EP0319536A1 - Produits fibreux modifies et procede de fabrication. - Google Patents

Produits fibreux modifies et procede de fabrication.

Info

Publication number
EP0319536A1
EP0319536A1 EP87905214A EP87905214A EP0319536A1 EP 0319536 A1 EP0319536 A1 EP 0319536A1 EP 87905214 A EP87905214 A EP 87905214A EP 87905214 A EP87905214 A EP 87905214A EP 0319536 A1 EP0319536 A1 EP 0319536A1
Authority
EP
European Patent Office
Prior art keywords
chitosan
sample
microcrystalline chitosan
microcrystalline
well
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
EP87905214A
Other languages
German (de)
English (en)
Other versions
EP0319536B1 (fr
Inventor
Henryk Struszczyk
Pertti Nousiainen
Olli Kivekas
Mikael Epstein
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FIREXTRA Oy
Original Assignee
FIREXTRA Oy
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 FIREXTRA Oy filed Critical FIREXTRA Oy
Publication of EP0319536A1 publication Critical patent/EP0319536A1/fr
Application granted granted Critical
Publication of EP0319536B1 publication Critical patent/EP0319536B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • 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

Definitions

  • the invention relates to modified fibrous products and method for their manufacture.
  • the standard chitosan pol (2-deoxy-2-amino-glucose) has been used in several applications especially in the textile industry for the modification of fibrous products.
  • the standard chitosan has been applied for coated textiles as a water repellent agent, for nonwoven fabrics and paper as a preparate improving wet and dry strength and also as a bonding agent and for textiles as a agent improving dyeability especially in the case of printing.
  • the standard chitosan was used also for textiles made » from wool fibres to improve their shrinkage and for textiles of synthethic fibres as an antistatic agent.
  • the standard chitosan was applied together with chlorophospharenes to produce the flame resistant textiles and plastics.
  • the well-known textiles modified by chitosan and methods for their manufacture require the use of standard chitosan dissolved in the aqueous acidic solution.
  • the products obtained on a base of the chitosan salts are characterized by non-durability against water.
  • the manufacture of water durable products impregnated by chitosan according to the well-known methods is concerned with regeneration of chitosan salts by using queous alkaline solutions as an additional treatment.
  • the well-known methods need several stages to obtain water durable products.
  • the products obtained at the same time change the specific properties under the additional treatments.
  • microcrystalline chitosan production method based on the aggregation system.
  • the product obtained according to this method has been formed in a form of gel-like dispersion or powder.
  • Microcrystalline chitosan showed a water retention value (WRV) in a powder form within a range of 200-500%, in a gel-like dispersion 500-2000% adequately, the average molecular weight of 10 4-106 as well as a deacetylation degree not less than 30%.
  • WRV water retention value
  • microcrystalline polymers are defined by 0. A. Battista in 0. A. Battista: "Microcrystalline Polymers Science", McGraw Holl Publ., New York, 1975.
  • the microcrystalline chitosan has got the same chemical structure as standard chitosan raw material. However, it differs from this raw material by super-molecular structure.
  • the object of this invention is to produce modified fibrous products containing chitosan by means of microcrystalline chitosan, especially a gel-like dispersion, using for example spraying or foularding in different forms.
  • modified fibrous products especially fabrics, nonwovens, knitwears, leathers and the like, comprising chitosan after treatment by chitosan in a microcrystalline form, the product containing microcrystalline chitosan f particles bonded to adjacent particles and the structure of the fibrous product mainly by hydrogen bonds.
  • the product contains not less than 0.01 wt.% of microcrystalline chitosan, preferably 0.5-10 wt.%.
  • the product contains also modifying chemical additives up to 10 wt.% on the microcrystalline chitosan weight.
  • the microcrystalline chitosan used as a modifying material for the modified fibrous products manufacture such as a gel-like dispersion preferably in water, has especially a water retention value of the gel-like form within a range 500-2000% and
  • the microcrystalline chitosan gel-like dispersion, especially in water is brought in contact with the fibrous products, especially fabrics, nonwovens, knitwears, leathers and the like, preferably by dipping, immersing, spraying or foularding, whereafter the products are dried.
  • the microcrystalline * gel-like dispersion used contains not less than 0.001 wt.% of the' polymer on a dry weight and has a pH not less than 7.00, especially in a range 7.00-10.00.
  • the addition of the modifying chemical additives is carried out directly to the microcrystalline chitosan before or during distribution of microcrystalline particles into a liquid medium or to the liquid medium as well as during the modification of fibrous products, preferably by spraying through nozzles or similar.
