EP3189187B1 - Composition d'encollage pour fibres, fils et/ou tissus, et procédé de préparation de celle-ci - Google Patents

Composition d'encollage pour fibres, fils et/ou tissus, et procédé de préparation de celle-ci Download PDF

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Publication number
EP3189187B1
EP3189187B1 EP15775804.6A EP15775804A EP3189187B1 EP 3189187 B1 EP3189187 B1 EP 3189187B1 EP 15775804 A EP15775804 A EP 15775804A EP 3189187 B1 EP3189187 B1 EP 3189187B1
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Prior art keywords
chitosan
sizing composition
derivatives
fibers
impeller
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EP15775804.6A
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German (de)
English (en)
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EP3189187A1 (fr
EP3189187B8 (fr
Inventor
Elisabetta CANEPA
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Candiani SpA
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Canepa SpA
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Priority to PL15775804T priority Critical patent/PL3189187T3/pl
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/08—Organic compounds
    • D06M10/10—Macromolecular compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

Definitions

  • the present invention relates to a sizing composition for fibers and yarns and/or fabrics made from such fibers, particularly for natural animal fibers, vegetable fibers, synthetic polymer fibers, man-made natural polymer fibers, continuous filaments of animal origin and/or discontinuous filaments of animal origin, to be used at a pure state or blended together.
  • weaving is generally used both for designating warp-and-weft weaving and knit-weaving.
  • the technique of applying a sizing composition to yarn fibers has been long known and is generally used to improve weavability of yarns, particularly thin yarns which are inherently difficult to weave as weft and/or warp yarns due o their thinness and their low tensile breaking load.
  • Sizing compositions can be generally removed from fabrics by suitable hydrolysis processes (e.g. acid, oxidizing or enzymatic hydrolysis) or are watersoluble such that they may be entirely removed from the fibers by appropriate finishing processing steps, such as washing or dyeing.
  • suitable hydrolysis processes e.g. acid, oxidizing or enzymatic hydrolysis
  • watersoluble such that they may be entirely removed from the fibers by appropriate finishing processing steps, such as washing or dyeing.
  • sizing compositions have been tested, which could have a lasting effect on the fibers upon which they are applied, i.e. remain on the fibers even after the above mentioned finishing steps or after successive repeated washing steps.
  • a substantially permanent presence of the sizing composition on the fibers of a yarn or a knit will allow fulfillment of the above mentioned additional needs.
  • sizing compositions comprising chitosan
  • the chitosan contained in the sizing composition is crosslinked, whereby such chitosan generates a crosslinked polymer which remains permanently anchored to the fibers.
  • Chitosan is a natural polymer derived from chitin, which is a polysaccharide contained in the exoskeleton of crustaceans, and is a nature-renewable material, since it is obtained from food industry by-products.
  • the chitosan-based reinforcement product used in the sizing composition has much better sizing properties than other natural substances.
  • the above chitosan crosslinking step has the purpose of imparting a considerable physical-mechanical resistance to the fibers upon which chitosan is applied, while ensuring a long-lasting sanitization effect, resisting many repeated washes with hot and/or soapy water, as well as a considerable improvement in the dye affinity, of the treated fibers.
  • the presence of the crosslinked chitosan and/or derivatives thereof on the fibers is likely to impart an excessive stiff feel to the fibers of the fabric or knit, and the fabric or knit are no longer soft and supple, i.e. are said to have a "hard feel", even when it is formed with thin fibers, e.g. cashmere fibers having a yarn count of 70 Nm.
  • the invention is based on the problem of conceiving and providing a sizing composition that fulfills all the above mentioned needs, without imparting stiffness to the fibers of the fabric or knit upon substantially permanent application of such sizing composition to the fibers due to crosslinking of chitosan and/or derivatives thereof, contained in the sizing composition.
  • another problem consists in conceiving a method of preparing a sizing composition comprising chitosan, which is effective and economic and can be easily implemented in a manufacturing process without requiring excessively long processing/preparation times, while providing a sizing composition in which chitosan is finely dissolved.
  • the invention also relates to a process as defined in claim 14 for crosslinking chitosan and/or derivatives thereof contained in the sizing composition of the invention on fibers impregnated with such sizing composition.
  • the sizing composition to be used for sizing the fibers is a sizing composition comprising chitosan and/or derivatives thereof.
  • the chitosan and/or derivatives thereof as used for preparing the sizing composition of the invention have:
  • the chitosan and/or derivatives thereof are dissolved in a 3% to 9% w/v organic acid solution, with a pH of less than 6.5.
  • the chitosan and/or derivatives thereof are dissolved in a 3% to 9% w/v acetic acid or citric acid solution, 3-9% v/v.
  • pyruvic acid and tartaric acid may be used as further organic acids.
  • the chitosan and/or derivatives thereof in the sizing composition are in a solid state (e.g. powder, granules or flakes) or in a fluid state (e.g. in the form of a high-density paste), before being dissolved by agitation and/or by dispersion in said sizing composition.
  • the above mentioned sizing composition also comprises starch and/or fish glue at a ratio of 1:1 to the amount of chitosan and/or derivatives thereof.
