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EP 2 134 899 B1 |
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EUROPEAN PATENT SPECIFICATION |
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Mention of the grant of the patent: |
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15.12.2010 Bulletin 2010/50 |
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Date of filing: 16.03.2007 |
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International Patent Classification (IPC):
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International application number: |
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PCT/IT2007/000190 |
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International publication number: |
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WO 2008/114284 (25.09.2008 Gazette 2008/39) |
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PROCESS FOR THE PREPARATION OF A SEMIFINISHED MATERIAL TO BE USED TO PRODUCE LEATHER-
LIKE ARTICLES OR COATED FABRICS AND MATERIAL THEREOF
VERFAHREN ZUR HERSTELLUNG EINES HALBZEUGS ZUR HERSTELLUNG LEDERARTIGER ERZEUGNISSE
ODER BESCHICHTETER GEWEBE UND MATERIAL DARAUS
PROCÉDÉ DE PRÉPARATION D'UN MATÉRIAU SEMI-FINI À UTILISER POUR PRODUIRE DES ARTICLES
EN SIMILICUIR OU DES TISSUS ENDUITS ET MATÉRIAU ASSOCIÉ
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Designated Contracting States: |
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AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO
SE SI SK TR |
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Date of publication of application: |
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23.12.2009 Bulletin 2009/52 |
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Proprietor: Fiscagomma S.p.A. |
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27029 Vigevano PV (IT) |
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Inventor: |
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- COSTAMAGNA, Achille
I-27029 Vigevano (PV) (IT)
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Representative: Long, Giorgio et al |
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Jacobacci & Partners S.p.A.
Via Senato 8 20121 Milano 20121 Milano (IT) |
(56) |
References cited: :
JP-A- 4 308 280 JP-A- 63 085 185
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JP-A- 5 163 683
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- DATABASE WPI Week 199330 Derwent Publications Ltd., London, GB; AN 1993-240367 XP002461886
& JP 05 163684 A (ACHILLES CORP) 29 June 1993 (1993-06-29)
- DATABASE WPI Week 198340 Derwent Publications Ltd., London, GB; AN 1983-779874 XP002461887
& JP 58 144185 A (KYOWA LEATHER CLOTH CO LTD) 27 August 1983 (1983-08-27)
- DATABASE WPI Week 200414 Derwent Publications Ltd., London, GB; AN 2004-136247 XP002461888
& JP 2003 138488 A (KURARAY CO LTD) 14 May 2003 (2003-05-14)
- DATABASE WPI Week 199249 Derwent Publications Ltd., London, GB; AN 1992-403218 XP002461889
& JP 04 300368 A (KURARAY CO LTD) 23 October 1992 (1992-10-23)
- DATABASE WPI Week 199118 Derwent Publications Ltd., London, GB; AN 1991-129586 XP002461890
& JP 03 069365 A (TOYO CLOTH CO) 25 March 1991 (1991-03-25)
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Note: Within nine months from the publication of the mention of the grant of the European
patent, any person may give notice to the European Patent Office of opposition to
the European patent
granted. Notice of opposition shall be filed in a written reasoned statement. It shall
not be deemed to
have been filed until the opposition fee has been paid. (Art. 99(1) European Patent
Convention).
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FIELD OF THE INVENTION
[0001] . The present invention relates to a process for preparing a semifinished material
to be used for manufacturing leather-like or coated fabric items and a semifinished
product that can be obtained by means of said process. Particularly, this invention
relates to a Process allowing to obtain a semifinished product provided with excellent
tactile, visual and mechanical characteristics suitable to make it advantageously
exploitable in a number of fields of leather-like or coated fabric items such as,
for example, shoes, bags, sofas.
BACKGROUND OF THE INVENTION
[0002] . Semifinished materials that can be used in the leather-like or coated fabrics fields
have been known for some time. These materials generally consist of a woven or nonwoven
backing which is treated with polymeric substances such as to give characteristics
of elasticity, resistance and touch as much similar as possible to natural hide and
leather.
[0003] . These characteristics are usually obtained by subjecting the substrate to a conventional
coagulation treatment in which a polymeric resin in the liquid state is deposited
on said backing, coated and treated by means of suitable equipment such as to obtain
the coagulation of the resin on the surface thereof. A polyurethane coating layer
is described in
JP 04 308280,
JP 63 085185 and
JP 05 163683.
[0004] . At the same time, a liquid polymeric layer is prepared on paper and then cured.
This step has the function of preparing the visible part of the semifinished material
according to patterns or designs as desired.
[0005] . The polymeric layer on paper is then coated, on the polymer side, with an adhesive
substance, also of polymeric nature, on which is placed said backing that has been
subjected to coagulation and the whole is treated such as to obtain an individual
sheet of multilayer material, which is used for manufacturing items such as shoes,
bags, upholstery for sofas.
[0006] . The materials resulting from the Process described above is provided with such
tactile, resistance, abrasion, ageing, lightfastness characteristics as to be suitable
to be used as a substitute for hide or natural leather in the manufacture of said
items.
[0007] . While the prior art semifinished material is successfully traded, it however has
important limitations mainly in terms of scratch resistance, abrasion resistance,
flex life, lightfastness.
[0008] . In other words, the performance of the material is limited, such that a need is
felt in the field to find a material with improved characteristics, which allows a
more convenient use or even novel characteristics.
SUMMARY OF THE INVENTION
[0009] . The technical problem addressed by the present invention is thus to provide a semifinished
material to be used in the manufacture of leather-like or coated fabric items which
is capable of having typical characteristics of said materials that are considerably
improved as compared with the currently marketed materials, as well as novel characteristics.
[0010] . This problem is solved by a process for manufacturing a semifinished material that
is capable of giving said characteristics thus making the final product not only substantially
identical to hide and natural leather, but also provides improved physical-mechanical
characteristics as compared with known materials.
[0011] . A first object of the present invention is, accordingly, a process for preparing
a semifinished product to be used in the manufacture of leather-like or coated fabric
items.
[0012] . A second object of the invention is a semifinished material that can be obtained
in accordance with said process.
