CN102561053A

CN102561053A - Method for dyeing silk by using laccase-catalyzed tea polyphenols

Info

Publication number: CN102561053A
Application number: CN2012100394292A
Authority: CN
Inventors: 唐人成; 孙莎莎
Original assignee: Suzhou University
Current assignee: Suzhou University
Priority date: 2012-02-21
Filing date: 2012-02-21
Publication date: 2012-07-11

Abstract

The invention discloses a method for dyeing silk by using laccase-catalyzed tea polyphenols, and belongs to the field of textile dyeing. Tea polyphenols, laccase and a pH buffer are taken as a dye solution. The method comprises the following steps of: dissolving the tea polyphenols in water, regulating the pH of a dye bath by using an acetate buffer until the dye bath is weakly acidic, adding the laccase, performing polymerization reaction on the tea polyphenols under the catalytic action of the laccase, and dyeing a silk fabric. The method for dyeing the silk by using the laccase-catalyzed tea polyphenols is simple and practicable, is mild in dyeing condition and has the advantages of environment friendliness and low probability of scratch defects.

Description

A kind of laccase catalysis Tea Polyphenols is used for the method for silk dyeing

Technical field

The present invention relates to the tint applications of a kind of oxidoreducing enzyme on silk, particularly a kind of laccase makes the catalytic polymerization of Tea Polyphenols and the colouring method that the dyeing of silk is carried out simultaneously as the catalyst of Tea Polyphenols polymerisation, belongs to the textile dyeing field.

Background technology

In traditional dyeing processing, silk mainly adopts ACID DYES, neutral dye and reactive dyeing, and there is the shortcoming that dyeing temperature is high, energy consumption is high, water consumption is big, chemicals usage is big inevitably in traditional handicraft.What is more, if the control of the technological parameter in the rope dyeing process is improper, then can produce scratch because of the frictional force between dyeing temperature height, the fabric causes fabric greatly, " the grey wound " defect occurs.If the employing low temperature dyeing then can effectively be avoided the generation of " ash is hindered " defect, can also cut down the consumption of energy simultaneously.

Along with society to the attention of environmental protection and consumer to self healthy concern, the ecological spinning grade is favored.Under this trend; Natural plant extracts or natural products are applied to the dyeing and finishing processing of silk [referring to document A. R. Lee; J.-U. Hong, Y. A. Yang, E. Yi. Dyeing properties and antimicrobial activity of silk fabric with extract of Unripe Citrus Unshiu fruits. Fibers and Polymers; 2010,11 (7): 982-988; K. N. Vinod; T. Puttaswamy; K. N. Ninge Gowda; R. Sudhakar. Natural colorant from the bark of Macaranga peltata:kinetic and adsorption studies on silk. Coloration Technology, 2010,126 (1): 48-53.].Simultaneously, because oxidoreducing enzyme, for example peroxidase; Thereby can act on the generation that various aminated compoundss and phenolic compounds cause color, so oxidoreducing enzyme can be used for dyeing system, thereby material is carried out painted [referring to document H. Hadzhiyska; M. Calafell, J. M. Gibert, J. M. Dag à; T. Tzanov. Laccase-assisted dyeing of cotton. Biotechnology Letters, 2006,28:755-759; S. Kim, D. Moldes, A. Cavaco-Paulo. Laccase for enzymatic coloration of unbleached cotton. Enzyme and Microbial Technology, 2007,40:1788-1793.].

One type of reduction-oxidation enzyme is a peroxidase; Another kind of reduction-oxidation enzyme is a laccase; Laccase is a cupric polysaccharide oxidizing ferment, the oxidation reaction of ability catalysis chemical compound lot, and substrate is more extensive; Comprise many with to diphenol structure similar compounds, like amino-phenol, adjacency pair benzenediol, polyphenol, polyamines, lignin, aryl diamine etc.

The mixture that WO 01/44563 discloses a kind of aromatic diamines of a kind of usefulness and one or more naphthols and amino naphthalenes is to the colouring method of a material (comprise thread), and used enzyme is peroxidase or halide catalase, laccase.

Enzymatic reaction and painted to silk can take place in a series of phenolic compounds and aminated compounds under the laccase effect.But when dyeing, phenolic compound that has and aminated compounds will be by organic solvent dissolutions owing to poorly water-soluble.Because most of organic solvents can influence the activity of enzyme, therefore, the Color of the silk fabric that this dyeing system dyes also can be adversely affected.So this field needs a kind of enzymatic method of improved silk dyeing.

Summary of the invention

In order to overcome the deficiency that prior art exists, the object of the present invention is to provide a kind of method of dyeing simple, dyeing condition is gentle, and the Tea Polyphenols with environmental protection, the difficult generation " ash is hindered " defect is used for the enzymatic colouring method of laccase to silk.

