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WO2002077358A1 - Utilisation de nanochitosanes - Google Patents

Utilisation de nanochitosanes Download PDF

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Publication number
WO2002077358A1
WO2002077358A1 PCT/EP2002/002820 EP0202820W WO02077358A1 WO 2002077358 A1 WO2002077358 A1 WO 2002077358A1 EP 0202820 W EP0202820 W EP 0202820W WO 02077358 A1 WO02077358 A1 WO 02077358A1
Authority
WO
WIPO (PCT)
Prior art keywords
nanochitosans
use according
sorbitan
chitosans
acid
Prior art date
Application number
PCT/EP2002/002820
Other languages
German (de)
English (en)
Inventor
Marta Domingo
Anna Tacies
Rafael Pi Subirana
Josep-Lluis Viladot Petit
Original Assignee
Cognis Iberia S.L.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cognis Iberia S.L. filed Critical Cognis Iberia S.L.
Publication of WO2002077358A1 publication Critical patent/WO2002077358A1/fr

Links

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
    • 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
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/08—Processes in which the treating agent is applied in powder or granular form

Definitions

  • the invention is in the field of textile technology and relates to the use of chitosans in a particularly finely divided form for finishing fibers, yarns, knitted fabrics, textile fabrics and textiles produced therefrom.
  • chitosans are cationic, ie positively charged biopolymers under these conditions.
  • the positively charged chitosans can interact with oppositely charged surfaces and are therefore used in cosmetic hair and personal care products and pharmaceutical preparations (cf. Ulimann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A6, Weinheim, Verlag Chemie, 1986, pp. 231-332), where they are used as moisturizers and film formers. Further overviews on this topic are also available, for example, from B. Gesslein et al. in HAPPI 27, 57 (1990), O.Skaugrud in Drug Cosm.Ind. 148: 24 (1991) and E. Onoyen et al. in Seifen- ⁇ le-Fette-Wwachs 117, 633 (1991).
  • Chitosans have nourishing properties, but they also have an anti-inflammatory and, to a lesser extent, mild biocidal properties, which predestines them for finishing textiles, ⁇ preferably when they are also - with cationic and therefore occasionally irritating to sensitive consumers have been activated.
  • the use of chitosans has so far not proven itself, since a fundamental problem is that these substances only adhere to the surface of the fibers and are washed out correspondingly quickly. Accordingly, the original effect is quickly lost.
  • the object of the invention was therefore to show a way in which textiles and their preliminary products can be equipped with chitosans, if not permanently, at least over a significantly longer period, so that the wearer can also be used after a number of washes and when used of fabric softeners still in enjoy the nourishing and anti-inflammatory properties of chitosan.
  • the invention relates to the use of nanochitosans for the production of fibers, yarns, knitted fabrics and textile fabrics, in which they are present in amounts of 0.01 to 1, preferably 0.05 to 0.5% by weight, based on the dry weight. can be present.
  • Chitosans are biopolymers and belong to the group of hydrocolloids. From a chemical point of view, these are partially deacetylated chitins of different molecular weights that contain the following - idealized - monomer unit:
  • chitosans is based on chitin, preferably the shell remains of crustaceans, which are available in large quantities as cheap raw materials.
  • the chitin is used in a process that was first developed by Hackmann et al. has been described, usually first deproteinized by adding bases, demineralized by adding mineral acids and finally deacidifying by adding strong bases. cetylated, whereby the molecular weights can be distributed over a broad spectrum.
  • Appropriate methods are, for example, made from Makromol. Chem. 177, 3589 (1976) or French patent application FR 2701266 AI known.
  • Preferred types are those as disclosed in German patent applications DE 4442987 AI and DE 19537001 AI (Henkel), which have an average molecular weight of 800,000 to 1,200,000 Daltons, a Brookfield viscosity (1% by weight in Glycolic acid) below 5000 mPas, a degree of deacetylation in the range from 80 to 88% and an ash content of less than 0.3% by weight.
  • anionically, nonionically or cationically derivatized chitosans such as carboxylation, succinylation, alkoxylation or quaternization products, as described, for example, in German patent DE 3713099 C2 (L 'Oreal) and the German patent application DE 19604180 AI (Henkel) are described.
  • Nanochitosans are to be understood as meaning approximately spherical solids which have an average diameter in the range from 10 to 300, preferably 50 to 200 and in particular 100 to 150 nm.
