EP1694903A1 - Method for the modification of polyacrylonitrile fibres containing vinyl acetate as a comonomer and polyamide fibres, using a cutinase enzyme - Google Patents

Method for the modification of polyacrylonitrile fibres containing vinyl acetate as a comonomer and polyamide fibres, using a cutinase enzyme

Info

Publication number
EP1694903A1
EP1694903A1 EP04775191A EP04775191A EP1694903A1 EP 1694903 A1 EP1694903 A1 EP 1694903A1 EP 04775191 A EP04775191 A EP 04775191A EP 04775191 A EP04775191 A EP 04775191A EP 1694903 A1 EP1694903 A1 EP 1694903A1
Authority
EP
European Patent Office
Prior art keywords
enzyme
fibre
fibres
vinyl acetate
comonomer
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.)
Withdrawn
Application number
EP04775191A
Other languages
German (de)
French (fr)
Inventor
Artur Manuel Cavaco Paulo
Ana Filipa Gonçalves Da Costa CARNEIRO
Carla Manuela Pereira Da Silva
Rita Isabel Lima De Ara Jo
George Guebitz
Margarida Paula Pedra Amorim Casal
Maria Teresa Gonçalves De Macedo MATAMA
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universidade do Minho
Original Assignee
Universidade do Minho
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 Universidade do Minho filed Critical Universidade do Minho
Publication of EP1694903A1 publication Critical patent/EP1694903A1/en
Withdrawn legal-status Critical Current

Links

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
    • 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

Definitions

  • the quality and the processing properties of filaments in the extrusion line, fibres, yarns and textile f brics can be improved by modifying their surface .
  • the traditional processes used for their modification require chemical agents with negative environmental effects. These negative effects can be prevented by using new processing techniques based on biotechnology.
  • Enzymatic processes can be used to modify the surface of fabrics constituted by synthetic fibres. Hydrolysis of polyacrylonitrile fibres containing vinyl acetate as a comono er and polyamide fibres results in the formation of hydrophilic groups. The increase in these groups at the surface of the fibres provides hydrophilic characteristics, therefore improving the comfort properties. This treatment also allows these fibres to be dyed with specific reactive dyes. Background of the invention
  • Cutinase 3.1.1.74 is an esterase which degrades cutine, a structural polymeric component of plants composed of fatty acids (Carvalho et al . , Biotech . Bioeng. , 1999, 66 , 17-34) . This is an enzyme which is not very specific and which hydrolyses soluble and non-soluble p-nitrophenyl esters and triglycerides .
  • Cutinase is an esterase which shares the catalytic triad of serine-histidine-aspartic acid with other esterases and amidases, meaning that the degradation of amides besides ester groups is theoretically possible.
  • Recent research demonstrates that cutinase has activity in more hydrophobic media due to the external amino acids in the 3D structure (Vidinha et al . (2003) "Effect of immobilization support, water activity and enzyme ionization state on cutinase activity and enantioselectivity in organic media", Biotechn . Bioeng . , accepted) .
  • the chemical agents of fibre modification described in general do not restrict their action to the fibre surface, rather they also penetrate inside and degrade the fibres with deterioration of their properties.
  • One of the treatments that was normally carried out to improve touch and increase the hydrophilicity of synthetic fibres was alkaline treatment with high concentrations of caustic soda. These treatments were damaging, not only to the physical performance of the fibres but also to the environment where the residues of this product were deposited (US20030119172) .
  • This invention describes the use of cutinase to modify the surface of synthetic polyacrylonitrile fibres containing vinyl acetate as a comonomer and polyamide fibres.
  • Superficial hydrolysis of the ester and amide groups of the polyacrylonitrile fibres containing vinyl acetate as a comonomer and polyamide fibres, respectively, causes the formation of hydroxyl groups in the polyacrylonitrile fibres containing vinyl acetate as a comonomer and carboxylic and amino groups in the polyamide fibres .
  • the increase in these groups at the surface of the fibres gives the fabric hydrophilic characteristics, therefore improving the comfort properties.
  • a first embodiment of the invention consists of a method for the treatment of polyacrylonitrile fibre containing vinyl acetate as a comonomer, which comprises the contact of the fibre with an enzyme solution in order to modify the chemical surface of the fibre, increasing the number of hydrophilic hydroxyl groups.
  • a second embodiment of the invention consists of a method for the treatment of polyamide fibre, which comprises the contact of the fibre with an enzyme solution in order to modify the chemical surface of the fibre, increasing the number of hydrophilic amino groups.
  • the treatment of the polyacrylonitrile fibre containing vinyl acetate as a comonomer or the polyamide fibre is preferably carried out using an enzyme with esterase action.
  • the enzyme preferably contains the catalytic triad of serine-histidine-aspartic acid.
  • the abovementioned enzyme esterase is preferably a hydrolase that degrades cutine.
  • the amount of enzyme used is normally between 1 and 400 g of protein per kg of fibre.
  • a treatment bath with a retrievable and reusable enzyme is used.
  • the method consists of the chemical modification of the surface of polyacrylonitrile fibres containing vinyl acetate as a comonomer (constituted by about 93% acrylonitrile and 7% vinyl acetate) and polyamide fibres through the action of a cutinase solution obtained from the heterologous expression of Fusarium solani pisi cutinase, by the Escherichia coli DHB4 transformed strain.
  • the treatment was carried out in a ROTAASH machine that simulates dyeings and other textile treatments.
  • Each container had between 1 and 2U ( ⁇ mol/min as pNPP - paranitrophenolpalmitate) of cutinase activity.
  • Samples of 0.7 g of polyacrylonitrile fabric containing vinyl acetate as a comonomer were washed with water containing 1 g/L of Lutensol and dried at 50 °C.
  • the samples were then placed in a container with 1 U of cutinase, in a bath ratio of 1:35 (p/v) .
  • the treatment was carried out at pH 7.5 and at 30°C, for a period of 700 hours.
  • the samples were removed from the solution, washed with water containing 2 g/L of Na 2 C0 3 and dried at room temperature .
  • the samples treated for 97 hours were dyed with 2% reactive dye (Lanasol Red 66) , obtained from CIBA, using a bath ratio of 1:100, at 60 °C.
  • K/S spectral coefficient

