WO2008003358A1 - Déminéralisation et désencollage combinés de matériaux de fibres textiles - Google Patents

Déminéralisation et désencollage combinés de matériaux de fibres textiles Download PDF

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Publication number
WO2008003358A1
WO2008003358A1 PCT/EP2007/002356 EP2007002356W WO2008003358A1 WO 2008003358 A1 WO2008003358 A1 WO 2008003358A1 EP 2007002356 W EP2007002356 W EP 2007002356W WO 2008003358 A1 WO2008003358 A1 WO 2008003358A1
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WO
WIPO (PCT)
Prior art keywords
amylase
aqueous medium
acidic aqueous
textile fiber
acid
Prior art date
Application number
PCT/EP2007/002356
Other languages
German (de)
English (en)
Inventor
Peter Weiler
Bernhard Seidl
Bettina Knauer
Original Assignee
Dystar Textilfarben Gmbh & Co. Deutschland Kg
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 Dystar Textilfarben Gmbh & Co. Deutschland Kg filed Critical Dystar Textilfarben Gmbh & Co. Deutschland Kg
Publication of WO2008003358A1 publication Critical patent/WO2008003358A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
    • D06L1/14—De-sizing

Definitions

  • the invention relates to the use of an acidic aqueous medium comprising an acid-stable amylase and a complexing agent for the combined demineralization and desizing of textile fiber materials and a process for the combined demineralization and desizing of textile fiber materials, wherein the acidic aqueous medium is exposed to the textile fiber material leaves.
  • Textile fibers are provided with sizing in the course of the processing process in order to improve the machine-processability of the textile fibers.
  • sizing various materials can be used, for example polyacrylates or cellulose derivatives, although for ecological reasons starch is often used for sizing.
  • the starch may be, for example, potato, corn or rice starch.
  • Amylases are enzymes belonging to the group of hydrolases which break down starch into maltose or glucose either directly or via dextrins and occur in the digestive glands of humans and animals, in cereals, malt, bacteria and fungi.
  • Industrial uses include amylases as additives in detergents, in the manufacture of beer, ethanol, confectionery and corn syrup, in screen and felt cleaning of papermaking machines, and desizing described above. Amylases are usually not stable in a strongly acidic medium (pH ⁇ 5) and only in a pH range of about 6 - 9 active, so that the desizing of textile fibers so far in this pH range of about 6 - 9 was carried out.
  • thermoacidophilic ⁇ -amylases from Thermoplasma acidophilum, Picrophilus torridus and Picrophilus oshimae. Schwermann et al. describe in Eur. J Biochem. 1994, 981-991 a thermoacidophilic ⁇ -amylase from Alicyclobacillus acidocaldarius. Ng, T.K. and Kenealy, WR (1986) disclose in "Industrial applications of thermostable enzymes", "Thermophiles, general, molecular and applied microbiology" (Brock, TD, ed.), pp.
  • WO 2005/118800 A1 discloses an acid-stable ⁇ -amylase from Aspergillus kawachi.
  • the object of the present invention is therefore to provide a composition for the simplified demineralization and desizing of textile fiber materials without the disadvantages of Prior art and to provide a simplified process for the demineralization and desizing of textile fiber materials.
  • This object is achieved by using an acidic aqueous medium for combined, i. single-stage demineralization and desizing of texas fiber materials, wherein the acidic aqueous medium comprises an acid-stable amylase and a complexing agent. Further, this object is achieved by a process for the combined demineralization and desizing of textile fiber materials, in which an acidic aqueous medium is allowed to act on the textile fiber material, the acidic aqueous medium comprising an acid-stable amylase and a complexing agent.
  • acid-stable amylases can be used in an aqueous medium together with complexing agents for combined demineralization and desizing.
  • complexing agents for combined demineralization and desizing.
  • the same degree of desizing could be achieved as in the conventional two-stage process of demineralization and desizing.
  • whiteness of the textile fiber materials is increased after the bleaching process carried out following the process according to the invention compared with the two-stage process of the prior art.
  • the use according to the invention of the acidic aqueous medium and the process according to the invention for the combined demineralization and desizing of textile fiber materials are distinguished by a high degree of desizing of the textile fiber materials after the treatment which is comparable to the degree of desizing of the two-stage process of the prior art and the use according to the invention and the invention Methods also have the advantage that a second energy, resource and time consuming step is saved.
  • the whiteness of the textile fiber materials is increased after bleaching compared to the two-stage process of the prior art, which in turn brings with it the advantage that white textile fiber materials need not be re-bleached again and the dyeing, especially the color of light colors succeeds particularly well.
