WO2016034997A1 - Sizing composition for fibers, yarns and/or fabrics and process for preparing such sizing composition - Google Patents
Sizing composition for fibers, yarns and/or fabrics and process for preparing such sizing composition Download PDFInfo
- Publication number
- WO2016034997A1 WO2016034997A1 PCT/IB2015/056588 IB2015056588W WO2016034997A1 WO 2016034997 A1 WO2016034997 A1 WO 2016034997A1 IB 2015056588 W IB2015056588 W IB 2015056588W WO 2016034997 A1 WO2016034997 A1 WO 2016034997A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sizing composition
- chitosan
- derivatives
- fibers
- impeller
- Prior art date
Links
- 238000004513 sizing Methods 0.000 title claims abstract description 97
- 239000000203 mixture Substances 0.000 title claims abstract description 94
- 239000000835 fiber Substances 0.000 title claims abstract description 66
- 239000004744 fabric Substances 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title description 4
- 229920001661 Chitosan Polymers 0.000 claims abstract description 75
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000006196 deacetylation Effects 0.000 claims abstract description 7
- 238000003381 deacetylation reaction Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 20
- 238000004132 cross linking Methods 0.000 claims description 17
- 241001465754 Metazoa Species 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 150000007513 acids Chemical class 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims description 6
- 230000002093 peripheral effect Effects 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 4
- 229920005615 natural polymer Polymers 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229920001059 synthetic polymer Polymers 0.000 claims description 4
- 235000013311 vegetables Nutrition 0.000 claims description 4
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 claims description 3
- 239000004833 fish glue Substances 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- 235000021388 linseed oil Nutrition 0.000 claims description 3
- 239000000944 linseed oil Substances 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 235000019198 oils Nutrition 0.000 claims description 3
- 150000002888 oleic acid derivatives Chemical class 0.000 claims description 3
- 229940107700 pyruvic acid Drugs 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 238000007669 thermal treatment Methods 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims description 2
- 241000763859 Dyckia brevifolia Species 0.000 claims 1
- 235000004879 dioscorea Nutrition 0.000 description 5
- 238000005406 washing Methods 0.000 description 4
- 238000009941 weaving Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 210000000085 cashmere Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 240000008564 Boehmeria nivea Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 244000089742 Citrus aurantifolia Species 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 241001416177 Vicugna pacos Species 0.000 description 1
- 241000282840 Vicugna vicugna Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009990 desizing Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- 238000009950 felting Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011012 sanitization Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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.
- - thin yarns are intended to cover yarns having a yarn count ranging from 40 to 200 Nm, more preferably a yarn count of 65 Nm or more;
- - animal fibers are intended to cover fleece or hair fibers (such as wool, alpaca, vicuna, cashmere, etc.);
- - continuous filaments of animal origin are intended to cover filaments obtained by reeling from whole cocoons (such as silk);
- - discontinuous filaments of animal origin are intended to cover filaments obtained by unravelling from defective cocoons (such as waste silk);
- - vegetable fibers are intended to cover all the fibers obtained from plants, shrubs, inflorescences, roots, leaves (such as cotton, flax, hemp, jute, coir, ramie, bamboo, and others);
- - synthetic polymer fibers are intended to cover, for example, polyamide, polyester, acrylic, polypropylene fibers, and others;
- - man-made natural fibers are intended to cover, for example, rayon viscose, modal, acetate, cupro, lyocell, and others.
- the technique of applying a sizing composition to yarn fibers has been long known and is generally used to improve weavability of yams, particularly thin yams 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 water- soluble 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
- water- soluble 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 crosslinldng of cliitosan and/or derivatives thereof, contained in the sizing composition.
- another problem consists in conceiving a method of preparing a sizing composition comprising cliitosan, which is effective and economic and can be easily implemented in a manufacturing process without requiring excessively long processing/preparation limes, while providing a sizing composition in which cliitosan is finely dissolved.
- the invention also relates to a process as defined in claim 20 for crosslinldng cliitosan 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 cliitosan and/or derivatives thereof.
- the chitosan and/or derivatives thereof as used for preparing the sizing composition of the invention have:
- molecular weight ranging from 120,000 Da to 1 80,000 Da, preferably a molecular weight of the order of 150,000 Da, such molecular weight being expressed as viscosity average molecular mass, or Mv
- the chitosan and/or derivatives thereof are preferably dissolved in a 3% to 9% w/v inorganic 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 crosslinking agents, comprising:
- linseed oil consisting of oleic and linoleic acid
- the above mentionedacrylic monomers are 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), or 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.