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

This invention relates a new enzymatic process for the modification of the surface of synthetic fibres using a cutinase enzyme (3.1.1.74). The enzymatic action causes the hydrolysis of the polyacrylonitrile fibres containing vinyl acetate as a comonomer and polyamide fibres, improving their hydrophilic characteristics and dyeing properties.

Description

DESCRIPTION
"METHOD FOR THE MODIFICATION OF POLYACRYLONITRILE FIBRES CONTAINING VINYL ACETATE AS A CO ONOMER AND POLYAMIDE FIBRES, USING A CUTINASE ENZYME"
Field of the invention
The quality and the processing properties of filaments in the extrusion line, fibres, yarns and textile f brics can be improved by modifying their surface . The traditional processes used for their modification require chemical agents with negative environmental effects. These negative effects can be prevented by using new processing techniques based on biotechnology.
Enzymatic processes can be used to modify the surface of fabrics constituted by synthetic fibres. Hydrolysis of polyacrylonitrile fibres containing vinyl acetate as a comono er and polyamide fibres results in the formation of hydrophilic groups. The increase in these groups at the surface of the fibres provides hydrophilic characteristics, therefore improving the comfort properties. This treatment also allows these fibres to be dyed with specific reactive dyes. Background of the invention
Cutinase 3.1.1.74 is an esterase which degrades cutine, a structural polymeric component of plants composed of fatty acids (Carvalho et al . , Biotech . Bioeng. , 1999, 66 , 17-34) . This is an enzyme which is not very specific and which hydrolyses soluble and non-soluble p-nitrophenyl esters and triglycerides . Several patents exist relating to the genetic enhancement of Fusarium solani cutinases and their application in the formulation of detergents for washing machines and dishwashers. These products have shown better lipolytic action than other products previously used (IN183592, EP1290150, AU1503800, AU5488090, US5512203, W09414964, GB2296011, O8809367, EP0399681) . In the textile field, the use of cutinases to reduce backstaining during stone-wash processes in cotton denim fabrics is also described (CA2413838, US2002066144) . Cutinase is also described as being able to degrade aliphatic and aromatic polyesters (US6255451) .
Cutinase is an esterase which shares the catalytic triad of serine-histidine-aspartic acid with other esterases and amidases, meaning that the degradation of amides besides ester groups is theoretically possible. Recent research demonstrates that cutinase has activity in more hydrophobic media due to the external amino acids in the 3D structure (Vidinha et al . (2003) "Effect of immobilization support, water activity and enzyme ionization state on cutinase activity and enantioselectivity in organic media", Biotechn . Bioeng . , accepted) . The chemical agents of fibre modification described in general do not restrict their action to the fibre surface, rather they also penetrate inside and degrade the fibres with deterioration of their properties. One of the treatments that was normally carried out to improve touch and increase the hydrophilicity of synthetic fibres was alkaline treatment with high concentrations of caustic soda. These treatments were damaging, not only to the physical performance of the fibres but also to the environment where the residues of this product were deposited (US20030119172) .
Several chemical methods have been used in order to improve the structure of polya ide fibre. The modification of this fibre, according to the method described in the patent GB1072070, is carried out by acylation of the peptidic groups as well as of the terminal amino groups of the polyamide for greater polyamide reactivity. Another method already described in the patent US5599698 specifies the treatment of polyacrylonitrile fibre containing vinyl acetate as a comonomer with a nitryl hydratase enzyme, in order to modify its hydrophilicity and consequently its comfort properties, also allowing the polyacrylonitrile fibres containing vinyl acetate as a comonomer to be dyed with acid dyes. Detailed Description of the Invention
