EP2000583A1 - Method for treating textiles containing cellulose - Google Patents
Method for treating textiles containing cellulose Download PDFInfo
- Publication number
- EP2000583A1 EP2000583A1 EP08009672A EP08009672A EP2000583A1 EP 2000583 A1 EP2000583 A1 EP 2000583A1 EP 08009672 A EP08009672 A EP 08009672A EP 08009672 A EP08009672 A EP 08009672A EP 2000583 A1 EP2000583 A1 EP 2000583A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- textile
- treatment
- alkaline
- solution
- alkaline substance
- 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
Links
- 239000004753 textile Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims description 30
- 229920002678 cellulose Polymers 0.000 title claims description 13
- 239000001913 cellulose Substances 0.000 title claims description 13
- 238000011282 treatment Methods 0.000 claims abstract description 47
- 239000000243 solution Substances 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 25
- 108010059892 Cellulase Proteins 0.000 claims abstract description 18
- 229940106157 cellulase Drugs 0.000 claims abstract description 18
- 239000012670 alkaline solution Substances 0.000 claims abstract description 9
- 230000002255 enzymatic effect Effects 0.000 claims abstract description 5
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 5
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 4
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000835 fiber Substances 0.000 claims description 29
- 239000004744 fabric Substances 0.000 claims description 23
- 238000007639 printing Methods 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000003906 humectant Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 3
- 239000002562 thickening agent Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 2
- 230000004913 activation Effects 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000003513 alkali Substances 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 7
- 239000008103 glucose Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 6
- 102000004190 Enzymes Human genes 0.000 description 6
- 229940088598 enzyme Drugs 0.000 description 6
- 108010084185 Cellulases Proteins 0.000 description 5
- 102000005575 Cellulases Human genes 0.000 description 5
- 229920000297 Rayon Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920000433 Lyocell Polymers 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920003043 Cellulose fiber Polymers 0.000 description 3
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229940097275 indigo Drugs 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007071 enzymatic hydrolysis Effects 0.000 description 2
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000004627 regenerated cellulose Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 108010008885 Cellulose 1,4-beta-Cellobiosidase Proteins 0.000 description 1
- 101710166469 Endoglucanase Proteins 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- 101000959121 Xenopus laevis Peptidyl-alpha-hydroxyglycine alpha-amidating lyase A Proteins 0.000 description 1
- 239000008351 acetate buffer Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007515 enzymatic degradation Effects 0.000 description 1
- 238000006911 enzymatic reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- COHYTHOBJLSHDF-BUHFOSPRSA-N indigo dye Chemical compound N\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-BUHFOSPRSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Images
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
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/16—Processes for the non-uniform application of treating agents, e.g. one-sided treatment; Differential treatment
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/06—Hydroxides
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
-
- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/144—Alcohols; Metal alcoholates
- D06M13/148—Polyalcohols, e.g. glycerol or glucose
-
- 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
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
- D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/12—Soft surfaces, e.g. textile
-
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Definitions
- the invention relates to a process for the enzymatic treatment of cellulose-containing textile by means of a solution comprising at least one kind of cellulase.
- cellulose-splitting enzymes have become very important in the textile-chemical treatment of cellulose fiber-containing materials.
- the technically most commonly used "total crude” cellulases are a mixture of microbiologically produced erido-, exocellullases and cellobiohydrolases.
- the object of the cellulases is the hydrolytic degradation of the cellulose by selective cleavage of the ⁇ -1,4-glycosidic bond, whereby soluble fragments are removed from the polymers and taken up by the treatment solution, where a further hydrolysis to glucose takes place.
- Object of the present invention is therefore to provide a method of the type mentioned, in which the textile loses imperceptible to mechanical resistance.
- Such a method of the type mentioned is characterized in that prior to treatment with the cellulase-containing solution, an alkaline substance, preferably an alkaline solution, is applied only in regions on the textile.
- a textile comprises both textile fibers, semi-finished and finished textile products such as yarn or textile fabrics and textile finished goods such as textile clothing etc. It is essential to the invention that the textile comprises cellulose (eg blended fabric) - but the textile does not have to consist of it.
- the textile for example the textile fiber
- the textile fiber is pretreated on the surface with an alkaline substance such that the alkaline substance penetrates only slightly into the textile or the textile fiber.
- the alkaline substance preferably alkaline solution
- the alkaline substance is applied to the surface of the textile fiber or textile such that it remains substantially on the surface of the textile.
- substantially remaining on the surface of the textile fiber is meant that the alkaline substance can not penetrate to the core of the textile fiber or the textile, but under 20 to 30% of the thickness of the textile fiber, preferably less than 10% of the thickness of the textile fiber in the textile fiber penetrates.
- the alkaline substance is applied by spraying and / or patting and / or doctoring and / or printing.
- the textile fiber or the flat textile obtained from a textile fiber is provided with patterns which, on the one hand, can have a different color ("stone-wash effect"), on the other hand a more pleasant or altered feel.
- the textile fibers are present in a flat textile, preferably textile fabric, it is possible to apply individual patterns to the textile which can be predetermined, in particular by printing a predefinable printing pattern.
- the alkaline substance is applied at least partially on one side of the flat textile.
- a different treatment of the two sides of the textile fabric is of interest in order to achieve advantages in terms of functional properties (water transport, absorbency, smoothness, etc.).
- the invention is based on the fact that in the areas where an alkaline substance has been applied, an increased rate of degradation can be achieved, since the cellulase has a higher reaction rate at these points. It is favorable if the alkaline substance comprises an aqueous solution of at least one metal hydroxide, preferably an alkaline earth metal hydroxide and / or alkali metal hydroxide, wherein it is preferably provided that the metal hydroxide is NaOH.
