Background technology
Reactive dyestuffs have characteristics such as chromatogram is complete, bright in colour, colour fastness is better, thereby extensively are applied to the stamp and the dyeing of fabric.
In the printing technology process of reactive dyestuffs, the principal element of influence and restriction printing with reactive dye output and quality is traditional reactive dyestuffs operations of sizing mixing.
The tradition reactive dyestuffs are sized mixing, and because of human factor is difficult to guarantee each component metering accuracy in the reactive dye printing slurry, are difficult to guarantee the stamp product quality stability.Simultaneously, traditional reactive dyestuffs are sized mixing operation again because of inefficiency, usually run into the stamp board aborning and wait the phenomenon of sizing mixing, and it also restricts stamp board production efficiency, affect stamp output and improve.Therefore printing and dyeing enterprise requires traditional printing with reactive dye size mixing technology is reformed, and introduces the printing with reactive dye full-automatic feed proportioning system of sizing mixing.
Automatic batching system is a labor savings, and can implement the preparation " just in time timely " of printing paste.For colored type given on some textiles with to the printing paste quantity of the required consumption of a collection of order, can before stamp, more easily calculate, and correspondingly be prepared.Like this, the residual content of printing paste just can be reduced to minimum.The printing paste reprocessing that can both stay between most of automatization electronics color matchings is also reused.Therefore such waste material will significantly reduce, and help to increase economic efficiency, reduce pollution.
Digital ink-jet printed technology from the nineties in 20th century since promote in the textile printing field, in order to adapt to the feature of fabric, technically done many improvement that are different from ink jet printing paper and book film, and obtained encouraging progress.Stork company showed about report and the related data that world's stamp develops in 2002: calendar year 2001, digital ink-jet printed production of woven fabric was included statistical item first in, its output accounts for 1%~3% of world's stamp total amount, illustrate that digital ink-jet printed technology occupies a tiny space in the textile printing field, and show one's promises day by day.Current, the principal element applied rapidly of holding it back is that ink-jet printed speed is too slow and cost is too high.Digital ink-jet printed cost prints black quality and price and will restrict digital ink-jet printed popularizing and promoting mainly from ink-jet printed Yin Mo.Yin Mo divides two types: dye-type and pigment style.Dye-type seal China ink is most of to be that the reactive dyestuffs seal is black, and reactive dyestuffs print black quality and depend primarily on liquid reactive dye stability.
The stability that solves liquid reactive dye mainly should be started with from improving physical stability and chemical stability two aspects.
Aspect the raising chemical stability, main according to the percent hydrolysis difference of different activities dyestuff under condition of different pH, regulate liquid system to the minimum pH of dyestuff hydrolysis, reduce the hydrolysis of dyestuff, thereby improve the chemical stability of liquid reactive dye.Present foreign-made company substantially also follows this method and solves the liquid reactive dye hydrolysis problem.
Aspect the raising physical stability, early stage, adopt adding solubility promoter and simple auxiliary agent to improve physical stability in the reaction solution after dyestuff is synthetic; Along with the development of chemical engineering, adopt freezing desalination method and add corresponding additive and improve stability; In the recent period, along with the development of membrane technique, adopt membrane permeation desalination method, and add corresponding additive raising physical stability, because dye structure is different with synthesis technique, it is also different that the liquid reactive dye physical stability improves method applicability.
The domestic production that does not also have liquid reactive dye at present production unit was once arranged through the trial Journal of Sex Research, but because the fine solution stability problem of failing fails to organize effective production.Therefore be necessary to carry out the further investigation of liquid reactive dye stability, promote the production of stabilising liq dyestuff.
Though, add the hydrolysis hold back agent, the liquid reactive dye system is after long-time the placement, though solution does not produce muddiness, precipitation, substantially solved chemical stability, but visible a little crystalline particle in the liquid dye liquid, in addition, compare with the powdery solid stamp with power part, the fixation rate of liquid reactive dye still has 20%~30% decline.Therefore be necessary that liquid reactive dye is deposited stablizer develops research.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind of liquid reactive dye stablizer and preparation method thereof, to overcome the defective that prior art exists, satisfy the needs of field of printing and dyeing development.
