 15 to 25% by weight
(determined according to DIN EN ISO 3251).
[0038] If the binder system used according to the invention shall
be utilized as an aqueous dispersion or solution, the viscosity is
preferably 1 to 3000 mPa*s, in particular 2 to 2500 mPa*s, most
preferably 5 to 2000 mPa*s (determined according to DIN EN ISO 2555
and 23.degree. C.).
[0039] If the binder system according to the invention shall be
used as an aqueous polymer dispersion, conventional and known
emulsifying agents or protective colloids can be added for
stabilization. These are known to the person skilled in the art
(cf. Houben-Weyl, Methoden der org. Chemie, vol. XIV/1, 1961,
Stuttgart). Examples of emulsifying agents are polyglycolethers,
fatty alcohol-polyglycolethers, phosphoric esters and their salts,
sulfonated paraffin hydrocarbons, higher alkyl sulfates (such as
lauryl sulfate), alkali metal salts of fatty acids, such as sodium
stearate or sodium oleate, sulfuric acid semi-ester of ethoxylated
fatty acid alcohols, salts of esters and semi-esters of alkyl
polyoxyethylene sulfosuccinates, salts of sulfonated alkyl
aromatics, such as sodium dodecyl benzolsulfonate, ethoxylated
C4-C12-alkylphenols and their sulfonation products such as ester of
the sulfosuccinic acid. Examples for protective colloids are
alkylhydroxyalkyl celluloses, partly or completely hydrolyzed
polyvinyl alcohols and copolymers thereof, acrylic acid,
homopolymers and copolymers and partly neutralized salts thereof,
acrylamide copolymers, polyacrylate copolymers and salts thereof,
carboxyalkyl cellulose, such as carboxymethyl cellulose and its
salts.
[0040] If the binder system according to the invention shall be
utilized as an aqueous polymer dispersion, the pH-value (measured
as a 10% by weight solution in water) is between 2 and 10,
preferably between 4 and 8 (determined according to DIN EN ISO
976).
[0041] The textile fabric consolidated by means of the binder
system according to the invention has satisfactory strength and
thermostability. Furthermore, the textile fabrics consolidated by
means of the binder system according to the invention have an
elongation which is at least as good or even improved.
Surprisingly, the tear resistance is markedly improved and usually
increased by almost 10% by means of the binder system according to
the invention however.
[0042] Beyond that, the binder system of the invention is only
slightly hygroscopic and has a low water suction performance, so
that no restrictions on the use of the consolidated textile fabrics
as lining materials in the manufacture of PVC floorings, for
example by blistering, can be observed.
[0043] Likewise surprising is the aging behavior of the
consolidated textile fabric which is almost constant even though a
person skilled in the art would expect a worsening of the aging
behavior.
[0044] By means of the partial replacement with starch and
polyvinyl acetate or starch and special polymerizates based on
carboxylic acid derivatives, considerable cost saving effects are
realized, it being possible in addition to starch to also use
further additives, for example amphoteric hydroxides, salts of the
first and second main groups of the periodic table, mineral
additives which are of synthetic or natural origin, kaolin, carbon
blacks or mixtures of the same with starch. In addition, a binder
system almost completely free of formaldehyde is obtained without
being obliged to cut back on the product properties.
[0045] The binder system of the invention does not comprise
polymerizates produced by polymerization of conjugated aliphatic
dienes, in particular butadiene, isoprene, pentadiene-1,3, dimethyl
butadiene and/or cyclopentadiene.
[0046] The polymerizates based on carboxylic acid derivatives which
are used according to the invention are known per se (e.g., they
can be seen from the technical data sheets).
[0047] The polymerizate based on carboxylic acid derivatives used
according to the invention is materials which have been obtained by
polymerization of monomeric carboxylic acid derivatives which have
at least one terminal double bond.
[0048] The basic monomers are unsaturated carboxylic acid esters,
preferably unsaturated acrylates and/or methacrylates which have
been esterified by converting the basic acids and mono- or
polyvalent, branched or linear C.sub.1 to C.sub.4 alcohol.
Preferably, the preceding alcohols are methanol, ethanol, propanol,
iso-propanol, butanol, 1-butanol, 2-butanol or tert-butanol.
Preferably, the preceding unsaturated carboxylic acids are acrylic
acid and/or methacrylic acid.
