Dyestuff complex reducing agent and the method that adopts this complex reducing agent to dye
Technical field
The present invention relates to dyestuff complex reducing agent and colouring method thereof, belong to the stock-dye technical field, especially use the technical field of reduction class dyeing.
Background technology
Reducing dye has COLOR FASTNESS preferably, and especially Exposure to Sunlight, the staining fastness of soaping are good, but remains in problems such as poor permeability, suspended substance dyeing look flower, leuco compound instabilities unresolved with its vat acid, leuco compound dyeing.
The leuco vat dye decoration method is that insoluble reducing dye is become the water-soluble dyestuff of energy by alkali treatment, but the sodium salt of dyeing this moment has not been original color, so be leuco compound, the method that leuco dye is dyeed is called leuco dyeing process.Use the method for oxidation after having dyed again, become original insoluble color status again.Tradition leuco vat dye dyeing because pH is too big to fibre damage about 12.0, and to some fiber and be not suitable for, is unfavorable to polyester, polyurethane, polyamide, wool etc. for example.
The reducing dye cutting that reducing dye suspended substance decoration method is used for dyeing is dispersed into tiny solids (water insoluble) and is suspended in the method that dyeing liquor dyes.The difficulty of suspended substance dyeing is and must disperses the reducing dye cutting very thin, otherwise the meeting dyeing flower.The tradition reducing dye is with the suspended substance decoration method between the pH4.0-5.5, but so far because dye particles is too thick in the suspended substance, the suspension instability, and produce look flower problem and do not break through solving dyeing.Though and the suspended substance between the external existing pH4.0-5.5 dyes, because of the harmful substance that contains not environmental protection also should not be used, the dyestuff grain of suspended substance formation is still thin inadequately in addition, and look flower problem does not have thoroughly solution.
The dyeing quality of reducing dye depends on the stability of reduction leuco compound, vat acid to a great extent.External some relevant patent was done some improvement when addressing the above problem; but all there is certain problem: R.C.SHAH (Textile Chemist and Colorist; VOL4; No11; NOV7; 1972, P59-61) add protecting colloid and can delay the oxidation rate of sodium hydrosulfite, thereby increased the stability of leuco vat dye, vat acid.ELLIS (USP4582510 (1985)) has optimized GUAR guar gum and the XANTHAN xanthans suitable colloid as reduction leuco compound, vat acid in numerous colloids.Yet add the stabilizing agent of xanthans protecting colloid as dye liquor, cause that the viscosity of dyeing liquor significantly rises, leuco dye, vat acid permeability and diffusivity sharply descend, and have increased the weight of " Bai Xin " problem.
(USP6007587,1999 (BASF) propose to add the N-sodium hydroxymethanesulfinate to people such as GANG on sodium hydrosulfite (sodium dithionite) basis, to promote the stability of reduction leuco compound.(USP6802873,2004 (CARLFREADENBERG, KG (DE)) proposes with sodium hydrosulfite: N-methylol sulfinic acid (being commonly called as formaldehyde sodium sulfoxylate), ratio are 1: 10 o'clock to people such as BAKTL, can make reduction stable.But when dyeing temperature was higher, N-methylol sulfinic acid can discharge a large amount of formaldehyde, can cause serious injury the environment and the mankind.Obviously, these stabilizing agents are out of use in the high temperature occasion.Dye as the polyester/polyurethane reducing dye, if temperature is with 60 ℃ of-85 ℃ of segment limits, and Dry Sack is very shallow, and the degree of depth of dark slightly light color does not reach yet, need just can obtain the degree of depth of needs in 120 ℃ of-125 ℃ of scopes, this moment, N-methylol sulfinic acid can discharge a large amount of formaldehyde.
People such as VAINSHELBOIM (USR6592632,2003) propose to add vitamin C to increasing stability effectively in leuco compound.Yet this method is too high to the large-scale industrial production cost, can not be extensive use of.