- the above mentioned 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.
- 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:
- an exposure time ranging from 20 to 80 seconds preferably for an exposure time ranging from 30 to 65 seconds, at a distance from the UV lamp ranging from 15 cm to 30 cm, preferably at a distance of the order of 20 cm from the 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 and/or thermal 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.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
A sizing composition for fibers and yarns and/or fabrics made from such fibers, comprises chitosan having a molecular weight Mvof 150.000 Da, with a degree of deacetylation of 75-85% and an ambient temperature viscosity of 20-200 cps, said chitosan being dissolved in a 3% to 9% w/v acetic acid or citric acid solution, 3-9% v/v.
Description
Sizing composition for fibers, yarns and/or fabrics and process for preparing such sizing composition
DESCRIPTION
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.
As used herein, the term weaving is generally used both for designating warp-and-weft weaving and knit-weaving.
As used herein, for example:
- thin yarns are intended to cover yarns having a yarn count ranging from 40 to 200 Nm, more preferably a yarn count of 65 Nm or more;
- animal fibers are intended to cover fleece or hair fibers (such as wool, alpaca, vicuna, cashmere, etc.);
- continuous filaments of animal origin are intended to cover filaments obtained by reeling from whole cocoons (such as silk);
- discontinuous filaments of animal origin are intended to cover filaments obtained by unravelling from defective cocoons (such as waste silk);
- vegetable fibers are intended to cover all the fibers obtained from plants, shrubs, inflorescences, roots, leaves (such as cotton, flax, hemp, jute, coir, ramie, bamboo, and others);
- synthetic polymer fibers are intended to cover, for example, polyamide, polyester, acrylic, polypropylene fibers, and others;
- man-made natural fibers are intended to cover, for example, rayon viscose, modal, acetate, cupro, lyocell, and others.
The technique of applying a sizing composition to yarn fibers has been long known and is generally used to improve weavability of yams, particularly thin yams 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 water- soluble such that they may be entirely removed from the fibers by appropriate finishing processing steps, such as washing or dyeing.
It shall be noted that additional needs are felt, such as:
- enhancing the mechanical properties of abrasion resistance of thin yarns, while reducing mechanical friction between weft yams and warp yarns, for trouble-free weaving;
- developing an environment-friendly and low-power-consumption process for making a yarn having improved weavability features;
- developing a process for making a yam having improved features in terms of resistance to pilling, felting and rubbing, as well as superior mechanical properties while maintaining the desired softness, volume, brightness and lightness features;
- developing a process for making a yam having improved dye affinity, or improved affinity for the later finishing steps, such as printing.
In view of the above needs, 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.
For example, the use of sizing compositions comprising chitosan has been suggested, wherein, after application to the fibers, 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.
It shall be noted that 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.
Conversely, 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.
Therefore, 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 crosslinldng of cliitosan and/or derivatives thereof, contained in the sizing composition.
This problem is solved by a sizing composition as defined in claim 1.
In a further aspect, another problem consists in conceiving a method of preparing a sizing composition comprising cliitosan, which is effective and economic and can be easily implemented in a manufacturing process without requiring excessively long processing/preparation limes, while providing a sizing composition in which cliitosan is finely dissolved.
According to the invention, this additional technical problem is solved by means of a process as defined in claim 9 or in claim 10 for preparing a sizing composition of the invention.
In a further aspect, the invention also relates to a process as defined in claim 20 for crosslinldng cliitosan and/or derivatives thereof contained in the sizing composition of the invention on fibers impregnated with such sizing composition.
According to the invention, the sizing composition to be used for sizing the fibers (particularly 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) or theyarns, fabrics or knits obtained from such fibers is a sizing composition comprising cliitosan and/or derivatives thereof.
Advantageously, the chitosan and/or derivatives thereof as used for preparing the sizing composition of the invention have:
- a molecular weight ranging from 120,000 Da to 1 80,000 Da, preferably
a molecular weight of the order of 150,000 Da, such molecular weight being expressed as viscosity average molecular mass, or Mv
- a degree of deacetylation of 70-90%, preferably a degree of deacetylation of 75-85% and/or
- a viscosity at ambient temperature (indicatively a temperature of about
25°C, Brookfield viscosity) of 20-200 cps, 1% w/w chitosan in 1 % w/v acetic or citric acid.
