CN1017623B - Improvements in or relating to organic compounds - Google Patents

Abstract

Liquid compositions of sulfur dyes in reduced form containing no more than 13 wt.% inorganic sulphide based on total composition and low content other inorganic salts except the sulfid are obtained by reducing a sulfur dye in an alkaline medium to which no sulfide reducing agent has been added, preferably employing a reducing sugar as reducing agent.

Description

Improvements in or relating to organic compounds

The present invention relates to be reduced into the thioxine dyes liquid preparation of colorless form.

Make (colorless form) thioxine dyes of prereduction and forms, wherein have a step at least and make one or more salt existence are arranged in the product by many steps.For example, in the condensation reaction of preparation indophenols intermediate and after sulfuration, from solution, be settled out in the step of various thioxine dyess, normal sulfuric acid and the hydrochloric acid of using, these acid can with widely used sodium sulphite in thioxine dyes is made and (or) the sodium hydroxide reaction generates salt.Often use the salt such as sodium sulphite, copper sulfate and sodium-chlor in vulcanisation step, this step is the basic step of preparation thioxine dyes, and the use of salt also can help dyestuff to precipitate from solution.In addition, when the colourless thioxine dyes of preparation, often use sodium sulphite as reductive agent.In certain stage of the thioxine dyes for preparing prereduction, other salt adding or that generate has Sulfothiorine, Sodium Nitrite and Sodium Thiocyanate 99.

Have now found that, can make the liquid preparation of the low and prereduction thioxine dyes that preferably various inorganic salt contents are all very low of inorganic sulphide content, these inorganic salt usually generate when preparation prereduction thioxine dyes.

Therefore, this just provides a kind of liquid dye preparation, and it contains at least a thioxine dyes of colorless form and the reductive agent of this dyestuff of being reduced into, and this reductive agent is selected from a kind of sulfide and a kind of reducing sugar that forms or result from sulfuration on the spot.The total content of inorganic sulphide is less than 3% of the total formulation weight amount in the preparation.

Sulfide content is preferably available known analytical procedure and determines in the above-mentioned liquid dye preparation, for example makes iodometric determination with Sulfothiorine, and meter is made the sodium sulphite and the Sodium sulfhydrate total amount that exist.According to a kind of method preferably, at first also use usual method with acetate, as carbon dioxide gas stream, sodium sulphite and Sodium sulfhydrate are separated from dye solution, and then handled with 0.1N iodine solution and 0.1N hypo solution.The method that also has other mensuration sulfide content; But, generally acknowledged that some method tends to disturb thioxine dyes, for example carry out potentiometric titration and can provide sulfide content up to 13% with the 0.2N ammonium copper sulfate solution.

The inorganic sulphide content of liquid sulfurate dye preparation of the present invention better is to be no more than 2.5% of liquid dye preparation gross weight, and is better in the 1-2.5% scope, best in 1.5-2.5%.By prereduction thioxine dyes weight, inorganic sulphide content is usually in the 0-18.5% scope, and is especially better in the 1-14% scope.

With regard to thioxine dyes, refer to the mixture of a kind of known water-soluble or water-insoluble thioxine dyes, a kind of sulphur vat dye or these dyestuffs.

Liquid dye preparation of the present invention preferably contains a kind of alkali, and preferably contains a kind of reducing sugar as reductive agent.

The present invention also provides the method for preparing this liquid sulfurate dye preparation.Method of the present invention is included in the alkaline aqueous solution medium the thioxine dyes reduction, contain in the medium a kind of reducing sugar and (or) one form or result from the reductive agent of the sulfide of sulfuration on the spot as thioxine dyes.