[0049] Free unsaturated carboxylic acids may also still be present
in the polymerizate based on carboxylic acid derivatives used
according to the invention, it being possible for the proportion
thereof to be up to 30% by weight (with respect to unsaturated
carboxylic acid esters present). In this case, up to 30% by weight
of an alcohol is added to the binder system according to the
invention as cross-linking agent. The degree of consolidation or
cross-linking can be set by means of the ratio of free unsaturated
carboxylic acid to alcohol.
[0050] In addition to the alcohols mentioned, polyols, polyamines,
polyalkanolamines or mixtures thereof are also possible as
cross-linking agents.
[0051] Among the polyols, glycols, glycol ethers, polyester
polyols, polyether polyols, polysaccharides, polyvinyl alcohols, or
their mixtures are preferred. Trimethylolpropane, pentaerythritol,
ethylene glycol, propylene glycol, triethylene glycol, glycerol and
sugar alcohols, such as sorbite and inositol, are particularly
preferred polyols. Besides the aforementioned polyols, polyvalent
alcohols can also be used as cross-linking agents. The term
polyvalent alcohols refers to alcohols having at least two hydroxyl
groups which can be branched or straight-chained. The
alcohols/polyols can also be used as a mixture, i.e., a mixture of
two different alcohols or polyols.
[0052] Among the polyamines, hexanediamine, ethylenediamine,
melamine, diethylenetriamine, triethylenetetramine, aminoanilin,
aminoamides, or their mixtures are preferred. Among the
polyalkanolamines, alkanolamines, in particular monoethanolamine,
diethanolamine, triethanolamine, or their mixtures are
preferred.
[0053] The polymerizates based on carboxylic acid derivatives,
particularly carboxylic acid esters, used according to the
invention, which have been obtained by polymerization of monomeric
carboxylic acid derivatives, particularly monomeric carboxylic acid
esters, which have at least one terminal double bond, have
preferably been polymerized by heating. The polarization can be
controlled by using suitable stabilizers, for example
hydroquinone.
[0054] The polyvinyl acetates used according to the invention are
known per se. Polyvinyl acetates are understood as being
homopolymers of the vinyl acetate and co- or terpolymerizates of
the vinyl acetate with acrylic acid, acrylates, crotonic acid,
vinyl laurate, vinyl chloride or also ethylene.
[0055] Homopolymers preferably used are those of the polyvinyl
acetate which contain up to 5 mole % of further constituents which
are derived from other monomers than vinyl acetate.
[0056] The glass temperature of the polyvinyl acetate used
according to the invention is preferably 18 to 45.degree. C. and
depends on the degree of polymerization.
[0057] The degree of polymerization of the polyvinyl acetate used
according to the invention is preferably 100 to 5000.
[0058] The molecular weight (weight-average) of the polyvinyl
acetate used according to the invention is preferably between
10,000 and 1,500,000 g/mol.
[0059] The polyvinyl acetates used according to the invention are
commercially available from Celanese, for example, under the name
Mowilith.RTM. DN 60 or from Clariant under the name
Appretan.RTM.TT.FR as an aqueous dispersion or solution.
[0060] The starches used according to the invention are not subject
to restrictions; however, they must be compatible with the other
components.
[0061] Suitable starches according to the invention are
natural--so-called native--starches and modified starches, such as
cationic or anionic starches, or starch derivatives (so-called
chemically modified starches). Starches with a sufficient
solubility in cold and/or hot medium are generally
advantageous.
[0062] A group of starches that might be used within the scope of
the invention comprises starches extracted from vegetable raw
materials. These include among others starches from tubers, such as
potatoes, manioc, arrowroot, batata, from seeds, such as wheat,
maize, rye, rice, barley, millet, oat, sorghum, from fruits, such
as chestnuts, acorns, beans, peas, and other pulses, bananas, as
well as from plant marrow, e.g. of the sago palm.
[0063] The starches usable within the scope of the invention
essentially consist of amylose and amylopectin in changing
proportions.
[0064] The molecular weights of the starches useful according to
the invention can vary over a wide range. The starches consisting
essentially of a mixture of amylose and amylopectin preferably have
molecular weights M.sub.w in the range of between 5.times.10.sup.2
and 1.times.10.sup.8, particularly preferably between
5.times.10.sup.4 and 1.times.10.sup.7.
