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 its use of chitosans in a particularly finely divided form for finishing fibers, yarns, knitted fabrics, textile fabrics and textiles made 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. Ullmann'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 slightly mild biocidal, which makes them ideal for finishing textiles, preferably then when these are also cationic and therefore sensitive Occasionally, irritating plasticizers have been used. In In practice, however, the use of chitosans has so far not proven itself, because it is a fundamental one The problem is that these substances only adhere to the surface of the fibers and can be washed out quickly. The original goes accordingly Effect quickly lost.
• the object of the invention was therefore to show a way in which one Textiles and their preliminary products with chitosans, if not permanently, at least so can equip for a significantly longer period of time, so that the wearer can Series of washes and when using fabric softener still enjoy the care and anti-inflammatory properties of chitosan.
• the invention relates to the use of nanochitosans for the production of fibers, Yarns, knits and fabrics in which they are used in quantities from 0.01 to 1, preferably 0.05 to 0.5 wt .-% - based on the dry weight - be present can.
• Chitosans are biopolymers and belong to the group of hydrocolloids. Chemically speaking, these are partially deacetylated chitins of different molecular weights, which 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 deacetylated by adding strong bases, it being possible for the molecular weights to be distributed over a broad spectrum.
• Appropriate methods are, for example, made from Makromol. Chem. 177 , 3589 (1976) or French patent application FR 2701266 A1 .
• German patent applications DE 4442987 A1 and DE 19537001 A1 (Henkel), and which have an average molecular weight of 800,000 to 1,200,000 Daltons, a viscosity according to Brookfield (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'Oréal ) and the German patent application DE 19604180 A1 (Henkel).
• Nanochitosans are to be understood as approximately spherical solids, some average diameter in the range of 10 to 300, preferably 50 to 200 and in particular Have 100 to 150 nm.
• a particularly simple process for producing the nanochitosans is the spray drying of chitosan solutions in water and / or organic Solvents, such as alcohols or (hydroxy) carboxylic acids. typically, spray drying takes place at temperatures in the range from 100 to 110 ° C. and pressures from 10 to 100 mbar.
• Another suitable method for producing the nanoscale particles is offered by the evaporation technology, which has parallels with conventional spray drying.
• the starting materials are first in a suitable organic solvent (e.g. Alkanes, vegetable oils, ethers, esters, ketones, acetals and the like) dissolved.
• a suitable organic solvent e.g. Alkanes, vegetable oils, ethers, esters, ketones, acetals and the like
• the solutions are so in water or other non-solvent, if necessary in the presence of a surfactant dissolved therein that there is by homogenizing the two immiscible solvents into one
• the organic solvent preferably evaporating.
• O / W emulsions or O / W microemulsions can also be used be used.
• Suitable protective colloids are included e.g. Gelatin, casein, gum arabic, lysalbic acid, starch and polymers such as Polyvinyl alcohols, polyvinyl pyrrolidones, polyalkylene glycols and polyacrylates.
• the 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 mixtures of homologs whose average degree of alkoxylation is the ratio of the amounts of ethylene oxide and / or propylene oxide and substrate, with which the addition reaction is carried out.
• C 12/18 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 oligoglycosides their preparation and their use are out known in the art. They are manufactured in particular through implementation of glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms.
• glycoside residue both monoglycosides in which a cyclic sugar residue is glycosidically bound to the fatty alcohol, as well as oligomeric Glycosides with a degree of oligomerization of up to preferably about 8 are suitable.
• the degree of oligomerization is a statistical mean, one for such technical products are based on the usual homolog distribution.
• Typical examples of suitable partial glycerides are hydroxystearic acid monoglyceride, Hydroxystearic acid diglyceride, isostearic acid monoglyceride, isostearic acid diglyceride, Oleic acid monoglyceride, oleic acid diglyceride, ricinoleic acid moglyceride, ricinoleic acid diglyceride, Linoleic acid monoglyceride, linoleic acid diglyceride, linolenic acid monoglyceride, linolenic acid diglyceride, Erucic acid monoglyceride, erucic acid diglyceride, tartaric acid monoglyceride, Tartaric acid diglyceride, citric acid monoglyceride, citric diglyceride, malic acid monoglyceride, Malic acid diglyceride and their technical mixtures, the subordinate may still contain small amounts of triglyceride from the manufacturing process. Likewise Addition products of
• polyglycerol esters are polyglyceryl-2 dipolyhydroxystearates (Dehymuls® PGPH), polyglycerol-3-diisostearate (Lameform® TGI), polyglyceryl-4 Isostearate (Isolan® GI 34), Polyglyceryl-3 Oleate, Diisostearoyl Polyglyceryl-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 Dimerate isost
• polystyrene resin examples include the mono-, di- and optionally reacted with 1 to 30 mol ethylene oxide Triester of trimethylolpropane or pentaerythritol with lauric acid, coconut fatty acid, Tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid and the like.
• Typical anionic emulsifiers are aliphatic fatty acids with 12 to 22 carbon atoms, such as palmitic acid, stearic acid or behenic acid, and dicarboxylic acids with 12 to 22 carbon atoms, such as azelaic acid or Sebacic acid.
• Zwitterionic surfactants can also be used as emulsifiers.
• Zwitterionic surfactants are those surface-active compounds which carry 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 the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammoniumglycinate, for example the cocoacylaminopropyidimethylammoniumglycinate, and 2-alkyl-3-carboxylm -hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylglycinate.
• betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example the cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammoniumglycinate, for example the
• Suitable emulsifiers are ampholytic surfactants.
• Ampholytic surfactants are surface-active compounds which, in addition to a C 8/18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO 3 H group in the molecule and are capable of forming internal salts.
• ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 carbon atoms in the alkyl group.
• Particularly preferred ampholytic surfactants are N-coconut alkylaminopropionate, coconut acylaminoethylaminopropionate and C 12/18 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 which are encased in a protective colloid and / or an emulsifier.
• the protective colloids or emulsifiers in amounts of 0.1 to 20, preferably 5 to 15 wt .-% - based on the chitosans and / or chitosan derivatives - used.
• 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 crystallization of solutes.
• the compressed gas phase is in the primary solution of the starting materials initiated and absorbed there, which increases the liquid volume, the solubility decreases and fine particles are excreted.
• 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 a The finest particles are precipitated.
• the starting materials melted by injecting gas (e.g. carbon dioxide or propane). Pressure and Temperatures reach near or supercritical conditions. The gas phase dissolves in Solid and causes a reduction in the melting temperature, viscosity and surface tension. When expanding through a nozzle, there are cooling effects to form the finest particles.
• gas e.g. carbon dioxide or propane.
• the invention further relates to fibers, yarns, knitted fabrics and textile fabrics, including consumer end products as well as textiles using of these precursors have been produced and nanochitosans, preferably in Amounts of 0.01 to 1 and in particular 0.05 to 0.5 wt .-% - based on the dry weight - contain.
• the finishing of finished textiles can by impregnation in the immersion bath and subsequent drying.
• fibers and yarns can also be finished by using 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.
• nanoparticles E.g. Chitosan (derivative) Solv.

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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)

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Cited By (8)

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Citations (5)

• 2001
  • 2001-03-22 EP EP01107163A patent/EP1243688A1/fr not_active Withdrawn
• 2002
  • 2002-03-14 WO PCT/EP2002/002820 patent/WO2002077358A1/fr not_active Application Discontinuation

Patent Citations (5)

Non-Patent Citations (4)

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