In order to the alkali that forms alkaline medium normally alkali metal hydroxide, carbonate or phosphoric acid salt (for example tetrasodium pyrophosphate salt, tricresyl phosphate sodium salt or disodic alkaliine), potassium hydroxide or sodium hydroxide are better, preferably sodium hydroxide.The quantity of alkali should be enough to keep the pH of alkalescence, normally in 9 to 14 scope.Preferably, use enough alkali to make the pH value at first in 10 to 12 scope, when using reducing sugar (as described below), because some reducing sugars change into organic acid, pH value is decline slightly.The quantity of alkali is reaction mixture gross weight about 1 to 17% normally, and particularly 2 to 13%.

Preferably the alkaline aqueous solution medium is heated to 60 to 110 ℃, be heated to 70 to 95 ℃ then better, to improve the reducing activity of reductive agent.The dyestuff that heating should continue to q.s is reduced, so as to make at least 90%, 95% better, the preferably dyestuff of at least 99% weight dissolving that becomes.

When using some thioxine dyes (for example C.I. SULPHUR BLACK 1 200 and 2), find that not adding any reductive agent in alkaline medium can produce sufficient reductive action.Alkali (for example sodium hydroxide) and with dyestuff bonded reaction of Salmon-Saxl, form sulfide (for example sodium sulphite and Sodium sulfhydrate) on the spot, they are again with reducing dyes and it is dissolved in the alkaline aqueous solution medium.

Preferably contain a kind of reducing sugar in the alkaline aqueous solution medium.

Can reduce any carbohydrate of Fehling's solution or its combination all can be used as reducing sugar and uses, for example monose is (as the aldopentose of arabinose, ribose, wood sugar and so on, the hexose of glucose, fructose, seminose, semi-lactosi and so on, and their deoxidation, dideoxy and amino deoxy derivative), disaccharides (as sucrose, lactose, maltose and cellobiose) and three, four and pentasaccharides.Also can use maize treacle, Nulomoline, molasses etc. to contain the product of reducing sugar, because can from sucrose, prepare glucose on the spot.The most desirable reducing sugar is a glucose.

The quantity of reducing sugar will become with concrete thioxine dyes and the concentration in the alkaline aqueous solution medium thereof.Should use enough quantity so that dyestuff is fully reduced, make its dissolving or at least 90% miscible fully in the alkaline aqueous solution medium.Preferably, under any Pressure, Concentration, Temperature that dye formulations possibility quilt is stored and transported, the quantity of reducing sugar all sufficient to guarantee dyestuff is dissolved fully or is miscible in the dye formulations.Usually, the quantity of reducing sugar is 1 to 25% of reaction mixture total amount, preferably 4 to 18%.By dyestuff weight, when using reducing sugar, be everlasting 2 to 200% scope of its quantity, particularly 8 to 95%, especially 20 to 85%.

Preferably do not add sodium sulphite or other sulfide reductive agent in alkalitropism aqueous medium.If in the process of preparation reductive thioxine dyes liquid, only adding reducing sugar, to make reductive agent then more desirable.But, since may have with the form of elementary sulfur or with many sulfenyls form attached to the sulphur on the dye chromophore, it and alkali and (or) and the electronic action of reductive agent oxidation during reducing dyes, may form a spot of sulfide on the spot, for example sodium sulphite or Sodium sulfhydrate.The quantity of the elementary sulfur that may exist in the sulfur product can reduce with known method, for example the sulfur product of oxidation is handled with dissolve sulfur with sodium sulfite aqueous solution, filters then.

If be necessary that the method for the quantity of alkali number, particularly reducing sugar in the inorganic sulphide total content available adjustment reaction mixture in the liquid dye preparation is controlled.

Used thioxine dyes in the inventive method can be that will there be narration the back with any this class dyestuff of common vulcanization reaction (or be right after behind vulcanization reaction, or after precipitation and random separating step) gained.Typical this class dyestuff has SULPHUR BLACK 1 200 (CI 53185), sulphur black 2(CI 53195), SULPHUR BLACK 1 200 1(CI 53290) and SULPHUR BLACK 1 200 8, sulfur green 2(CI 53571), 16 and 36, vat blue 43(CI 53630), SULPHUR BLUE BRN 150 7 and 13(CI 53440 and 53450), vulcanize red 10(CI 53228) and 14, sulfur brown 37,10(CI 53055), 96,52(CI 53320), vulcanize orange 1(CI 53050) and SULPHUR YELLOW 22.