The chitosan and/or derivatives thereof are preferably dissolved in a 3% to 9% w/v inorganic acid solution, with a pH of less than 6.5.
Preferably, 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.
By way of example only, pyruvic acid and tartaric acid may be used as further organic acids. Preferably, 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.
Preferably, 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.
Preferably, to facilitate UV crosslinking of chitosan and/or derivative, the above mentioned sizing composition is enriched with additional crosslinking agents, comprising:
- double-bond monomers, preferably acrylic monomers with low environmental impact,
- drying oils, preferably linseed oil consisting of oleic and linoleic acid,
and/or
- polycarboxylic acids.
Preferably, the above mentionedacrylic monomers are added in an amount substantially equal to the w/v percent of chitosan and/or derivatives thereof in the sizing composition.
Preferably, 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.
Furthermore, 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), or polycarboxylic acids, such as citric acid.
Advantageously, before being used for sizing fibers, 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.
In a different and more advantageous production mode, alternative to the above described dissolution by agitation, 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.
The above mentioned 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.
Preferably, 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.
According to a preferred embodiment, 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. Preferably, the diameter of the COWLES-type impeller or the impeller with blades ranges from 12 cm to 40 cm.
In short, 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. This will afford a surprising and effective dispersion of the particles of chitosan and/or derivatives thereof in the bath, to complete and rapid dissolution of the particles of chitosan and/or derivatives thereof in the bath, leading to the formation of the sizing composition of the invention.
According to a preferred embodiment, 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.
Advantageously, 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.
It shall be further noted that the above mentioned complete dissolution by dispersion of particles of chitosan and/or derivatives thereof in the bath, which is achieved using a COWLES impeller or an impeller with blades, can be also achieved at ambient temperature, indicatively also at temperatures of about
15°C, optimal results being also achievable with temperatures of less than 40°C. Therefore, said dissolution by dispersion of chitosan and/or derivatives thereof in the bath does not require extended heating at temperatures of the order of 60- 80°C, as required in dissolution by agitation as described above.
Advantageously, 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.
Preferably, 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:
- having a power of 400 W to 600 W, preferably a power of about 500W, and
- having an intensity of 10 mV/cm2 to 30 mV/cm2, preferably an intensity of about 20 mV/cm2,
for an exposure time ranging from 20 to 80 seconds, preferably for an exposure time ranging from 30 to 65 seconds, at a distance from the UV lamp ranging from 15 cm to 30 cm, preferably at a distance of the order of 20 cm from the UV lamp.
Preferably, 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.
Alternatively, as described above, the crosslinking of the fibers of chitosan and/or derivatives thereof, contained in the above mentioned sizing
composition may be obtained by chemical and/or thermal treatment, possibly after a step of wringing, partially drying or completely drying the fibers.
Experimental tests proved that the use of the sizing composition of the invention for sizing the fibers, and the later step of crosslinking and/or derivatives thereof contained in the sizing composition can provide fibers, e.g. in the forms of a yarn, a fabric or a knit, that can fulfill the above mentioned needs. This is because said fibers have an amount of crosslinked chitosan and/or chitosan derivatives substantially permanently applied thereto, such amount allowing to achieve the desired beneficial effects, without causing the fibers to have a stiff or poorly soft feel.
Namely, according to the specific compounds that form the sizing composition in use, the specific method of producing such sizing composition and the specific crosslinking method, 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.
In the light of the above disclosure, 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.
The above disclosure is susceptible to a number of changes and variants
within the inventive concept, as outlined by the annexed claims.
Claims
1. 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, wherein said sizing composition comprises chitosan and/or derivatives thereof, characterized in that:
- said chitosan and/or derivatives thereof have a molecular weight Mv ranging from 120,000 Da to 180,000 Da, preferably a molecular weight Mv of the order of 1 50,000 Da, with a degree of deacetylation of 70-90%, and an ambient temperature viscosity of 20-200 cps with 1 % w/w chitosan in 1 % w/v acetic or citric acid;
- said sizing composition comprises an inorganic acid solution with a pH of less than 6.5 at 3-9% v/v, in which 3% to 9% w/v of said chitosan and/or derivatives thereof are dissolved:
- by agitation or
- by a dispersion step that is carried out using a COWLES-type impeller or an impeller with blades, preferably a sawblade impeller, which can impact the solid particles of chitosan and/or derivatives thereof at high speed.