DETAILED DESCRIPTION OF THE INVENTION
[0013] . As extensive testing has proved, it has been surprisingly found that when a suitable
backing is treated with a particular selection of polymeric substances, a semifinished
material can be obtained, which is provided with unexpectedly improved characteristics
as compared with the currently marketed materials.
[0014] . In accordance with the present invention, the process for preparing a semifinished
material for manufacturing leather-like or coated fabric items, thus comprises the
steps of:
- providing a woven or nonwoven substrate;
- providing a liquid coagulation mixture comprising an aliphatic or aromatic polycarbonate-base
polyurethane polymer, an organic solvent, and optionally water;
- depositing at least one layer of said liquid mixture on said substrate;
- coagulating said mixture on said substrate.
[0015] . Preferably, the woven or nonwoven substrate can be selected from polyester and/or
cotton fabrics, polyester microfiber, polyester elastomer, polyamide, polyamide elastomer,
mono or multilayer spunlace and/or spunbonded and/or carded nonwoven, needled polyester
viscose, polyamide polyester, viscose polyamide nonwovens. More preferably, the substrate
is a woven fabric, polyester and cotton twill weave cloth, thickness of 0.3 to 0.6
mm, weft linear density Ne 6 ± 1, 100% cotton, 14 beat-up ± 1, warp linear density
Ne 16 ± 1, 25 polyester threads (65%) cotton (35%) or nonwoven 100% polyester, 150
gr/m
2 Spunlace, linear density 1.950 dtex, thickness 0.3/0.6 mm.
[0016] . The coagulation liquid mixture comprises an aliphatic or aromatic polycarbonate-base
polyurethane polymer. More preferably, it is an aliphatic polycarbonate-base polyurethane
polymer. Still more preferably, the polymer is in liquid form and is characterised
by a solid content of 29% to 31% by weight upon the weight of the liquid dissolved
in DMF (dimethylformamide) of 71% to 69% by weight upon the weight of the liquid,
by a viscosity of 800-1200 DPA.S (calculated by means of a Brookfield viscometer according
to the manufacturer's procedure) at 25°C under dynamic rotation, by 350% elongation
rate, by 100% modulus (MPa) of 3.5 and 300% modulus (MPa) of 18. Particularly, a polymer
provided with said characteristics is for example the product sold by DAINIPPON under
the trade name of CRISVON
™ SPM 12.
[0017] . The organic solvent can be any of the organic solvents commonly used for diluting
polymer resins such as, for example, a polar solvent such as methoxy propanol methyl
acetate and dimethylformamide. This solvent is added at amounts ranging between 60%
and 50% by weight upon the weight of the coagulation mixture such that the final polymer
amount in this mixture ranges between 11.6% and 15.5%. Preferably, this solvent is
dimethylformamide (DMF). Dimethylformamide can be used at such amounts as to dilute
the polymeric moiety of the mixture to 40-50% by weight upon the mixture total weight.
[0018] . Furthermore, said mixture can preferably also comprise cellulose fiber ranging
between 1% and 25% by weight upon the mixture total weight.
[0019] . The coagulation mixture can further comprise a flame retardant preferably phosphates
and chlorides-based at a ratio between 1% and 20% by weight upon the mixture total
weight. This flame retardant can be selected from conventional organic derivate halogens.
[0020] . Said first mixture is prepared by first mixing the dimethylformamide (DMF) with
the optional flame retardants and the optional cellulose fiber and then adding the
polyurethane resin and the colouring agents at said amounts under stirring.
[0021] . The step of depositing the mixture on the substrate can be preferably carried out
based on a type of technique known in the field.
[0022] . This technique provides coating the mixture. The coating is carried out by continuously
depositing the liquid mixture on a rotating smooth roller upon which and at a predetermined
distance from the surface thereof is positioned a blade having the function of controlling
and keeping a constant and uniform layer of mixture applied to the substrate.
[0023] . In any case, independently of the technique used, the deposit is carried out such
as to release one or more layers of said coagulation mixture on the substrate, having
a thickness of 0.1 to 2 mm, preferably of 0.5 to 1.5 mm.
[0024] . The coagulation is carried out by dipping the substrate with the respective mixture
being applied thereto into a water-containing tank at a temperature ranging between
10° and 50°C, preferably between 20° and 40°C, for a time ranging between 8 minutes
and 10 minutes. Preferably, the tank comprises water and dimethylformamide at a ratio
of 95% water and 5% dimethylformamide to 5% water and 95% dimethylformamide upon total
weight.
[0025] . Subsequently, the coagulation is ended with washing and drying steps. The washing
is carried out by passing the substrate into more washing tanks where water at a temperature
ranging between 15° and 50°C, preferably between 20° and 40°C, flows countercurrently
relative to the feeding direction of the substrate. The drying can be carried out
in a conventional oven at a temperature ranging between 100° and 150°C, preferably
between 120° and 130°C for a time ranging between 5 minutes and 8 minutes, according
to the type of substrate being treated.
[0026] . Preferably, furthermore, the process according to the invention can comprise a
step of wetting said substrate with water optionally admixed to an organic solvent
prior to the application of the coagulation mixture layer. This step has the purpose
of preventing the coagulation mixture from passing through the entire thickness of
the substrate and thus maintaining, after the mixture polymer has been coagulated,
a higher level of softness of the substrate mainly when the final material must meet
particular requirements just in terms of touch.
[0027] . The step of wetting said woven or nonwoven substrate before applying the liquid
coagulation mixture can be carried out by dipping the substrate in a water-containing
tank or in a water/organic solvent wetting solution in which 2% to 60% organic solvent
is provided upon the total weight of the wetting solution. Particularly, the organic
solvent can be any conventional organic solvent. For example, the dimethylformamide
can be used in solution with water.
[0028] . Said wetting step can be followed by a drying step. Particularly, the drying step
can comprise a twisting step, for example by passing through a pair of rollers, and
a heating step into a conventional oven at a temperature ranging between 30° and 100°C
for a time ranging between 5 minutes and 8 minutes according to the type of substrate
being used.