- the rate of reaction of the fiber-enzyme reaction depends on the fiber type presented (cotton, viscose fibers, lyocell fibers, etc.) as well as the concentration and activity of the enzymes used. Depending on the processing stage in the textile finishing process, the fiber changes in its reactivity. For example, it is known in the prior art that cotton textiles after treatment in concentrated caustic soda show an increased degradation rate by cellulases, which is mainly due to reduced crystallinity and increased accessibility of the fiber.
- the alkaline solution has a thickening agent.
- the alkaline substance is a humectant wherein it is particularly preferred that the humectant comprises glycerin.
- Alkaline treatment solutions known in the art may contain alkali ions (Li, Na, K ions), as well as, for example, alkaline earth hydroxides and quaternary ammonium hydroxides.
- the treatment in Nahsmlttelsystemen (alcoholic solutions of Banlmittein) has been described in the prior art.
- the present invention is therefore based on the idea to make the activation of the fiber only localized and thus to limit the rate of hydrolytic degradation of the cellulase on certain areas of the textile structure.
- the application of the activating alkali solution can be carried out by spraying, paddling, knife coating, and minimal application techniques on one or both sides of the product by the usual methods, in a particularly advantageous embodiment, printing techniques (stencil printing, foam printing) are mentioned.
- printing techniques stencil printing, foam printing
- Alkali solutions may be alkali hydroxides, alkaline earth hydroxides, quaternary ammonium bases as well as amines or other basic compounds known to those of ordinary skill in the art.
- concentrations of the application solutions are in the range of 0.5 to 10 mol / l of alkali solution, the concentration due to the desired activation effect, the textile substrate to be treated and optionally provided intermediate drying is determined.
- intermediate drying a concentration of the non-volatile alkali takes place on the surface; so that higher concentrations are achieved here compared to the applied application solution.
- concentration range for a desired result will be easy to determine with knowledge of the invention, even for the average expert by series experiments.
- the applied solution beforehand admixed with humectants such as glycerin to prevent complete drying and hardening.
- Textile structures can be, for example, woven fabrics, knitted fabrics, nonwovens, films, etc., with no restrictions with regard to the material form to be treated.
- Cellulosic substrates may preferably consist of cotton, bast fibers, viscose, modal, lyocell fibers or mixtures thereof with other fibers of cellulose or other fibrous materials, in particular synthetic materials.
- dyed textiles of cotton or other cellulosic fibers, or their blends are treated with synthetic fibers (such as Lycra, polyester fibers, polyamide), in a particularly preferred embodiment, indigo dyed denim webs of cellulosic fibers are treated.
- Suitable cellulase treatment methods may be selected from the methods proposed in the prior art.
- indigo ring-dyed denim fabric is activated, which has the advantage which provides faster detachment of the indigo dye from the tissue surface.
- a drying step takes place, preferably by heating the textile.
- the textile is at least partially dyed, preferably indigo-dyed, wherein it is particularly preferred that the textile comprises textile fibers which are woven into a fabric, preferably denim fabric, or the alkaline substance in ready-made textiles before a washing treatment.
- woven textile fibers woven into a textile fabric in the form of a textile fabric 1 are shown schematically.
- On the textile fabric 1 is partially applied to the checkered areas 2 an alkaline substance.
- the white areas 3 are untreated.
- the alkaline paste was washed with water, rinsed three times with cold water and neutralized at 40 ° C with 1% acetic acid.
- the enzyme treatment was then carried out in a laboratory dyeing plant (Pretema Multicolor laboratory dyeing unit type MC 360, Caromatic, Switzerland), a "total crude cellulose” Genencor, USA, was used with a concentration of 3.0 IU / mg tissue (30 mUL treatment bath).
- the solution was adjusted to pH 4.8 by a 50 mM acetate buffer.
- the liquor ratio was 1 g of tissue: 25 ml of treatment bath.
- Treatment of material I was 1.5 hours, material II, 0.75 hours at a temperature of 55 ° C.
- the enzymatic hydrolysis was stopped by raising the temperature to 75 ° C. and raising the pH to 10 and treating for 10 minutes.
- the samples were rinsed and air dried.
- Table 1 compares the results of the untreated and activated tissues. The increased brightness due to the increased degradation on the surface of the materials is clearly visible. The total color difference ⁇ E is also calculated and shown. The ⁇ E values above 6 clearly show the increased color loss on the alkaline pretreated areas.
- Example 2 shows the increase in the rate of degradation by alkaline pretreatment using the example of regenerated fibers
- Viscose fabric (staple fiber yarn 38 mm, 1.3 dtex) was used as a substrate. Plain weave warp 20 tex, weft, 24 tex, twist 19 rounds / inch, 143 g / m 2 , 37/29 fd / cm was used.
- the treatment solution was prepared by diluting a 50% (w / w) sodium hydroxide solution with water (1.04, 2.20, 3.48 and 4.91 mol / L NaOH).
- the fabric was pretensioned in different alkali solutions for 1 minute at a liquor ratio of 1: 3.
- the concentration of the treatment solutions is given in Table 2.
- the enzyme treatment was then carried out in a laboratory dyeing plant (Pretema Multicolor laboratory dyeing unit type MC 360, Caromatic, Switzerland).
- a "total crude cellulose” Genencor, USA was used at a concentration of 3.5 IU / mg tissue (30 mg protein per mL).
- the solution was buffered through a 50 mM acetate adjusted to pH 4.8.
- the liquor ratio was 1 g tissue 25 ml treatment bath.
- the hydrolysis was carried out at 55 ° C (+/- 1 ° C). After 1 hour of treatment, the weight loss was evaluated by measuring the concentration of glucose formed in the solution. Comparative measurements were performed with non-pretreated materials.
- Table 2 shows the altered degradation measured as the concentration of glucose formed per L treatment bath after one hour.
- Table 2 Glucose concentration in solution on enzymatic hydrolysis of viscose with and without alkaline activation glucose concentration fabric pattern [G / L] Untreated control 1.81 Activation with 1.04 mol / L NaOH, 60 sec 2.50 Activation with 2.20 mol / L NaOH, 60 sec 7.15 Activation with 3.48 mol / L NaOH, 60 sec 11.29
- Fabrics made from other regenerated cellulose fibers can be treated in the same way.