  • a particularly simple method for producing the nanochitosans consists in spray drying chitosan solutions in water and / or organic solvents, such as, for example, alcohols or (hydroxy) carboxylic acids. Spray drying typically takes place at temperatures in the range from 100 to 110 ° C. and pressures from 10 to 100 mbar.
  • the starting materials are first dissolved in a suitable organic solvent (for example alkanes, vegetable oils, ethers, esters, ketones, acetals and the like).
  • a suitable organic solvent for example alkanes, vegetable oils, ethers, esters, ketones, acetals and the like.
  • the solutions are then added to water or another non-solvent, optionally in the presence of a surface-active compound dissolved therein, so that the homogenization of the two immiscible solvents leads to precipitation of the nanoparticles, the organic solvent preferably evaporating.
  • O / W emulsions or O / W microemulsions can also be used. Production of nanochitosans using the RESS process
  • nanoscale chitosans and / or chitosan derivatives are used, which are obtained by
  • Suitable protective colloids are e.g. Gelatin, casein, gum arabic, lysalbic acid, starch and polymers, such as polyvinyl alcohols, polyvinyl pyrrolidones, polyalkylene glycols and polyacrylates.
  • Suitable emulsifiers are nonionic surfactants from at least one of the following groups:
  • Partial esters of polyglycerol (average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides with (e.g. / or unsaturated, linear or branched fatty acids with 12 to 22 carbon atoms and / or hydroxycarboxylic acids with 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide;
  • Block copolymers e.g. Polyethylene glycol 30 dipolyhydroxystearate;
  • Polymer emulsifiers e.g. Pemulen types (TR-1, TR-2) from Goodrich;
  • adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols or with castor oil are known, commercially available products. These are homolog mixtures whose average degree of alkoxylation is the ratio of the quantities of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out.
  • Ci 2 / ⁇ 8 fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE 2024051 PS as refatting agents for cosmetic preparations. > Alkyl and / or alkenyl olefin glycosides
  • Alkyl and / or alkenyl oligoglycosides their preparation and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms.
  • the glycoside residue both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to preferably about 8 are suitable.
  • the degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.
  • Suitable partial glycerides are Hydroxystearin Textremonogly- cerid, hydroxystearic acid diglyceride, isostearic acid, Isostearin Text- rediglycerid, oleic acid monoglyceride, oleic acid diglyceride, Ricinolklaremoglycerid, ricinoleic klarediglycerid, Linolklaremonoglycerid, Linolklarediglycerid, Linolenklamo- noglycerid, LinolenLiterediglycerid, Erucaklaremonoglycerid, Erucaklakladiglycerid, Weinklaremonoglycerid, Weinklarediglycerid, CitronenLiteremonoglycerid, citric nendiglyceride, malic acid monoglyceride, malic acid diglyceride and their technical mixtures, which may still contain minor amounts of triglyceride from the manufacturing process. Addition products
  • sorbitan sorbitan As sorbitan sorbitan, sorbitan sesquiisostearate, sorbitan come tan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan Bitan dioleate, trioleate, Sorbitanmonoerucat, Sorbitansesquierucat, sorbitan dierucat, Sorbitantrierucat, Sorbitanmonoricinoleat, Sorbitansesquiricinoleat, sorbitan tandiricinoleat, Sorbitantriricinoleat, Sorbitanmonohydroxystearat, Sorbitansesqui - hydroxystearate, sorbitan dihydroxystearate, sorbitan trihydroxystearate, sorbitan mono-notartrate, sorbitan sesqui-tartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate,
  • polyglycerol esters are polyglyceryl-2 dipolyhydroxystearate (Dehymuls® PGPH), polyglycerol-3-diisostearate (Lameform® TGI), polyglyceryl-4 isostearate (Isolan® GI 34), polyglyceryl-3 oleate, diisostearoyl po- lyglyceryl-3 diisostearate (Isolan® PDI), polyglyceryl-3 methylglucose distearate (Tego Care® 450), polyglyceryl-3 beeswax (Cera Bellina®), polyglyceryl-4 caprate (polyglycerol caprate T2010 / 90), polyglyceryl-3 cetyl ether ( Chimexane® NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and Polyglyceryl Polyricinoleate (Admul® WOL 1403) Polyglyceryl Dimer
  • polystyrene resin examples include the mono-, di- and triesters of trimethylolpropane or pentaerythritol with lauric acid, coconut fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like which are optionally reacted with 1 to.30 mol of ethylene oxide.
  • Typical anionic emulsifiers are aliphatic fatty acids with 12 to 22 carbon atoms, such as, for example, palmitic acid, stearic acid or behenic acid, and dicarboxylic acids with 12 to 22 carbon atoms, such as, for example, azelaic acid or sebacic acid.