[0029] . It should be noted that said liquid coagulation mixture can further comprise conventional
inorganic and/or organic pigment-based colouring agents such as to give colours to
the semifinished material suitable to the final purpose, i.e. providing items such
as those illustrated above.
[0030] . In addition, the material resulting from the process described above can be subjected
to further peculiar processing steps of the textile/tanning finishing operations,
aiming at changing the appearance and touch according to particular requirements or
preferences also dictated by the type of the desired final product to be manufactured.
Examples of conventional processing can be mechanical processing in a dry/humid environment,
optionally additioned with silicone softeners, such as drumming, creasing, ageing
processing, pleating, tumbler working, perching.
[0031] . In accordance with a variant embodiment, the process for preparing a semifinished
material for manufacturing leather-like or coated fabric items can comprise the further
steps of:
- providing a "skin" liquid mixture, comprising a polymer of polyurethanes, polyesters,
both aromatic and aliphatic polyesters or polycarbonates, in solution with a mixture
of at least two organic solvents;
- depositing at least one layer of said mixture on said layer of coagulated mixture
of said woven or nonwoven substrate;
- hardening said at least one layer.
[0032] . The step of depositing the skin mixture can be carried out by means of two types
of techniques. The first technique provides depositing the mixture on the substrate
and then passing the substrate through a pair of rollers of which at least one is
provided with a surface carrying drawings or patterns suitable to model the mixture
prior to hardening, according to the desired final appearance to be obtained for the
material.
[0033] . The second type is substantially identical to the coating step described above
with reference to the treatment of the woven or nonwoven substrate with the coagulation
mixture with the difference that the coating or deposit is carried out on a paper
backing (release paper) which is then joined to the woven or nonwoven substrate.
[0034] . Particularly, the second type comprises:
- depositing at least one layer of said "skin" mixture on a paper backing;
- hardening said at least one layer of "skin" mixture on said paper backing;
- providing an liquid adhesion mixture comprising a polymer such as set forth with reference
to the coagulation mixture and organic solvents;
- depositing said adhesion mixture on said at least one layer of said "skin" mixture;
- placing said coagulated backing on said adhesion mixture layer such that the coagulated
layer of the substrate mixture is contacted with said adhesion mixture;
- curing said adhesion mixture such as to obtain the adhesion between said substrate
and said paper backing to form the semifinished material.
[0035] . The polymers that can be used for the "skin" mixture preferably comprise a polymer
of polyurethanes, polyesters, both aromatic and aliphatic polyesters or polycarbonates
at amounts ranging between 1,9% and 18.9% by weight upon the mixture total weight,
More preferably, the polymer is polycarbonate base aliphatic polyurethane. Still more
preferably, the polymer is in liquid form and is characterised by a solid content
of 19% to 21% by weight, by a viscosity ranging between 300 and 600 DPA.S (calculated
by means of a Brookfield viscometer according to the manufacturer's procedure) at
25°C under dynamic rotation, by an elongation rate of 330%, by a 100% modulus (MPa)
of 20 and 300% modulus (MPa) of 46.5. Particularly, a polymer provided with said characteristics
is for example the product sold by DAINIPPON under the trade name of CRISVON
™ NY 324D.
[0036] . The organic solvents used for diluting the "skin" mixture polymer are preferably
prepared in a mixture of at least two selected from toluene, isobutyl methyl ketone,
methoxy propanol methyl acetate, cyclohexanone, acetone, methyl ethyl ketone and dimethylformamide.
Particularly, the solvents are used at amounts ranging between 10% and 90% by weight
upon the total weight of the "skin" mixture. More preferably, the solvent mixture
consists of DMF and MEK (methyl ethyl ketone) used at amounts of 28% and 7% by weight
upon the total weight of "skin" mixture, respectively.
[0037] . The "skin" mixture can further comprise 0.05% to 5% by weight upon the total weight
of the silicone oil mixture. Preferably, the silicone oils are selected from touch
modifiers or low-migration flow additives, which are well known in the field, for
example the product sold by Cytec under the trade name of Ucecoat
™ stm.
[0038] . Furthermore, the mixture can comprise inorganic and/or organic colouring agents,
for example in the form of pastes with high weathering and chemical resistance at
amounts of 10% to 20% by weight upon the mixture weight and can be selected from the
series of Poliplast
™ LA products sold by Irsea S.p.a.
[0039] The step of hardening said mixture on a paper backing is carried out by means of
heating at a temperature ranging between 60° and 150°C for a period of time ranging
between 3 minutes and 5 minutes according to the type of backing. Particularly, the
mixture is coated on the paper backing by means of conventional equipment (for flexographic
printing) such as to create a thickness ranging between 0.50 mm and 1.05 mm.
[0040] . The liquid adhesion mixture comprises a polymer identical to the polymer described
above with reference to the coagulation mixture.
[0041] . Particularly, the adhesion mixture differs from the coagulation mixture in that
the polymer is diluted with an organic solvent mixture comprising at least two solvents
that are preferably selected from toluene, methyl isobutyl ketone, methoxy propanol
methyl acetate, cyclohexanone, acetone, methyl ethyl ketone and dimethylformamide.
Particularly, the solvents are provided in the adhesion mixture at amounts ranging
between 15% and 40% by weight such as to obtain a polymer amount of 2.9% to 12.4%
by weight upon the mixture total weight. More preferably, the mixture consists of
14% DMF and 20% MEK (methyl ethyl ketone) upon the total weight of the adhesion mixture.
[0042] . The step of depositing the adhesion mixture on: the backing is substantially carried
out in the same manner in which the "skin" mixture is deposited, again, on the paper
backing. Preferably, a layer of said mixture is deposited with a thickness ranging
between 0.5 to 1.00 mm.
[0043] . The step of curing the adhesion mixture is carried out after the coagulated substrate
has been deposited on the hardened backing and covered with the adhesion mixture still
in the liquid state, such that the corresponding faces that have been treated with
the mixtures come in contact with each other. This curing is preferably carried out
by heating in oven at temperatures ranging between 60° and 150°C for a time ranging
between 2 and 5 minutes.