Liquid reactive dye stablizer of the present invention is a kind of aqueous solvent, and its component and concentration comprise:
Water-soluble polymers P 0.025mol/L~4mol/L
Solubility promoter 0.05mol/L~3mol/L
Tensio-active agent 0.04mol/L~0.3mol/L
Water is supplied 1L
Said tensio-active agent is selected from Nekal BX (isobutyl-how sodium sulfonate), paregal O-10 (fatty alcohol-polyoxyethylene ether O-10), O-15, O-20, O-25, TX-10 (alkylphenol polyoxyethylene TX-10), TX-21, TX-30, TX-40, TX-50, Span-80 (sorbitan fatty acid ester-80), Twen-80 (sorbitan-fatty acid ester Soxylat A 25-7-80), levelling agent AN (aliphatic amine polyoxyethylene ether AN), dispersion agent NNO (sodium methylene bis-naphthalene sulfonate), sodium lauryl sulphate or Sodium dodecylbenzene sulfonate and ammonium lignosulphonate.The main effect of tensio-active agent is stably dispersing liquid dye systems, stops with solubility promoter and water-soluble polymers P that liquid dye are separated out, layering.
Solubility promoter comprises a kind of in urea, hexanolactam, dimethyl formamide, glycol ether, pyridine, ethylene glycol or the ethylene glycol monobutyl ether, it is to help the dyestuff dissolving that solubility promoter mainly acts on, and stops dyestuff crystallization, precipitation and layering with tensio-active agent assisted water soluble polymer P;
Said water-soluble polymers P is that a kind of molecular weight that is obtained at 70~90 ℃ of reaction 6~7h by water, methylene-succinic acid, methacrylic acid or methacrylic ester and ammonium persulphate is 2500~5000 orange transparent copolymer solution, and wherein: the mol ratio of methylene-succinic acid and methacrylic acid or methacrylic ester is during synthetic polymer P:
Methylene-succinic acid: methacrylic acid or methacrylic ester=2~2.5: 2.5~3;
In the aqueous solution, the weight concentration of methylene-succinic acid and methacrylic acid or methacrylic ester is 25~40%, and ammonium persulphate is an amount of, is generally with the mol ratio of methylene-succinic acid:
Methylene-succinic acid: ammonium persulphate=2~2.5: 0.00003~0.0005
It is shielding or constraint ionogen that water-soluble polymers P mainly acts on, and stops dyestuff crystallization, precipitation and layering with tensio-active agent and solubility promoter.
The preparation method of liquid reactive dye stablizer of the present invention comprises the steps:
Water-soluble polymers P's is synthetic: with the mixture of methacrylic acid or methacrylic ester and ammonium persulphate mixing solutions adding deionized water and methylene-succinic acid, at 70~90 ℃ of reaction 6~7h, the back cooling obtains orange transparent copolymer solution;
Mix with conventional physical admixture with solubility promoter, tensio-active agent and hydromining then, promptly obtain the liquid reactive dye stablizer.
Liquid reactive dye stablizer of the present invention, liquid reactive dye had high stabilization, liquid reactive dye stablizer of the present invention is added and liquid reactive dye with 1%~5% weight percent concentration, deposited at ambient temperature 6 months, liquid reactive dye does not condense, non-crystallizable, not precipitating and layering.Add after the stablizer, the solubleness of reactive dyestuffs also improves greatly, in addition, by as by maximum absorption λ
MaxTest shows, add stablizer after, the coloured light of reactive dyestuffs is constant substantially, liquid reactive dye stamp fixation rate can improve more than 20%.Therefore, chemical stability and the physical stability problem that solves liquid reactive dye substantially of the present invention can adapt to modern reactive dyeing and the stamp full-automatic feed proportioning system of sizing mixing fully.