The synthetic leather manufacturing that particularly ultra-fine polyester/polyurethane is done substrate is risen just at home.Because the problem that exists in the above-mentioned dyeing, make index such as COLOR FASTNESS not reach requirement, show that the class of product and added value are low, had a strong impact on the quality of product, its price only be abroad (as Japan) like product 1/10th.If aspect COLOR FASTNESS, can make a breakthrough, will make the synthetic leather trade out of trade of China increase significantly change.
Before this, the ultra-fine leather of polyester/polyurethane also is main dyeing with the DISPERSE DYES, but in Exposure to Sunlight, soap, aspect such as crock fastness is very poor, do not reach instructions for use, only can be used for cleaning cloth for glasses, decorative wall cloth, bed clothes bunting, toy cloth etc., and can not be used for carplane interior trim cloth, more can not make clothes.
Polyester superfine fibre and polyurethane dye with bathing, Dry Sack rate and form and aspect, and it is also far apart promptly to use sight to measure.Polyester/polyurethane synthetic leather permeability the time shows very poorly in dyeing, shows after dying that " Bai Xin " of " Bai Xin " problem, especially sample is serious, makes sample lose directive significance to full-page proof.The KODAYASHI (TEIJIN) of Japan proposed the dyeing temperature of ultra-fine polyester is brought up to 150 ℃ from 130 ℃ in USP5441543 in nineteen ninety-five, and this makes permeability, dye uptake and the COLOR FASTNESS of dyestuff that very big enhancement all be arranged.Yet increase the weight of because high temperature causes the polyester superfine fibre damage, thereby cause the powerful decline of leather, simultaneously, energy consumption is higher in the production, and this temperature promotes that the means of COLOR FASTNESS have been limited greatly.
Summary of the invention
Goal of the invention of the present invention does not contain formaldehyde for providing a kind of, makes the leuco dye good stability, the dye uptake height, be applicable to the dyestuff complex reducing agent of multiple stock-dye.
The technical scheme that realizes the foregoing invention purpose is as follows:
Dyestuff complex reducing agent of the present invention, by weight, composed as follows:
Sodium hydrosulfite 8~20
Thiourea dioxide 5~40
Sodium sulfite 5~15
The optimum ratio of dyestuff complex reducing agent of the present invention, by weight, composed as follows:
Sodium hydrosulfite 10
Thiourea dioxide 10
Sodium sulfite 5
Method with above-mentioned dyestuff complex reducing agent dyes comprises the following steps:
A, with above-mentioned dyestuff complex reducing agent, solid NaOH and water preparation reducing solution, wherein dyestuff composite reduction agent concentration is 27.0g/L, NaOH concentration is 11.5g/L; With reducing solution with the vatting method to reducing dyes, form leuco compound, wherein reducing solution: dyestuff=37.5: 0.80-2.0 (weight ratio), standby;
B, add acid buffer agent and adjust pH value, the leuco compound in the steps A is modulated into vat acid, and/or adds levelling agent and pervasion swelling agent, add and dye base and dye, cooling is washed then;
C, carry out oxidative color-developing, fixation, cooling flushing then;
D, renew bright water-bath, reduction cleaning, cooling flushes out machine.
Also have pretreatment stage between steps A and the B in said method, promptly add dispersant and defoamer in dye vat, regulating dye bath pH with NaOH liquid is pH=11.5, adds to dye base, is warming up to 80 ℃ by 1 ℃/min, handles 30~40 minutes.
By weight, described pervasion swelling agent is composed as follows:
Compositing range preferable range optimum ratio
Lauryl azone 0.00016-0.0006 0.00016-0.0006 0.00018-0.00025
N-Methyl pyrrolidone 1-5 2-4 3.5
Diacetone alcohol 5-10 6-8 7.0
Salethyl 5-15 8-12 10.0
Isopropyl salicylate 5-10 8-10 9.0
1. the dye structure that reductant of the present invention is suitable for
It is the anthraquinone reducing dye of, Er oxazole system, acridone system, sulphur xanthene ketone system, pyrazine system, blue anthrone system that the dye structure that reductant of the present invention is suitable for has acid amides system, imines system, carbazole system, triazine Xi, oxazole system, thiazole system, imidazoles; Benzene embedding anthrone system, anthracene are formed the anthrone reducing dye of anthrone system, pyrene anthrone system, pyrazole anthrone system, pyrimidine anthrone system, pyridine anthrone system, dianthrone ethane system; The dyestuff of perylene system; It is indigoid reducing dye, soluble vat dye and SULPHUR DYES etc. that the indigo of indigo, thioindigo system is arranged.