[0044] . The advantage offered by this variant embodiment is that the semifinished material
can be provided with aesthetic characteristics of various nature according to the
requirements or preferences. In fact, both the use of embossed rolls and paper backing
act as a negative impression for forming predetermined aesthetic designs.
[0045] . The final product obtained is a semifinished material comprising a woven or nonwoven
layer having a thickness of 0.3 mm to 0.6 mm and a polymeric layer having a thickness
of 0.1 mm to 4.05 mm, preferably the latter ranges from 0.5 to 1.5 mm.
[0046] . Particularly, said material is characterized by having the following features:
- softness identical to or higher than that typical of natural leather;
- abrasion resistance according to EN 13520 Martindale test higher than 30,000 dry cycles,
preferably 1 million cycles and higher than 6,000 wet cycles, preferably 300,000 cycles;
- flex life according to EN 13512 Bally test at ambient temperature higher than 150,000,
preferably 400,000 and at a temperature of -10°C higher than 30,000, preferably 100,000;
- lightfastness according to UNI 9427 Xenotest with 1500 watt lamp higher than 72 h,
preferably 150H (8 blue scale) ;
- fastness to ageing, according to EN 12749 hydrolysis test, 8 week duration, does not
exhibit any physical-mechanical deterioration.
[0047] . A further object of the present invention is a leather-like or coated fabric item
comprising a semifinished material as described above. Particularly, items that can
comprise the subject material can be typical items of the shoe industry, bags and
suitcases, briefcases, wallets, key rings, belts, furnishing items such as pieces
of furniture, sofas, armchairs (also in the nautical field), sanitary coverings, and
various furnishing accessories.
[0048] . An embodiment given by way of non-limiting example of the invention is given herein
below.
PREPARATION OF THE COAGULATED SUBSTRATE
[0049] . A fabric roll, polyester and cotton twill weave cloth, thickness of 0.4 to 0.6
mm, weft linear density Ne 6 ± 1, 100% cotton, 14 beat-up ±1, warp linear density
Ne 16 ±1, 25 polyester threads (65%) cotton (35%) or nonwoven, 100% polyester, 150
gr/m
2 Spunlace, linear density 1.950 dtex, thickness 0.4/0.6 mm is unwound and passed through
a conventional coagulation equipment where it is dipped into a tank containing water
such as to obtain the complete wetting of the same. Subsequently, the woven or nonwoven
fabric is passed through a pair of rollers to carry out twisting and eliminating most
of the water. The woven or nonwoven fabric is then passed into a heated oven at a
temperature of 60°C for 3 minutes to be dried. After it has been dried, it is sent
to the coating station where the coagulation mixture is applied, which consists of
CRISVON
™ SPM 12 sold by DAINIPPON diluted with 55% DMF. Particularly, a tube positioned above
the woven or nonwoven fabric roll deposits, continuously and with a back and forth
movement along the roll axis, the mixture in the liquid form during the unwinding
rotation of said roll. Simultaneously, both adjacent and downstream of the tube, a
blade ensures that the proper amount of mixture is evenly coated all over the surface
of the woven or nonwoven fabric.
[0050] . Thereafter, the coated woven or nonwoven fabric enters a coagulation station embodied
by a tank containing a solution of 10% DMF and 90% water at a temperature of 30°C
and is left there for 10 minutes.
[0051] . The woven or nonwoven fabric exiting the coagulation tank is sent to six different
washing tanks where countercurrent water flows in order to take up the solvent.
PREPARATION OF THE PAPER BAKING (RELEASE PAPER)
[0052] . A roll of plasticized release paper having a desired pattern is unwound within
a conventional release paper-treating equipment. In this equipment, during said unwinding,
a blade for flexographic printing continuously deposits a first mixture consisting
of the CRISVON
™ NY 324D liquid polymer sold by DAINIPPON diluted with 27% DMF and 7% MEK and additioned
with 1% silicone oils and 15% conventional colouring pastes in the same manner as
described above with reference to the deposit of the coagulation mixture. After the
deposit has been carried out, the backing is continuously passed into a heated oven
at a temperature of 100°C and resides there for a time of 5 minutes, thereby ensuring
the hardening of the same.
[0053] . At this stage, an adhesion mixture consisting of CRISVON
™ SPM 12 diluted with 13% DMF and 20% MEK and 15% conventional colouring pastes is
deposited in an entirely similar manner to what has been described above on the hardened
layer of the first mixture.
COMPOSITION OF THE SEMIFINISHED MATERIAL
[0054] . By means of a conventional equipment, the coagulated substrate roll is unwound
and the woven or nonwoven fabric is placed with the coagulated side thereof on the
substrate on which the adhesion mixture has been just deposited. At this stage, the
coagulated woven or nonwoven substrate and coated release paper backing, thus overlapped,
are passed into a heated oven at 100°C for a time of 5 minutes during which the adhesion
mixture is cured, such as to join the substrate to the backing. Finally, the material
exiting from the oven is cooled on water-cooled cylinders and the release paper is
removed therefrom. The thus-obtained semifinished material has been subjected to some
testing and has exhibited surprising characteristics. Particularly, said material
is characterised in that it has the following characteristics:
- abrasion resistance according to EN 13520 Martindale test, 1 million dry cycles and
300,000 wet cycles;
- flex life according to the EN 13512 Bally test, at ambient temperature of 400,000
and at -10°C temperature of 100,000;
- lightfastness according to UNI 9427 Xenotest with 1500 watt lamp of 150H (8 blue scale);
- fastness to ageing, according to the EN 12749 hydrolysis test, 8 week-ageing, it does
not exhibit any physical-mechanical deterioration.
[0055] . Now, it should be understood that the material in accordance with the invention
allows meeting the requirements as set forth in the introductory part of the present
description.
[0056] . Particularly, the characteristics found during the testing have surprisingly evidenced
incredibly improved values as compared with conventional materials produced in accordance
with known techniques. Furthermore, the appearance and touch sensation have proved
to be very similar to, and in some cases, better than natural hide and leather.
[0057] . Further variant embodiments of the process and material can be conceived and carried
out by those skilled in the art while remaining within the scope of protection of
the invention such as defined in the annexed claims herein below.