[0065] Besides starches of native vegetable origin, starches which
are chemically modified, have been obtained by fermentation, are of
recombinant origin or have been produced by biotransformation
(biocatalysis), are also equally preferred.
[0066] The term "biotransformation" is interchangeable with the
term "biocatalysis".
[0067] "Chemically modified starches" means starches whose
properties have been chemically modified compared to the natural
properties. This is essentially reached by polymer-analogous
reactions during which starch is treated with monofunctional,
bifunctional or polyfunctional reagents or oxidizing agents. In
this process, preferably the hydroxyl groups of the starch are
modified by etherification, esterification or selective oxidation;
or the modification is based on a radically initiated graft
copolymerization of copolymerizable unsaturated monomers on the
starch backbone.
[0068] Particular chemically modified starches include, among
others, starch esters, such as xanthogenates, acetates, phosphates,
sulfates, nitrates, starch ethers, such as nonionic, anionic or
cationic starch ethers, oxidized starches, such as dialdehyde
starch, carboxy starch, persulfate-degraded starches and similar
substances.
[0069] In the linguistic usage of the invention, "fermentative
starches" refers to starches which are extracted in fermentative
processes using natural organisms, such as fungi, algae or
bacteria, or which may be extracted with the activation and help of
fermentative processes. Examples for starches obtained from
fermentative processes include among others gum arabic and related
polysaccharides (gellan gum, ghatti gum, karaya gum, gum
tragacanth), xanthan, emulsan, rhamsan, wellan, schizophyllan,
polygalacturonates, laminarin, amylose, amylopectin and
pectines.
[0070] "Starches of recombinant origin" or "recombinant starches"
in the invention refers to starches which are extracted in
fermentative processes using organisms not occurring in nature, but
with the help of natural organisms that are modified by using
genetic methods, such as fungi, algae or bacteria, or which may be
extracted with the activation and help of fermentative processes.
Examples for starches obtained from fermentative, genetically
modified processes include, among others, amylose, amylopectin and
polyglucanes.
[0071] For the purposes of the present invention, "starches
prepared by biotransformation" means that starches, amylose,
amylopectin or polyglucans are produced by a catalytic reaction of
monomeric basic components, generally of oligomeric saccharides, in
particular of mono- or disaccharides, by using a biocatalyst (or:
enzyme) under specific conditions. Examples for starches obtained
from biocatalytic processes are, among others, polyglucan and
modified polyglucans, polyfructan and modified polyfructans.
[0072] Furthermore, the invention also comprises derivatives of the
starches particularly mentioned. In this context, the terms
"derivative of starches" or "starch derivatives" generally refer to
modified starches, i.e. such starches in which the natural
amylose/amylopectin ratio were modified to change their properties,
a pre-gelatinization was carried out, which were subject to a
hydrolytic degradation or were chemically derivatized.
[0073] Examples of particular derivatives of starches are, among
others, oxidized starches, e.g., dialdehyde starch or other
oxidation products having carboxyl functions, or native ionic
starches (e.g., with phosphate groups) or starches which have been
further modified ionically, wherein this term covers both anionic
and cationic modifications.
[0074] The destructurized starches, which may be used in the
context of the invention, comprise those which, for example, were
homogenized by means of glycerol such that no more crystalline
reflexes occur in the X-ray diffraction and starch grains or
double-refracting regions are no longer visible at a thousand-fold
magnification in the polarization microscope. In this context,
reference is made to DE-A1-3931363 of which the disclosure of
destructurized starches is also part of the this description.
[0075] The starches used according to the invention are
commercially available from Avebe, Cargill, National Starch,
Penford Products Co, Purac or Sudstarke, for example.
[0076] Especially advantageous are starches which have a sufficient
solubility in cold and/or hot medium. A sufficient solubility is
given if the viscosity of the binder system according to the
invention allows a corresponding workability.
[0077] The additives used according to the invention selected from
the group of amphoteric hydroxides, salts of the first and second
main groups of the periodic table, mineral additives which are of
synthetic or natural origin, kaolin, carbon blacks or mixtures are
basically not subject to any limitation but must be compatible with
the other components.
[0078] Those hydroxide compounds which are soluble both in an
acidic and in an alkaline medium are termed as amphoteric
hydroxides in the sense of the present invention.