This invention describes the use of cutinase to modify the surface of synthetic polyacrylonitrile fibres containing vinyl acetate as a comonomer and polyamide fibres. Superficial hydrolysis of the ester and amide groups of the polyacrylonitrile fibres containing vinyl acetate as a comonomer and polyamide fibres, respectively, causes the formation of hydroxyl groups in the polyacrylonitrile fibres containing vinyl acetate as a comonomer and carboxylic and amino groups in the polyamide fibres . The increase in these groups at the surface of the fibres gives the fabric hydrophilic characteristics, therefore improving the comfort properties. This treatment also allows the polyacrylonitrile fibre containing vinyl acetate as a comonomer to be dyed with reactive dyes (used for cotton) and the polyamide fibre to be dyed with reactive dyes (used for wool) . To date, no method for the modification of the vinyl acetate comonomer of acrylic or polyamide has been described in scientific literature or patents .
A first embodiment of the invention consists of a method for the treatment of polyacrylonitrile fibre containing vinyl acetate as a comonomer, which comprises the contact of the fibre with an enzyme solution in order to modify the chemical surface of the fibre, increasing the number of hydrophilic hydroxyl groups. A second embodiment of the invention consists of a method for the treatment of polyamide fibre, which comprises the contact of the fibre with an enzyme solution in order to modify the chemical surface of the fibre, increasing the number of hydrophilic amino groups.
The treatment of the polyacrylonitrile fibre containing vinyl acetate as a comonomer or the polyamide fibre is preferably carried out using an enzyme with esterase action.
The enzyme preferably contains the catalytic triad of serine-histidine-aspartic acid. The abovementioned enzyme esterase is preferably a hydrolase that degrades cutine.
The amount of enzyme used is normally between 1 and 400 g of protein per kg of fibre.
In both of the embodiments described above, a treatment bath with a retrievable and reusable enzyme is used. Examples
The method consists of the chemical modification of the surface of polyacrylonitrile fibres containing vinyl acetate as a comonomer (constituted by about 93% acrylonitrile and 7% vinyl acetate) and polyamide fibres through the action of a cutinase solution obtained from the heterologous expression of Fusarium solani pisi cutinase, by the Escherichia coli DHB4 transformed strain.
The treatment was carried out in a ROTAASH machine that simulates dyeings and other textile treatments. Each container had between 1 and 2U (μmol/min as pNPP - paranitrophenolpalmitate) of cutinase activity.
Example 1 :
Enzymatic modification of polyacrylonitrile fibre containing vinyl acetate as a comonomer
Samples of 0.7 g of polyacrylonitrile fabric containing vinyl acetate as a comonomer were washed with water containing 1 g/L of Lutensol and dried at 50 °C. The samples were then placed in a container with 1 U of cutinase, in a bath ratio of 1:35 (p/v) . The treatment was carried out at pH 7.5 and at 30°C, for a period of 700 hours. The samples were removed from the solution, washed with water containing 2 g/L of Na2C03 and dried at room temperature .
Hydrolysis was confirmed by the formation of acetic acid and the dyeing of the treated samples. No acetic acid was detected in the treatment baths. The samples were dyed with 2% reactive dye Remazol Brilliant Blue, using a bath ratio of 1:50 (p/v), at 70°C. In the samples treated for 700 hours with the enzymatic solution of cutinase, the value of K/S (spectral coefficient) increased by an average of 30% in relation to the non- treated sample .
Example 2 :
Enzymatic modification of polyamide fibre
Similar treatments were carried out to polyamide fabric using the following parameters: fabric samples of 1 g were washed with water containing 1 g/L of Lutensol and dried at 40 °C. They were then placed in a specific container in the ROTAWASH machine with 2 U of cutinase, in a bath ratio of 1:200 (p/v) . The treatment was carried out at pH 8.5 at 30 °C, for a period of 97 hours. The samples were removed from the solution, washed with water containing 2 g/L of Na2C03 and dried at 40°C. The hydrolysis that occurred in the samples treated with the enzymatic solution was verified through dyeing with a reactive dye. The samples treated for 97 hours were dyed with 2% reactive dye (Lanasol Red 66) , obtained from CIBA, using a bath ratio of 1:100, at 60 °C. In the samples treated, the value of K/S (spectral coefficient) increased in relation to the non-treated sample by 11.67% (60°C) .