1. A process for preparing a semifinished material for manufacturing leather-like or
coated fabric items comprises the steps of:
- providing a woven or nonwoven substrate;
- providing a liquid coagulation mixture comprising a polymer of aliphatic or aromatic
polycarbonate base polyurethane, an organic solvent, and optionally water;
- depositing at least one layer of said liquid mixture on said substrate;
- coagulating said mixture on said substrate; characterised in that said substrate is wetted with water optionally admixed to an organic solvent before
depositing the coagulation mixture.
2. The process according to claim 1, wherein the woven or nonwoven substrate is selected
from polyester and/or cotton fabrics, polyester microfiber, polyester elastomer, polyamide,
polyamide elastomer, mono or multilayer spunlace and/or spunbonded and/or carded nonwoven,
needled polyester viscose, polyamide polyester, viscose polyamide nonwovens.
3. The process according to claim 1 or 2, wherein the substrate is a woven fabric, polyester
and cotton twill weave cloth, thickness of 0.4 to 0.6 mm, weft linear density Ne 6
± 1, 100% cotton, 14 beat-up ± -1, warp linear density Ne 16 ± -1, 25 polyester threads
(65%) cotton (35%) or 100% polyester nonwoven, 150 gr/m2 Spunlace, 1,950 dtex linear density, thickness 0.4/0.6 mm.
4. The process according to any claim 1 to 3, wherein said polymer is provided at amounts
of 11.6% to 15.5% by weight upon the total weight of the coagulation mixture.
5. The process according to any claim 1 to 4, wherein said coagulation mixture comprises
a liquid polymeric portion wherein the polymer is characterized by a solid content of 29% to 31% by weight upon the weight of the liquid dissolved in
organic solvent, viscosity ranging between 800 and 1200 DPA.S at 25°C under dynamic
rotation, elongation rate of 350%, 100% module (MPa) of 3,5 and 300% module (MPa)
of 18.
6. The process according to any claim 1 to 5, wherein said organic solvent is a polar
solvent such as methoxy propanol methyl acetate and dimethylformamide provided at
amounts ranging between 50% and 60% by weight upon the total weight of the coagulation
mixture.
7. The process according to claim 6, wherein said organic solvent is dimethylformamide
used at amounts of 50-60% by weight upon the total weight of the mixture.
8. The process according to any claim 1 to 7, wherein said coagulation mixture comprises
cellulose fiber at amounts ranging between 1% and 25% by weight upon the mixture total
weight.
9. The process according to any claim 1 to 8, wherein said first mixture comprises a
flame retardant at amounts ranging between 1% and 20% by weight upon the mixture weight.
10. The process according to any claim 1 to 9, wherein the deposit of one or more layers
of said coagulation mixture is carried out such as to form a thickness ranging between
0.1 and 2 mm.
11. The process according to any claim 1 to 10, comprising the further steps of:
- providing a "skin" liquid mixture, comprising a polymer of polyurethanes, polyesters,
both aromatic and aliphatic polyesters or polycarbonates, in solution with a mixture
of organic solvents;
- depositing at least one layer of said mixture on said layer of coagulated mixture
of said woven or nonwoven substrate on the coagulated side;
- hardening said at least one "skin" mixture layer.
12. The process according to claim 11, wherein the depositing step comprises depositing
the "skin" mixture on said substrate and subsequently passing the substrate through
a pair of rolls of which at least one is provided with a surface carrying drawings
or patterns.
13. The process according to claim 11, wherein the depositing step comprises:
- depositing at least one layer of said "skin" mixture on a paper backing;
- hardening said at least one layer on said paper backing;
- providing a liquid adhesion mixture, comprising a polymer of polyurethanes, polyesters,
both aromatic and aliphatic polyesters or polycarbonates, in solution with at least
two organic solvents;
- depositing said adhesion mixture on said at least one layer of said "skin" mixture;
- placing said coagulated backing on said adhesion mixture layer such that the coagulated
layer of the substrate mixture is contacted with said adhesion mixture;
- curing said adhesion mixture such as to obtain the adhesion between said substrate
and said paper backing to form the semifinished material.
14. The process according to claim 13, wherein said polymer of said "skin" mixture is
provided at amounts ranging between 1.9% and 18.9% by weight upon the mixture total
weight and said at least two organic solvents are provided at amounts between 10%
and 90% by weight upon the weight of said "skin" mixture.
15. The Process according to claim 14, wherein said at least two organic solvents are
selected from toluene, methyl isobutyl ketone, methoxy propanol methyl acetate, cyclohexanone,
acetone, methyl ethyl ketone and dimethylformamide.
16. The process according to any claim 11 to 15, wherein said "skin" mixture comprises
a liquid polymeric portion wherein the polymer is characterized by a solid content of 19% to 21% by weight upon the mixture weight, by a viscosity ranging
between 300 and 600 DPA.S at 25°C under dynamic rotation, elongation rate of 330%,
100% module (MPa) of 20 and 300% module (MPa) of 46.5.
17. The process according to any claim 11 to 15, wherein said "skin" mixture comprises
28% DMF and 7% MEK (methyl ethyl ketone) upon the total weight of said mixture, as
the organic solvents.
18. The process according to any claim 11 to 17, wherein said "skin" mixture comprises
silicone oils at amounts ranging between 0.05% and 5% by weight upon the mixture weight.
19. The process according to any claim 13 to 18, wherein the step of hardening said skin
mixture on a paper backing takes place such as to create a thickness ranging between
0.50 mm and 1.05 mm.
20. The process according to any claim 13 to 19, wherein the adhesion mixture comprises
a polymer identical to that used for the coagulation mixture, diluted with a mixture
of at least two organic solvents selected from toluene, methyl isobutyl ketone, methoxy
propanol methyl acetate, cyclohexanone, acetone, methyl ethyl ketone and dimethylformamide.
21. The process according to any claim 13 to 20, wherein the polymer of said adhesion
mixture is provided at amounts of 2.9% to 12.4% by weight upon the total weight of
the mixture.