- Table 3 shows the increase in degradation rate measured after 1 hour of hydrolysis time.
- Table 3. Degradation measured as g / L glucose and activation Concentration in g / L glucose Treatment in comparison sample 3.48 mol / L NaOH % Activation viscose 1.81 11.28 625 Modal 0.65 6.45 992 lyocell 0.47 3.95 848 Lyocell networked 0.33 5.26 1594
- the degradation rate is increased by a factor of 6 - 15.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Microbiology (AREA)
- Inorganic Chemistry (AREA)
- Emergency Medicine (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur enzymatischen Behandlung von cellulosehältigem Textil mittels einer Lösung, die zumindest eine Sorte von Cellulase aufweist.The invention relates to a process for the enzymatic treatment of cellulose-containing textile by means of a solution comprising at least one kind of cellulase.
Enzymatische Prozesse haben in der Behandlung textiler Substrate breite Anwendung gefunden. In den vergangenen Jahren ist den Cellulose spaltenden Enzymen (Cellulasen) eine hohe Bedeutung bei der textilchemischen Behandlung Cellulosefasern enthaltender Materialien zu Teil geworden. Die technisch am häufigsten eingesetzten "Total crude" Cellullasen sind ein Gemisch von mikrobiologisch erzeugten Erido-, Exocellullasen und Cellobiohydrolasen. Aufgabe der Cellulasen ist dabei der hydrolytische Abbau der Cellulose durch selektive Spaltung der β-1,4-glycasidischen Bindung, wodurch lösliche Bruchstücke aus den Polymeren entfernt und von der Behandlungslösung aufgenommen werden, wo eine weitere Hydrolyse bis zur Glucose erfolgt. Meist wird dabei auf die Veränderung des Griffs der Materialien, eine Entfernung von Flusen und eine Verbesserung der unerwünschten Pillneigung der Materialien abgezielt. Ein besonderer Anwendungsbereich ist auch in der Wäsche indigogefärbter Denim-Textilien zu finden, wo die enzymatische Behandlung als, Ersatz oder Ergänzung für die Bleichbehandlung eingesetzt wird. Hier ermöglichen die Enzyme den sogenannten Wash-down, welcher in Waschprozessen der fertigen Textilien zum Used-Look der Jeans führt.Enzymatic processes have found wide application in the treatment of textile substrates. In recent years cellulose-splitting enzymes (cellulases) have become very important in the textile-chemical treatment of cellulose fiber-containing materials. The technically most commonly used "total crude" cellulases are a mixture of microbiologically produced erido-, exocellullases and cellobiohydrolases. The object of the cellulases is the hydrolytic degradation of the cellulose by selective cleavage of the β-1,4-glycosidic bond, whereby soluble fragments are removed from the polymers and taken up by the treatment solution, where a further hydrolysis to glucose takes place. It is mostly aimed at changing the feel of the materials, removing lint, and improving the undesirable pilling tendency of the materials. A particular area of application is also found in the wash of indigo-dyed denim textiles, where the enzymatic treatment is used as a, replacement or supplement for the bleaching treatment. Here the enzymes enable the so-called wash-down, which leads to the used look of the jeans in washing processes of the finished textiles.
Weiters ist aus dem Stand der Technik bekannt, cellulosehältige Fasern mit alkalischer Cellulaselösung zu behandeln, da die Abbaugeschwindigkeit von Cellulose im alkalischen Medium höher ist als im neutralen pH-Bereich. Schließlich ist es bekannt, Baumwollfasern vor der Cellulasebehandlung mit einem Quellmittel zu versetzen, um einen enzymatischen Abbau in dem Bereich, der das Quellmittel aufnimmt, zu verringern.Furthermore, it is known from the prior art to treat cellulose-containing fibers with alkaline cellulase solution, since the degradation rate of cellulose in the alkaline medium is higher than in the neutral pH range. Finally, it is known to provide cotton fibers with a swelling agent prior to cellulase treatment in order to reduce enzymatic degradation in the region which receives the swelling agent.
Die Textilien werden bei allen Prozessen in Großwaschmaschinen den Cellulasebehandlungen ausgesetzt, welche durch hydrolytischen Angriff das Textil schwächen und hierdurch in Kombination mit der Waschmechanik den Abrieb eines allfälligen Farbstoffes unterstützen, was zur Entwicklung eines Wash-downs führt. Cellulasebehandlungen sind stets mit Verlusten in der mechanischen Beständigkeit des Textils verbunden, was sich in herabgesetzter Festigkeit und verminderter Scheuerbeständigkeit der behandelten Produkte im Vergleich zu nicht behandelten Produkten zeigt. Diese Verminderung des Gebrauchswertes stellt eine unerwünschte Folge der Cellulasebehandlung dar.The textiles are exposed to the cellulase treatments in all processes in large washing machines, which weaken the fabric by hydrolytic attack and thereby support in combination with the washing mechanism the abrasion of a possible dye, leading to the development of a wash-down. Cellulasebehandlungen are always associated with losses in the mechanical resistance of the textile, which manifests itself in reduced strength and reduced abrasion resistance of the treated products compared to untreated products. This reduction in utility value is an undesirable consequence of cellulase treatment.
Aufgabe der vorliegenden Erfindung ist es daher, ein Verfahren der eingangs genannten Gattung bereitzustellen, bei dem das Textil nur unmerklich an mechanischer Beständigkeit verliert.Object of the present invention is therefore to provide a method of the type mentioned, in which the textile loses imperceptible to mechanical resistance.
