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EP 1 941 094 B1 |
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EUROPEAN PATENT SPECIFICATION |
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Mention of the grant of the patent: |
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02.03.2011 Bulletin 2011/09 |
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Date of filing: 04.09.2006 |
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International Patent Classification (IPC):
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International application number: |
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PCT/SM2006/000003 |
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International publication number: |
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WO 2007/030084 (15.03.2007 Gazette 2007/11) |
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PROCEDURE FOR THE PROCESSING OF CELLULOSE MATERIAL TO OBTAIN A PRODUCT SIMILAR TO
LEATHER
VERFAHREN ZUR VERARBEITUNG VON CELLULOSEMATERIAL ZU EINEM LEDERÄHNLICHEN PRODUKT
PROCÉDURE POUR LE TRAITEMENT DE MATÉRIAU CELLULOSIQUE POUR OBTENIR UN PRODUIT SEMBABLE
AU CUIR
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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 NL PL PT RO SE
SI SK TR |
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Priority: |
09.09.2005 SM 200500021
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Date of publication of application: |
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09.07.2008 Bulletin 2008/28 |
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Proprietor: OKINAWA S.r.l. |
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35044 Montagnana (IT) |
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Inventor: |
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- TOMASELLI, Claudio
I-31100 Treviso (IT)
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Representative: Gallo, Luca et al |
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Gallo & Partners S.r.l.
Via Trieste 49 35121 Padova 35121 Padova (IT) |
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References cited: :
EP-A- 0 504 701 US-A- 4 212 927
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EP-A2- 0 164 076
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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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TECHNICAL FIELD
[0001] This invention concerns a procedure for processing cellulose material, by means of
dyeing and softening, to obtain an unalterable finished material.
[0002] More specifically, this invention refers to a dyeing and softening process of cellulose
material that makes it possible to obtain a finished product similar in appearance
and resistance to leather, and resistant to water, that is to say to washing with
detergents and in washing machines, or to dry cleaning professes with ethylene perchlorate.
[0003] The procedure according to the invention substantially foresees the use of a method
for processing animal skins employed in tanning, using cellulose as the raw material,
to obtain a finished skin to be used for manufacturing leather products, with the
feature of not altering if subjected to water washing or dry cleaning.
[0004] This invention can be applied in the sector for the production of fabrics and products
similar to leather used in clothing, furnishing and coverings in general.
BACKGROUND ART
[0005] It is known that in the sector of fabrics and materials for coverings, furnishing
and clothing there has always been a demand for the production of natural materials
derived from artificial products or from other natural but less expensive products.
[0006] The typical example is leather, which has been proposed in an artificial form, or
reprocessed or recomposed also with natural products in a plurality of solutions,
some of which are described below.
[0007] The US patent
US 4,212,927 proposes a process for the production of artificial leather that foresees the processing
of cellulose fibres with aqueous baths following the techniques used for the production
of paper. In particular, the process foresees:
- placing the support made from fibres in an aqueous dispersion containing at least
one bonding agent;
- impregnating the fibre support with a water bath containing at least one macromolecule
chosen from a group containing acrylic polymers and copolymers;
- covering the fibre support with a water bath containing at least one macromolecule
chosen from a group containing vinyl and acrylic polymers and copolymers to obtain
an intermediate layer;
- subjecting the material thus obtained to coating by means of a water bath containing
at least one macromolecule chosen from a group containing vinyl and acrylic polymers
and copolymers and at least one coalescent agent to obtain a finish layer.
[0008] The solution proposed in the Italian patent
IT 1.178.956, on the other hand, foresees implementation of a procedure to obtain synthetic skins
similar to natural ones, subjecting porous synthetic materials (synthetic leather),
imitating natural skins, to a procedure comparable to tanning.
[0009] This patent shows that subjecting a synthetic material to a tanning process produces
a product similar to leather even though tanning is not designed to characterize a
product but to prevent it from rotting.