  • Zwitterionic surfactants can also be used as emulsifiers.
  • Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyldimethylammonium glycinate, and 2 alkyl-3-carboxylmethyl-3-hydroxyethyl thylimidazolines each with 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate.
  • betaines such as N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate,
  • Suitable emulsifiers are ampholytic surfactants.
  • Ampholytic surfactants are surface-active compounds which, in addition to a C 8 / i 8 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -S0 3 H group in the molecule and are capable of forming internal salts.
  • suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N- alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-
  • Alkyl taurines N-alkyl sarcosines, 2-alkyl aminopropionic acids and alkyl amino acetic acids, each with about 8 to 18 carbon atoms in the alkyl group.
  • Particularly preferred ampholytic surfactants are N-coconut alkyl aminopropionate, coconut acyl amino aminoethyl propionate and C 2 8 -acyl sarcosine.
  • cationic surfactants are also suitable as emulsifiers, those of the esterquat type, preferably methylquaternized difatty acid triethanolamine ester salts, being particularly preferred.
  • the preferred nanoscale chitosans or chitosan derivatives to be used are therefore those which are encased in a protective colloid and / or an emulsifier.
  • the protective colloids or emulsifiers are usually used in amounts of 0.1 to 20, preferably 5 to 15% by weight, based on the chitosans and / or chitosan derivatives.
  • GAS process Gas Anti Solvent Recrystallization
  • the process uses a highly compressed gas or supercritical fluid (e.g. carbon dioxide) as a non-solvent for the crystallization of solutes.
  • the compressed gas phase is introduced into the primary solution of the starting materials and absorbed there, which increases the volume of the liquid, reduces the solubility and separates fine particles.
  • the PCA method (Precipitation with a Compressed Fluid Anti-Solvent) is similarly suitable.
  • the primary solution of the starting materials is introduced into a supercritical fluid, whereby finely divided droplets form in which diffusion processes take place, so that the finest particles are precipitated.
  • the starting materials are melted by injecting gas (e.g. carbon dioxide or propane). Pressure and temperature reach near or supercritical conditions.
  • the gas phase dissolves in the solid and causes a lowering of the melting temperature, the viscosity and the surface tension. When expanding through a nozzle, cooling effects lead to the formation of very fine particles.
  • Another object of the invention relates to fibers, yarns, knitted fabrics and textile fabrics, including the end products for the consumer and textiles that have been produced using these precursors and nanochitosans, preferably in amounts of 0.01 to 1 and in particular 0.05 to 0.5 wt .-% - based on the dry weight - included.
  • Finished textiles for example, can be finished by immersion bath immersion and subsequent drying. Fibers and yarns can also be finished in the same way, namely by applying the nanochitosans, for example, as components of winding oils or spin fiber preparations.
  • the resulting supercritical, ie fluid mixture was sprayed through a laser-drawn nozzle (length 830 ⁇ m, diameter 45 ⁇ m) at a temperature T2 into a plexiglass expansion chamber which contained a 4% by weight aqueous solution of an emulsifier or protective colloid.
  • the fluid medium evaporated and the dispersed nanoparticles enclosed in the protective colloid remained.
  • a 1% by weight solution of chitosan in glycolic acid was added dropwise to a 4% by weight aqueous solution of Coco Glucosides with vigorous stirring at 40 ° C. and a reduced pressure of 40 mbar.
  • the evaporating solvent was condensed in a cold trap while the dispersion with the nanoparticles remained.
  • the process conditions and the mean particle size range are given in Table 1 below.
  • 100 g of polyester fabric was impregnated three times at 25 ° C. over a period of 20 min each with a 5% by weight aqueous solution of (a) nanochitosan according to Example 1 and (b) conventional chitosan powder (Hydagen® DCMF, Cognis Deutschland GmbH) and then dried. The fabrics were then also washed three times in a launder-o-meter with a commercially available liquid mild detergent (30 ° C., 16 ° dH) and the content of chitosan in the wash liquors was determined by HPLC.
  • the chitosan content for the first wash was set at 100% using the comparative product for all other tests.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Cosmetics (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