Suitable kind is pressed Colour index number (world's dye species 2000, Shenyang Chemical Engineering Inst) and is exemplified below:
C.I.VAT. yellow .2#, 3#, 4#, 20#, 29#, 30#.
C.I.VAT. orange .7#, 39#.
C.I.VAT. red .1#, 3#, 10#, 14#, 15#, 23#, 28#, 29#, 31#.
C.I.VAT. blue .4#, 6#, 18#, 20#, 43#, 64#.
C.I.VAT. brown .1#, 5#, 9#, 39#, 45#, 57#, 68#, 72#.
C.I.VAT. purple .1#, 8#, 14#.
C.1.VAT. green .1#, 2#, 3#, 4#, 29#.
C.1.VAT. black .1#, 8#, 16#, 25#.
C.I.PIGMENT. orange .43#.
C.I.PIGMENT. red .179#, 189#, 190#, 194# fly 195#, 224#.
C.I.PIGMENT. purple .31#.
C.I.PIGMENT. brown .26#, 27#.
C.1 PIGMENT. deceives .32#.
C.I.SOLUBILIZED.VAT. yellow .4#.
C.I.SOLUBILIZED.VAT. red .1#, 3#.
C.I.SOLUBILIZED.VAT. purple .8#.
C.I.SOLUBILIZED.VAT. green .2#.
C.I.SOLUBILIZED.VAT. brown .1#, 5#.
C.I.SOLUBILIZED.VAT. black .1#.
C.I.SULPHUR.. black .1#.
2, reductant dyeing useful fiber kind of the present invention
The present invention not only is used for dermatine dyeing, also can be used for the dyeing of artificial fibre and natural fabric simultaneously.Reductant dyeing useful fiber kind of the present invention has the fiber of ultra-fine polyester, ultra-fine polyesteramine, polyurethane, wool, silk, cotton, day silk, PBT, PPT, azelon, model, acetate, zein fiber and mutual blending thereof.
Dyestuff complex reducing agent of the present invention as the special-purpose reducing agent of reducing dye, SULPHUR DYES, perylene pigment system reduction leuco compound, increases the stability of leuco compound, improves the Dry Sack rate, Color reproduction, COLOR FASTNESS and color uniformity.Simultaneously can exempt the harm of formaldehyde to environmental protection and human body.The good of method all dyed than foreign patent (USP6942706) method and tradition in the various aspects of performance aspect.
The invention proposes with lauryl azone, N-Methyl pyrrolidone, diacetone alcohol, salethyl and isopropyl salicylate composite, and the pervasion swelling agent as with reducing dye and pigment dyeing the time further solves " Bai Xin " problem that contains polyurethane fiber.
The invention leuco vat dye alkalies, 80 ℃ in earlier stage of dyeing, pre-treatment in 40 minutes can promote the absorption of hyperfine polyester fiber to reduction leuco compound, vat acid, with the further homochromatism of improving two kinds of components in the synthetic leather.
The specific embodiment
The invention will be further described below in conjunction with embodiment and Comparative Examples, dye method and foreign patent (USP6942706) method as a comparison case with the reducing dye tradition, the reducing dye tradition is dyed method, method is drawn from volume such as Zhao Wei rope " reducing dye " the 457th page, 1993.12. chemical engineering industry publishing house, front page, reductant are simple sodium hydrosulfites.Foreign patent (USP6942706) method, reductant be contain formaldehyde, with sodium hydrosulfite: N-methylol sulfinic acid=1.0: 1.0 proportionings are mixed and are pieced together.The used reductant of the present invention does not contain formaldehyde, is three reductant sodium hydrosulfites: thiourea dioxide: sodium sulfite=1.0: 1.0: 0.5 proportionings are mixed and are pieced together.Pervasion swelling agent used among the embodiment is: lauryl azone 0.00025 weight portion, and N-Methyl pyrrolidone 3.5 weight portions, diacetone alcohol 7.0 weight portions, salethyl 10.0 weight portions, isopropyl salicylate 9.0 weight portions are formed.