[0010] The sheet base consists of a vacuolated polyurethane matrix with internal polyester
or polyethylene fibres and a coating of polyurethane resin printed with a design similar
to natural leather.
[0011] According to this patent, the sheet material is subjected to:
- a) wetting in drums with water at 50-60°C with surfactants added;
- b) the action of an aqueous solution of bi-trivalent metallic salts (tanning-like
saline solutions);
- c) if necessary, additional processing with an aqueous solution of polyaldehyde;
- d) a tanning-like action with caustic soda;
- e) a process of greasing with an emulsion of mineral oils and/or fatty acid esters.
[0012] The dyeing phase is carried out after greasing with sulphonated esters in a rotating
drum for a couple of hours with mixtures of specific metallocomplex dyes for polyester
fibres and polyurethane polymers.
[0013] These solutions are, however, subject to very obvious practical problems substantially
concerning the limits from the point of view of consistency and resistance of the
material obtained.
[0014] The first solution foresees the use and processing of cellulose and involves the
processing of cellulose fibres with aqueous baths following the techniques for the
production of paper.
[0015] The limits of this type of material essentially concern the fact that the finished
product cannot withstand washing processes. In particular, this material undergoes
evident alterations if washed in water with detergents either in a washing machine
or when dry cleaned using the ethylene perchlorate.
[0016] According to the solution proposed in the second document, the Italian patent, the
raw material consists of synthetic skins similar to natural ones, which are subjected
to a procedure comparable to tanning.
[0017] This method, however, is not designed for essentially natural products but for products
which are mainly synthetic which primarily consist of polyurethane materials, containing
polyester or polyethylene fibres coated with a polyurethane resin printed with a design
similar to natural leather.
[0018] This material has nothing natural about it, and as a result the finished product
will have all the problems typical of artificial products made on a synthetic base.
DESCRIPTION OF THE INVENTION
[0019] This invention proposes to provide a procedure for the creation of materials similar
to leather and that can eliminate or at least reduce the drawbacks described above.
[0020] The invention proposes to provide a procedure for the creation of a material that
foresees the features of being similar to leather, both from the point of view of
softness and in appearance, and which at the same time guarantees the non-alterability
when processed with water or ethylene perchlorate.
[0021] The raw material is based on cellulose and is chemically processed in an aqueous
solution to dye it and soften it so that it acquires a more leather-like "feel" while
maintaining its particular features.
[0022] This invention therefore consists of a procedure for the production of a material
similar to leather starting from a cellulose base, whose features are described in
the main claim.
[0023] The dependent claims of the solution in question describe advantageous embodiments
of the invention.
[0024] The main advantages of this solution, in addition to those based on its production
simplicity, concern first of all the fact that the material obtained is resistant
and remains unaltered, while having a consistency similar to leather, if subjected
to washing in water with detergents, also in a washing machine, or when dry cleaned
using ethylene perchlorate.
[0025] The procedure according to the invention therefore foresees the use of cellulose
as the raw material, in particular a special cellulose material in the form of a white
card-like sheet, wound in reels which are then cut into sheets.
[0026] One of the features of the cellulose material is that it does not alter when it comes
into contact with water or ethylene perchlorate, allowing it to be chemically processed
in an aqueous solution to dye it and soften it so that it acquires a leather-like
"feel" and maintains its particular features.
[0027] According to an essential feature of the invention, the cellulose material is one
that is generally used to make labels for jeans and commercially known as TEXON
® 601 produced by Texon International.
[0028] This consists of cellulose fibres impregnated with a dispersion of carboxylated styrene-butadiene
polymer and containing vulcanizing and ageing agents and non-nitrogenous pigments.
[0029] The stages of the procedure according to the invention are as follows:
- 1) Dyeing of the cellulose-based material;
- 2) Softening (or greasing) of the material;
- 3) Fixing of the material.
[0030] The procedure is carried out inside rotating cylinders, known as "drums", inserting
the sheets of cellulose material and aqueous solutions, and starts with the so-called
"wetting" of the material, which consists of soaking it in hot water at 50/60°C and
rotating the drum for several hours so that the fibres can react with the chemical
products they will subsequently come into contact with.