[0079] Technically suitable examples for amphoteric hydroxides are
copper (II) hydroxide Cu(OH).sub.2, tin hydroxide Sn(OH).sub.2 or
Sn(OH).sub.4, antimony hydroxide Sb(OH).sub.3 or Sb(OH).sub.5,
aluminum hydroxide Al(OH).sub.3, chromium (III) hydroxide
Cr(OH).sub.3, lead hydroxide Pb(OH).sub.2 and zinc hydroxide:
Zn(OH).sub.2, wherein some of the compounds mentioned are
technically suitable, however, they cannot be used due to their
environmental relevance.
[0080] Amphoteric hydroxides of aluminum are particularly
preferably used. Precipitated amphoteric aluminum hydroxide
Al(OH).sub.3 is very particularly preferably used. It should be
noted that the material does not induce dehydration up to a
temperature of 200.degree. C. and is not hygroscopic.
[0081] The aluminum hydroxides used according to the invention are
commercially available from Nabaltec, for example, under the name
Apyral.
[0082] The salts of the first and second main groups of the
periodic table are preferably hydroxides, sulfates, hydrogen
carbonates and carbonates which must be compatible with the other
components. Examples of these are magnesium hydroxide, calcium
carbonate, barium sulfate.
[0083] Mineral additives, which are of synthetic or natural origin,
in the sense of the present invention are preferably marble powder,
kaolinite (china clay) and/or kaolinite-containing clays such as
kaolin (porcelain clay).
[0084] The kaolins used according to the invention are not subject
to restrictions; however, they must be compatible with the other
components.
[0085] For the purposes of the present invention, kaolins are china
clays and/or porcelain clays. These essentially comprise the
mineral kaolinite, which can be described by means of the chemical
formula Al.sub.2[(OH).sub.4/Si.sub.2O.sub.5] or
Al.sub.2O.sub.3*2SiO.sub.2*2H.sub.2O. The kaolinites usually have a
composition with 39.7% Al.sub.2O.sub.3, 46.4% SiO.sub.2 and 13.9%
H.sub.2O.
[0086] Kaolinite and the chemically identically composed clay
minerals dickite and nacrite are so-called double layer silicates
which belong to the phyllosilicates. These have to be equated with
the kaolins of the invention and shall be encompassed by the
invention.
[0087] The kaolins used according to the invention are commercially
available from Huber, for example, under the name Huber 90.
[0088] The kaolins used have to be stable up to a temperature of
200.degree. C., i.e., they must not dehydrate or be
hydroscopic.
[0089] The carbon blacks are preferably commercially available
products.
[0090] In a particular embodiment of the present invention, in
addition to the starch, the binder system has at least two
constituents selected from the group of amphoteric hydroxides,
salts of the first and second main groups of the periodic table,
mineral additives which are of synthetic or natural origin, kaolin,
carbon blacks or mixtures thereof, ratios of 1:10 to 10:1
(proportions by weight) proving particularly preferred.
[0091] The binder system used according to the invention may also
contain up to 10% by weight of additives. These are commercially
available additives such as preservatives, stabilizers,
antioxidants, anti-foaming agents, hydrophobizing agents, UV
stabilizers, fillers and/or pigments. They are partly contained in
the commercial products and serve to stabilize storage and
transport or may be added later in order to meet the customer's
specifications.
[0092] Within the scope of this description, the term "textile
fabric" is to be understood in its widest meaning. It may be used
for all structures composed of fibers which have been manufactured
according to a surface-forming method. The fiber-forming materials
are natural fibers, mineral fibers, glass fibers, fibers composed
of synthetic products and/or fibers composed of synthesized
polymers. For the purposes of the present invention, textile
fabrics are in particular understood as being woven fabrics, yarn
sheets, knitted fabrics or non-woven fabrics, in particular
non-woven fabrics.
[0093] Textile fabrics on the basis of mineral fibers and/or glass
fibers are in particular non-woven fabrics on the basis of mineral
fibers and/or glass fibers. The aforementioned non-woven fabrics on
the basis of mineral fibers and/or glass fibers can also be
combined with other textile fabrics, in particular non-woven
fabrics.
[0094] The employed non-woven fabrics composed of glass fibers or
mineral fibers can be manufactured by means of any known method.
Non-woven glass fiber fabrics which have been manufactured by means
of the wet laid process, the dry laid process or the air laid
process are particularly suitable. In the course of the
manufacturing process, in particular the wet laid process, these
non-woven fabrics may contain small proportions of chemical
auxiliary substances as a result of the process, for example
thickening agents, anti-foaming agents, etc. These substances
originate from the circulation water in the manufacture of
non-woven fabrics.