Embodiment
Embodiment 1
Plant and instrument
DDS-11A type conductivity meter, Shanghai thunder magnetic instrument plant
JV-9100 UV, visible light spectrophotometer, blue sky instrument company
Water-soluble polymers P's is synthetic:
In the reactor that condenser, thermometer, agitator, dropper are housed, add the deionized water of raw material gross weight 25% and the methylene-succinic acid of 2mol mole, be warming up to 65 ℃, start stir treat that methylene-succinic acid dissolves fully after, drip 220ml methacrylic acid and ammonium persulphate mixing solutions, wherein, the methacrylic acid content is-3 moles, the ammonium persulphate amount is 0.00003 mole, then, slowly heats up, be controlled at (90 ± 1) ℃, lower the temperature behind the reaction 7h, obtain orange transparent copolymer solution, molecular weight is 2500.
The composition of liquid reactive dye stablizer:
Water-soluble polymers P 4mol/L
Hexanolactam 3mol/L
TX-10 0.3mol/L
Water is supplied 1L
Above-mentioned raw materials is mixed, promptly obtain stablizer of the present invention.
Embodiment 2
Water-soluble polymers P's is synthetic:
In the reactor that condenser, thermometer, agitator, dropper are housed, add the deionized water of raw material gross weight 40% and the methylene-succinic acid of 2.5mol mole, be warming up to 65 ℃, start stir treat that methylene-succinic acid dissolves fully after, drip 305ml methacrylic ester and ammonium persulphate mixing solutions, wherein, methacrylate content is 2.5 moles, the ammonium persulphate amount is the 0.0005mol% mole, then, slowly heats up, be controlled at (90 ± 1) ℃, lower the temperature behind the reaction 7h, obtain orange transparent copolymer solution, molecular weight is 5000.
The composition of liquid reactive dye stablizer:
Water-soluble polymers P 4mol/L
Glycol ether 3mol/L
Sodium lauryl sulphate 0.3mol
Water is supplied 1L
Embodiment 3
Treatment process
Is 1: 0.05 mixed with the liquid reactive dye stablizer of reactive dyestuffs solution and embodiment 1 according to weight ratio, by following method test dye solubleness, stability, stamp fixation rate, analyzes the effect of stablizer to reactive dyestuffs.
Performance test methods
1. the mensuration of reactive dyestuffs solubleness: reactive dyestuffs solubleness is pressed water-soluble dye solubleness and stability of solution measuring method GB/T3671.1-1996.
2. the liquid reactive dye physical stability is measured: will deposit at ambient temperature 6 months by the liquid reactive dye of various compound method preparations, observe cohesion, crystallization, precipitating and the layering of liquid reactive dye, if there is not above-mentioned phenomenon, can think stable, otherwise, as long as there is an above-mentioned phenomenon to occur just thinking unstable.
3. will deposit the liquid dye of certain hour, carry out reactive dyestuffs direct printing technology, the fixation rate of comparative liquid reactive dyestuffs and powdered activated dyestuff (Dry Sack rate) with powdered activated dyestuff.
4. the reactive dyestuffs electrical conductivity of solution is measured on DDS-11A type conductivity meter.
5. reactive dyestuffs solution optical density(OD) is measured on JV-9100 UV, visible light spectrophotometer.
Result
1. the relation of reactive dyestuff molecule structure and solubleness
For the better effect of understanding the liquid reactive dye stablizer, earlier the solubleness of various reactive dyestuffs to be tested, it the results are shown in Table 1.
The solubleness of table 1 different activities dyestuff (20 ℃, the g/L of unit)
The purple K-of the yellow K-orange of the yellow K-of the black dark blue bright blue gorgeous indigo plant of K-K-bright red bright red
BR K-R GL K-3R RN 6G GN K-2BP K-2G 3R
10 20 70 100 30 120 60 60 110 100
As seen from Table 1, the solubleness of different activities dyestuff differs bigger, and the colorant dissolubility that has has only 10g/L, and have 120g/L arranged, differ up to 12 times.The difference in size of reactive dyestuffs solubleness is relevant with the reactive dyestuff molecule structure, and the reactive dyestuff molecule amount is big more, and sulfonate group is few more, and solubleness is just low more; Otherwise, then high; Relevant with the residing position of sulfonate group in addition, general sulfonate group is big in the solubleness of dye molecule latter end at molecular structure of dye intermediary ratio.During liquid reactive dye, guaranteeing to select the high dye molecule of those solubleness under the dyestuff chromatogram prerequisite in preparation as far as possible, be convenient to prepare liquid reactive dye and need not add or add less solubility promoter and just reach better physical and stablize the minimizing cost.