  • Acid-stable or acid-resistant amylases are understood in the context of the invention to be amylases which are stable in an aqueous medium at a pH of about 0-6, preferably 1-5, more preferably 1.5-4.8, ie within the Duration of use according to the invention or the duration of the method according to the invention of approximately 1 minute to 48 hours in the aqueous medium, so that the activity does not decrease below 50%, preferably not below 75%, more preferably below 90% of the initial activity at the same pH.
  • the pH of the acidic aqueous medium acting on the textile fiber material increases. It is believed that this is due to the complexation of the alkaline earth metal ions and the heavy metal ions, which release hydroxides bound to the metal ions.
  • the demineralization takes place in the use according to the invention and the process according to the invention primarily in the initial low pH range and the enzymatic desizing takes place primarily in the later higher but still acidic pH range. This is due to the fact that the acid-resistant amylases in the initially particularly low pH range are usually not sufficiently active in order to significantly advance the desizing.
  • the amylases must therefore be stable in the initial low pH range, in which the complexation is particularly effective, while they can already partially develop their activity, and in the later higher, but still acidic pH range, the amylases must have sufficient Develop activity to facilitate the desizing within the exposure time.
  • the demineralization and desizing are therefore controlled in the inventive use of an acidic aqueous medium by changing the pH controlled in a process step, d. H. single stage. Demineralization and desizing are thus carried out in concert, but usually staggered, with the activity profiles of the complexing agents and the amylases more or less overlapping, i.
  • the maximums of the activity profiles are reached in succession, but the activity of the amylases can already increase in the region of the decaying activity curve of the complexing agents, so that in a transitional pH range the demineralization and the desizing run at speeds below the maximum more or less parallel.
  • the acidic aqueous medium is applied to the textile fiber material at a pH of 0-2.5, preferably 1-2, more preferably 1.5-1.9, for example the textile fiber material is impregnated in the acidic aqueous medium.
  • a portion of the acidic aqueous medium remains on the textile fiber material and acts on it.
  • the acidic aqueous medium used according to the invention therefore has a total pH of about 0-6 over the contact time.
  • This pH of the acidic aqueous medium is preferably in the range from 1 to 5, more preferably in the range from 1.5 to 4.8, over the entire reaction time.
  • acid-stable amylases acid-stable natural amylases from the digestive glands of humans and animals, from cereals, malt, bacteria, fungi or acid-stable amylases obtained or prepared by microbiological processes can be used. Preference is given to bacterial or fungal, ie derived from fungi amylases are used, in particular ⁇ - and ß-amylases, depending on the application, mixtures of several amylases can be used with advantage, for example if the sizings are composed inconsistently or to synergistic effects of the amylases use.
  • bacterial amylases in particular bacterial ⁇ -amylases from the bacterial strains Bacillus licheniformis, Bacillus subtilis, Bacillus stearothermophilus, Sulfolobus acidocaldarius, Alicyclobacillus acidocaldarius, Thermoplasma acidophilum, Picrophilus torridus or Picrophilus oshimae and fungal amylases, especially fungal ⁇ -amylases from Aspergillus niger, Aspergillus oryzae, Aspergillus kawachi or Aspergillus sp. or a mixture of several of these amylases used and used in the inventive method.
  • bacterial and fungal amylases can also be used.
  • acid-stable bacterial ⁇ -amylases from Alicyclobacillus acidocaldarius and acid-stable fungal ⁇ -amylases from Aspergillus niger, Aspergillus oryzae and Aspergillus sp. used.
  • complexing agents are meant all chemical compounds that can bind metal ions to form complexes.
  • Suitable complexing agents which comprise the acidic aqueous medium used according to the invention are all inorganic and organic complexing agents which are capable of binding alkaline earth metal ions and / or heavy metal ions in an aqueous medium.
  • An aqueous medium or medium in the sense of the present invention is understood to mean a liquid medium which is at least 50% by weight, preferably at least 75% by weight, more preferably at least 90% by weight and even more preferably at least 95% by weight. Contains% water.
  • Suitable complexing agents are in particular compounds which bind alkaline earth metal ions and heavy metal ions to form cyclic complexes (chelating agents).
  • di-, tri-, tetra-, penta-, hexa- and multi-functional compounds come into consideration, in each case two functionalities equipped with lone pairs of electrons in 1, 2, 1, 3 or 1.4 position are.
  • 1, 2-difunctional compounds form 5-rings in the complexation or chelation
  • 1, 3-difunctional compounds form 6-rings and 1,4-difunctional compounds 7-rings.
  • compounds which are 1, 2 and 1, 3-diamino, 1, 2 and 1, 3-dicarbonyl, 1, 2 and 1, 3-dihydroxy, 1,2 and 1, 3 are suitable Hydroxycarbonyl, 1, 2 and 1, 3-hydroxyamino and 1,2 and 1, 3-aminocarbonyl groups contain.
  • cyclic compounds such as bipyrroles, bipyrrolidines, bipyridines and similar chelating agents can be used.
  • Preferred complexing agents are aminocarboxylic acids, phosphonates and polyacrylic acids and their copolymers, for example copolymers with maleic acid, or mixtures thereof.