2. A sizing composition as claimed in claim 1 , wherein said inorganic acid solution with a pH of less than 6.5 at 3-9% v/v, is an acetic acid, a citric acid, a pyruvic acid or a tartaric acid solution.
3. A sizing composition as claimed in claim 1 or 2, wherein the degree of deacetylation of said chitosan and/or derivatives thereof is 75-85%.
4. A sizing composition as claimed in claim 1 , 2 or 3, wherein the chitosan
and/or derivatives thereof are in a solid state, preferably 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 dispersion in said solution containing an inorganic acid with a pH of less than 6.5 at 3-9% v/v.
5. A sizing composition as claimed in any of claims 1 to 4, wherein said solution of chitosan and/or derivatives thereof in an inorganic acid, with a pH of less than 6.5 comprises starch and/or fish glue at a ratio of 1 : 1 to the amount of chitosan and/or derivatives thereof.
6. A sizing composition as claimed in any of claims 1 to 5 wherein, to facilitate UV crosslinking of chitosan and/or derivative, said sizing composition is enriched with additional crosslinking agents, comprising:
- double-bond monomers, preferably acrylic monomers with low environmental impact,
- drying oils, preferably linseed oil consisting of oleic and linoleic acid, and/or
- polycarboxylic acids.
7. A sizing composition as claimed in claim 6, wherein said acrylic monomers are added in an amount substantially equal to the w/v percent of chitosan and/or derivatives thereof in the sizing composition.
8. A sizing composition as claimed in claim 6, wherein said polycarboxylic acids comprise citric acid added in an amount not more than 2% based on the amount of dry chitosan in the sizing composition.
9. A process of preparing a sizing composition as claimed in any of claims 1 to 8, wherein said sizing composition comprising chitosan and/or derivatives thereof undergoes agitation, for dissolving the chitosan and/or
derivatives thereof for a period of more than 10 hours, and preferably 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.
10. A process of preparing a sizing composition as claimed in any of claims 1 to 8, wherein said sizing composition comprising chitosan and/or derivatives thereof undergoes a step of dissolution by dispersion, which is carried out by dispersion means that are adapted to achieve fine dispersion of the chitosan and/or derivatives thereof contained in the sizing composition by high-speed impacts with the solid particles of chitosan and/or derivatives thereof contained in the bath, to dissolution of said solid particles of chitosan and/or derivatives thereof in the bath.
11. A process of preparing a sizing composition as claimed in claim 10, wherein said dispersion means for carrying out said step of dispersion of chitosan and/or derivatives thereof comprise at least one COWLES-type impeller or an impeller having blades, particularly a toothed-disk impeller, with the teeth formed of blades, preferably having a sawtooth shape.
12. A process of preparing a sizing composition as claimed in claim 1 1 , wherein said step of dispersion of chitosan and/or derivatives thereof is carried out by introducing the bath in which chitosan and/or derivatives thereof have been added in a solid or fluid state, into a tank of a disperser in which said COWLES impeller or said impeller with blades is rotatably, preferably at a peripheral speed of rotation of the impeller of more than 10 meters/second and less than 40 m/second, preferably at a peripheral speed of the impeller of 13-32 meters/second.
13. A process of preparing a sizing composition as claimed in any of claims
9 to 12, wherein said chitosan and/or derivatives thereof have a molecular weight Mv ranging from 120,000 Da to 180,000 Da, preferably a molecular weight Mv of the order of 150,000 Da, with a degree of deacetylation of 70- 90%, and an ambient temperature viscosity of 20-200 cps with 1% w/w chitosan in 1% w/v acetic or citric acid;
- said sizing composition comprises an inorganic acid solution with a pH of less than 6.5 at 3-9% v/v, in which 3% to 9% w/v of said chitosan and/or derivatives thereof are dissolved, preferably an acetic acid, a citric acid, a pyruvic acid or a tartaric acid solution.
14. A process of preparing a sizing composition as claimed in claim 13, wherein the degree of deacetylation of said chitosan and/or derivatives thereof is 75-85%.
15. A process of preparing a sizing composition as claimed in any of claims 9 to 14, wherein said chitosan and/or derivatives thereof are dissolved by agitation or by dispersion in said sizing composition from a solid state, preferably powder, granules or flakes, or from a fluid state, preferably in the form of a high-density paste.