Diese Aufgabe wird mit einem Verfahren gemäß Anspruch 1 gelöst. Ein solches Verfahren der eingangs genannten Gattung ist dadurch gekennzeichnet, dass vor der Behandlung mit der cellulasehältigen Lösung eine alkalische Substanz, vorzugsweise eine alkalische Lösung, nur bereichsweise auf das Textil aufgebracht wird.This object is achieved by a method according to
Gemäß DIN 60 000 umfasst ein Textil gleichermaßen Textilfasern, textile Halb- und Fertigfabrikate wie zB Gam oder Textilgewebe und textile Fertigwaren wie textile Kleidung etc. Dabei ist erfindungswesentlich, dass das Textil Cellulose aufweist (zB Mischgewebe) - jedoch muss das Textil nicht daraus bestehen.According to DIN 60 000, a textile comprises both textile fibers, semi-finished and finished textile products such as yarn or textile fabrics and textile finished goods such as textile clothing etc. It is essential to the invention that the textile comprises cellulose (eg blended fabric) - but the textile does not have to consist of it.
Bei einem solchen Verfahren kann vorgesehen sein, dass das Textil (zB die Textilfaser) derart an der Oberfläche mit einer alkalischen Substanz vorbehandelt wird, dass die alkalische Substanz nur geringfügig in das Textil bzw. die Textilfaser eindringt. Zu diesem Zweck kann vorgesehen sein, dass vor der Behandlung mit der cellulasehaltigen Lösung die alkalische Substanz, vorzugsweise alkalische Lösung, derart auf die Oberfläche der Textilfaser bzw. des Textils aufgebracht wird, dass sie im Wesentlichen an der Oberfläche des Textils bleibt. Unter "im Wesentlichen an der Oberfläche der Textilfaser bleiben" ist gemeint, dass die alkalische Substanz nicht bis zum Kern der Textilfaser oder des Textils vordringen kann, sondern unter 20 bis 30% der Dicke der Textilfaser, bevorzugt unter 10% der Dicke der Textilfaser in die Textilfaser eindringt.In such a method it can be provided that the textile (for example the textile fiber) is pretreated on the surface with an alkaline substance such that the alkaline substance penetrates only slightly into the textile or the textile fiber. For this purpose, it may be provided that, prior to treatment with the cellulase-containing solution, the alkaline substance, preferably alkaline solution, is applied to the surface of the textile fiber or textile such that it remains substantially on the surface of the textile. By "substantially remaining on the surface of the textile fiber" is meant that the alkaline substance can not penetrate to the core of the textile fiber or the textile, but under 20 to 30% of the thickness of the textile fiber, preferably less than 10% of the thickness of the textile fiber in the textile fiber penetrates.
Dies wird insbesondere dadurch erreicht, dass die alkalisch Substanz durch Sprühen und / oder Pflatschen und / oder Rakeln und / oder Aufdrucken aufgebracht wird.This is achieved in particular by the fact that the alkaline substance is applied by spraying and / or patting and / or doctoring and / or printing.
Bevorzugt ist vorgesehen, dass die Textilfaser oder das aus einer Textilfaser gewonnene flächige Textil wie zB Textilgewebe mit Mustern versehen wird, die einerseits unterschiedliche Farbe ("Stone-Wash-Effekt"), andererseits einen angenehmeren oder veränderten Griff aufweisen können. Für den Fall, dass die Textilfasern in einem flächigen Textil, vorzugsweise Textilgewebe, vorliegen, lassen sich einzelne Muster auf das Textil aufbringen, die vorgebbar sind, insbesondere durch das Aufdrucken eines vorgebbaren Druckmusters. Dabei kann vorgesehen sein, dass die alkalische Substanz nur auf einer Seite des flächigen Textils zumindest bereichsweise aufgebracht wird. Insbesondere bei funktionellen Textilien ist eine unterschiedliche Behandlung der beiden Seiten des Textilgewebes von Interesse, um dadurch Vorteile bei den Funktionseigenschaften (Wassertransport, Saugfähigkeit, Glätte etc.) zu erreichen.It is preferably provided that the textile fiber or the flat textile obtained from a textile fiber, for example textile fabric, is provided with patterns which, on the one hand, can have a different color ("stone-wash effect"), on the other hand a more pleasant or altered feel. In the event that the textile fibers are present in a flat textile, preferably textile fabric, it is possible to apply individual patterns to the textile which can be predetermined, in particular by printing a predefinable printing pattern. It can be provided that the alkaline substance is applied at least partially on one side of the flat textile. In particular, in the case of functional textiles, a different treatment of the two sides of the textile fabric is of interest in order to achieve advantages in terms of functional properties (water transport, absorbency, smoothness, etc.).
Der Erfindung liegt zugrunde, dass in den Bereichen, wo eine alkalische Substanz aufgebracht wurde, eine erhöhte Abbaugeschwindigkeit erzielt werden kann, da die Cellulase an diesen Stellen eine höhere Reaktionsgeschwindigkeit aufweist. Es ist günstig, wenn die alkalische Substanz eine wässrige Lösung zumindest eines Metallhydroxides, vorzugsweise eines Erdalkalimetallhydroxides und/oder Alkalimetallhydroxides, umfasst, wobei bevorzugt vorgesehen ist, dass das Metallhydroxid NaOH ist.The invention is based on the fact that in the areas where an alkaline substance has been applied, an increased rate of degradation can be achieved, since the cellulase has a higher reaction rate at these points. It is favorable if the alkaline substance comprises an aqueous solution of at least one metal hydroxide, preferably an alkaline earth metal hydroxide and / or alkali metal hydroxide, wherein it is preferably provided that the metal hydroxide is NaOH.