  • the above mentioned sizing composition is enriched with additional double-bond monomers crosslinking agents comprising acrylic monomers with low environmental impact, added in an amount substantially equal to the w/v percent of chitosan and/or derivatives thereof in the sizing composition.
  • the above mentioned polycarboxylic acids comprise citric acid added in an amount not more than 2% w/v based on the amount of dry chitosan in the sizing composition.
  • crosslinking of chitosan and/or derivatives thereof, applied to the fibers may be obtained by chemical and/or thermal treatment, with the sizing composition bath including formulations containing double-bond acrylic monomers, e.g. 2-hydroxy ethyl methacrylate (HEMA), and optionally polycarboxylic acids, such as citric acid.
  • HEMA 2-hydroxy ethyl methacrylate
  • polycarboxylic acids such as citric acid
  • the above mentioned sizing composition undergoes a dissolution step, by agitating the chitosan and/or derivatives thereof in the sizing composition for a period of more than 10 hours, and preferably the sizing composition undergoes agitation for a period of 12 hours to 24 hours, at a temperature ranging from 60°C to 80°C, preferably a temperature of about 70°C.
  • the above mentioned sizing composition is prepared by submitting the sizing composition to be prepared to a step of dissolution by dispersion, during which the chitosan that has been added into the sizing composition is dissolved after being finely dispersed in the sizing composition.
  • step of dissolution by dispersion of the chitosan and/or derivatives thereof is carried out by dispersion means that are adapted to achieve fine dispersion of the chitosan and/or derivatives thereof in the bath (i.e. the sizing composition) by high-speed impacts with the solid chitosan particles contained in the bath.
  • These dispersion means comprise at least one COWLES-type impeller or an impeller having blades, particularly, but without limitation, a toothed-disk impeller, with the teeth formed of blades, preferably having a sawtooth shape. According to preferred embodiment, these blades or teeth are placed at the outer peripheral edge of the impeller disk and/or project out of both sides of said disk.
  • the COWLES-type impeller or the impeller with blades comprises a varying number of peripheral teeth, e.g. ranging from ten to forty.
  • the number of teeth of the impeller varies, namely increases, with the outside diameter of the impeller.
  • the outside diameter of the COWLES-type impeller or the impeller with blades is at least 5 cm, and may be up to 100 cm in the case of large dispersers.
  • the diameter of the COWLES-type impeller or the impeller with blades ranges from 12 cm to 40 cm.
  • the bath in which the chitosan and/or derivatives thereof are added in a solid state (e.g. powder, granules or flakes) or in a fluid state (e.g. in the form of a high-density paste) is contained in a tank of a disperser in which said COWLES impeller or said impeller with blades is rotatably actuated at high speed, i.e. at a peripheral speed of rotation of the impeller of 10 meters/second or more and less than 40 m/second, preferably at a peripheral speed of the impeller of 13-32 meters/second.
  • the inside diameter of the above mentioned tank is twice to six times the maximum outside diameter of the COWLES-type impeller or the impeller with blades. More preferably, the inside diameter of the above mentioned tank is three to four times the maximum outside diameter of the COWLES-type impeller or the impeller with blades, which will provide an advantageous condition when the inside diameter of the tank is about three times the maximum outside diameter of the COWLES-type impeller or the impeller with blades.
  • complete dispersion of particles of chitosan and/or derivatives thereof in the bath which is achieved using a COWLES impeller or an impeller with blades, and leads to the dissolution of such particles of chitosan and/or derivatives thereof in the bath, and to the formation of the sizing composition comprising chitosan and/or derivatives thereof, is obtained in very short process times, indicatively also less than one hour, e.g. of the order of 35-45 minutes, with no need to extend said dispersion step to multiple hours, as required by the dissolution by agitation as described above.
  • the crosslinking of chitosan and/or derivatives thereof contained in the above mentioned sizing composition on fibers impregnated with such sizing composition is obtained by exposing the fibers impregnated with said sizing composition to the radiation of a UV lamp.
  • the step of crosslinking on the fibers impregnated with chitosan and/or derivatives thereof contained in such sizing composition is obtained by exposing the fibers impregnated with said sizing composition to the radiation of a UV lamp:
  • the above mentioned step of exposure of the impregnated fibers to the radiation of the UV lamp is preceded by a step of wringing, partially drying or completely drying the fibers.
  • the crosslinking of the fibers of chitosan and/or derivatives thereof, contained in the above mentioned sizing composition may be obtained by chemical treatment, possibly after a step of wringing, partially drying or completely drying the fibers.
  • the sized fibers only have crosslinked, i.e. permanently applied, thereto, the amount of crosslinked chitosan and/or crosslinked chitosan derivatives that is required to achieve the desired effects, and the rest of the sizing composition may be removed, by desizing, with a simple washing step with water at 35-40°C or a later finishing step. Particularly, such later water washing or finishing step only removes the chitosan and/or derivatives thereof that have been crosslinked but do not adhere to the fibers.
  • the sizing composition as described above, and the process of preparing the sizing compositionof the invention and the crosslinking process in use can fulfill the above mentioned needs, while obviating the lamented drawbacks.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (15)