Claims

1. Method for the treatment of polyacrylonitrile fibre containing vinyl acetate as a comonomer, characterised in that it comprises the contact of the fibre with an enzyme solution in order to modify the chemical surface of the fibre, increasing the number of hydrophilic hydroxyl groups.
2. Method according to claim 1, characterised in that it comprises the treatment of the polyacrylonitrile fibre containing vinyl acetate as comonomer with an enzyme with esterase action.
3. Method according to claim 1, characterised in that the enzyme contains the catalytic triad of serine- histidine-aspartic acid.
4. Method according to claim 1, characterised in that the enzyme esterase is a hydrolase that degrades cutine.
5. Method according to claim 1, characterised by the use of an amount of enzyme between 1 and 400 g of protein per Kg of fibre.
6. Method for the treatment method of polyamide fibre, characterised in that it comprises the contact of the fibre with an enzyme solution in order to modify the chemical surface of the fibre, increasing the number of hydrophilic amino groups.
7. Method according to claim 6, characterised in that it comprises the treatment of the polyamide fibre with an enzyme with esterase action.
8. Method according to claim 6, characterised in that the enzyme contains the catalytic triad of serine- histidine-aspartic acid.
9. Method according to claim 6, characterised in that the enzyme esterase is a hydrolase that degrades cutine.
10. Method according to claim 6, characterised by the use of an amount of enzyme between 1 and 400 g of protein per Kg of fibre.
11. Method according to claims 1 and 6, characterised by the use of a treatment bath with a retrievable and reusable enzyme.
EP04775191A 2003-10-29 2004-10-28 Method for the modification of polyacrylonitrile fibres containing vinyl acetate as a comonomer and polyamide fibres, using a cutinase enzyme Withdrawn EP1694903A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PT103035A PT103035A (en) 2003-10-29 2003-10-29 METHOD FOR MODIFYING POLYACRYLONYRYL FIBERS WITH VINYL ACETATE AS A COMONOMER AND POLYAMIDE, USING A CUTINASE ENZYME
PCT/PT2004/000025 WO2005040487A1 (en) 2003-10-29 2004-10-28 Method for the modification of polyacrylonitrile fibres containing vinyl acetate as a comonomer and polyamide fibres, using a cutinase enzyme