  • aminocarboxylic acids nitrilotriacetic acid
  • Ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, methylglycinediacetic acid and modified anionic polyamines and among the phosphonates are 1-hydroxyethane- (1,1-diphosphonic acid) (HEDP) and its salts, amino-tris (methylenephosphonic acid) (ATMP) and its salts, diethylenetriamine penta (methylenephosphonic acid) (DTPMP) and its salts, ethylenediaminetetra (methylenephosphonic acid) (EDTMP) and its salts, hydroxyethylamino-di (methylenephosphonic acid) (HEMPA) and its salts, hexamethylenediaminetetra (methylenephosphonic acid) (HDTMP) and their salts and phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and salts thereof are particularly preferred.
  • HEDP 1-hydroxyethan
  • the medium may additionally contain solubilizers, wetting agents, surface-active substances and / or organic solvents.
  • solubilizers for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycols, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycols, ethylene-propylene glycols and alcohol polyglycol ethers, in particular fatty alcohol polyglycol ethers, as well as commercially available surfactants and detergents may be added.
  • preference is given to using alcohol polyglycol ethers in which the saturated or unsaturated, branched or unbranched alcohol radical has 6 to 20, more preferably 12 to 18
  • Isotridecyl alcohol myristyl alcohol, cetyl alcohol, stearyl alcohol or mixtures of C 12-18
  • the gycol ether radical of the alcohol polyglycol ethers is preferably composed of ethylene glycols and / or propylene glycols.
  • alcohol polyglycol ethers of the formula nC m H 2m + 1 - (OCH 2 CH 2 ) p - (OCH 2 CHCH 3 ) q -OH individually or as mixtures in which m is 12, 13, 14, 15, 16, 17 or Is 18 and p and q can independently be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
  • m is 12, 13, 14, 15, 16, 17 or Is 18 and p and q can independently be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
  • p and q are not both 0.
  • Particularly preferred is the sum of p and q 4 to 16, in particular 6 to 14.
  • Examples of particularly preferred alcohol polyglycol ethers are ⁇ -C m H 2m + 1 - (OCH 2 CH 2 ) - ( OCH 2 CHCH 3 ) -OH, n-CJH 2 H 2 O 2 H 2 O 3 M 2 OCH 2 OH / 7-C m H 2m + 1 - (OCH 2 CH 2 ) 2 - (OCH 2 CHCH 3 ) 2 -OH, nC m H 2m + 1 - (OCH 2 CH 2 ) - (OCH 2 CHCH 3 ) 3 - OH, nC m H 2m + 1 - (OCH 2 CH 2 ) 2 - (OCH 2 CHCH 3 ) 3 -OH, nC m H 2m + 1 - (OCH 2 CH 2 ) 2 - (OCH 2 CHCH 3 ) 3 -OH,
  • the acid-resistant amylase and the complexing agent are placed under tubes in water or in a dilute aqueous salt solution, for example saline solution, optionally with the addition of further components that support demineralization and / or desizing.
  • a dilute aqueous salt solution for example saline solution
  • the enzyme is added in an amount such that the enzyme activity concentration about 200,000 to 6,000,000 ISU (lodine-Starch-Activity Units) / ml at about 20 0 C and a pH from about 3 to 4.5.
  • Enzyme activity concentrations of 400,000 to 5,000,000 ISU / ml are preferred and enzyme activity concentrations of 600,000 to 4,000,000 ISU / ml are particularly preferred.
  • the complexing agent should be present in order to ensure a sufficient effectiveness of the acid-resistant aqueous medium in a concentration of 0.1 to 100 mmol / l.
  • the complexing agent is preferably present in a concentration of 0.1-75 mmol / l and more preferably in an amount of 0.1-50 mmol / l. Even more preferred are concentrations of 0.1-25 mmol / l.
  • the aqueous acidic medium may contain conventional demineralization or desizing aids.
  • the aqueous acidic medium additionally contains one or more acids and / or one or more buffers as adjuvants to adjust and control the pH of the acidic aqueous medium so that demineralization and / or desizing proceeds effectively.
  • a buffer can be used which allows the maintenance of a low pH value over a certain period of time in order to support the demineralization and / or a buffer can be used which ensures the retention of a later, higher pH in the acidic area over a period of time to assist in the desizing. In this way, the pH gradient of the acidic aqueous medium can be influenced and adapted to the desired use.
  • the one or more buffers are advantageously designed to set a pH in the range of 0-6, preferably in the range of 1-5, more preferably in the range of 1.5-4.8.
  • Suitable buffers for these pH ranges are, for example, phosphate buffers.
  • textile fiber materials are understood to mean all natural and synthetic fiber materials and their mixtures which can be processed textile.
  • the acidic aqueous medium comprising an acid-stable amylase and a complexing agent can be used according to the invention for the combined demineralization and desizing of acetate (CA), alginate (ALG) 5 aramid (AR), asbestos (AS), cotton (CO), cupro ( CUP), Elastane (EL), Flax, Linen (LI), Guanaco (WU), Hemp (HA), Henequen (HE), Jute (JU), Kanin (WN), Kapok (KP), Kenaf (KE), Coco (CC), modacrylic (MAC), modal (CMD), polyacrylic (PAN), polyamide (PA), polyester (PES), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVAL), ramie (RA), Rosella (JS), Silk (SE), Sisal (SI), Sunn (SN), Triacetate (CTA), Urena (JR), Vikunja (WG), Viscose (CV) and similar textile fibers.
  • CA
  • the textile fiber material may be in the form of a thread which has not yet been woven or the textile fiber material may be in the form of a woven product.