[0031] The first chemical reaction to which the cellulose material is subjected consists
of dyeing, carried out with a predetermined quantity of hot water at 40/50°C using
either mixtures of metallocomplex dyes alone or adding azodyes and tannin extracts
to the solution, this operation lasting from 45 to 60 minutes.
[0032] To soften the sheets, so that they acquire a similar "feel" to leather, greasing
products are added to the solution in a mixture consisting of sulphonated fish and
vegetable oils and synthetic fats, with a further rotation for around 120 minutes.
[0033] As is usual when processing leather, the chemical products are then fixed on the
material by adding a solution of formic acid to the solution in the drum, and if necessary
also a solution of trivalent metal salts, reacting for around 60/90 minutes.
[0034] To reinforce the reaction between the chemical products and the cellulose material,
a new solution of formic acid is used, after replacing the aqueous solution, with
the addition of a resin and left to soak for around 60 minutes.
[0035] Processing is now complete and the sheets can be left to dry on heated steel plates.
DESCRIPTION OF SOME EMBODIMENTS OF THE INVENTION
[0036] A detailed description of the procedure is now given, referring to the following
examples.
EXAMPLE I
[0037] Six sheets of TEXON
® 601 cellulose material measuring 150 x 150 cm are inserted in a drum of around 0.4
m
3 in volume, which rotates at a speed of 12 rpm, with 73.5 1 of hot water at a temperature
of around 50°C and rotated for 3 hours and then left to soak overnight.
[0038] In the morning, the water is drained off and 19.6 1 of hot water at 40°C are added
together with 0.132 kg (from 0.004 kg to 0.224 kg) of a powder mixture of metallocomplex
dyes and azodyes and 0.196 kg of tannin extract of quebracho in powder and rotated
for 45 minutes.
[0039] A 2.058 kg solution is now added, consisting of 60% of sulphonated fish oil, 30%
of long-chain phosphoric ester-based synthetic oils and 10% of natural and vegetable
oils, and rotated for 120 minutes. The bath is acidified with 0.245 kg of formic acid
and rotated for 20 minutes. Another 0.147 kg (up to 0.245 kg) of formic acid is added,
rotating the drum for another 30 minutes.
[0040] The solution in the drum is now drained off and the material is thoroughly rinsed
before adding 29.4 1 of hot water at 40°C with 0.098 kg of formic acid, rotating the
drum for 10 minutes and then adding 0.098 kg of a solution of acrylic polymer and
rotating for another 30 minutes. The solution is then drained off and the material
is rinsed thoroughly again.
[0041] The sheets are removed from the drum and left to dry on steel plates.
EXAMPLE II
[0042] Proceed as with example I up to the first acidification after the greasing operation
with 2.058 kg of oils and add 0.196 kg of chrome sulphate and rotate for 90 minutes.
Drain and rinse thoroughly and then proceed as in example I.
EXAMPLE III
[0043] As for example I but the 30% solution of synthetic oils is reduced to 25%, adding
5% of modified acrylic polymer.
[0044] Following the treatments described above, the finished product is identical to leather
both in consistency and in appearance, presenting the fundamental advantage of being
resistant to washing and to stress.
[0045] The invention is described above with reference to a series of preferred embodiments.
It is nevertheless clear that the invention is susceptible to numerous variations
that lie within its scope, within the framework of technical equivalents.
1. A procedure for the production of material similar to leather in terms of consistency
and appearance,
characterised in that the raw material is cellulose fibres impregnated with a copolymer dispersion and
in that the raw material is subjected to the following processing stages:
• Dyeing;
• Softening;
• Fixing.
2. A procedure according to claim 1, in which the dyeing phase comprises the insertion
of the cellulose material in a drum and processing with hot water with a mixture of
powder dyes and tannin extract.
3. A procedure according to any of the foregoing claims, in which the softening phase
comprises the addition of a solution of sulphonated fish oil, synthetic oils and fatty
acid esters and acidification of the bath with formic acid.