  • the modified fibrous products as fabrics, nonwovens, knitwears or leather according to the invention are produced on a base microcrystalline chitosan.
  • Microcrystalline chitosan forms the small .aggregates in a dispersion, especially in a water, with average dimension within a range of 0.01-100 ⁇ m.
  • Application of the microcrystalline chitosan gel-like dispersion for the fibrous products allows to cover their surface as well as to introduce to their porous system to form especially polymeric film. It ' can be possible to compress the individual aggregates of microcrystalline chitosan by a drying method for example to produce the modified fibrous produts.
  • microcrystalline chitosan dispersion contains preferable 0.01-10 wt.% of polymer according to possibilities for covering the modified fibrous products characterized by optimal mechanical and super-molecular properties.
  • the well-known modified textiles containing standard chitosan are formed according to preparation of the chitosan acetate covered impregnated textiles, 'and eventually regeneration of chitosan in the aqueous alkaline solutions as well as subsequent purification of products obtained and drying. Therefore the well-known modified textiles need for preparation minimum 1-2 hours, whereas the modified fibrous products according to the invention can be prepared using a microcrystalline chitosan dispersion already after 1 minute. No more operations excluding drying is need for production of the fibrous products modified by microcrystalline chitosan.
  • Figure 1 shows the photographs of the microcrystalline chitosan gel-like dispersion made by optical microscope (Fig. la. Magnification 400) and by scanning electron microscope (Fig. lb, magnification 1000).
  • Figure 2 shows the scanning electron microscope photographs of the nonwoven modified by the microcrystalline chitosan (Fig. 2a, -x200/600) and the nonwoven fibres covered by the microcrystalline chitosan film (Fig. 2b, c, xlOOO) as well as the standard non-bonded nonwoven used as raw material (Fig. 2d, x200/600) and standard nonwoven bonded by acrylic resin (Fig. 2e, x200/600).
  • Figure 3 shows the scanning electron microscope photographs of the- cotton fabric modified by microcrystalline chitosan (Fig. 3a, x200/600) as well as the individual cotton fibres of fabric (Fig. 3b, xl800).
  • Figure 3c shows the standard cotton fabric for comparison.
  • Figure 4 shows the " scanning electron microscope photographs of the cotton knitwear modified by microcrystalline chitosan (Fig. 4a, x200/600) as well as non-modified raw material (Fig. 4b, x200/600).
  • the modification of the fibrous products in accordance to the invention allows to obtain the microcrystalline chitosan products, especially films formed directly on the surface of fibrous products as fabrics, nonwovens, knitwears or leathers as well as into their porous structure.
  • the thickness of microcrystalline chitosan film layer formed on the fibrous products is dependent among others to amount of microcrystalline chitosan used, type of method applied or system of drying.
  • microcrystalline chitosan film is produced by formation of the powerful hydrogen bonds between microcrystalline particles, especially gel-like aggregates. At the same time the suitable powerful hydrogen bonds are formed between microcrystalline chitosan and the covered fibrous products. The energy of these type of hydrogen bonds is connected mainly with type of fibrous material and conditions applied.
  • microcrystalline chitosan used for modification of the fibrous products effect directly on. the- modified products obtained.
  • the main invention of: the fibrous products modification as well as the method of their manufacture is the utilization of possibilities for the formation of hydrogen bonds between microcrystalline chitosan aggregates as well as microcrystalline chitosan and covered materials.
  • Another important object is to eventually apply chemical additives to th'e microcrystalline chitosan for modifying the structure and properties of products obtained " .
  • the modificators applied in the invention allow to moderate the possibilities for the suitable hydrogen bonds formation.
  • the modificators create also suitable higher energetic hydrogen bonds reducing at the same time possibilities to connexion of the individual particles of microcrystalline chitosan.
  • a wetting agent in the invention as example of modificators in a case of the modified nonwoven made of polyester fibres using the spraying system of microcrystalline chitosan dispersion containing 0.5 wt.% of polymer and 0.1 wt.% of lithium chloride on the dry weight of polymer causes to obtain the product characterized by a change of properties, in comparison with microcrystalline chitosan-nonwoven not modified with LiCl, for example tensile strength reduced for 1.12 times.
  • the important object of the invention is also to use a different reaction of the microcrystalline chitosan gel-like dispersion for manufacture of modified fibrous products.