Die Umsatzgeschwindigkeit der Reaktion Faser-Enzym hängt dabei von der vorgelegten Fasertype (Baumwolle, Viskosefasern, Lyocellfasern usw.) sowie der Konzentration und Aktivität der verwendeten Enzyme ab. Je nach Verarbeitungsstufe im textilen Veredlungsablauf verändert sich die Faser in ihrer Reaktivität. So ist beispielsweise nach dem Stand der Technik bekannt, dass Baumwoll-Textilen nach einer Behandlung in konzentrierter Natronlauge eine erhöhte Abbaurate durch Cellulasen zeigen, was hauptsächlich durch verminderte Kristallinität und erhöhte Zugänglichkeit der Faser begründet wird.The rate of reaction of the fiber-enzyme reaction depends on the fiber type presented (cotton, viscose fibers, lyocell fibers, etc.) as well as the concentration and activity of the enzymes used. Depending on the processing stage in the textile finishing process, the fiber changes in its reactivity. For example, it is known in the prior art that cotton textiles after treatment in concentrated caustic soda show an increased degradation rate by cellulases, which is mainly due to reduced crystallinity and increased accessibility of the fiber.
Um für die entsprechende Textilfasertype geeignete Bedingungen auszuwählen, sodass die oben genannten Vorgaben erfüllt werden, kann es günstig sein, wenn die alkalische Lösung ein Verdickungsmittel aufweist. Um den Reaktionsverlauf zu begünstigen, ist es weiter günstig, wenn die alkalische Substanz ein Feuchthaltemittel aufweist, wobei besonders bevorzugt vorgesehen ist, dass das Feuchthaltemittel Glycerin umfasst.In order to select suitable conditions for the corresponding textile fiber type, so that the above-mentioned requirements are met, it may be favorable if the alkaline solution has a thickening agent. In order to favor the course of the reaction, it is further favorable if the alkaline substance is a humectant wherein it is particularly preferred that the humectant comprises glycerin.
Die Behandlung cellulosischer Substrate in Lösungen verschiedenster alkalischer Substanzen ist aufgrund der Möglichkeit zur Veränderung der Reaktivität der Cellulose umfangreich untersucht worden. Nach dem Stand der Technik bekannte alkalische Behandlungslösungen können Alkallionen (Li-, Na-, K-ionen) enthalten, ebenso sind beispielsweise Erdalkalihydroxide und Quartäre Ammoniumhydroxide bekannt. Auch die Behandlung in Lösungsmlttelsystemen (alkoholische Lösungen von Quellmittein) ist nach dem Stand der Technik beschrieben worden.The treatment of cellulosic substrates in solutions of various alkaline substances has been extensively studied because of the possibility of changing the reactivity of the cellulose. Alkaline treatment solutions known in the art may contain alkali ions (Li, Na, K ions), as well as, for example, alkaline earth hydroxides and quaternary ammonium hydroxides. The treatment in Lösungsmlttelsystemen (alcoholic solutions of Quellmittein) has been described in the prior art.
Der vorliegenden Erfindung liegt daher die Idee zu Grunde, die Aktivierung der Faser nur lokalisiert vorzunehmen und damit die Geschwindigkeit des hydrolytischen Abbaus der Cellulase auf bestimmten Bereiche der textilen Struktur zu begrenzen.The present invention is therefore based on the idea to make the activation of the fiber only localized and thus to limit the rate of hydrolytic degradation of the cellulase on certain areas of the textile structure.
Dies wird erreicht, indem die Einwirkung der aktivierenden Alkalibehandlung nur auf Bereiche des Materials beschränkt erfolgt. Dies kann beispielsweise an der Oberfläche der textilen Struktur erfolgen, indem die Menge an Alkali so aufgebracht wird, dass nur die äusserste Struktur für den Cellulaseangriff aktiviert wird. Unerwarteterweise kann dadurch eine starke Oberflächenaktivierung erfolgen, sodass eine vor allem auf die Oberfläche begrenzte hydrolytische Wirkung der Enzyme erfolgt.This is achieved by the action of the activating alkali treatment is limited only to areas of the material. This can be done for example on the surface of the textile structure by the amount of alkali is applied so that only the outermost structure for the cellulase attack is activated. Unexpectedly, this can lead to a strong surface activation, so that there is a hydrolytic effect of the enzymes, which is mainly limited to the surface.
Die Aufbringung der aktivierenden Alkalilösung kann nach den üblichen Verfahren durch Sprühen, Pflatschen, Rakeln, und Minimalauftragstechniken auf einer oder beiden Warenseiten erfolgen, wobei in einer besonders vorteilhaften Ausführungsform Drucktechniken (Schablonendruck, Schaumdruck) zu nennen sind. Hierdurch kann sowohl eine einseitige oberflächliche Aktivierung der Cellulose erfolgen wie auch ein Musterungseffekt realisiert werden.The application of the activating alkali solution can be carried out by spraying, paddling, knife coating, and minimal application techniques on one or both sides of the product by the usual methods, in a particularly advantageous embodiment, printing techniques (stencil printing, foam printing) are mentioned. As a result, both a one-sided surface activation of the cellulose can be carried out as well as a patterning effect can be realized.
Alkalilösungen können Alkalihydroxide, Erdalkalihydroxide, quartäre Ammoniumbasen ebenso wie Amine oder andere dem Durchschnittsfachmann bekannte basische Verbindungen sein.Alkali solutions may be alkali hydroxides, alkaline earth hydroxides, quaternary ammonium bases as well as amines or other basic compounds known to those of ordinary skill in the art.
Vorteilhafte Konzentrationen der Anwendungslösungen sind im Bereich von 0.5 bis 10 mol/l Alkalilösung, wobei die Konzentration durch den erwünschten Aktivierungseffekt, das zu behandelnde textile Substrat und eine gegebenenfalls vorgesehene Zwischentrocknung bestimmt wird. Bei der Zwischentrocknung erfolgt eine Aufkonzentrierung des nicht flüchtigen Alkalis auf der Oberfläche; sodass hier gegenüber der aufgebrachten Anwendungslösung höhere Konzentrationen erreicht werden. Der optimale Konzentrationsbereich für ein gewünschtes Resultat wird bei Kenntnis der Erfindung auch für den Durchschnittsfachmann durch Serienversuche einfach zu ermitteln sein.Advantageous concentrations of the application solutions are in the range of 0.5 to 10 mol / l of alkali solution, the concentration due to the desired activation effect, the textile substrate to be treated and optionally provided intermediate drying is determined. In the intermediate drying, a concentration of the non-volatile alkali takes place on the surface; so that higher concentrations are achieved here compared to the applied application solution. The optimum concentration range for a desired result will be easy to determine with knowledge of the invention, even for the average expert by series experiments.