  1. Composition d'encollage pour des fibres et fils et/ou des étoffes fabriquées à partir de telles fibres, en particulier pour des fibres naturelles animales, des fibres végétales, des fibres polymères synthétiques, des fibres polymères naturelles de fabrication humaine, des filaments continus d'origine animale et/ou des filaments discontinus d'origine animale, destinés à être utilisés dans un état pur ou mélangés les uns avec les autres, ladite composition d'encollage comprenant du chitosane et/ou des dérivés de celui-ci, où :
    - ledit chitosane et/ou lesdits dérivés de celui-ci présentent une masse moléculaire Mv allant de 120.000 Da à 180.000 Da, de préférence une masse moléculaire Mv de l'ordre de 150.000 Da, avec un degré de désacétylation de 70 à 90 %, et une viscosité à température ambiante de 20 à 200 cps avec 1 % m/m de chitosane dans 1 % m/v d'acide acétique ou citrique,
    caractérisée en ce que :
    - ladite composition d'encollage comprend une solution d'acide organique avec un pH inférieur à 6,5 à 3-9 % v/v, dans laquelle sont dissous 3 % à 9 % m/v dudit chitosane et/ou desdits dérivés de celui-ci :
    . par agitation ou
    . par une étape de dispersion qui est réalisée au moyen d'un rotor de type Cowles ou d'un rotor à lames, de préférence un rotor à lame de scie, qui peut percuter les particules solides de chitosane et/ou de dérivés de celui-ci à grande vitesse, et
    - pour faciliter la réticulation UV du chitosane et/ou du dérivé, ladite composition d'encollage est enrichie avec des agents de réticulation à monomères double liaison supplémentaires comprenant des monomères acryliques à faible impact environnemental ajoutés dans une quantité égale au pourcentage m/v de chitosane et/ou de dérivés de celui-ci dans la composition d'encollage.
  2. Composition d'encollage selon la revendication 1, ladite composition d'encollage étant, pour faciliter la réticulation UV du chitosane et/ou du dérivé, enrichie avec des agents de réticulation supplémentaires comprenant :
    . des huiles siccatives, de préférence de l'huile de lin constituée d'acide oléique et linoléique, et/ou
    . des acides polycarboxyliques.
  3. Composition d'encollage selon la revendication 1 ou 2, dans laquelle ladite solution d'acide organique avec un pH inférieur à 6,5 à 3-9 % v/v, est une solution d'acide acétique, d'acide citrique, d'acide pyruvique ou d'acide tartrique.
  4. Composition d'encollage selon la revendication 1, 2 ou 3, dans laquelle le degré de désacétylation dudit chitosane et/ou desdits dérivés de celui-ci est de 75 à 85 %.
  5. Composition d'encollage selon la revendication 1, 2, 3 ou 4, dans laquelle le chitosane et/ou les dérivés de celui-ci sont dans un état solide, de préférence de la poudre, des granulés ou des paillettes, ou dans un état fluide, par exemple sous la forme d'une pâte à haute densité, avant d'être dissous par agitation et/ou dispersion dans ladite solution contenant un acide organique avec un pH inférieur à 6,5 à 3 à 9 % v/v.
  6. Composition d'encollage selon l'une quelconque des revendications 1 à 5, dans laquelle ladite solution de chitosane et/ou de dérivés de celui-ci dans un acide organique, avec un pH inférieur à 6,5, comprend de la colle d'amidon et/ou de poisson dans une proportion de 1:1 par rapport à la quantité de chitosane et/ou de dérivés de celui-ci.
  7. Composition d'encollage selon l'une quelconque des revendications 1 à 6, dans laquelle :
    - ladite composition d'encollage comprend :
    - des huiles siccatives, de préférence de l'huile de lin constituée d'acide oléique et linoléique, et/ou
    - des acides polycarboxyliques, de préférence comprenant de l'acide citrique ajouté dans une quantité d'au plus 2 % basée sur la quantité de chitosane sec dans la composition d'encollage.
  8. Procédé de préparation d'une composition d'encollage pour des fibres et fils et/ou des étoffes fabriquées à partir de telles fibres, en particulier pour des fibres naturelles animales, des fibres végétales, des fibres polymères synthétiques, des fibres polymères naturelles de fabrication humaine, des filaments continus d'origine animale et/ou des filaments discontinus d'origine animale, destinés à être utilisés dans un état pur ou mélangés les uns avec les autres, dans lequel ladite composition d'encollage comprend :
    - du chitosane et/ou des dérivés de celui-ci présentant une masse moléculaire Mv allant de 120.000 Da à 180.000 Da, de préférence une masse moléculaire Mv de l'ordre de 150.000 Da, avec un degré de désacétylation de 70 à 90 %, et une viscosité à température ambiante de 20 à 200 cps avec 1 % m/m de chitosane dans 1 % m/v d'acide acétique ou citrique et