An embodiment who recommends according to the present invention, thioxine dyes have removed normal and this class sulfur product bonded salt through washing.Therefore, another part of the inventive method is to be added in the alkaline aqueous solution medium so that before the reduction at thioxine dyes, washes the step of this dyestuff earlier with water.The temperature of washing water should be selected in and can not dissolve a large amount of dyestuffs except that desalting most effectively, and for example 20 to 70 ℃, 30 to 50 ℃ then better.Washing should proceed to mineral sulfates content less than 6% of solid weight in the filter cake, less than 2% better, be preferably less than 0.6%.If above-mentioned percentage ratio has represented the maximum percentage ratio of whole inorganic salt then better.When a kind of definite salts contg just calculates the enough low method that makes things convenient for is to measure the specific conductivity of washing water sample.The electricity that washing lasts till the washing water after washing sample is always led enough low, the washing electrical conductivity of water before should approaching, preferably equaling to wash.Can use conductivity meter, for example Chemtrix type 700 conductivity meters for this reason.With this instrument and with specific conductivity be 60 to 80 gemmhos/centimetre water washing, when washing extremely used washing electrical conductivity of water be 60 to 200, preferably 60 to 120 gemmhos/centimetre the time, effect is fine.But the minority thioxine dyes has to a certain degree water-soluble when oxidised form, may show high slightly specific conductivity, for example high to 400 gemmhos/centimetre, this is owing to also have a spot of lysed dyestuff except that inorganic salt in used washing water.

Thioxine dyes preferably when oxidation state through following stand the test: with 5.0 gram filter cakes in 10 ml waters under the room temperature in Fischer Benchtop ultrasonic cleaning machine vibrating dispersion 15 minutes.The dispersion liquid of gained is filtered with film filter (Millipore company, numbering XX 1004700) through 0.45 micron metering of 47 millimeters of diameters.Filtrate should be colourless.

As mentioned above, sulfuration and the settling step in order to the used in the methods of the invention thioxine dyes of preparation is conventional steps.For example, can be according to 4475 to 4501 pages of (third edition in 1971) described vulcanization reactions that carry out in Colour Index (Colour Index) Volume Four.By this data as can be known, many kinds of organic compound can be used as raw material.Sulfuration reagent is generally sulphur or alkali metals polysulfide, and preferably uses by minimum.Vulcanization reaction can carry out with roasting or with the mode that reactant refluxes in liquid medium (for example lower alcohol such as water or ethanol, butanols).If necessary, when particularly vulcanizing with the roasting mode, product at high temperature is dissolved in moisture sodium sulphite or the liquid caustic usually.

With sulfur product oxygenant and acid optionally or alkaline purification with capacity in water medium, make the thioxine dyes precipitation, finish precipitating action.Any known oxygenant that can use in this area all can use, such as Sodium Nitrite, hydrogen peroxide, oxygen or air etc.Suitable acid comprises sulfuric acid and/or hydrochloric acid.The quantity of oxygenant and/or acid will become with concrete sulfur product character (for example sulfide quantity of concrete dyestuff of Chan Shenging and existence), preferably be enough to make thioxine dyes to precipitate fully.When using alkaline medium, as has been noted, it can contain the alkali up to 5% weight.

Thioxine dyes used among the present invention preferably draws with the method for oxidation precipitation.Oxidizing reaction proceeds to when no longer including sodium sulphite, Sodium sulfhydrate in the oxysome better, and this can determine with known analytical procedure, for example carry out iodometric titrationiodimetry titration with hypo solution.Preferably, sulfur product water or dense alkali hydroxide soln are diluted and in about 40 to 90 ℃ of air blowings, precipitate fully up to dyestuff.