In einer vorteilhaften Ausführungsform werden der aufgebrachten Lösung vorher Feuchthaltemittel wie beispielsweise Glycerin beigemischt, um eine vollständige Trocknung und Verhärtung zu verhindern.In an advantageous embodiment, the applied solution beforehand admixed with humectants such as glycerin to prevent complete drying and hardening.
Textile Strukturen können beispielsweise Gewebe, Gestricke, Vliese, Folien etc. sein, wobei in Hinblick auf die zu behandelnde Materialform keine Einschränkungen bestehen. Cellulosische Substrate können bevorzugt aus Baumwolle, Bastfasern, Viskose, Modal, Lyocellfasern bzw. deren Mischungen mit anderen Fasern aus Cellulose oder anderen Faserstoffen insbesondere synthetischen Materialien bestehen. In einer bevorzugten Form werden gefärbte Textilien aus Baumwolle oder anderen Cellulosefasern bzw. deren Mischungen mit Synthesefasern (wie z.B. Lycra, Polyesterfasern, Polyamid) behandelt, wobei in einer besonders bevorzugten Ausführungsform Indigo gefärbte Denim Gewebe aus Cellulosefasern behandelt werden.Textile structures can be, for example, woven fabrics, knitted fabrics, nonwovens, films, etc., with no restrictions with regard to the material form to be treated. Cellulosic substrates may preferably consist of cotton, bast fibers, viscose, modal, lyocell fibers or mixtures thereof with other fibers of cellulose or other fibrous materials, in particular synthetic materials. In a preferred form, dyed textiles of cotton or other cellulosic fibers, or their blends, are treated with synthetic fibers (such as Lycra, polyester fibers, polyamide), in a particularly preferred embodiment, indigo dyed denim webs of cellulosic fibers are treated.
Geeignete Cellulasebehandlungsverfahren können aus den nach dem Stand der Technik vorgeschlagenen Verfahren ausgewählt werden.Suitable cellulase treatment methods may be selected from the methods proposed in the prior art.
Durch die lokale Aktivierung kommt es zu einer bescheunigten Hydrolyse der Cellulose in diesen Bereichen. Erfolgt die Behandlung an der Oberfläche, so wird vor allem die Oberfläche hydrolytisch durch die Cellulasen angegriffen und die Festigkeit und mechanische Beständigkeit des Materials im Kern der textilen Struktur wird weniger angegriffen, In einer besonders bevorzugten Behandlungsform wird mit Indigo ringgefärbtes Denimgewebe aktiviert, was den Vorteil der rascheren Ablösung des Indigofarbstoffs von der Gewebeoberfläche bietet. Hierdurch können die Waschprozesse in der Denimwäsche in vorteilhafter Weise verkürzt werden, erfolgt die Aktivierung nach vorgegebenen Musterungen, so können besondere Mustereffekte und Dessins realisiert werden.Local activation leads to accelerated hydrolysis of the cellulose in these areas. If the treatment is carried out on the surface, especially the surface is hydrolytically attacked by the cellulases and the strength and mechanical resistance of the material in the core of the textile structure is less affected. In a particularly preferred treatment, indigo ring-dyed denim fabric is activated, which has the advantage which provides faster detachment of the indigo dye from the tissue surface. As a result, the washing processes in the denim wash can be shortened in an advantageous manner, the Activation according to predetermined patterns, so special pattern effects and designs can be realized.
Günstig kann weiters vorgesehen sein, dass nach dem Aufbringen der alkalischen Lösung und vor der Cellulasebehandlung ein Trocknungsschritt, vorzugsweise durch Erwärmen des Textils erfolgt.Conveniently, it may further be provided that after the application of the alkaline solution and before the cellulase treatment a drying step takes place, preferably by heating the textile.
Die bevorzugte Ausführung sieht vor, dass das Textil zumindest bereichsweise gefärbt, bevorzugt indigo-gefärbt ist, wobei besonders bevorzugt vorgesehen ist, dass das Textil Textilfasern aufweist, die zu einem Gewebe, vorzugsweise Denimgewebe, verwoben sind bzw. die alkalische Substanz an fertig konfektionierten Textilien vor einer Waschbehandlung erfolgt.The preferred embodiment provides that the textile is at least partially dyed, preferably indigo-dyed, wherein it is particularly preferred that the textile comprises textile fibers which are woven into a fabric, preferably denim fabric, or the alkaline substance in ready-made textiles before a washing treatment.
Weitere Details der Erfindung werden anhand der folgenden Beispiele und der Figur erläutert. Es zeigt die Figur ein Druckmuster auf ein Textilgewebe in Draufsicht.Further details of the invention will be explained with reference to the following examples and the figure. It shows the figure a print pattern on a textile fabric in plan view.
In der Figur sind zu einem flächigen Textil in der Form eines Textilgewebes 1 verwobene Textilfasern schematisch dargestellt. Auf das Textilgewebe 1 ist bereichsweise auf den kariert dargestellten Bereichen 2 eine alkalische Substanz aufgebracht. Die weiß dargestellten Bereiche 3 sind unbehandelt.In the figure, woven textile fibers woven into a textile fabric in the form of a
Entschlichtetes Denimgewebe (indigogefärbtes Baumwollgewebe) Qualität 1 (483 g/m2, Kette 27 Fd/cm, Schuß 19 Fd/cm) Qualität II (466 g/m2, Kette 18 Fd/cm, Schuß 18 Fd/cm) wurde verwendet.Desized denim fabric (indigo dyed cotton fabric) grade 1 (483 g / m 2 , warp 27 Fd / cm, weft 19 Fd / cm) grade II (466 g / m 2 , warp 18 Fd / cm, weft 18 Fd / cm) was used ,
Die Aktivierung erfolgte durch Aufdruck einer mit Verdickungsmittel viskos eingestellten Alkalilösung nach dem Siebdruckverfahren. Rezeptur der Druckpaste:The activation was carried out by printing on a thickener viscous alkali solution by the screen printing method. Formulation of printing paste:
73 % w/w alkalistabile Druckverdickung (20 g/L Prisulon GT 1000 M, Bezema AG, Schweiz) 23 % w/w NaOH 50%.73% w / w alkali-stable pressure thickening (20 g / l Prisulon GT 1000 M, Bezema AG, Switzerland) 23% w / w NaOH 50%.