In order to reach the foregoing invention purpose; The technical scheme that the present invention adopts provides the method that a kind of laccase catalysis Tea Polyphenols is used for silk dyeing; With concentration is the Tea Polyphenols preparation dye bath soluble in water of 2 ~ 6 g/L, and the pH value of using acetate buffer to regulate dye bath is 3.5～6.5; Dye bath ratio is 10:1 ~ 30:1, adds silk fabric, adds laccase solution, and the active concentration of laccase is 0.5 ~ 6 U/mL in the dye bath, and U is an enzyme unit alive; Speed with 1 ~ 2.5 ℃/min is warming up to 40 ~ 80 ℃, is incubated 2 ~ 4 hours, obtains dark yellow silk DYED FABRICS.

PH of the present invention need be chosen in laccase is had in the scope of enough enzymatic activities, and preferably between 3.5 to 6.5, more preferably from about between 4.5 to 6, most preferred is 5.

The laccase concentration of the present invention's dyeing, preferably between 0.5 to 6 U/mL, more preferably from about between 4 to 6 U/mL, most preferred is 4 U/mL.

The present invention dyes in following temperature range, and preferably between 40 to 80 ℃, more preferably from about between 40 to 70, most preferred is 50 ℃.

The pH value of dye bath of the present invention is 4.5 ~ 6.

The dissolubility of Tea Polyphenols in water is better; In the aqueous solution, can fully dissolve and polymerization reaction take place under the catalysed oxidn of laccase; The dye liquor color is by the orange-yellow dark-brown that becomes; Coloured Tea Polyphenols polymer reaches the purpose to silk dyeing with the protein macromolecule effect in active force such as Van der Waals force and the silk.

Laccase catalysis Tea Polyphenols is used for the method for silk dyeing; The activity of laccase is defined as: under 30 ℃, the condition of pH 6.5; When using syringaldehyde to join nitrogen as substrate, it is enzyme unit (U) alive that the reaction substrate of 3 mL per minute under the 530nm wavelength changes 0.001 required enzyme amount of absorbance.

Laccase catalysis Tea Polyphenols of the present invention is used for the method for silk dyeing; Can contain the conventional auxiliary agent that uses in the textile dyeing process; For example: anion and non-ionic surface active agent, short salt sodium chloride or the glauber salt of dying, more than single mixture of planting auxiliary agent or several kinds of auxiliary agents.Certainly, those skilled in the art tackle this or these optional compounds that replenish are made careful selection, so that laccase catalysis Tea Polyphenols of the present invention is when being used for silk dyeing, Color does not receive or do not receive basically above-mentioned reinforced harmful effect.

Through dyeing, the color and the COLOR FASTNESS that are colored fabric are estimated its color parameter L*, a* and b* value (the color bright-dark degree of L* value representation DYED FABRICS; The a* value is red green index; The b* value is the champac index, and specific DYED FABRICS has specific a* and b* value, is in the ad-hoc location in the color hue circle) and the COLOR FASTNESS demonstration; Adopt the technical scheme of laccase catalysis Tea Polyphenols of the present invention to silk dyeing, Color is good.

Tea Polyphenols is applied to the laccase enzymatic dyeing of silk; Institute dyes the silk fabric color fastness to light and tests aircraft measurements according to ISO 105-B02 standard at Atlas XenoTest Alpha light fastness tester; Compare with blue wool standard specimen, show that the light fastness of coloring matter on cotton that Tea Polyphenols generates is 3 grades in the presence of laccase; Water-fast wash COLOR FASTNESS according to ISO 105-CO1 standard in the aircraft measurements of Washtec-P washing fastness, with standard gray scale opinion rating, show that the staining fastness to the multi-fibre STANDARD ADJACENT FABRIC is 5 grades, the variable color fastness is 3 grades; Colour fastness to rubbing is measured on the colour fastness to rubbing appearance according to ISO 105-X12 standard, with standard gray scale opinion rating, shows that anti-dry fastness is 5 grades, and the moisture-proof crock fastness is 5 grades.

Compared with prior art, the advantage that has of the present invention is:

1, the dyestuff former that adopts in the methods of the invention is a Tea Polyphenols, and Tea Polyphenols and laccase oxidation product thereof all have good biologically active such as antibiotic, anti-oxidant, and in to silk dyeing, it is antibiotic, anti-oxidant etc. functional also to give silk fabric.

2, a kind of laccase catalysis Tea Polyphenols of the present invention's application is used for the method for silk dyeing, and is simple, and dyeing condition is gentle, has the advantage of environmental protection, the difficult generation " the grey wound " defect.

The practical implementation method

Following non-limiting examples further specifies the present invention.