[0095] The non-woven fabrics composed of mineral fibers and used
according to the invention can be consolidated by means of the
binder system according to the invention and additionally by
mechanical methods, e.g., needling or hydrodynamic needling. They
are most preferably carded non-woven fabrics composed of filaments,
i.e. endlessly long fibers, or of staple fibers. The average
diameter of the mineral fibers is between 8 and 15 .mu.m,
preferably between 10 and 12 .mu.m.
[0096] Suitable mineral fibers include aluminosilicate fibers,
ceramic fibers, dolomite fibers, or fibers of vulcanite, such as
basalt, diabase, melaphyre. These are commonly referred to as
palaeobasalts; alternatively, diabase is also often called
greenstone.
[0097] The weight per unit area of the non-woven fabrics composed
of mineral fibers and used according to the invention is between 20
and 350 g/m.sup.2, preferably between 25 and 90 g/m.sup.2. The
information given above also applies to the glass non-woven fabrics
described below.
[0098] The non-woven fabrics composed of glass fibers and used
according to the invention can be consolidated by means of binders
or else by mechanical methods, e.g., needling or hydrodynamic
needling. The glass fibers may be filaments or finite or cut glass
fibers wherein in the latter case, the length of the fibers is
between 1 and 40 mm, preferably 4 to 20 mm. The average diameter of
the glass fibers is between 6 and 20 .mu.m, preferably between 8
and 15 .mu.m.
[0099] Suitable glass fibers include glass types such as E-glass,
S-glass, R-glass or C-glass, wherein E-glass or C-glass is
preferred for economic reasons.
[0100] Among the textile fabrics on the basis of synthetic
polymers, non-woven fabrics composed of fibers from synthetic
polymers, in particular spinbonded fabrics, so-called spunbonds,
which are produced by random deposition of freshly melt-spun
filaments, are preferred. They consist of continuous synthetic
fibers composed of melt-spinnable polymer materials. Suitable
polymer materials include, for example, polyamides, such as e.g.
polyhexamethylene diadipamide, polycaprolactam, wholly or partly
aromatic polyamides ("aramids"), aliphatic polyamides, such as e.g.
nylon, partly or wholly aromatic polyesters, polyphenylene sulfide
(PPS), polymers having ether and keto groups, such as e.g.
polyether ketones (PEKs) and polyether ether ketone (PEEK),
polyolefins, such as e.g. polyethylene or polypropylene, or
polybenzimidazoles.
[0101] Preferably, the spinbonded fabrics consist of melt-spinnable
polyesters. The polyester material can, in principle, be any known
type suitable for fiber production. Such polyesters consist
predominantly of components derived from aromatic dicarboxylic
acids and from aliphatic diols. Commonly used aromatic dicarboxylic
acid components are bivalent residues of benzenedicarboxylic acids,
especially of the terephthalic acid and the isophthalic acid;
commonly used diols have 2 to 4 carbon atoms, wherein ethylene
glycol is particularly suitable. Spinbonded fabrics which consist
of at least 85 mole % of polyethylene terephthalate are
particularly advantageous. The remaining 15 mole % are then
comprised of dicarboxylic acid units and glycol units which act as
so-called modifiers and allow the person skilled in the art to
targetedly influence the physical and chemical properties of the
produced filaments. Examples of such dicarboxylic acid units are
residues of isophthalic acid or aliphatic dicarboxylic acid, such
as e.g. glutaric acid, adipic acid, and sebacic acid; examples of
modifying diol residues are those composed of longer-chain diols,
e.g. propane diol or butane diol, of diethylene or triethylene
glycol or, if present in small quantities, of polyglycol with a
molecular weight of ca. 500 to 2000.
[0102] Polyesters containing at least 95 mole % of polyethylene
terephthalate (PET) are particularly preferred, especially those
composed of unmodified PET.
[0103] The individual titers of the polyester filaments in the
spinbonded fabric amount to between 1 and 16 dtex, preferably
between 2 and 8 dtex.