Nach einer Minute Einwirkzeit wurde die alkalische Paste mit Wasser ausgewaschen, dreimal mit kaltem Wasser gespült und bei 40°C mit 1% Essigsäure neutralisiert.After one minute exposure time, the alkaline paste was washed with water, rinsed three times with cold water and neutralized at 40 ° C with 1% acetic acid.
Die Enzymbehandlung erfolgte anschließend in einer Laborfärbeanlage (Pretema Multicolor laboratory dyeing unit Typ MC 360; Caromatic, Schweiz), Eine "total crude cellulose" Genencor, USA, wurde mit einer Konzentration von 3.0 IU/mg Gewebe (30 mUL Behandlungsbad) eingesetzt. Die Lösung wurde durch einen 50 mM Azetat Puffer auf pH 4.8 eingestellt. Das Flottenverhältnis betrug 1 g Gewebe :25 ml Behandlungsbad.The enzyme treatment was then carried out in a laboratory dyeing plant (Pretema Multicolor laboratory dyeing unit type MC 360, Caromatic, Switzerland), a "total crude cellulose" Genencor, USA, was used with a concentration of 3.0 IU / mg tissue (30 mUL treatment bath). The solution was adjusted to pH 4.8 by a 50 mM acetate buffer. The liquor ratio was 1 g of tissue: 25 ml of treatment bath.
Die Behandlung von Material I erfolgte 1.5 Stunden, Material II, 0.75 Stunden bei einer Temperatur von 55°C. Die enzymatische Hydrolyse wurde durch Temperaturerhöhung auf 75°C und pH-Anhebung auf pH 10 und Behandlung für 10 min gestoppt. Die Muster wurden gespült und an der Luft getrocknet.Treatment of material I was 1.5 hours, material II, 0.75 hours at a temperature of 55 ° C. The enzymatic hydrolysis was stopped by raising the temperature to 75 ° C. and raising the pH to 10 and treating for 10 minutes. The samples were rinsed and air dried.
Die Effektivität der Behandlung der aktivierten Flächen Qualität I und Qualität II wurde mit der nicht aktivierten Oberfläche durch Farbmessung verglichen.The effectiveness of treatment of the activated areas quality I and quality II was compared with the non-activated surface by colorimetry.
In Tabelle 1 sind die Resultate der unbehandelten und aktivierten Gewebe gegenübergestellt. Die erhöhte Helligkeit durch den verstärkten Abbau an der Oberfläche der Materialien ist gut erkennbar. Die Gesamt-Farbdüferenz Δ E ist ebenfalls berechnet und dargestellt. Die ΔE Werte von über 6 zeigen deutlich den erhöhten Farbverlust an den alkalisch vorbehandelten Bereichen.Table 1 compares the results of the untreated and activated tissues. The increased brightness due to the increased degradation on the surface of the materials is clearly visible. The total color difference Δ E is also calculated and shown. The ΔE values above 6 clearly show the increased color loss on the alkaline pretreated areas.
Tabelle 1. Farbkoordinaten der Qualitäten I und II nach einer Cellulasebehandlung mit und ohne vorhergehende Aktivierungsbehandlung (L* = Helligkeit (0 = Schwarz, 100 = Weiß) a* = Rot - Grün (-Wert = Grün, +Wert = Rot) b* = Gelb - Blau (-Wert = Blau, +Wert = Gelb) und ΔE symbolisieren die CIELab-Koordinaten bzw. die entsprechende Farbdifferenz. Das CIE-Lab-System ist ein von der Internationalen Beleuchtungskommission (Commission Internationale d'Eclairage, CIE) 1976 festgelegter Farbraum).
Beispiel 2 zeigt die Erhöhung der Abbaugeschwindigkeit durch alkalische Vorbehandlung am Beispiel von RegeneratfasernExample 2 shows the increase in the rate of degradation by alkaline pretreatment using the example of regenerated fibers
Viskosegewebe (CV) (Stapelfasergarn 38 mm, 1.3 dtex) wurde als Substrat verwendet. Leinwandbindung Kette 20 tex, Schuß, 24 tex, Drehung 19 Umdr./inch, 143 g/m2, 37/29 Fd/cm wurde verwendet.Viscose fabric (CV) (staple fiber yarn 38 mm, 1.3 dtex) was used as a substrate. Plain weave warp 20 tex, weft, 24 tex, twist 19 rounds / inch, 143 g / m 2 , 37/29 fd / cm was used.
Die Behandlungslösung wurde durch Verdünnen einer 50% (w/w) Natronlauge mit Wasser hergestellt (1.04, 2.20, 3.48 and 4.91 mol/L NaOH).The treatment solution was prepared by diluting a 50% (w / w) sodium hydroxide solution with water (1.04, 2.20, 3.48 and 4.91 mol / L NaOH).
Das Gewebe wurde in unterschiedlichen Alkalilösungen für 1 Minute bei einem Flottenverhältnis von 1:3 spannungslos vorbehandelt. Die Konzentration der Behandlungslösungen ist in Tabelle 2 angegeben.The fabric was pretensioned in different alkali solutions for 1 minute at a liquor ratio of 1: 3. The concentration of the treatment solutions is given in Table 2.