  • the specific porperties of microcrystalline chitosan is connected with Z-potential influence on the properties of the modified fibrous products.
  • Increase of pH of the microcrystalline chitosan reaction dispersion in the invention causes suitable changes of the modified fibrous products properties. For example augmentation of pH from 8.0 to 9,5 in a case of the microcrystalline ciitosan dispersion used for modification of nonwovens causes to obtain the product characterized by a reduction of tensile strangth within a range of 8-15%.
  • modified fibrous products obtained according to •the invention covered by the ' microcrystalline chitosan, especially in a form of film, contain water insoluble modifying chitosan also in every stage of the formation process as well as contain through the whole formation time chitosan in the free a ino form.
  • microcrystalline chitosan material especially films, formed on the surface of modified fibrous products or into their porous structure improves their mechanical properties such as for example tensile strength, acts as a bonding agent for nonwoven both combining the fibres as well as improving the mechanical properties.
  • other properties of the modified fibrous, products are improved by application of microcrystalline chitosan as. for example better dyability, ability for printing, shrinkage reduction, water repellency and flame resistancy or bacteriostatic action.
  • tensile strength was increased minimum by 100-500% in comparison to raw materials.
  • the amount of the microcrystalline chitosan applied in a case of nonwoven is minimum 15 times lower than in a case of the standard bonding agents, such as acrylic resins.
  • suitable better mechanical properties in a case of the invented modified nonwovens in comparison to well-known bonded nonwovens are obtained.
  • the use of 4.3 wt.% of the microcrystalline chitosan on a dry weight of polymer in a case of nonwoven made of polyester fibres allows to obtain by a spraying method a modified product with a tensile strength of 37.3 cN/50 mm and elongation of 2%.
  • this same nonwoven bonded by the standard acrylic bonding agent in amount of 33 wt.% on the dry weight of polymer is characterized by tensile strength of 34.8 cN/50 mm and elongation of 16%.
  • the method in accordance with the invention is uncommonly simple and easy for practical realization, in comparison to well-known methods, giving the valuable products directly first of all by application of microcrystalline chitosan dispersion without any special additional finishing process.
  • the object is further to defelop the modified fibrous products containing microcrystalline chitosan that can be used in a wide range of products as textiles, paper leather etc.
  • Microcrystalline chitosan gel-like dispersion according to Polish Patent 125 995 was obtained.
  • Microcrystalline chitosan dispersion was prepared on a base of non-degraded and degraded chitosan.
  • Lithium chloride acts as an inorganic example of the structure moderator.
  • Sandozin NIT is a trade name of wetting agent. The function of this substance in the invented modified fibrous products is to moderate the structure of microcrystalline chitosan materials, especially films, as an example of organic moderating compound.
  • R-N1809 is a trade name of standard acrylic resin containing 45 wt.% on polymer. The function of this substance in the nonwoven is to bond the fibres together.
  • the 3.39 weight parts of the modified nonwoven sample containing 4.95 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 34.7 N/50 mm and elongation of 2% as well as LOI of 17.6%.
  • the 3.39 weight parts of the modified nonwoven sample containing 4.95 wt.% of microcrystalline chitosan was 10 obtained.
  • the sample was characterized by tensile strength of 35,7 N/50 mm, elongation of 2% and LOI of 17,7%.
  • the 3.49 weight parts of the modified nonwoven sample containing 3.56 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 28.3 N/50 mm, elongation of 2% and LOI of 17,6%.
  • the 3.48 weight parts of the modified nonwoven sample containing 2.4 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 32 N/50 mm, elongation of 2% as well as LOI of 17.1%.
  • the standard acrylic bonding agent of RN-1809 was used by this same method.
  • the acrylic resin content in a nonwoven sample was 33 wt.% on a sample weight.
  • the sample was characterized by tensile strength of 34.8 N/50 mm, elongation of 16% and LOI of 16.7%.
  • the 3.48 weight parts of the modified nonwoven sample containing 2.4 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 29.5 N/50 mm, elongation of 2% and LOI of 17,2%.
  • the 3.36 weight parts of the modified nonwoven sample containing 2.8 -wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 32.6 N/50 mm.
  • the acrylic resin content in a nonwoven sample was 33 wt.% on a sample weight.
  • the sample was characterized by tensile strength of 34.8 N/50 mm, elongation of 16% and LOI of 16.7%.