  • the textile fiber material is preferably in the form of a woven product. It is particularly preferable to use cotton fabric and cotton blend fabric.
  • the process according to the invention can be carried out at a pH of the aqueous medium of 0-6, preferably 1-5, particularly preferably 1.5-4.8.
  • the suitable exposure time of the acidic aqueous medium to the textile desiccant for combined desizing and demineralization is determined by the thickness and structure of the sizings, the amount of alkaline earth metal ions and heavy metal ions to be complexed, the nature, texture and texture of the textile fiber material, the pH and the temperature of the fabric acidic aqueous medium, the complexing agent used and the amylase used and can be determined by the expert without difficulty in some orienting experiments.
  • the exposure time is 1 minute to 48 hours. At lower temperatures, longer exposure times are generally selected, while shorter exposure times are sufficient at higher temperatures.
  • the exposure time is usually 8-48 h, in the warm-residence process 1-16 h and in the pad-steam process 1-10 min.
  • the above parameters are adjusted to the effect that the exposure time is in the range of 1 minute to 16 hours.
  • the acidic aqueous medium comprises 600,000 to 4,000,000 ISU / ml of acid-stable ⁇ -amylase and 0.1 to 75 mmol / liter of complexing agent.
  • the complexing agent is selected from the group consisting of aminocarboxylic acids, phosphonates, polyacrylic acids and polyacrylic acid copolymers and / or the textile fiber material is a cellulose-containing fiber material, in particular cotton.
  • the acidic aqueous medium can act on the textile fiber material at a temperature of 0-120 0 C, wherein the temperature is advantageously chosen so that the activities of complexing agent and amylase are as high as possible and the amylase is not destroyed by the selected elevated temperature.
  • a temperature profile or a temperature gradient can also be set with advantage optionally in combination with a pH gradient.
  • the process according to the invention can be carried out batchwise or continuously.
  • the textile fiber material is impregnated in a liquor in the acidic aqueous medium, then squeezed off and the remaining acidic aqueous medium then acts on the textile fiber material at the selected reaction temperature.
  • the process according to the invention can also be carried out continuously by drawing the textile fiber material for impregnation through a liquor with the acidic aqueous medium, then squeezing it in continuous process control and then acting on the textile fiber material.
  • ISU iodine starch activity units
  • the iodine-starch test does not give an absolute measure of the converted starch in moles per minute. However, the change in absorbance at 700 nm (A700) per minute is a relative indicator of the starch hydrolysis rate, all comparisons being made according to the same protocol. In the protocol used here, the amylase reaction is carried out in the presence of 0.1% strength with a suitable buffer at a predetermined pH and temperature in a volume of 1 ml.
  • the enzyme source is normally added as 0.1 ml of the total reaction volume of 1 ml.
  • At predetermined times becomes 100 ⁇ l supernatant of the reaction mixture withdrawn, mixed with 900 .mu.l of deionized water and 50 .mu.l of iodine reagent and the A700 determined against deionized water as a blank.
  • the activity is reducing the A700 over time during the consumption of the starch.
  • An iodine-starch unit (ISU) of activity is defined as a reduction of 0.001 absorbance units at 700 nm (A700) per minute at a given pH and temperature during the amylase reaction being measured.
  • the Berger whiteness is a standard value for whiteness (Claudio Puebla, Whiteness Assessment: A Primer, Axiphos, page 26). Berger's whiteness was measured with the Minolta Spectrophotometer CM-3600d.
  • a liquor containing 25 g / l OPTIAMYLASE thermocacidophilic ⁇ -amylase from Alicyclobacillus acidocaldarius strain ATCC 27009, according to Schwermann et al., Eur. J.
  • a pad-steam bleaching is performed.
  • the cotton fabric is treated for 5 minutes at 100 0 C and 100% steam.
  • the degree of purification is determined by the TEGP ⁇ 'A method.
  • a liquor containing 5 g / l LAVISTA-ZYM R & D (dilution of a fungal ⁇ -amylase from Aspergillus sp. In an aqueous saline solution, concentration of enzyme activity 3.278.000 ISU / ml at 70 ° C.
  • a pad-steam bleaching is performed.
  • the cotton fabric is treated for 5 minutes at 100 ° C and 100% steam.
  • the degree of desizing is determined by the TEGEW A method. Comparative example
  • the fleet intake is 80%.
  • the cotton fabric is treated at 70 ° C. for 4 hours.
  • the cotton fabric (100% cotton) is demineralized with a liquor of 3 g / l of product A (mixture of concentrated sulfuric acid, 1-hydroxyethane- (1,1-diphosphonic acid) and diethylenetriamine penta (methylenephosphonic acid)) and 3 g / l PRODUCT B (mixture of a C 12 - polyglycol ether with 12 ethylene oxide and 2 propylene oxide units, a C 10 polyglycol ether with 6 ethylene oxide units and a lsononankla 2-ethylhexylamid) soaked, squeezed and 1 hour at 70 ° C treated.
  • a pad-steam treatment is carried out.
  • the cotton fabric is treated for 5 minutes at 100 0 C and 100% steam.
  • the degree of desizing is determined by the TEGEW A method.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