    - une solution d'acide organique avec un pH inférieur à 6,5 à 3-9 % v/v, dans laquelle sont dissous 3 % à 9 % m/v dudit chitosane et/ou desdits dérivés de celui-ci, ladite composition d'encollage étant soumise à une étape de dissolution par dispersion réalisée à l'aide de moyens de dispersion qui sont aptes à obtenir une dispersion fine du chitosane et/ou des dérivés de celui-ci présents dans la composition d'encollage par des impacts à haute vitesse avec les particules solides de chitosane et/ou de dérivés de celui-ci présents dans le bain, jusqu'à dissolution desdites particules solides de chitosane et/ou de dérivés de celui-ci dans le bain, lesdits moyens de dispersion pour réaliser ladite étape de dispersion du chitosane et/ou des dérivés de celui-ci comprenant au moins un rotor de type Cowles ou un rotor à disque denté comportant des lames, les dents étant formées par des lames, de préférence présentant la forme de dents de scie,
    dans lequel, pour faciliter la réticulation UV du chitosane et/ou du dérivé, ladite composition d'encollage est enrichie avec des agents de réticulation à monomères double liaison supplémentaires comprenant des monomères acryliques ajoutés dans une quantité égale au pourcentage de chitosane et/ou de dérivés de celui-ci dans la composition d'encollage.
  9. Procédé de préparation d'une composition d'encollage selon la revendication 8, dans lequel ladite étape de dispersion de chitosane et/ou de dérivés de celui-ci est réalisée en introduisant le bain dans lequel ont été ajoutés le chitosane et/ou les dérivés de celui-ci dans un état solide ou fluide, dans une cuve d'un disperseur dans lequel ledit rotor Cowles ou ledit rotor à lames est à rotation, de préférence à une vitesse périphérique de rotation du rotor supérieure à 10 mètres/seconde et inférieure à 40 m/seconde, de préférence à une vitesse périphérique du rotor de 13 à 32 mètres/seconde.
  10. Procédé de préparation d'une composition d'encollage selon l'une quelconque des revendications 8 à 9, dans lequel ledit chitosane et/ou lesdits dérivés de celui-ci sont dissous par agitation ou par dispersion dans ladite composition d'encollage à partir d'un état solide, de préférence de la poudre, des granulés ou des paillettes, ou d'un état fluide, de préférence sous la forme d'une pâte à haute densité.
  11. Procédé de préparation d'une composition d'encollage selon l'une quelconque des revendications 8 à 10, dans lequel ladite solution de chitosane et/ou de dérivés de celui-ci dans un acide organique, avec un pH inférieur à 6,5, comprend de la colle d'amidon et/ou de poisson dans une proportion de 1:1 par rapport à la quantité de chitosane et/ou de dérivés de celui-ci.
  12. Procédé de préparation d'une composition d'encollage selon l'une quelconque des revendications 8 à 11, dans lequel, pour faciliter la réticulation UV du chitosane et/ou du dérivé, ladite composition d'encollage est enrichie avec des agents de réticulation supplémentaires comprenant :
    - des huiles siccatives, de préférence de l'huile de lin constituée d'acide oléique et linoléique, et/ou
    - des acides polycarboxyliques.
  13. Procédé de préparation d'une composition d'encollage selon la revendication 8 ou 12, dans lequel lesdits acides polycarboxyliques comprennent de l'acide citrique ajouté dans une quantité d'au plus 2 % basée sur la quantité de chitosane sec dans la composition d'encollage.
  14. Procédé de réticulation de chitosane et/ou de dérivés de celui-ci présents dans la composition d'encollage selon l'une quelconque des revendications 1 à 7, sur des fibres imprégnées avec ladite composition d'encollage, dans lequel ladite étape de réticulation est réalisée :
    - en exposant les fibres imprégnées avec ladite composition d'encollage au rayonnement d'une lampe UV et
    - par traitement chimique.
  15. Procédé de réticulation de chitosane et/ou de dérivés de celui-ci selon la revendication 14, dans lequel ladite étape de réticulation est réalisée en exposant lesdites fibres imprégnées avec ladite composition d'encollage au rayonnement d'une lampe UV :
    - ayant une puissance de 400 W à 600 W, de préférence une puissance d'environ 500 W, et
    - ayant une intensité de 10 mV/cm2 à 30 mV/cm2, de préférence une intensité d'environ 20 mV/cm2,
    pendant un temps d'exposition allant de 20 à 80 secondes, de préférence pendant un temps d'exposition allant de 30 à 65 secondes, à une distance de la lampe UV allant de 15 cm à 30 cm, de préférence à une distance de la lampe UV de l'ordre de 20 cm.
EP15775804.6A 2014-09-03 2015-08-31 Composition d'encollage pour fibres, fils et/ou tissus, et procédé de préparation de celle-ci Active EP3189187B8 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL15775804T PL3189187T3 (pl) 2014-09-03 2015-08-31 Kompozycja zaklejająca do włókien i przędz i/lub tkanin i sposób wytwarzania takiej kompozycji zaklejającej