Publications (1)

Publication Number Publication Date
EP1694903A1 true EP1694903A1 (en) 2006-08-30

Family

ID=34511367

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04775191A Withdrawn EP1694903A1 (en) 2003-10-29 2004-10-28 Method for the modification of polyacrylonitrile fibres containing vinyl acetate as a comonomer and polyamide fibres, using a cutinase enzyme

Country Status (5)

Country Link
US (1) US20070275453A1 (en)
EP (1) EP1694903A1 (en)
CA (1) CA2543818A1 (en)
PT (1) PT103035A (en)
WO (1) WO2005040487A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2145904A1 (en) * 2008-07-18 2010-01-20 Basf Se Method for enzyme-catalysed hydrolysis of polyacrylic acid esters and esterases to be used

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5599698A (en) * 1994-12-27 1997-02-04 Montefibre S.P.A. Modified materials based on polyacrylonitrile and process for their production
FR2736928B1 (en) * 1995-07-18 1997-10-17 Rhone Poulenc Fibres & Polymer ENZYMES HAVING AMIDASE ACTIVITY MICRO-ORGANISMS LIKELY TO PRODUCE SUCH ENZYMES AND METHOD FOR HYDROLYSIS OF AMIDES USING THE SAME
BR9707840A (en) * 1996-03-06 2000-01-04 Univ California Processes to alter the wettability and water absorbency of textile fibers, to increase the wettability and water absorbency in cotton fibers and to alter the physical properties of polyester fibers, and aromatic polyester fiber.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005040487A1 *

Also Published As

Publication number Publication date
PT103035A (en) 2005-04-29
CA2543818A1 (en) 2005-05-06
WO2005040487A1 (en) 2005-05-06
US20070275453A1 (en) 2007-11-29

Similar Documents

Publication Publication Date Title
Madhu et al. Developments in application of enzymes for textile processing
Parvinzadeh et al. Biohydrolysis of nylon 6, 6 fiber with different proteolytic enzymes
EP0885311B1 (en) Enzyme treatment to enhance wettability and absorbency of textiles
DE60132327T2 (en) PREVENTING REPRODUCTION OR RECYCLING DURING THE STONE-WASH PROCESS
US6077316A (en) Treatment of fabrics
EP0580707B1 (en) Removal of excess dye from new textiles
US6551358B2 (en) Alkaline enzyme scouring of cotton textiles
EP0739982A1 (en) Bacillus cellulase and its applications
US20060042020A1 (en) Treatment of fabrics, fibers, or yarns
KR19990008083A (en) Detergents containing cellulase
NZ504197A (en) Cellulase produced by Actinomycetes, probes and method of producing thereof
WO1997001629A1 (en) A cellulase with reduced mobility
Hoque et al. Enzymatic wet processing
Roy Choudhury Sustainable textile wet processing: Applications of enzymes
CA2132300A1 (en) A process for defuzzing and depilling cellulosic fabrics
Paul et al. The use of enzymatic techniques in the finishing of technical textiles
EP0628105B1 (en) Methods of enhancing printing quality of pigment compositions onto cotton fabrics
Silva et al. Enzymatic biofinishes for synthetic textiles
Choudhury Enzyme applications in textile chemical processing
US20070275453A1 (en) Method for the Modification of Polyacrylonitrile Fibres Containing Vinyl Acetate as a Comonomer and Polyamide Fibres, Using a Cutinase Enzyme
JPH1088472A (en) Scouring and bleaching of natural cellulose-based fiber
Nyanhongo et al. Microbial applications for fabric and textile industries
Islam Enzymatic Wet Processing
Heine et al. Bioprocessing for smart textiles and clothing
US20060010615A1 (en) Method for treating cellulosic grey fabric, products obtained by this process and their use

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20060526

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20091209

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

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20100420