4. A procedure according to any of the foregoing claims, in which the fixing phase comprises
the draining of the solution in the drum, rinsing and adding of hot water and formic
acid with rotation of the drum and adding of a solution of acrylic polymer.
5. A procedure according to any of the foregoing claims, characterised in that the cellulose fibre is
impregnated with a dispersion of carboxylated styrene-butadiene coplymer.
6. A procedure according to claim 5, characterised in that the cellulose fibre is impregnated with a dispersion of carboxylated styrene-butadiene
copolymer that contains vulcanizing and ageing agents.
7. A procedure according to claim 5 or 6, characterised in that the cellulose fibre is impregnated with a dispersion containing pigments advantageously
non-nitrogenous.
8. A procedure according to any of the foregoing claims, characterised in that several sheets of cellulose fibre impregnated with a copolymer dispersion are inserted
in a drum with a predetermined volume, together with a predetermined quantity of hot
water at a predetermined temperature, advantageously 50°C, and in that the drum is rotated for a predetermined time, advantageously three hours, and in that the material is then left to soak for several hours.
9. A procedure according to claim 8, characterised in that it foresees the subsequent draining of water and the addition of a predetermined
quantity of hot water at a predetermined temperature, advantageously 40°C, with a
predetermined quantity of a powder mixture of metallocomplex dyes, azodyes and tannin
extract of quebracho in powder, followed by rotation of the drum for a predetermined
time, advantageously for 45 minutes.
10. A procedure according to claim 9, characterised in that it foresees the further addition of a solution consisting of 60% of sulphonated fish
oil, 30% of long-chain phosphoric ester-based synthetic oils and superior fatty acids
and 10% of natural and vegetable oils, and the subsequent rotation for a predetermined
time, advantageously 120 minutes, followed by the acidification of the bath with a
predetermined quantity of formic acid and rotation for a predetermined time, advantageously
20 minutes, and the subsequent addition of a further quantity of formic acid and rotation
for a predetermined time, advantageously 30 minutes.
11. A procedure according to claim 10, characterised in that it foresees the draining of the solution in the drum and thorough rinsing, followed
by the addition of a predetermined quantity of water at a predetermined temperature,
advantageously 40°C, with a predetermined quantity of formic acid and rotation of
the drum for a predetermined time, for example 10 minutes, and the subsequent addition
of a predetermined quantity of an acrylic polymer solution followed by rotation of
the drum for a predetermined time, for example 30 minutes, and finally the draining
of the solution and thorough rinsing.
12. A procedure according to any of the claims from 8 to 11, characterised in that it foresees the removal of the sheets and their drying on heated steel plates.
1. Verfahren zur Herstellung eines in Beschaffenheit und Aussehen lederähnlichen Materials,
dadurch gekennzeichnet, dass es als Grundmaterial eine mit einer Copolymerdispersion imprägnierte Cellulosefaser
verwendet, und
dadurch, dass dieses Grundmaterial den folgenden Arbeitsstufen unterzogen wird:
- Färben;
- Weichmachen;
- Fixieren.
2. Verfahren nach Anspruch 1, bei dem die Stufe des Färbens das Eingeben des Cellulosematerials
in eine Trommel und das Behandeln in warmem Wasser mit einem pulverförmigen Gemisch
aus Farbstoffen und Gerbstoffextrakt umfasst.
3. Verfahren nach einem der vorherigen Ansprüche, bei dem die Stufe des Weichmachens
das Hinzufügen einer Lösung aus sulfoniertem Fischöl, synthetischen Ölen und Fettsäureestern
und das Säuern des Bads mit Ameisensäure umfasst.
4. Verfahren nach einem der vorherigen Ansprüche, bei dem die Stufe des Fixierens das
Ablaufenlassen der in der Trommel enthaltenen Lösung, das Spülen und das Einleiten
von warmem Wasser und Ameisensäure mit Rotation der Trommel und einer Acrylpolymerlösung
umfasst.