Just as in above-mentioned Colour Index (Colour Index) the 4487th page about SULPHUR BLUE BRN 150 11(CI 53235) description in point out, add the precipitation that a kind of salt (for example sodium-chlor) can help dyestuff sometimes.

The thioxine dyes that is settled out is with currently known methods, for example filter and to separate, preferably by discussed above through washing.

Except thioxine dyes, alkali, reducing sugar and the water of prereduction, can also comprise the reagent of a kind of further increase vat dyes solubleness wherein in the dye solution.As soon as the dyestuff that is settled out has been separated from the resistates of vulcanization reaction mixture and through washing, then preferably avoid past any ionic component that wherein adds.Therefore, the reagent of increase solubleness is preferably non-ionic.What be suitable for is non-ionic hydrotropic agent, for example ethylene glycol, Diethylene Glycol, polyoxyethylene glycol, Diethylene Glycol list C _1-6Alkyl oxide (diethylene glycol monomethyl ether or single ether are better), diethylene glycol bis-C _1-4Alkyl oxide, propylene glycol and urea, and trolamine.Diethylene Glycol is a hydrotropic agent preferably.Hydrotropic consumption is 2 to 35% of a liquid dye preparation gross weight, normally 4 to 22%.

The adding order of each component is not strict.Can be with all components, promptly the reagent of dyestuff, reducing sugar, alkali, water and the increase solubleness that can add arbitrarily mixes heating then.But preferably other component outside the reducing sugar is lumped together and be heated to 60 to 110 ℃, 80 to 95 ℃ then better, adds reducing sugar then.Heating should last till that all components is dissolved in the solution, preferably accompanies by stirring.

According to another embodiment that recommends, the reduction of thioxine dyes of the present invention is to carry out under inert atmosphere, under for example nitrogen.Dye liquid and oxygen are isolated, have increased reduction efficiency and have reduced the requirement of reducing sugar and alkali, thereby might improve the dye strength in the final product.

Reductive condition be may wish to control in some situation and excessive sulfide, for example sodium sulphite gone out to avoid symbiosis.This may cause a fraction of, for example keep insoluble with dyestuff interior, that preferably be not more than 5% weight 10%.In this case, making the thioxine dyes liquid of prereduction will be useful through a last clarification steps.Its practice is a filter liquide, preferably still or approach to carry out filtering under the reductive temperature.Better the practice is to add filtration adjuvant under stirring in liquid, and for example diatomite or gac filter then.The quantity of this filtration adjuvant can change in very wide scope, but is generally 1 to 12% of dye solution weight, and preferably 2 to 6%.

The liquid preparation that the present invention recommended is except the content of inorganic sulphide is low, and the content of inorganic salt is also low.The weight of the mineral sulfates that contains in the preparation should be less than 3%, be less than 1.5% better, be less than 0.4% better, preferably be less than 0.1%; Preferably the total inorganic salt amount outside the sulfide is less than above-mentioned percentage ratio.

The thioxine dyes content of the prereduction in the preparation should surpass 8% weight, and is better between 8.5 to 40%, preferably 15 to 36% weight.Generally, preparation of the present invention also contain (by weight) 1 to 25%, particularly 4 to 18% reducing sugar and/or the derivative of its oxidation, 1 to 17%, particularly 2 to 13% alkali metal hydroxide, carbonate or phosphoric acid salt (or being enough to make pH about 9 to 14), 22 to 75%, 22 to 55% water particularly, and if any, the reagent of about increase solubleness of 2 to 35%, particularly 4 to 22%.

Liquid dye preparation of the present invention has several advantages.

The content of its inorganic sulphide (for example sodium sulphite, Sodium sulfhydrate and sodium polysulphide) is low, thereby reduced offending smell, reduced the danger that forms hydrogen sulfide, reduced and handled the necessary of liquid effluent and reduced loss (embrittlement) through the cotton goods tensile strength of black sulfur dyeing.