16. A process of preparing a sizing composition as claimed in any of claims 9 to 15, wherein said solution of chitosan and/or derivatives thereof in an inorganic acid, with a pH of less than 6.5 comprises starch and/or fish glue at a ratio of 1 : 1 to the amount of chitosan and/or derivatives thereof.
17. A process of preparing a sizing composition as claimed in any of claims 9 to 16 wherein, to facilitate UV crosslinking of chitosan and/or derivative, said sizing composition is enriched with additional crosslinking agents, comprising:
- double-bond monomers, preferably acrylic monomers with low
environmental impact,
- drying oils, preferably linseed oil consisting of oleic and linoleic acid, and/or
- polycarboxylic acids.
18. A process of preparing a sizing composition as claimed in claim 17, wherein said acrylic monomers are added in an amount substantially equal to the percent of chitosan and/or derivatives thereof in the sizing composition.
19. A process of preparing a sizing composition as claimed in claim 18, wherein said polycarboxylic acids comprise citric acid added in an amount not more than 2% based on the amount of dry chitosan in the sizing composition.
20. A process of crosslinking chitosan and/or derivatives thereof contained in the sizing composition as claimed in any of claims 1 to 8, on fibers impregnated with said sizing composition, wherein said crosslinking step is earned out by:
- by exposing the fibers impregnated with said sizing composition to the radiation of a UV lamp and/or
- by chemical and/or thermal treatment, preferably with the sizing composition bath including formulations containing double-bond acrylic monomers, preferably 2-hydroxy ethyl methacrylate (HEMA), or polycarboxylic acids, preferably citric acid.
21. A process of crosslinking chitosan and/or derivatives thereof as claimed in claim 20, wherein said crosslinking step is carried out by exposing said fibers impregnated with said sizing composition to the radiation of a UV lamp:
- having a power of 400W to 600W, preferably a power of about 500W, and
2 2
- having an intensity of 10 mV/cm to 30 mV/cm , preferably an intensity of about 20 mV/cm ,
for an exposure time ranging from 20 to 80 seconds, preferably for an exposure time ranging from 30 to 65 seconds, at a distance from the UV lamp ranging from 15 cm to 30 cm, preferably at a distance from the UV lamp of the order of 20 cm.
22. A process for crosslinking chitosan and/or derivatives thereof as claimed in claim 20 or 21, comprising a step of wringing, partially drying or completely drying the fibers impregnated with said sizing composition, before carrying out said crosslinking step on the impregnated fibers.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP15775804.6A EP3189187B8 (en) | 2014-09-03 | 2015-08-31 | Sizing composition for fibers, yarns and/or fabrics and process for preparing such sizing composition |
| DK15775804.6T DK3189187T3 (en) | 2014-09-03 | 2015-08-31 | PREPARATION COMPOSITION FOR FIBERS, YARNS AND / OR SUBSTANCES AND METHODS OF PREPARATION OF SUCH PREPARATION COMPOSITION |
| PL15775804T PL3189187T3 (en) | 2014-09-03 | 2015-08-31 | Sizing composition for fibers, yarns and/or fabrics and process for preparing such sizing composition |
| ES15775804T ES2882122T3 (en) | 2014-09-03 | 2015-08-31 | Sizing composition for fibers, yarns and / or fabrics and process for preparing such sizing composition |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI2014A001534 | 2014-09-03 | ||
| ITMI20141534 | 2014-09-03 | ||
| ITMI2015A000270 | 2015-02-23 | ||
| ITMI20150270 | 2015-02-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2016034997A1 true WO2016034997A1 (en) | 2016-03-10 |
Family
ID=54261041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/IB2015/056588 WO2016034997A1 (en) | 2014-09-03 | 2015-08-31 | Sizing composition for fibers, yarns and/or fabrics and process for preparing such sizing composition |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP3189187B8 (en) |