Nach dem Abquetschen in einem Foulard wurde das Gewebe mit destilliertem Wasser gespült und mit 0.02 mol/L Essigsäure neutralisiert. Vergleichsproben wurden ohne alkalische Vorbehandlung behandelt.After squeezing in a pad, the fabric was rinsed with distilled water and neutralized with 0.02 mol / L acetic acid. Comparative samples were treated without alkaline pretreatment.
Die Enzymbehandlung erfolgte anschließend in einer Laborfärbeanlage (Pretema Multicolor laboratory dyeing unit Typ MC 360; Caromatic, Schweiz). Eine "total crude cellulose" Genencor, USA, wurde mit einer Konzentration von 3.5 IU/mg Gewebe eingesetzt (30 mg Protein pro mL). Die Lösung wurde durch einen 50 mM Azetat Puffer auf pH 4.8 eingestellt. Das Flottenverhältnis betrug 1 g Gewebe 25 ml Behandlungsbad.The enzyme treatment was then carried out in a laboratory dyeing plant (Pretema Multicolor laboratory dyeing unit type MC 360, Caromatic, Switzerland). A "total crude cellulose" Genencor, USA, was used at a concentration of 3.5 IU / mg tissue (30 mg protein per mL). The solution was buffered through a 50 mM acetate adjusted to pH 4.8. The liquor ratio was 1 g tissue 25 ml treatment bath.
Die Hydrolyse wurde bei 55°C (+/-1°C) durchgeführt. Nach 1 Stunde Behandlung erfolgte die Bewertung des Gewichtsverlusts durch Messung der Konzentration der in der Lösung gebildeten Glucose. Vergleichsmessungen wurden mit nicht vorbehandelten Materialien durchgeführt.The hydrolysis was carried out at 55 ° C (+/- 1 ° C). After 1 hour of treatment, the weight loss was evaluated by measuring the concentration of glucose formed in the solution. Comparative measurements were performed with non-pretreated materials.
Tabelle 2 zeigt den veränderten Abbau gemessen als Konzentration an Glucose die pro L Behandlungsbad nach einer Stunde gebildet wird.
Gewebe aus anderen Celluloseregeneratfasern können in gleicher Weise behandelt werden. Tabelle 3 zeigt die Erhöhung der Abbaugeschwindigkeit, gemessen nach 1 Stunde Hydrolysezeit.
Durch eine alkalische Behandlung wird die Abbaugeschwindigkeit um einen Faktor 6 - 15 gesteigert.By an alkaline treatment, the degradation rate is increased by a factor of 6 - 15.
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AT0088407A AT505369A1 (en) | 2007-06-05 | 2007-06-05 | METHOD FOR THE TREATMENT OF CELLULOSE-RELATED TEXTILE |
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EP2278063A1 (en) | 2009-07-24 | 2011-01-26 | Universität Innsbruck | Method for enzymatic treatment of textiles containing cellulose |
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US5122159A (en) * | 1988-09-15 | 1992-06-16 | Ecolab Inc. | Cellulase compositions and methods that introduce variations in color density into cellulosic fabrics, particularly indigo dyed denim |
US5232851A (en) * | 1990-10-16 | 1993-08-03 | Springs Industries, Inc. | Methods for treating non-dyed and non-finished cotton woven fabric with cellulase to improve appearance and feel characteristics |
EP0636740A1 (en) * | 1993-02-18 | 1995-02-01 | Meiji Seika Kabushiki Kaisha | Cellulase preparation and method of treating cellulosic fiber therewith |
US20020115193A1 (en) * | 1996-03-06 | 2002-08-22 | Hsieh You-Lo | Enzyme treatment to enhance wettability and absorbancy of textiles |
US20060225224A1 (en) * | 2005-04-08 | 2006-10-12 | Taylor Lawnie H | Formation of patterns of fades on fabrics |
-
2007
- 2007-06-05 AT AT0088407A patent/AT505369A1/en not_active Application Discontinuation
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2008
- 2008-05-28 EP EP08009672A patent/EP2000583B1/en not_active Not-in-force
- 2008-05-28 AT AT08009672T patent/ATE517208T1/en active
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US5122159A (en) * | 1988-09-15 | 1992-06-16 | Ecolab Inc. | Cellulase compositions and methods that introduce variations in color density into cellulosic fabrics, particularly indigo dyed denim |
US5232851A (en) * | 1990-10-16 | 1993-08-03 | Springs Industries, Inc. | Methods for treating non-dyed and non-finished cotton woven fabric with cellulase to improve appearance and feel characteristics |
EP0636740A1 (en) * | 1993-02-18 | 1995-02-01 | Meiji Seika Kabushiki Kaisha | Cellulase preparation and method of treating cellulosic fiber therewith |
US20020115193A1 (en) * | 1996-03-06 | 2002-08-22 | Hsieh You-Lo | Enzyme treatment to enhance wettability and absorbancy of textiles |
US20060225224A1 (en) * | 2005-04-08 | 2006-10-12 | Taylor Lawnie H | Formation of patterns of fades on fabrics |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2278063A1 (en) | 2009-07-24 | 2011-01-26 | Universität Innsbruck | Method for enzymatic treatment of textiles containing cellulose |
WO2011009803A2 (en) | 2009-07-24 | 2011-01-27 | Universitaet Innsbruck | Method for enzymatically treating a cellulosic textile |
WO2011009803A3 (en) * | 2009-07-24 | 2011-04-21 | Universitaet Innsbruck | Method for enzymatically treating a cellulosic textile |
US20120180229A1 (en) * | 2009-07-24 | 2012-07-19 | Universitaet Innsbruck | Method for enzymatic treatment of cellulose-containing textiles by means of a solution that comprises at least one cellulase type |
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ATE517208T1 (en) | 2011-08-15 |
AT505369A1 (en) | 2008-12-15 |
EP2000583B1 (en) | 2011-07-20 |
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