[0104] In another embodiment of the invention, the textile fabric
of the spinbonded fabric may also be a melt binder-bonded non-woven
fabric which contains lining and hot-melt adhesive fibers. The
lining and hot-melt adhesive fibers can be derived from any
thermoplastic, fiber-forming polymers. Additionally, lining fibers
can also be derived from non-fusing filament-forming polymers. Such
spinbonded fabrics which have been consolidated by means of a melt
binder are described, for example, in EP-A-0,446,822 and
EP-A-0,590,629.
[0105] In a preferred embodiment of the invention, the textile
fabric was subjected to mechanical and chemical consolidation with
the binder system according to the invention. Such a consolidation
further improves the application properties of the lining
material.
[0106] The textile fabric may have a single-layer or multi-layer
structure.
[0107] The weight per unit area of the textile fabric, in
particular the spunbonded fabric, is between 20 and 500 g/m.sup.2,
preferably between 40 and 400 g/m.sup.2, in particular between 90
and 250 g/m.sup.2.
[0108] In a further embodiment of the invention, such textile
fabrics have at least one reinforcement, in particular if they are
used as lining materials. They are preferably designed such that
the reinforcement absorbs a force so that the reference force in
the force-elongation diagram (at 20.degree. C.) of the lining
material with reinforcement compared to the lining material without
reinforcement differs within the range between 0 and 1% of
elongation in at least one point by at least 10%.
[0109] In another embodiment, the reinforcement can be incorporated
in such a way that, due to the reinforcement, forces are only
absorbed at higher elongations.
[0110] Multifilaments and/or monofilaments on the basis of aramids,
preferably so-called high-modulus aramids, carbon, glass, glass
rovings, mineral fibers (basalt), high-strength polyester
monofilaments or multifilaments, high-strength polyamide
monofilaments or multifilaments, as well as so-called hybrid
multifilament yarns (yarns containing reinforcing fibers and
lower-melting binding fibers) or wires (monofilaments) composed of
metals or metal alloys, are preferably used as reinforcing
filaments.
[0111] For economic reasons, preferred reinforcements consist of
glass multifilaments in the form of--essentially--parallel warp
sheets or scrims. In most cases, the non-woven fabrics are
reinforced in the longitudinal direction by--essentially--parallel
warp sheets.
[0112] The reinforcing filaments may be used as such or in the form
of a discrete textile fabric, for example as a woven fabric, yarn
sheet, knitted fabric or non-woven fabric. Reinforcements with
reinforcing yarns running parallel to each other, that is warp
sheets, as well as scrims or woven fabrics are preferred.
[0113] The measurement of the reference force is carried out in
accordance with EN 29073, part 3, on 5 cm wide samples at a
restraint length of 200 mm. Here, the numerical value of the
pretension, given in centinewton, corresponds to the numerical
value of the area mass of the sample, given in gram per square
meter.
[0114] The reinforcement may be carried out by the inclusion of the
reinforcements in the textile fabric, on at least one face of the
textile fabric or else at any location of the lining material, in
particular in other textile fabrics differing from the first
textile fabric, or as an individual textile fabric.
[0115] The lining materials according to the invention containing
the textile fabric consolidated according to the invention may be
equipped with further functional layers. This means measures or
functional layers which increase the resistance to penetration of
roots of the lining material, for example. These are also a subject
matter of the invention.
[0116] The lining material according to the invention may have
further textile fabrics in addition to the textile fabric according
to the invention already described. Preferably, these further
textile fabrics differ from the textile fabric first mentioned,
i.e. they are made of a different material.
[0117] Insofar as the textile fabric is made up of synthetic
polymers, it may be necessary to include further textile fabrics in
the lining material according to the invention in order to optimize
the application properties.
[0118] It is surprising to the person skilled in the art that the
use of the binder system of the invention can improve the
properties of the textile fabric, particularly with regard to tear
resistance.
[0119] The textile fabric consolidated according to the invention
can be used as a lining material itself or in combination with
further textile fabrics as a lining material for coated sarking
membranes, roofing sheets and water-proof sheetings as well as a
textile backing or a textile reinforcement in floorings, in
particular carpets and PVC floorings which are also a
subject-matter of the invention.
[0120] The textile fabric consolidated according to the invention
can be used as a lining material itself or in combination with
further textile fabrics as a lining material for the manufacture of
coated sarking membranes, roofing sheets and water-proof sheetings,
preferably for the manufacture of bituminized sarking membranes,
roofing sheets and water-proof sheetings. Apart from that, the
linings according to the invention may also be used in flooring
applications and in the field of filtration.