5. Verfahren nach einem der vorherigen Ansprüche, dadurch gekennzeichnet, dass die Cellulosefaser mit einer Dispersion von carboxyliertem Styrol-Butadien-Copolymer
imprägniert wird.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass die Cellulosefaser mit einer Dispersion von carboxyliertem Styrol-Butadien-Copolymer
imprägniert wird, die Vulkanisierungs- und Alterungsmittel enthält.
7. Verfahren nach einem der Ansprüche 5 und 6, dadurch gekennzeichnet, dass die Cellulosefaser mit einer Dispersion imprägniert wird, die Pigmente enthält, die
vorteilhafterweise keinen Stickstoff enthalten.
8. Verfahren nach einem der vorherigen Ansprüche, dadurch kennzeichnet, dass mehrere Bögen aus mit einer Copolymerdispersion imprägnierten Cellulosefaser in eine
Trommel mit einem vorbestimmten Volumen zusammen mit einer vorbestimmten Menge warmen
Wassers mit einer vorbestimmten Temperatur, vorteilhafterweise 50°C, eingegeben werden,
und dadurch, dass diese Trommel dann für eine vorbestimmte Zeit, vorteilhafterweise drei Stunden,
rotieren gelassen wird, und dadurch, dass das Material dann für mehrere Stunden im Bad gelassen wird.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass es das anschließende Ablaufenlassen des Wasserbads und das Einleiten einer vorbestimmten
Menge warmen Wassers mit einer vorbestimmten Temperatur, vorteilhafterweise 40°C,
mit einer vorbestimmten Menge eines pulverförmigen Gemischs aus Metallkomplex- und
Azofarbstoffen und Quebrachogerbstoffextrakt in Pulverform vorsieht, wobei dann die
Trommel für eine vorbestimmte Zeit, vorteilhafterweise 45 Minuten, rotieren gelassen
wird.
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass es das weitere Hinzufügen einer zu 60% aus sulfoniertem Fischöl, zu 30% aus synthetischen
Ölen auf der Basis von langkettigen Phosphorsäureestern und höheren Fettsäuren und
zu 10% aus natürlichen und pflanzlichen Ölen bestehenden Lösung und die anschließende
Rotation für eine vorbestimmte Zeit, vorteilhafterweise hundertzwanzig Minuten, sowie
das Säuern des Bads mit einer vorbestimmten Menge Ameisensäure und die Rotation für
eine vorbestimmte Zeit, vorteilhafterweise 20 Minuten, und das anschließende Hinzufügen
einer weiteren Menge Ameisensäure und die Rotation für eine vorbestimmte Zeit, vorteilhafterweise
30 Minuten, vorsieht.
11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass es das Ablaufenlassen der in der Trommel enthaltenen Lösung und ein reichliches Spülen,
woraufhin dann eine vorbestimmte Wassermenge mit einer vorbestimmten Temperatur, vorteilhafterweise
40°C, mit einer vorbestimmten Menge Ameisensäure eingeleitet wird, und die anschließende
Rotation der Trommel für eine vorbestimmte Zeit, beispielsweise 10 Minuten, und das
anschließende Hinzufügen einer vorbestimmten Menge einer Acrylpolymerlösung und die
anschließende Rotation für eine vorbestimmte Zeit, beispielsweise 30 Minuten, und
schließlich das Ablaufenlassen der Lösung und ein reichliches Spülen vorsieht.
12. Verfahren nach einem der Ansprüche 8 bis 11, dadurch gekennzeichnet, dass es das Herausnehmen der Bögen und das Trocknen derselben auf beheizten Stahlplatten
vorsieht.
1. Procédé pour la production de matière similaire au cuir par consistance et aspect,
caractérisé en ce que il utilise comme matière de base une fibre de cellulose imprégnée avec une dispersion
de copolymère et
en ce que ladite matière de base est soumise aux étapes de traitement suivantes :
- teinture ;
- assouplissement ;
- fixation.