  • the 3.52 weight parts of the modified nonwoven sample containing 2.6 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 22.1 N/50 mm and elongation of 2%.
  • Example 7 3.45 weight parts of the nonwoven made of polyester fibres characterized by properties from Example 7 was introduced to spraying using 0.5 wt.% water dispersion of microcrystalline chitosan characterized by properties described in Example 1. The wettness of sample was 668 wt.%. Then the product was dried at 105°C for 5 minutes. The 3.60 weight parts of the modified nonwoven sample containing 4.3 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 36.8 N/50 mm, elongation of 2%, LOI of 18.3% and as wet, after soaking in water for 10 min, the sample was characterized by tensile strength of 11.5 N/50 mm and elongation of 2%.
  • the 360 weight parts of the modified nonwoven sample containing 4.3 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 37,3 N/50 mm and elongation of 2%.
  • the 3.37 weight parts of the modified nonwoven sample containing 2.7 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 15.6 N/50 mm, elongation of 3% as well as LOI of 18.1%.
  • the acrylic resin content in a nonwoven sample was 33 wt.% on a sample weight.
  • the sample was characterized by tensile strength of 37.2 N/50 mm, elongation of 31.2% and LOI of 18.1%.
  • the 3.37 weight parts of the modified nonwoven sample containing 2.7 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 16.8 N/50 mm, elongation of 3%, LOI of 18.1% and as wet, after soaking in water for 10 min, 10 the sample was characterized by tensile strength of 3.2 N/50 mm and elongation of 6%.
  • the 5.77 weight parts of the modified nonwoven sample containing 2.7 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 15.6 N/50 mm, elongation of 3% as well as LOI of 17.9%.
  • Example 12 5.62 weight parts of the nonwoven made of polyester fibres characterized by properties from Example 12 was introduced to spraying using 0.5 wt.% water dispersion of microcrystalline chitosan characterized by properties described in Example 1. The wetness of sample was 274 wt.%. Then the product was dried at 105°C for 5 minutes.
  • the 5.77 weight parts of the modified nonwoven sample containing 2.7 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 16.8 N/50 mm, elongation of 2% and LOI of 17,9%.
  • Example 14 25 3.36 weight parts of the nonwoven made of polyester fibres characterized by properties from Example 14 was introduced to spraying using 0.5 wt.% water dispersion of microcrystalline chitosan characterized by properties described in Example 14. The wetness of sample was 205 wt.%. Then the product was dried at 105°C for 5 minutes.
  • the 3.43 weight parts of the modified nonwoven sample containing 2.1 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 30.1 N/50 mm and elongation of 1.8%.
  • the 3.42 weight parts of the modified nonwoven sample containing 7.9 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 44.8 N/50 mm, ' elongation" of 3% and LOI of 17,8%.
  • the 3.34 weight parts of the modified nonwoven sample containing 2.1 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 30.0 N/50 mm and elongation of 2%.
  • the 3.33 weight parts of the modified nonwoven sample containing 1.2 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 22.5 N/50 mm and elongation of 2%.
  • a sample, where the well-known acrylic resin was used as a bonding agent of nonwoven according to this same method was also obtained. The properties of the obtained well-known sample are described in Example 1.
  • the 3.55 weight parts of the modified nonwoven sample containing 8.6 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 20.5 N/50 mm and elongation of 2%.
  • the 3.40 weight parts of the modified nonwoven sample containing 4.0 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 32.8 N/50 mm, elongation of 2% as well as LOI of 17.0%.
  • the 3.28 weight parts of the modified nonwoven sample containing 3.5 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 32.3 N/50 mm, elongation of 2% as well as LOI of 1.6.8%.
  • the 17.37 weight parts of modified cotton fabric was obtained.
  • the sample contained 4.1% of microcrystalline chitosan.
  • the sample was characterized by tensile strength of 771 N/50 mm, elongation of 20% and LOI of 18.4.
  • the sample was dyeable also by the acid dyes.
  • the 18.07 weight parts o.f modified cotton fabric containing 1.8 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by, tensile strength of 689 N/50 mm, elongation of .14% and LOI of 17.8%.
  • the sample was dyeable also by the acid dyes.
  • modified knitwear sample containing 1.6 wt.% of microcrystalline chitosan was 5 obtained.
  • the sample was characterized by tensile strength of 304 N/50 mm, elongation of 55% and LOI of
  • Example 21 3.41 weight parts of the leather sample characterized by properties described in Example 26 was sprayed on both sides with the microcrystalline chitosan water dispersion as in Example 21 containing 0.01 wt.% Sandozin NIT as in Example 21. The sample was dried at 40°C until dry.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Sampling And Sample Adjustment (AREA)