[0121] Polyethylene or polyvinyl chloride, polyurethanes, EPDM or
TPO (polyolefins) are used as coating compounds for floorings or
carpet backings. Besides that, bitumen is used for the coated
sarking membranes, roofing sheets and water-proof sheetings.
[0122] The bituminized sheets contain at least
one--above-described--lining sheet which is embedded in a bitumen
matrix, wherein the percentage by weight of the bitumen related to
the weight per unit area of the bituminized roofing sheet is
preferably 60 to 97% by weight and that of the spinbonded fabric 3
to 40% by weight.
[0123] The manufacture of the textile fabrics used according to the
invention is carried out by means of known methods and processes.
The manufacture of the consolidated textile fabric according to the
invention is carried out by means of the following measures:
[0124] A) formation of a textile fabric and optionally mechanical
consolidation thereof,
[0125] B) application of the binder system according to the
invention, comprising: [0126] I) 10 to 90% by weight, preferably 30
to 70% by weight of polymerizates based on carboxylic acid, in
particular polycarboxylic acid, which can be cross-linked by means
of a cross-linking agent, and [0127] II) 10 to 90% by weight,
preferably 30 to 70% by weight of polyvinyl acetate, and [0128]
III) 90 to 10% by weight, preferably 70 to 30% by weight of one or
more starches and [0129] IV) 0 to 60% by weight of at least one
additive from the group of amphoteric hydroxides, salts of the
first and second main groups of the periodic table, mineral
additives which are of synthetic or natural origin, kaolin, carbon
blacks or mixtures thereof and [0130] V) 0 to 10% by weight of
additives,
[0131] C) drying and consolidation of the binder,
[0132] wherein the specified percentages by weight refer to the dry
weight of the binder system, i.e., without water.
[0133] The formation of the textile fabric is carried out by means
of known measures.
[0134] The implementation of the mechanical consolidation
optionally carried out also takes place by means of known
methods.
[0135] The inclusion of the optionally present reinforcement is
carried out during or after the formation of the textile fabric or
before or during the application of the binder system according to
the invention. The supply of the reinforcement and optionally any
further heat treatment in the manufacturing process preferably
takes place under stress, in particular longitudinal stress.
[0136] The supply of further textile fabrics optionally to be
included takes place before or during the consolidation of the
binder system according to the invention.
[0137] The application of the binder system in step B) is also
carried out by means of known methods. The applied layer of binder
(after drying) is preferably between 5 and 35% per weight, in
particular 10 and 30% by weight, most preferably 10 and 25% by
weight dry binder referring to the total weight of the untreated
textile fabric.
[0138] Drying or consolidation of the binder is also carried out by
means of methods known to the person skilled in the art, wherein
temperatures of 160.degree. C. to 210.degree. C. prove to be
advantageous. The drying or consolidation process causes among
other things the condensation of the cross-linking agent with the
carbonic acid with formation of the corresponding condensates.
[0139] The individual procedure measures are known per se, but
patentable in the combination or order according to the invention
and with the use of the binder system according to the
invention.
[0140] Measurement Methods:
[0141] The specific strength is a measure of the influence of the
binder on the strength of the non-woven fabric:
F.sub.s=(BW(I)+BW(q))/G.sub.b.
[0142] The tensile strength BW (lengthwise, crosswise) corresponds
to the tear strength which, according to DIN EN 29 073-3, is
measured on samples of 5 cm width and 30 cm length. G.sub.b
corresponds to the weight per unit area with binders in
g/m.sup.2.
[0143] The hot strength is a measure of the longitudinal strength
of the non-woven fabric at 200.degree. C. The strength is
determined in accordance with DIN EN 29 073-3, wherein the
measurement is carried out at 200.degree. C. in a furnace.
[0144] The permeability is measured according to DIN EN ISO 9237 in
[l/m.sup.2 sec]; the solids content is measured according to DIN EN
ISO 3251.
[0145] The viscosity is measured according to DIN EN ISO 2555 at
23.degree. C.
[0146] The pH value is determined as a 10% by weight solution in
water according to DIN ISO 976.
[0147] The tear resistance is determined according to DIN EN ISO
9073-4, the elongation and strength are determined according to DIN
EN 29073-3. The determination of the shrinkage takes place at
200.degree. C. for 10 min.
[0148] The water absorption capacity is measured according to DIN
18191.
* * * * *