Because the molecular weight height of thioxine dyes, and the sulf onyl hydroxyl is as solubilizing group, so their solubleness in water is limited.Therefore, the existence of salt has the intensive salting-out effect to dyestuff.Inorganic salt content is very low in the preparation for preparing, and this makes them have transporting and package stability of having improved.They can be stablized 24 hours at least at-6 ℃, were more preferably and stablized more than 48 hours.Though may resemble the top said inorganic sulphide that contains limited quantity in the preparation, it is believed that under the quantity of this control the mode of the reducing power that these sulfide can be by increasing reducing sugar improves stability of formulation.

Because except that dyestuff and alkali in order to the necessary amount that reaches required pH value, all ion components all are greatly reduced or get rid of fully, so above-mentioned prescription forms a kind of dye liquid of uniqueness, the ion characteristics of dye solution significantly reduce, when this liquid application was on fabric, non-ionic more precisely (or organic liquid) character was dominant.

Their less salt amount also makes preparation of the present invention that high dyestuff content can be arranged.

Be inclined to because saltout and reduce, the dye sheet of this preparation reveals the penetrating quality of improvement.At the initial penetration stage of dip method, make dye exhaustion before on the fiber with salt, dyestuff becomes comparatively even in the distribution of whole fiber.Thereby this has just reduced dyestuff and has been deposited in the possibility that causes uneven distribution and disagreeable " bronzing " effect on the fiber rawly.

Preparation of the present invention also demonstrates the affinity or the affinity of appropriateness to fibrous material.Therefore, they can be used for the continuous dyeing of cotton and cotton/polyester, obtain the effect of level dyeing, are characterized in not existing one center, limit to replace dyeing difference and minimal head pin difference effect on one side.

Liquid dye preparation of the present invention can be used for the matrix of available colourless sulfur dyeing (for example cellulosic materials and they and other fiber, as the blending thing of polyester) is dyeed or stamp, the method of using is the ordinary method that prereduction (colourless) thioxine dyes with previously known dyes and uses with stamp, and for example the visible dyes element draws (Colour Index) the 3rd and rolls up narration in 3649 pages (1971 the 3rd edition).Staining fluid of the present invention can be used for intermittently or the successive dyeing process, also can be used for stamp, for example footpath axle dyeing, dye gigging dyeing, package dyeing, rope dyeing, jet dyeing, pad steam dyeing, pad-dry-pad-decatize dyeing or pad-dry-thermosol-pad-decatize dyes.They can be mixed into dye bath or printing paste with simple dilution method.

The quantity that is added to the liquid dye preparation in dye bath or the seal slurry depends on dyestuff content and desired dyeing or the stamp characteristics in the used concrete liquid, can be determined by Technology.Add in common every liter of dye bath 7 to 350 the gram, preferably 25 to 200 the gram dye liquid.

Though the quantity of the reductive agent that is comprised when dye liquid prepares generally is enough to guarantee dyestuff dissolving well in dye bath, it is still beneficial to add some reductive agents sometimes in dye bath.These reductive agents comprise the compound commonly used of used as said purpose, such as sodium sulphite, Sodium sulfhydrate, sodium polysulphide, sodium bisulfite or sodium formaldehyde sulphoxylate.But the best reductive agent of adding is above-mentioned reducing sugar, especially glucose.This reductive agent that can add arbitrarily should be enough to guarantee dyestuff dissolving fully in dye bath, and uniform and reproducible Color.According to used concrete dye liquid and reductive agent and dyeing condition, can determine only add-on fully on the Technology.Usually this quantity is every liter of dye bath 7 to 120 grams, preferably 15 to 60 grams.

Preferably in dye bath, also add a part of alkali with reductive agent, for example carbonate of sodium or potassium, oxyhydroxide or phosphoric acid salt, its quantity is about every liter 3.5 to 60 gram, preferably 5 to 30 grams.