Abstract

Les produits fibreux modifiés décrits, soit notamment des tissus, des fibres non tissées, des tricots, des cuirs et autres, comprennent du chitosane après traitement au chitosane utilisé comme matériau de modification. Le chitosane utilisé est un chitosane microcristallin et le produit obtenu contient des particules de chitosane microcristallin liées aux particules adjacentes et à la structure du produit fibreux essentiellement par des liens d'hydrogène. Dans un procédé de fabrication desdits produits modifiés, la dispersion en forme de gel du chitosane microcristallin est mise en contact avec lesdits produits, lesquels sont ensuite séchés.
EP87905214A 1986-08-18 1987-08-18 Produits fibreux modifies et procede de fabrication Expired - Lifetime EP0319536B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI863331A FI77902C (fi) 1986-08-18 1986-08-18 Modifierade fiberprodukter och foerfarande foer deras framstaellning.
FI863331 1986-08-18

Publications (2)

Publication Number Publication Date
EP0319536A1 true EP0319536A1 (fr) 1989-06-14
EP0319536B1 EP0319536B1 (fr) 1992-03-04

Family

ID=8523014

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87905214A Expired - Lifetime EP0319536B1 (fr) 1986-08-18 1987-08-18 Produits fibreux modifies et procede de fabrication

Country Status (6)

Country Link
EP (1) EP0319536B1 (fr)
DE (1) DE3777189D1 (fr)
FI (1) FI77902C (fr)
NO (1) NO169973C (fr)
RU (1) RU2004661C1 (fr)
WO (1) WO1988001316A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8517979B2 (en) 2008-12-22 2013-08-27 Abbott Laboratories Carriers for hemostatic tract treatment
US8715719B2 (en) 2010-06-16 2014-05-06 Abbott Vascular, Inc. Stable chitosan hemostatic implant and methods of manufacture

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5114788A (en) * 1988-10-17 1992-05-19 Asahi Kasei Textile Ltd. Fabric having water absorption property and method of manufacturing the fabric
FI895893A (fi) * 1989-12-08 1991-06-09 Kemira Oy Saeteri Modifierade viskosfibrer och foerfarande foer deras framstaellning.
US5352480A (en) * 1992-08-17 1994-10-04 Weyerhaeuser Company Method for binding particles to fibers using reactivatable binders
US5308896A (en) * 1992-08-17 1994-05-03 Weyerhaeuser Company Particle binders for high bulk fibers
US5300192A (en) * 1992-08-17 1994-04-05 Weyerhaeuser Company Wet laid fiber sheet manufacturing with reactivatable binders for binding particles to fibers
MXPA01010947A (es) * 1999-04-27 2002-05-06 Procter & Gamble Composiciones de tratamiento que contienen polisacaridos.
CN1297706C (zh) * 2003-06-03 2007-01-31 陈立成 一种无甲醛织物防皱整理剂及制造方法
US7954190B2 (en) 2003-06-19 2011-06-07 The Procter & Gamble Company Process for increasing liquid extraction from fabrics
DE102005033347A1 (de) * 2005-07-16 2007-01-18 Henkel Kgaa Mittel, enthaltend mindestens ein Alkalimetallhalogenid als Tracer
AT506334B1 (de) * 2008-01-22 2010-12-15 Chemiefaser Lenzing Ag Verfahren zur behandlung cellulosischer formkörper
DE102009023878A1 (de) * 2009-06-04 2010-12-09 Werner & Mertz Gmbh Zusammensetzung mit imprägnierender Wirkung