Following table 1 is given an example for the consumption of the present invention and traditional method, foreign patent reductant and alkali preparation reducing solution
Table 1
Embodiment 1: polyester fiber and polyurethane are formed synthetic leather dyeing
Form synthetic leather by 0.02 dawn polyester fiber and polyurethane, substance 700g/M2, C.1.VAT. brown .5# of dyestuff, 6% (2006.11/22) uses leuco vat dye, vat acid dyeing.
(A) make the present invention by table 1 and reduce leuco compound, be Three kinds of hors d'oeuvres complex reducing agent, solid NaOH and water preparation reducing solution, wherein Three kinds of hors d'oeuvres composite reduction agent concentration is that 27.0g/L (is that the 10.8g/L sodium hydrosulfite adds 10.8g/L thiourea dioxide and 5.4g/L sodium sulfite, be total to 27.0g/L), NaOH concentration is 11.5g/L; With the vatting method reducing dyes is modulated leuco compound, reducing solution: dyestuff=37.5: 1 (weight ratio), add hot water (adding) after 8 minutes with 1: 1 amount of reducing dyes procrypsis body fluid, stand-by when making mixing temperature be 50 ℃;
(B) in the dye vat aqueous solution, add dispersant lignin sulfonic acid ammonium salt to concentration and reach 1g/L, and froth breaking king (the beautiful thunder auxiliary chemicals in Shanghai company) concentration to the solution reaches 1-2g/L, regulating dye bath pH with NaOH liquid (10% concentration) is about 11.5, add and dye base, rise to 80 ℃ of last stage leathers that dye with 10/min and handled 30-45 minute, this moment, dyestuff was reduction leuco compound state;
(C) be cooled to 40 ℃ indirectly, add by formic acid to dye bath, citric acid, acetic acid, the cushioning liquid that sodium acetate is formed, make the pH of dye bath reduce to pH3.8-3.9 from 11.5, with dyestuff furnishing vat acid, the high temperature levelling agent FZ810 that uses when adding the terylene disperse dyeing (Shanghai textile auxiliary factory), and make the concentration of high temperature levelling agent in dye bath reach 2g/L, adding the present invention makes its concentration in dye bath reach 2g/L with pervasion swelling agent, turned round 20 minutes, be warming up to 90 ℃ with 1 ℃/2min then, be warming up to 125 ℃ with 1 ℃/min again, the vat acid dyeing of reducing dye, cooling flushing were carried out in insulation in 40-60 minute;
(D) renew bright water-bath, add the oxidant ammonium persulfate, and make the concentration of ammonium persulfate in water-bath reach 2.5g/L, pH5.0 is warming up to 70 ℃ with 1 ℃/min, is incubated 20 minutes, carries out oxidative color-developing, fixation, cooling flushing then;
(E) renew bright water-bath, add reductant thiourea dioxide and cleaning agent neopelex, the concentration of thiourea dioxide reaches 2.5g/L to the water-bath, the concentration of neopelex reaches 4g/L, in pH6.0, be warming up to 55 ℃ with 1 ℃/min, be incubated 20 minutes reduction cleaning, cooling flushes out machine.
Following table 2 is present embodiment 1 and Comparative Examples coloration result
Table 2
Embodiment 2: ultra-fine polyamide and polyurethane are formed synthetic leather dyeing
To ultra-fine polyamide of 0.02 dawn: the blended fiber of polyurethane=65%: 35% (weight ratio) ratio dyes.