Embodiment 1

(1) mensuration of laccase activity: the method that is employed in oxidation syringaldehyde couplet nitrogen under the aerobic conditions is measured laccase activity, measures the color (purple sieve blueness) that the syringaldehyde that generates joins the nitrogen oxidation product at the 530nm place with the ultraviolet-visible AAS.Analysis condition is: under 30 ℃ and acetate buffer (pH 6.5) condition, when using syringaldehyde to join nitrogen as substrate, the reaction substrate of 3mL per minute under the 530nm wavelength changes 0.001 enzyme amount that absorbance is required.Enzyme unit alive is U.

(2) laccase catalysis Tea Polyphenols is to the dyeing of silk: Tea Polyphenols 3 g/L; PH is adjusted to 3.5,4.0,4.5,5.0,5.5,6.0 and 6.5 respectively with acetate buffer, and dye bath ratio is 20:1, adds the silk crepe de Chine; Adding concentration is the laccase (available from SIGMA company) that 2.5 U/mL obtain from Rhus vernicifera; Heat up 50 ℃ with 2 ℃/min speed, be incubated 2 hours, obtain dark yellow dyeing silk fabric.

Simultaneously, the dyeing control samples of silk crepe de Chine is set all under each pH, does not add laccase during control samples dyeing, all the other conditions are identical.The pH that present embodiment provides 3.5,4.0,4.5,5.0,5.5,6.0 and the silk crepe de Chine DYED FABRICS and the value of chromatism of control samples that obtained in 6.5 o'clock at the 360nm place be respectively 0.79,2.33,3.41,6.29,6.14,4.87,1.30.Said result shows that under the condition that adds Rhus vernicifera laccase, Tea Polyphenols deepens the dyed color of silk crepe de Chine; When pH 5.0, the adding of laccase can farthest improve the color of Tea Polyphenols DYED FABRICS.

Embodiment 2

Tea Polyphenols 3 g/L; PH is adjusted to 5.0 with acetate buffer, and dye bath ratio is 20:1, adds the silk crepe de Chine; Adding concentration is the laccase (available from SIGMA company) that 2.5 U/mL obtain from Rhus vernicifera; Heat up 40,50,60,70 and 80 ℃ with 2 ℃/min speed, be incubated 2 hours, obtain dark yellow dyeing silk fabric.

Table 1 provides under the present embodiment different temperatures enzymatic Tea Polyphenols to the color parameter of silk crepe de Chine DYED FABRICS.

Table 1

Temperature (℃)	40	50	60	70	80
						L*	81.64	77.61	79.66	78.88	75.85
a*	5.11	6.39	5.90	6.19	6.89
						b*	18.90	21.48	18.67	18.43	19.18

Embodiment 3

Tea Polyphenols 3 g/L; PH is adjusted to 5.0 with acetate buffer, and dye bath ratio is 20:1, adds the silk crepe de Chine; Adding concentration is the laccase (available from SIGMA company) that 1,2,3,4,5 and 6 U/mL obtain from Rhus vernicifera; Heat up 50 ℃ with 2 ℃/min speed, be incubated 2 hours, obtain the dark yellow dyeing silk fabric of the different depths.

Table 2 provides the color parameter that the enzymatic Tea Polyphenols dyes to the silk elephant crepe fabric under the different laccase consumptions of present embodiment.

Table 2

Laccase concentration (U/mL)	1	2	3	4	5	6
							L*	81.01	80.22	79.01	77.59	77.77	77.60
a*	5.26	5.70	6.13	6.73	6.68	6.71
							b*	15.46	17.34	19.75	22.99	22.14	22.65

Claims

1. a laccase catalysis Tea Polyphenols is used for the method that silk dyes, and it is characterized in that: with concentration is the Tea Polyphenols preparation dye bath soluble in water of 2 ~ 6 g/L, and the pH value of using acetate buffer to regulate dye bath is 3.5～6.5; Dye bath ratio is 10:1 ~ 30:1, adds silk fabric, adds laccase solution, and the active concentration of laccase is 0.5 ~ 6 U/mL in the dye bath, and U is an enzyme unit alive; Speed with 1 ~ 2.5 ℃/min is warming up to 40 ~ 80 ℃, is incubated 2 ~ 4 hours, obtains dark yellow silk DYED FABRICS.

2. laccase catalysis Tea Polyphenols according to claim 1 is used for the method for silk dyeing, it is characterized in that: described laccase solution is in 5.0 the acetate buffer solution for the solid laccase is dissolved in the pH value.

3. laccase catalysis Tea Polyphenols according to claim 1 is used for the method for silk dyeing, and it is characterized in that: the pH value of dye bath is 4.5 ~ 6.