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL133745B2 (en) * 1983-09-14 1985-06-29 Cosmetic preparation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8801316A1 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8517979B2 (en) 2008-12-22 2013-08-27 Abbott Laboratories Carriers for hemostatic tract treatment
US9533076B2 (en) 2008-12-22 2017-01-03 Abbott Laboratories Carriers for hemostatic tract treatment
US8715719B2 (en) 2010-06-16 2014-05-06 Abbott Vascular, Inc. Stable chitosan hemostatic implant and methods of manufacture

Also Published As

Publication number Publication date
FI77902C (fi) 1989-05-10
FI863331A (fi) 1988-02-19
FI77902B (fi) 1989-01-31
WO1988001316A1 (fr) 1988-02-25
NO881585D0 (no) 1988-04-13
NO169973C (no) 1992-08-26
DE3777189D1 (de) 1992-04-09
EP0319536B1 (fr) 1992-03-04
FI863331A0 (fi) 1986-08-18
NO881585L (no) 1988-04-13
RU2004661C1 (ru) 1993-12-15
NO169973B (no) 1992-05-18

Similar Documents

Publication Publication Date Title
EP0319536B1 (fr) Produits fibreux modifies et procede de fabrication
JPH10507496A (ja) セルロースファイバー
Roy et al. Chitosan-based sustainable textile technology: process, mechanism, innovation, and safety
JP4044155B2 (ja) 溶剤紡績セルロースファイバーの処理方法
Parvinzadeh Surface modification of synthetic fibers to improve performance: recent approaches
CN1077184C (zh) 织物处理
US5593779A (en) Fiber for clothing and production method therefor
CN109989268B (zh) 一种羊毛织物表面微溶防毡缩整理的方法
RU2370583C2 (ru) Способ придания волокнистым материалам гидрофильных свойств
JP2000256960A (ja) 精製セルロース繊維織編物の加工方法
JP2005535790A (ja) セルロース成型体の処理プロセス
CN111979765B (zh) 一种具有抗菌功能的羟基纤维的制备方法
JP5358192B2 (ja) 繊維にグラフトするために表面を改質したカプセル
EP0705868B1 (fr) Matériaux à base de cellulose régénérée présentant une résistance élevée à l'eau de Javel et procédé pour leur préparation
JP3915056B2 (ja) セルロース繊維の加工方法
JP3274567B2 (ja) 衣料用セルロース繊維及びその製造方法
JP3044302B1 (ja) 撥水性高分子素材およびその製造方法
JP3988020B2 (ja) セルロース繊維の加工方法
JPH08269873A (ja) 衣料用化学繊維及びその製造方法
JPH08302575A (ja) 染色繊維及びその製造法
JP2001164418A (ja) 改質セルロース再生繊維の製造法
JP2002212889A (ja) 嵩高パルプの製造方法
JPH0711575A (ja) セルロース系繊維含有繊維製品及びその製造方法
AHMAD et al. Morphological and thermal analysis of refitted rattan waste fibers
RU2300585C1 (ru) Способ получения нетканых текстильных материалов повышенной прочности

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19890217

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): CH DE FR GB IT LI

17Q First examination report despatched

Effective date: 19900920

ITF It: translation for a ep patent filed

Owner name: FIAMMENGHI - DOMENIGHETTI

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE FR GB IT LI

REF Corresponds to:

Ref document number: 3777189

Country of ref document: DE

Date of ref document: 19920409

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19950215

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19950222

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19950831

Ref country code: CH

Effective date: 19950831

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19960430

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19980813

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19980901

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990818

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19990818

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20000601

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20050818