Press table 1 preparation reducing solution of the present invention, sodium hydrosulfite wherein: thiourea dioxide: sodium sulfite=1.0: 1.0: 1.0, dyeing is with embodiment 1, just step (B) dyeing last stage alkali lye is regulated dye bath pH and is handled in the embodiment 1, directly in the reduction leuco compound, add acidic buffer, with dyestuff furnishing vat acid, add pervasion swelling agent of the present invention: lauryl azone 0.00025 weight portion, N-Methyl pyrrolidone 2.0 weight portions, diacetone alcohol 8.0 weight portions, salethyl 10.0 weight portions, isopropyl salicylate 9.0 weight portions, with vat acid dyeing, 1 ℃/2min is warming up to 105 ℃, is incubated 40 minutes.COLOR FASTNESS is fine.
Following table 3 is present embodiment 2 and Comparative Examples coloration result
Table 3
Ultra-fine as seen from the above table polyamide and Synthetic Leather with the prescription of the invention at the prescription that is better than aspect level-dyeing property, homochromatism and the COLOR FASTNESS with conventional method and foreign patent.
Embodiment 3: polyether polyols with reduced unsaturation is formed synthetic leather dyeing
Polyether polyols with reduced unsaturation dyeing.Press table 1 preparation reducing solution of the present invention, sodium hydrosulfite wherein: thiourea dioxide: sodium sulfite=2: 4: 1, dyeing is with embodiment 1, just step (B) the dyeing last stage in the embodiment 1 is regulated dye bath pH with alkali lye and handles, directly add acid buffer agent in the step in embodiment 1 (A), with dyestuff furnishing vat acid, add pervasion swelling agent of the present invention: lauryl azone 0.0002 weight portion, N-Methyl pyrrolidone 4 weight portions, diacetone alcohol 6.0 weight portions, salethyl 8.0 weight portions, isopropyl salicylate 10.0 weight portions, with the dyeing of reduction vat acid, 1 ℃/2min rises to 85 ℃, in 85 ℃ of insulations dyeing in 45-60 minute, COLOR FASTNESS is fine.
Following table 4 is present embodiment 3 and Comparative Examples coloration result
Table 4
Polyether polyols with reduced unsaturation dyes method and foreign patent prescription with the prescription of the invention being better than tradition aspect COLOR FASTNESS and the level-dyeing property as seen from the above table.
Embodiment 4: day silk regenerated celulose fibre dyeing
Press table 1 and make reducing solution of the present invention, sodium hydrosulfite wherein: thiourea dioxide: sodium sulfite=1: 2: 1, dyeing is with embodiment 1, just directly with the dyeing of embodiment 1 step (B) alkaline reduction leuco compound, with 1 ℃/min temperature rise to 105 ℃, be incubated 40 minutes, and form the process of vat acid without embodiment 1 step (C) with the acid buffer agent adjust pH.Dyeing back COLOR FASTNESS is fine.
Following table 5 is present embodiment 4 and Comparative Examples coloration result
Table 5
This shows that day silk is being better than the foreign patent prescription with the prescription of the invention aspect COLOR FASTNESS and the level-dyeing property.
Embodiment 5: woolen dyed
Press table 1 and make reducing solution of the present invention, sodium hydrosulfite wherein: thiourea dioxide: sodium sulfite=2: 1: 1, dyeing is identical with embodiment 1, just step (B) the dyeing last stage is regulated dye bath pH with alkali lye and handles in the embodiment 1, directly in reducing solution, add acid buffer agent, use the vat acid direct dyeing, COLOR FASTNESS is fine.
Following table 6 is present embodiment 5 and Comparative Examples coloration result
Table 6
Wool is being better than the foreign patent prescription with the prescription of the invention aspect COLOR FASTNESS and the level-dyeing property as seen from the above table.
Embodiment 6: cotton fiber dyeing
Press table 1 and make reducing solution of the present invention, sodium hydrosulfite wherein: thiourea dioxide: sodium sulfite=2: 1: 1, dyeing is identical with embodiment 1, just the step (C) in the embodiment 1, directly dye with the alkaline reduction leuco compound, and without the vat acid process.With 1 ℃/min temperature rise to 100 ℃, be incubated 40 minutes, COLOR FASTNESS is fine.
Following table 7 is present embodiment 6 and Comparative Examples coloration result
Table 7
This shows that cotton fiber is being better than the foreign patent prescription with the prescription of the invention aspect COLOR FASTNESS and the level-dyeing property.