EP0319536B1 - Modified fibrous products and method for their manufacture - Google Patents

Modified fibrous products and method for their manufacture Download PDF

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Publication number
EP0319536B1
EP0319536B1 EP87905214A EP87905214A EP0319536B1 EP 0319536 B1 EP0319536 B1 EP 0319536B1 EP 87905214 A EP87905214 A EP 87905214A EP 87905214 A EP87905214 A EP 87905214A EP 0319536 B1 EP0319536 B1 EP 0319536B1
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EP
European Patent Office
Prior art keywords
chitosan
sample
microcrystalline
microcrystalline chitosan
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.)
Expired - Lifetime
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EP87905214A
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German (de)
English (en)
French (fr)
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EP0319536A1 (en
Inventor
Henryk Struszczyk
Pertti Nousiainen
Olli KIVEKÄS
Mikael Epstein
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FIREXTRA Oy
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FIREXTRA Oy
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    • 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 poly(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 inproving wet and dry strength and also as a bonding agent and for textiles as a agent inproving 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 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 104-106 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.
  • 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 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
  • 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.
  • 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. 1a, Magnification 400) and by scanning electron microscope (Fig. 1b, 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, x1000) 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, x1800).
  • 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.
  • 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 the 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 sane tine 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 chitosan 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 tine chitosan in the free amino 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 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.
  • 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 standard acrylic bonding agent of RN-1809 was used by this sane 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 3.39 weight parts of the modified nonwoven sample containing 4.95 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 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 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%.
  • 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, 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%.
  • the 3.21 weight parts of the modified nonwoven sample containing 0.3 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 26.5 N/50 mm, elongation of 2% as well as LOI of 16.6%.
  • 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%.
  • 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 16.8%.
  • modified cotton fabric 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 of 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.
  • the 19.71 weight parts of the modified knitwear sample containing 4.6 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 369 N/50 mm, elongation of 58% and LOI of 18.9%.
  • modified knitwear sample containing 1.6 wt.% of microcrystalline chitosan was obtained.
  • the sample was characterized by tensile strength of 304 N/50 mm, elongation of 55% and LOI of 18.8%.
  • 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.

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  • 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)
EP87905214A 1986-08-18 1987-08-18 Modified fibrous products and method for their manufacture Expired - Lifetime EP0319536B1 (en)

Applications Claiming Priority (2)

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

Publications (2)

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

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Application Number Title Priority Date Filing Date
EP87905214A Expired - Lifetime EP0319536B1 (en) 1986-08-18 1987-08-18 Modified fibrous products and method for their manufacture

Country Status (6)

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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005033347A1 (de) * 2005-07-16 2007-01-18 Henkel Kgaa Mittel, enthaltend mindestens ein Alkalimetallhalogenid als Tracer
US7954190B2 (en) 2003-06-19 2011-06-07 The Procter & Gamble Company Process for increasing liquid extraction from fabrics

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.
US5300192A (en) * 1992-08-17 1994-04-05 Weyerhaeuser Company Wet laid fiber sheet manufacturing with reactivatable binders for binding particles to fibers
US5308896A (en) * 1992-08-17 1994-05-03 Weyerhaeuser Company Particle binders for high bulk fibers
US5352480A (en) * 1992-08-17 1994-10-04 Weyerhaeuser Company Method for binding particles to fibers using reactivatable binders
US6613733B1 (en) 1999-04-27 2003-09-02 The Procter & Gamble Company Treating compositions comprising polysaccharides
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
AT506334B1 (de) * 2008-01-22 2010-12-15 Chemiefaser Lenzing Ag Verfahren zur behandlung cellulosischer formkörper
US8517979B2 (en) 2008-12-22 2013-08-27 Abbott Laboratories Carriers for hemostatic tract treatment
DE102009023878A1 (de) * 2009-06-04 2010-12-09 Werner & Mertz Gmbh Zusammensetzung mit imprägnierender Wirkung
US8715719B2 (en) 2010-06-16 2014-05-06 Abbott Vascular, Inc. Stable chitosan hemostatic implant and methods of manufacture

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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Also Published As

Publication number Publication date
EP0319536A1 (en) 1989-06-14
RU2004661C1 (ru) 1993-12-15
DE3777189D1 (de) 1992-04-09
FI863331A (fi) 1988-02-19
NO169973C (no) 1992-08-26
NO881585D0 (no) 1988-04-13
NO169973B (no) 1992-05-18
FI863331A0 (fi) 1986-08-18
FI77902B (fi) 1989-01-31
NO881585L (no) 1988-04-13
FI77902C (fi) 1989-05-10
WO1988001316A1 (en) 1988-02-25

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