22. The process according to any claim 13 to 21, wherein the solvents are DMF and MEK
(methyl ethyl ketone) at amounts of 14% and 20% upon the mixture weight, respectively.
23. The process according to any claim 13 to 22, wherein a layer of said adhesion mixture
is applied with a thickness ranging between 0.5 and 1 mm.
1. Verfahren zum Herstellen eines Halbzeugs zur Produktion von lederartigen Gegenständen
oder Gegenständen aus beschichtetem Gewebe, umfassend die Schritte:
- Bereitstellen eines gewebten oder nichtgewebten Substrats;
- Bereitstellen einer flüssigen Koagulationsmischung umfassend ein Polymer aus Polyurethan
basierend auf aliphatischem oder aromatischem Polycarbonat, ein organisches Lösungsmittel
und gegebenenfalls Wasser;
- Abscheiden von wenigstens einer Schicht der flüssigen Mischung auf dem Substrat;
- Koagulieren der Mischung auf dem Substrat;
dadurch gekennzeichnet, dass das Substrat vor dem Abscheiden der Koagulationsmischung mit Wasser, das gegebenenfalls
mit einem organischen Lösungsmittel vermischt ist, angefeuchtet wird.
2. Verfahren nach Anspruch 1, wobei das gewebte oder nichtgewebte Substrat ausgewählt
ist aus Polyester- und/oder Baumwollgeweben, Polyester-Mikrofaser, Polyester-Elastomer,
Polyamid, Polyamid-Elastomer, Mono- oder Mehrschichten-Spunlace und/oder Spinnvlies
und/oder kardiertem Faservlies, genadelter Polyester-Viskose, Polyamid-Polyester,
Viskose-Polyamid-Faservliesen.
3. Verfahren nach Anspruch 1 oder 2, wobei das Substrat ein Gewebe, Polyester- und Baumwollköpergewebe,
Dicke 0,4 bis 0,6 mm, längenbezogene Masse des Schussfadens (weft linear density)
Ne 6 ± 1, 100 % Baumwolle, 14 Schussanschlag (beat-up) ± -1, längenbezogene Masse
des Kettfadens (warp linear density) Ne 16 ± -1, 25 Polyesterfäden (65 %) Baumwolle
(35 %) oder 100 % Polyester-Faservlies, 150 g/m2 Spunlace, 1950 dtex längenbezogene Masse, Dicke 0,4/0,6 mm ist.
4. Verfahren nach einem der Ansprüche 1 bis 3, wobei das Polymer in Mengen von 11,6 bis
15,5 Gew.-%, bezogen auf das Gesamtgewicht der Koagulationsmischung, bereitgestellt
wird.
5. Verfahren nach einem der Ansprüche 1 bis 4, wobei die Koagulationsmischung einen flüssigen
polymeren Anteil umfasst, wobei das Polymer gekennzeichnet ist durch einen Feststoffgehalt von 29 bis 31 Gew.-%, bezogen auf das Gewicht der Flüssigkeit,
gelöst in einem organischen Lösungsmittel, eine Viskosität im Bereich zwischen 800
und 1200 DPA.S bei 25 °C unter dynamischer Rotation, eine Dehnungsrate von 350 %,
100 % Modul (MPa) von 3,5 und 300 % Modul (MPa) von 18.
6. Verfahren nach einem der Ansprüche 1 bis 5, wobei das organische Lösungsmittel ein
polares Lösungsmittel wie Methoxypropanol, Methylacetat und Dimethylformamid ist,
das in Mengen im Bereich zwischen 50 und 60 Gew.%, bezogen auf das Gesamtgewicht der
Koagulationsmischung, bereitgestellt wird.
7. Verfahren nach Anspruch 6, wobei das organische Lösungsmittel Dimethylformamid ist,
das in Mengen von 50-60 Gew.-%, bezogen auf das Gesamtgewicht der Mischung, verwendet
wird.
8. Verfahren nach einem der Ansprüche 1 bis 7, wobei die Koagulationsmischung Cellulosefaser
in Mengen im Bereich zwischen 1 und 25 Gew.-%, bezogen auf das Gesamtgewicht der Mischung,
umfasst.
9. Verfahren nach einem der Ansprüche 1 bis 8, wobei die erste Mischung ein Flammschutzmittel
in Mengen im Bereich zwischen 1 und 20 Gew.-%, bezogen auf das Gewicht der Mischung,
umfasst.
10. Verfahren nach einem der Ansprüche 1 bis 9, wobei die Abscheidung von einer oder mehreren
Schichten der Koagulationsmischung so ausgeführt wird, dass eine Dicke im Bereich
zwischen 0,1 und 2 mm gebildet wird.
11. Verfahren nach einem der Ansprüche 1 bis 10, umfassend die weiteren Schritte:
- Bereitstellen einer "Haut"-Flüssigkeitsmischung, umfassend ein Polymer aus Polyurethanen,
Polyestern, sowohl aromatischen als auch aliphatischen Polyestern oder Polycarbonaten,
in Lösung mit einer Mischung von organischen Lösungsmitteln;
- Abscheiden von wenigstens einer Schicht der Mischung auf der Schicht der koagulierten
Mischung von dem gewebten oder nichtgewebten Substrat auf der koagulierten Seite;
- Härten der wenigstens einen "Haut"-Mischungsschicht.
12. Verfahren nach Anspruch 11, wobei der Abscheidungsschritt das Abscheiden der "Haut"-Mischung
auf dem Substrat und das anschließende Leiten des Substrats durch ein Paar von Walzen
umfasst, von denen wenigstens eine mit einer Oberfläche versehen ist, die Zeichnungen
oder Muster trägt.