2. Procédé selon la revendication 1, dans lequel l'étape de teinture comprend l'introduction
de matière cellulosique à l'intérieur d'un tonnelet et le traitement en eau chaude
avec un mélange en poudre de colorants et d'extrait tannique.
3. Procédé selon une des revendications précédentes, dans lequel l'étape d'assouplissement
comprend l'ajout d'une solution d'huile de poisson sulfurée, huiles synthétiques et
esters d'acides gras et l'acidification du bain avec de l'acide formique.
4. Procédé selon une des revendications précédentes, dans lequel l'étape de fixation
comprend l'égouttage de la solution présente dans le tonnelet, le rinçage et l'introduction
d'eau chaude et d'acide formique avec rotation du tonnelet et d'une solution de polymère
acrylique.
5. Procédé selon une des revendications précédentes, caractérisé en ce que ladite fibre de cellulose est imprégnée avec une dispersion de copolymère styrène
butadiène carboxylate.
6. Procédé selon la revendication 5, caractérisé en ce que ladite fibre de cellulose est imprégnée avec une dispersion de copolymère styrène
butadiène carboxylate qui contient des agents de vulcanisation et de vieillissement.
7. Procédé selon une des revendications 5 et 6, caractérisé en ce que ladite fibre de cellulose est imprégnée avec une dispersion contenant des pigments,
avantageusement non azotés.
8. Procédé selon une des revendications précédentes, caractérisé en ce que plusieurs feuilles de fibre de cellulose imprégnée avec une dispersion de copolymère
sont introduites à l'intérieur d'un tonnelet ayant un volume prédéterminé conjointement
à une quantité prédéterminée d'eau chaude à une température prédéterminée, avantageusement
de 50°C, et en ce que ledit tonnelet est ensuite mis en rotation pendant un temps prédéterminé, avantageusement
de trois heures, et en ce que la matière est ensuite laissé dans le bain pendant plusieurs heures.
9. Procédé selon la revendication 8, caractérisé en ce qu'il prévoit l'égouttage successif du bain d'eau et l'introduction d'une quantité prédéterminée
d'eau chaude à une température prédéterminée, avantageusement de 40°C, avec une quantité
prédéterminée d'un mélange en poudre de colorants de complexes métalliques et azoïques
et d'extrait tannique de québracho en poudre en faisant ensuite tourner le tonnelet
pendant un temps prédéterminé, avantageusement 45 minutes.
10. Procédé selon la revendication 9, caractérisé en ce qu'il prévoit l'ajout ultérieur d'une solution composée de 60% d'huile de poisson sulfurée,
de 30% d'huiles synthétiques à base d'esters phosphoriques à chaîne longue et d'acides
gras supérieurs et de 10% d'huiles naturelles et végétales, et la rotation successive
pendant un temps prédéterminé, avantageusement cent-vingt minutes, ainsi que l'acidification
du bain avec une quantité prédéterminée d'acide formique et la rotation successive
pendant un temps prédéterminé, avantageusement de 20 minutes, et l'ajout successif
d'une quantité ultérieure d'acide formique et la rotation pendant un temps prédéterminé,
avantageusement de 30 minutes.
11. Procédé selon la revendication 10, caractérisé en ce qu'il prévoit l'égouttage de la solution présente dans le tonnelet et un rinçage abondant
pour introduire ensuite une quantité prédéterminée d'eau à une température prédéterminée,
avantageusement de 40°C, avec une quantité prédéterminée d'acide formique et la rotation
successive du tonnelet pendant un temps prédéterminé, par exemple 10 minutes, et l'ajout
successif d'une quantité prédéterminée d'une solution de polymère acrylique et la
rotation successive pendant un temps prédéterminé, par exemple 30 minutes, et enfin
l'égouttage de la solution et un rinçage abondant.
12. Procédé selon une des revendications 8 à 11, caractérisé en ce qu'il prévoit l'extraction des feuilles et leur séchage sur des plaques en acier chauffées.
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