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Application Number Priority Date Filing Date Title
ITMI20141534 2014-09-03
ITMI20150270 2015-02-23
PCT/IB2015/056588 WO2016034997A1 (fr) 2014-09-03 2015-08-31 Composition d'empois pour des fibres, des fils et/ou des tissus, et procédé de préparation de celle-ci

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EP3189187A1 EP3189187A1 (fr) 2017-07-12
EP3189187B1 true EP3189187B1 (fr) 2021-06-09
EP3189187B8 EP3189187B8 (fr) 2021-07-21

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EP (1) EP3189187B8 (fr)
DK (1) DK3189187T3 (fr)
ES (1) ES2882122T3 (fr)
PL (1) PL3189187T3 (fr)
PT (1) PT3189187T (fr)
WO (1) WO2016034997A1 (fr)

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ITMI20111901A1 (it) 2011-10-19 2013-04-20 Alfonso Saibene Procedimento per il conferimento di idoneita' alla tessitura ad un filato e/o ordito sottili
IT201700042340A1 (it) * 2017-04-18 2018-10-18 Su S R L Metodo per la realizzazione di un tessuto tinto
CN115449954B (zh) * 2022-10-09 2024-04-26 深圳市卡熙赫服饰有限公司 一种抑菌抗紫外纺织面料的制备方法

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PT3189187T (pt) 2021-07-20
PL3189187T3 (pl) 2021-11-22
DK3189187T3 (da) 2021-07-26
WO2016034997A1 (fr) 2016-03-10
EP3189187A1 (fr) 2017-07-12
EP3189187B8 (fr) 2021-07-21

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