L'invention concerne l'utilisation d'un milieu aqueux acide pour la déminéralisation et le désencollage combinés de matériaux de fibres textiles, le milieu aqueux acide comprenant une amylase résistant aux acides et un agent complexant. En outre, l'invention concerne un procédé de déminéralisation et de désencollage combinés de matériaux de fibres textiles, selon lequel on laisse le milieu aqueux acide agir sur le matériau de fibres textiles.
PCT/EP2007/002356 2006-07-05 2007-03-16 Déminéralisation et désencollage combinés de matériaux de fibres textiles WO2008003358A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP06013948.2 2006-07-05
EP06013948A EP1876285A1 (fr) 2006-07-05 2006-07-05 Déminéralisation et désencollage de matériaux textiles en une seule operation

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WO2008003358A1 true WO2008003358A1 (fr) 2008-01-10

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CN103232982B (zh) * 2013-05-15 2015-03-04 常熟市诺科生化工程有限公司 一种高活力β-淀粉酶的制备方法
US11781086B2 (en) 2014-05-15 2023-10-10 Equus Uk Topco Ltd Lubricating oils and greases
US11104860B2 (en) 2014-05-15 2021-08-31 Croda, Inc. Lubricating oils

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2735816A1 (de) * 1977-08-09 1979-02-15 Basf Ag Verfahren zum bleichen und entschlichten von textilgut
EP0410498A2 (fr) * 1989-06-29 1991-01-30 Gist-Brocades N.V. Alpha-amylases microbiennes mutÀ©es avec une stabilité thermique, acide et/ou alcaline améliorée
WO1994028228A1 (fr) * 1993-05-21 1994-12-08 Basf Aktiengesellschaft Procede de pretraitement en continu d'un materiau textile contenant de la cellulose
WO2004065683A1 (fr) * 2003-01-17 2004-08-05 Cht R. Beitlich Gmbh Procede pour le finissage de matieres fibreuses textiles

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2735816A1 (de) * 1977-08-09 1979-02-15 Basf Ag Verfahren zum bleichen und entschlichten von textilgut
EP0410498A2 (fr) * 1989-06-29 1991-01-30 Gist-Brocades N.V. Alpha-amylases microbiennes mutÀ©es avec une stabilité thermique, acide et/ou alcaline améliorée
WO1994028228A1 (fr) * 1993-05-21 1994-12-08 Basf Aktiengesellschaft Procede de pretraitement en continu d'un materiau textile contenant de la cellulose
WO2004065683A1 (fr) * 2003-01-17 2004-08-05 Cht R. Beitlich Gmbh Procede pour le finissage de matieres fibreuses textiles

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