| DK (1) | DK3189187T3 (en) |
| ES (1) | ES2882122T3 (en) |
| PL (1) | PL3189187T3 (en) |
| PT (1) | PT3189187T (en) |
| WO (1) | WO2016034997A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT201700042340A1 (en) * | 2017-04-18 | 2018-10-18 | Su S R L | METHOD FOR THE REALIZATION OF A DYED FABRIC |
| US10174443B2 (en) | 2011-10-19 | 2019-01-08 | Canepa S.P.A. | Process for improving weavability of a yarn |
| CN115449954A (en) * | 2022-10-09 | 2022-12-09 | 董健 | Preparation method of antibacterial and ultraviolet-resistant textile fabric |
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| WO2007083870A1 (en) * | 2006-01-19 | 2007-07-26 | Seoul National University Of Technology Center For Industry Collaboration | Chitosan or hyaluronic acid-poly(ethylene oxide)- and chitosan-hyaluronic acid-poly(ethylene oxide)-based hydrogel and manufacturing method therefor |
| EP1897893A1 (en) * | 2006-09-08 | 2008-03-12 | Emsland-Stärke GmbH | Starch-chitosan compound, method for its manufacture and application |
| EP2105459A1 (en) * | 2007-01-16 | 2009-09-30 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Aqueous solution composition |
| WO2013057723A1 (en) * | 2011-10-19 | 2013-04-25 | Canepa S.P.A. | Process for improving weavability of a yarn |
| ITMI20121778A1 (en) * | 2012-10-19 | 2014-04-20 | Canepa S P A | PROCEDURE TO INCREASE THE FINE FINISHING OF A FABRIC, A JERSEY OR A FINISHED HEAD. |
| WO2015159262A1 (en) * | 2014-04-18 | 2015-10-22 | Canepa S.P.A. | Process for improving the chemical and/or physical properties of a yarn or fabric |
-
2015
- 2015-08-31 WO PCT/IB2015/056588 patent/WO2016034997A1/en active Application Filing
- 2015-08-31 PT PT157758046T patent/PT3189187T/en unknown
- 2015-08-31 ES ES15775804T patent/ES2882122T3/en active Active
- 2015-08-31 EP EP15775804.6A patent/EP3189187B8/en active Active
- 2015-08-31 DK DK15775804.6T patent/DK3189187T3/en active
- 2015-08-31 PL PL15775804T patent/PL3189187T3/en unknown
Patent Citations (6)
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| WO2007083870A1 (en) * | 2006-01-19 | 2007-07-26 | Seoul National University Of Technology Center For Industry Collaboration | Chitosan or hyaluronic acid-poly(ethylene oxide)- and chitosan-hyaluronic acid-poly(ethylene oxide)-based hydrogel and manufacturing method therefor |
| EP1897893A1 (en) * | 2006-09-08 | 2008-03-12 | Emsland-Stärke GmbH | Starch-chitosan compound, method for its manufacture and application |
| EP2105459A1 (en) * | 2007-01-16 | 2009-09-30 | Dainichiseika Color & Chemicals Mfg. Co., Ltd. | Aqueous solution composition |
| WO2013057723A1 (en) * | 2011-10-19 | 2013-04-25 | Canepa S.P.A. | Process for improving weavability of a yarn |
| ITMI20121778A1 (en) * | 2012-10-19 | 2014-04-20 | Canepa S P A | PROCEDURE TO INCREASE THE FINE FINISHING OF A FABRIC, A JERSEY OR A FINISHED HEAD. |
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|---|---|---|---|---|
| US10174443B2 (en) | 2011-10-19 | 2019-01-08 | Canepa S.P.A. | Process for improving weavability of a yarn |
| IT201700042340A1 (en) * | 2017-04-18 | 2018-10-18 | Su S R L | METHOD FOR THE REALIZATION OF A DYED FABRIC |
| EP3392402A1 (en) * | 2017-04-18 | 2018-10-24 | SU S.r.l | Method for manufacturing a dyed textile |
| CN115449954A (en) * | 2022-10-09 | 2022-12-09 | 董健 | Preparation method of antibacterial and ultraviolet-resistant textile fabric |
| CN115449954B (en) * | 2022-10-09 | 2024-04-26 | 深圳市卡熙赫服饰有限公司 | Preparation method of antibacterial anti-ultraviolet textile fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3189187B8 (en) | 2021-07-21 |
| EP3189187A1 (en) | 2017-07-12 |
| EP3189187B1 (en) | 2021-06-09 |
| PT3189187T (en) | 2021-07-20 |
| DK3189187T3 (en) | 2021-07-26 |
| ES2882122T3 (en) | 2021-12-01 |
| PL3189187T3 (en) | 2021-11-22 |
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