L'invention concerne l'utilisation de nanochitosanes dans la fabrication de fibres, de fils, de mailles, et de structures plates textiles.
PCT/EP2002/002820 2001-03-22 2002-03-14 Utilisation de nanochitosanes WO2002077358A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP01107163.6 2001-03-22
EP01107163A EP1243688A1 (fr) 2001-03-22 2001-03-22 Utilisation de nanoparticules de chitosane

Publications (1)

Publication Number Publication Date
WO2002077358A1 true WO2002077358A1 (fr) 2002-10-03

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Application Number Title Priority Date Filing Date
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EP (1) EP1243688A1 (fr)
WO (1) WO2002077358A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003042251A1 (fr) * 2001-11-09 2003-05-22 The Procter & Gamble Company Compositions a base de chitosane
CN100415807C (zh) * 2006-03-20 2008-09-03 扬州大学 N-琥珀二酰壳聚糖自组装纳米微粒及制备方法
DE102007017303A1 (de) 2007-04-11 2008-10-16 Institut für Textil- und Verfahrenstechnik der Deutschen Institute für Textil- und Faserforschung Denkendorf - Stiftung des öffentlichen Rec Antibakteriell wirksames Mittel und dessen Verwendung
CN101832938A (zh) * 2010-04-29 2010-09-15 山东华兴纺织集团有限公司 一种用于测定纺织品中壳聚糖纤维含量的方法
CN113444294A (zh) * 2021-06-28 2021-09-28 苏州市德赫亚新纺织科技有限公司 一种氧化壳聚糖/n，o-羧甲基壳聚糖纳米粒的制备方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040176477A1 (en) * 2003-03-06 2004-09-09 The Procter & Gamble Company Chitosan powder
FR2908427B1 (fr) * 2006-11-15 2009-12-25 Skin Up Procede d'impregnation de fibres et/ou de textiles par un compose d'interet et/ou un principe actif sous forme de nanoparticules
JP5338163B2 (ja) 2008-07-10 2013-11-13 Ｊｆｅスチール株式会社 錫めっき鋼板の製造方法
JP2013527329A (ja) 2010-03-25 2013-06-27 レンツィング アクチェンゲゼルシャフト セルロース繊維の使用
DK2920240T3 (da) * 2012-07-20 2022-05-30 Politechnika Gdanska Fremgangsmåde til fremstilling af en vandig opløsning af chitosan, chitosansammensætning, chitosanaerosol, fremgangsmåde til fremstilling af en chitosanhydrogelmembran og fremgangsmåde til fremstilling af et chitosan-protein-biopolymermateriale
CN110528146B (zh) * 2019-08-30 2020-04-17 浙江海明实业有限公司 一种基于咖啡碳纤维的除臭去异味功能面料及纱线制备工艺

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0810592A (ja) * 1994-06-27 1996-01-16 Tokuyama Corp 微多孔性膜
JPH093106A (ja) * 1995-06-20 1997-01-07 Kao Corp 高分子水分散体及びその製造方法
JPH0930957A (ja) * 1995-07-18 1997-02-04 Oji Paper Co Ltd 湿布材料
JPH1037018A (ja) * 1996-07-16 1998-02-10 Fuji Spinning Co Ltd 抗菌性セルロース再生繊維
WO2000047177A1 (fr) * 1999-02-09 2000-08-17 Cognis Deutschland Gmbh Utilisation de nanoparticules de chitosanes et/ou de derives de chitosanes

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0810592A (ja) * 1994-06-27 1996-01-16 Tokuyama Corp 微多孔性膜
JPH093106A (ja) * 1995-06-20 1997-01-07 Kao Corp 高分子水分散体及びその製造方法
JPH0930957A (ja) * 1995-07-18 1997-02-04 Oji Paper Co Ltd 湿布材料
JPH1037018A (ja) * 1996-07-16 1998-02-10 Fuji Spinning Co Ltd 抗菌性セルロース再生繊維
WO2000047177A1 (fr) * 1999-02-09 2000-08-17 Cognis Deutschland Gmbh Utilisation de nanoparticules de chitosanes et/ou de derives de chitosanes

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199711, Derwent World Patents Index; Class A18, AN 1997-115286, XP002177356 *
DATABASE WPI Section Ch Week 199715, Derwent World Patents Index; Class B07, AN 1997-161406, XP002158841 *
PATENT ABSTRACTS OF JAPAN vol. 1996, no. 05 31 May 1996 (1996-05-31) *
PATENT ABSTRACTS OF JAPAN vol. 1998, no. 06 30 April 1998 (1998-04-30) *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003042251A1 (fr) * 2001-11-09 2003-05-22 The Procter & Gamble Company Compositions a base de chitosane
US6638918B2 (en) 2001-11-09 2003-10-28 The Procter & Gamble Company Chitosan compositions
CN100415807C (zh) * 2006-03-20 2008-09-03 扬州大学 N-琥珀二酰壳聚糖自组装纳米微粒及制备方法
DE102007017303A1 (de) 2007-04-11 2008-10-16 Institut für Textil- und Verfahrenstechnik der Deutschen Institute für Textil- und Faserforschung Denkendorf - Stiftung des öffentlichen Rec Antibakteriell wirksames Mittel und dessen Verwendung
EP1992230A2 (fr) 2007-04-11 2008-11-19 NANO-X GmbH Produit antibactérien
CN101832938A (zh) * 2010-04-29 2010-09-15 山东华兴纺织集团有限公司 一种用于测定纺织品中壳聚糖纤维含量的方法
CN113444294A (zh) * 2021-06-28 2021-09-28 苏州市德赫亚新纺织科技有限公司 一种氧化壳聚糖/n，o-羧甲基壳聚糖纳米粒的制备方法

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