13. Verfahren nach Anspruch 11, wobei der Abscheidungsschritt umfasst:
- Abscheiden von wenigstens einer Schicht der "Haut"-Mischung auf einer Papierunterlage;
- Härten der wenigstens einen Schicht auf der Papierunterlage;
- Bereitstellen einer flüssigen Haftmischung, umfassend ein Polymer aus Polyurethanen,
Polyestern, sowohl aromatischen als auch aliphatischen Polyestern oder Polycarbonaten,
in Lösung mit wenigstens zwei organischen Lösungsmitteln;
- Abscheiden der Haftmischung auf der wenigstens einen Schicht der "Haut"-Mischung;
- Anordnen der koagulierten Unterlage auf der Haftmischungsschicht, so dass die koagulierte
Schicht der Substratmischung mit der Haftmischung in Berührung kommt;
- Härten der Haftmischung, so dass die Anhaftung zwischen dem Substrat und der Papierunterlage
erhalten wird, um das Halbzeug zu bilden.
14. Verfahren nach Anspruch 13, wobei das Polymer der "Haut"-Mischung in Mengen im Bereich
zwischen 1,9 und 18,9 Gew.-%, bezogen auf das Gesamtgewicht der Mischung, bereitgestellt
wird und die wenigstens zwei organischen Lösungsmittel in Mengen zwischen 10 und 90
Gew.-%, bezogen auf das Gewicht der "Haut"-Mischung, bereitgestellt werden.
15. Verfahren nach Anspruch 14, wobei die wenigstens zwei organischen Lösungsmittel ausgewählt
sind aus Toluol, Methylisobutylketon, Methoxypropanol, Methylacetat, Cyclohexanon,
Aceton, Methylethylketon und Dimethylformamid.
16. Verfahren nach einem der Ansprüche 11 bis 15, wobei die "Haut"-Mischung einen flüssigen
polymeren Anteil umfasst, wobei das Polymer durch einen Feststoffgehalt von 19 bis
21 Gew.-%, bezogen auf das Gewicht der Mischung, durch eine Viskosität im Bereich
zwischen 300 und 600 DPA.S bei 25 °C unter dynamischer Rotation, eine Dehnungsrate
von 330 %, 100 % Modul (MPa) von 20 und 300 % Modul (MPa) von 46,5 gekennzeichnet ist.
17. Verfahren nach einem der Ansprüche 11 bis 15, wobei die "Haut"-Mischung 28 % DMF und
7 % MEK (Methylethylketon), bezogen auf das Gesamtgewicht der Mischung, als die organischen
Lösungsmittel umfasst.
18. Verfahren nach einem der Ansprüche 11 bis 17, wobei die "Haut"-Mischung Siliconöle
in Mengen im Bereich zwischen 0,05 und 5 Gew.-%, bezogen auf das Gewicht der Mischung,
umfasst.
19. Verfahren nach einem der Ansprüche 13 bis 18, wobei der Schritt der Härtung der Hautmischung
auf einer Papierunterlage so stattfindet, dass eine Dicke im Bereich zwischen 0,50
mm und 1,05 mm erzeugt wird.
20. Verfahren nach einem der Ansprüche 13 bis 19, wobei die Haftmischung ein Polymer umfasst,
das identisch ist mit dem für die Koagulationsmischung verwendeten Polymer, verdünnt
mit einer Mischung von wenigstens zwei organischen Lösungsmitteln, ausgewählt aus
Toluol, Methylisobutylketon, Methoxypropanol, Methylacetat, Cyclohexanon, Aceton,
Methylethylketon und Dimethylformamid.
21. Verfahren nach einem der Ansprüche 13 bis 20, wobei das Polymer der Haftmischung in
Mengen von 2,9 bis 12,4 Gew.-%, bezogen auf das Gesamtgewicht der Mischung, bereitgestellt
wird.
22. Verfahren nach einem der Ansprüche 13 bis 21, wobei die Lösungsmittel DMF und MEK
(Methylethylketon) in Mengen von 14 bzw. 20 %, bezogen auf das Gewicht der Mischung,
sind.
23. Verfahren nach einem der Ansprüche 13 bis 22, wobei eine Schicht der Haftmischung
mit einer Dicke im Bereich zwischen 0,5 und 1 mm aufgetragen wird.
1. Procédé de préparation d'un matériau semi-fini pour la fabrication d'articles textiles
semblables au cuir ou enduits, lequel comprend les étapes consistant :
- à fournir un substrat tissé ou non tissé ;
- à fournir un mélange liquide de coagulation comprenant un polymère de polyuréthane
à base de polycarbonate aliphatique ou aromatique, un solvant organique et éventuellement
de l'eau ;
- à déposer au moins une couche dudit mélange liquide sur ledit substrat ;
- à faire coaguler ledit mélange sur ledit substrat ;
caractérisé en ce que ledit substrat est mouillé avec de l'eau éventuellement mélangée avec un solvant
organique avant le dépôt du mélange de coagulation.
2. Procédé selon la revendication 1, dans lequel le substrat tissé ou non tissé est choisi
parmi des textiles de polyester et/ou de coton, des non-tissés de microfibre de polyester,
d'élastomère de polyester, de polyamide, d'élastomère de polyamide, de polyester viscose,
de polyamide polyester, de viscose polyamide aiguilleté, non tissé, mono ou multicouche
lacé et/ou filé et/ou cardé.
3. Procédé selon la revendication 1 ou 2, dans lequel le substrat est une étoffe de textile
tissé, à armure croisée de polyester et de coton, épaisseur de 0,4 à 0,6 mm, densité
linéaire de trame Ne 6 + 1, 100 % de coton, 14 boucles par unité de surface ± -1, densité linéaire de chaîne
Ne 16 ± -1, non-tissé de 25 fils de polyester (65 %) coton (35 %) ou de 100 % de polyester,
150 g/m2 de lacé, densité linéaire 1 950 dtex, épaisseur 0,4/0,6 mm.
4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel ledit polymère
est fourni dans des quantités de 11,6 % à 15,5 % en poids par rapport au poids total
du mélange de coagulation.
5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel ledit mélange
de coagulation comprend une portion polymère liquide dans laquelle le polymère est
caractérisé par une teneur en matière solide de 29 % à 31 % en poids par rapport au poids du liquide
dissous dans un solvant organique, la viscosité étant comprise entre 800 et 1 200
DPA.S à 25°C sous rotation dynamique, taux d'allongement de 350 %, module à 100 %
(MPa) de 3,5 et module à 300 % (MPa) de 18.