By table 1 as seen, the solubleness of many reactive dyestuffs all can't satisfy the reactive dyestuffs desired solubleness of automatic blending (generally greater than 15%) of sizing mixing.The solubleness that needs to increase reactive dyestuffs just can reach application requiring.Generally speaking, for the solubleness of reactive dyestuffs, dye molecule is its influence factor, and in addition, the interpolation of the crystallization mode in the commercialization of dyes course of processing, degree of grind, granular size, auxiliary agent etc. all can influence the solubleness of dyestuff.
For this reason, in this patent in the stablizer of liquid reactive dye comprise that solubilizing agent, solubility promoter and water-soluble polymer additive form jointly.
2. add the Effect on Performance of stablizer to liquid reactive dye
With stablizer respectively with reactive black K-BR, reactive yellow K-6G and Reactive Brilliant Red K-2BP be made into aqueous dye solutions, test its solubleness, investigate package stability, it the results are shown in Table 2.
Table 2 stablizer is to the performance of liquid reactive dye
The active gorgeous K-2BP of performance reactive black K-BR reactive yellow K-6G
The no S 10 120 60 of solubleness (g/L)
Contain S 150 330 210
It is very unstable very unstable very unstable that package stability does not have S
Contain S do not condense, tie in 1 year and do not condense, tie in 1 year do not condense in 1 year, crystallization,
Crystalline substance, precipitating and branch layer crystal, precipitating and layering precipitating and layering
By table 2 as seen, add after the stablizer, the solubleness of reactive black K-BR is brought up to 150g/L by 10g/L, and Reactive Brilliant Red K-2BP is brought up to 210g/L by 60g/L, and reactive yellow K-6G brings up to 330g/L by 120g/L.The shelf-stable agent all improves a lot after adding stablizer, in addition, by as by maximum absorption λ
MaxTest shows, add stablizer after, the coloured light of reactive dyestuffs is constant substantially.
3. stablizer is to the influence of liquid reactive dye stamp fixation rate
The fixation rate of liquid reactive dye stamp (Dry Sack rate) can reflect its stability, as the fixation rate height, shows that then liquid dye are really stable.
In order to investigate function of stabilizer effect, H
1And H
2To stoping the hydrolysis situation of liquid reactive dye, with reactive yellow K-RN, reactive orange K-GN, active blue K-GRS, active emerald green blue K-GL is an example, carry out stamp with the liquid reactive dye that contains hydrolysis hold back agent H of identical power part, the liquid dye (depositing a year) that contain hydrolysis hold back agent H and stablizer with the powdery solid dyestuff, measure its fixation rate, it the results are shown in Table 3.
The printing with reactive dye fixation rate of table 3 different states
*
Active gorgeous reactive yellow reactive orange is active blue active emerald green blue
The dyestuff state
Red K-K-RN K-GN K-GRS K-GL
2BP
Powdery solid 100 100 100 100 100
Contain hydrolysis hold back agent H 78.75 81.46 69.87 74.78 80.54
Stablizer S and hydrolysis hold back agent H 98.67 96.98 90.34 94.35 99.19
*For convenience of explanation, with the fixation rate of powdery solid reactive dyestuffs in 100%.Following table is identical.
By table 3 as seen, compare with the system that only contains hydrolysis hold back agent H, the liquid reactive dye stamp fixation rate that contains stablizer and hydrolysis hold back agent H coexistence generally improves more than 20% again, illustrates that stablizer has good effect to the stability of liquid reactive dye; The stamp fixation rate that contains stablizer and the liquid reactive dye of hydrolysis hold back agent H is compared with the powdery solid dyestuff and is all reached more than 90%, what have reaches 99%, illustrate that the liquid reactive systems that contains stablizer and hydrolysis hold back agent H coexistence is very stable, substantially, solve the chemical stability and the physical stability problem of liquid reactive dye, can adapt to modern reactive dyeing and the stamp full-automatic feed proportioning system of sizing mixing fully.