6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel ledit solvant
organique est un solvant polaire, tel que le méthoxypropanol acétate de méthyle et
le diméthylformamide, fourni dans des quantités comprises entre 50 % et 60 % en poids
par rapport au poids total du mélange de coagulation.
7. Procédé selon la revendication 6, dans lequel ledit solvant organique est le diméthylformamide
utilisé dans des quantités de 50-60 % en poids par rapport au poids total du mélange.
8. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel ledit mélange
de coagulation comprend de la fibre de cellulose dans des quantités comprises entre
1 % et 25 % en poids par rapport au poids total du mélange.
9. Procédé selon l'une quelconque des revendications 1 à 8, dans lequel ledit premier
mélange comprend un retardateur de flamme dans des quantités comprises entre 1 % et
20 % en poids par rapport au poids du mélange.
10. Procédé selon l'une quelconque des revendications 1 à 9, dans lequel le dépôt d'une
ou plusieurs couches dudit mélange de coagulation est réalisé afin de former une épaisseur
comprise entre 0,1 et 2 mm.
11. Procédé selon l'une quelconque des revendications 1 à 10 comprenant les étapes supplémentaires
consistant :
- à fournir un mélange liquide de "peau" comprenant un polymère de polyuréthanes,
de polyesters, de polyesters ou de polycarbonates à la fois aromatiques et aliphatiques,
en solution avec un mélange de solvants organiques ;
- à déposer au moins une couche dudit mélange sur ladite couche de mélange coagulé
dudit substrat tissé ou non tissé sur le côté coagulé ;
- à faire durcir ladite au moins une couche de mélange de "peau".
12. Procédé selon la revendication 11, dans lequel l'étape de dépôt comprend le dépôt
du mélange de "peau" sur ledit substrat et le passage subséquent du substrat à travers
une paire de rouleaux dont au moins un est muni d'une surface portant des dessins
ou des motifs.
13. Procédé selon la revendication 11, dans lequel l'étape de dépôt comprend les étapes
consistant :
- à déposer au moins une couche dudit mélange de "peau" sur un support de papier ;
- à faire durcir ladite au moins une couche sur ledit support de papier ;
- à fournir un mélange liquide d'adhérence comprenant un polymère de polyuréthanes,
de polyesters, de polyesters ou de polycarbonates à la fois aromatiques et aliphatiques,
en solution avec au moins deux solvants organiques ;
- à déposer ledit mélange d'adhérence sur ladite au moins une couche dudit mélange
de "peau" ;
- à placer ledit support coagulé sur ladite couche de mélange d'adhérence de telle
sorte que la couche coagulée du mélange de substrat est mise en contact avec ledit
mélange d'adhérence ;
- à faire durcir ledit mélange d'adhérence afin d'obtenir l'adhérence entre ledit
substrat et ledit support de papier pour former le matériau semi-fini.
14. Procédé selon la revendication 13, dans lequel ledit polymère dudit mélange de "peau"
est fourni dans des quantités comprises entre 1,9 % et 18,9 % en poids par rapport
au poids total du mélange et lesdits au moins deux solvants organiques sont fournis
dans des quantités comprises entre 10 % et 90 % en poids par rapport au poids dudit
mélange de "peau".
15. Procédé selon la revendication 14, dans lequel lesdits au moins deux solvants organiques
sont choisis parmi le toluène, la méthylisobutylcétone, le méthoxypropanol acétate
de méthyle, la cyclohexanone, l'acétone, la méthyléthylcétone et le diméthylformamide.
16. Procédé selon l'une quelconque des revendications 11 à 15, dans lequel ledit mélange
de "peau" comprend une portion polymère liquide dans laquelle le polymère est caractérisé par une teneur en matière solide de 19 % à 21 % en poids par rapport au poids du mélange,
par une viscosité comprise entre 300 et 600 DPA.S à 25°C sous rotation dynamique,
un taux d'allongement de 330 %, un module à 100 % (MPa) de 20 et un module à 300 %
(MPa) de 46,5.
17. Procédé selon l'une quelconque des revendications 11 à 15, dans lequel ledit mélange
de "peau" comprend 28 % de DMF et 7 % de MEK (méthyléthylcétone) par rapport au poids
total dudit mélange en tant que solvants organiques.
18. Procédé selon l'une quelconque des revendications 11 à 17, dans lequel ledit mélange
de "peau" comprend des huiles de silicone dans des quantités comprises entre 0,05
% et 5 % en poids par rapport au poids du mélange.
19. Procédé selon l'une quelconque des revendications 13 à 18, dans lequel l'étape de
durcissement dudit mélange de peau sur un support de papier a lieu afin de créer une
épaisseur comprise entre 0,50 mm et 1,05 mm.
20. Procédé selon l'une quelconque des revendications 13 à 19, dans lequel le mélange
d'adhérence comprend un polymère identique à celui utilisé pour le mélange de coagulation,
dilué avec un mélange d'au moins deux solvants organiques choisis parmi le toluène,
la méthylisobutylcétone, le méthoxypropanol acétate de méthyle, la cyclohexanone,
l'acétone, la méthyléthylcétone et le diméthylformamide.
21. Procédé selon l'une quelconque des revendications 13 à 20, dans lequel le polymère
dudit mélange d'adhérence est fourni dans des quantités de 2,9 % à 12,4 % en poids
par rapport au poids total du mélange.
22. Procédé selon l'une quelconque des revendications 13 à 21, dans lequel les solvants
sont DMF et MEK (méthyléthylcétone) dans des quantités respectives de 14 % et de 20
% par rapport au poids du mélange.
23. Procédé selon l'une quelconque des revendications 13 à 22, dans lequel une couche
dudit mélange d'adhérence est appliquée avec une épaisseur comprise entre 0,5 et 1
mm.
REFERENCES CITED IN THE DESCRIPTION
This list of references cited by the applicant is for the reader's convenience only.
It does not form part of the European patent document. Even though great care has
been taken in compiling the references, errors or omissions cannot be excluded and
the EPO disclaims all liability in this regard.
Patent documents cited in the description