Can also contain dyeing auxiliary in dye bath and the stamp liquid, wetting agent for example, quantity is every liter 1.0 to 15 gram.

After application of dye, the ordinary method as with thioxine dyes or sulphur vat dye dyeing the time, pollutant will experience an oxidation step.Though some dyeing fully oxidation in the drift ice operation after dyeing had better be carried out chemical oxidation.The oxygenant that is suitable for has the combination of hydrogen peroxide and acetic acid, or a kind of catalytic sodium bromate system.

Following example has illustrated the present invention, and umber wherein and percentage number average refer to weight, and temperature is degree centigrade.

Example 1

The SULPHUR BLUE BRN 150 13(CI 53450 that 382 grams prepare with common sulfuration method) sulfuration body crude product is dissolved in the 800 gram water, and gained solution was blown 6 hours at 68 to 70 ℃, and dyestuff is precipitated out from solution fully.The dyestuff that filtering-depositing goes out with tap water filter wash cake at room temperature, is compared no longer and is increased after washing with before the washing up to the specific conductivity of washing water sample.Filter cake output is 349.4 grams, solids content 25.4%.

With the above-mentioned filter cake of 57 grams, 18 gram Diethylene Glycols, 10 gram water and 16 grams, 50% sodium hydroxide solution mix, and are heated to 80 ℃.Then with mixture under nitrogen in 85 ℃ of heating, under stirring, add 11 gram glucose gradually.Stop heating after 25 minutes.Obtain the stable liquid dye preparation of 110.3 grams, its sulfide content is that 6.5%(uses the 0.2N cuprammonium sulfate through potentiometric determination), pH value 10.9.

Example 2

The red 10(CI 53228 of sulfuration that 400 grams prepare with common sulfuration method) sulfuration body crude product is dissolved in the 3000 gram water at about 50 ℃.Solution heat to 70-75 ℃, was blown 6 hours under this temperature.Measure through 0.1N hypo solution iodometric titrationiodimetry titration, the sulfide content in the oxysome of generation is 0.The dye filtering that is settled out separates.Filter cake with specific conductivity be about 60 gemmhos/centimetre washing from the beginning, up to the washing electrical conductivity of water be 95 gemmhos/centimetre about.The filter cake of gained weighs 273.5 grams, and solids content is 63.0%.

Get 44.9 sodium hydroxide that restrain the filter cake, 30.0 gram Diethylene Glycols and 23.0 grams 50% that make above and mix, under nitrogen,, under agitation add 4.0 gram glucose therebetween gradually 85 ℃ of heating.Add 2 gram Filter Aid 4200 FW50(diatomite filtration auxiliary agent after 30 minutes), stirred liq 2 minutes through 11 centimetres Fischer filter paper filtering, obtains the stable liquid dye preparation of 100.0 grams, and pH value is 11.1.

Example 3

Sulfuration melt crude product with 192 gram SULPHUR YELLOW 22 within 20 minutes is added in the mixture of 180 gram water and 330 gram sodium hydroxide, 50% solution, and mixture is 115-120 ℃ of heating therebetween.Continued heating 2 hours and kept constant volume at 120 ℃.The mixture of gained is mended and is added water to 1500 milliliters, to wherein adding 200 gram sodium-chlor.Blowing 58 hours at 85 ℃ of mixtures to gained, is 0 up to sulfide content, is chilled to room temperature then.The sulphuric acid soln that adds 36.4 grams 75% transfers to 6.0 with PH, at room temperature stirs the mixture overnight that generates.Filter, filter cake is washed at 40 ℃ with 14 liters of tap water, up to wash electrical conductivity of water be 82 gemmhos/centimetre.Obtain 666.0 gram filter cakes, solids content is 11.2%.

Filter cake and 12.0 mixtures that restrain sodium hydroxide (50% solution) that 84.0 grams are made above are heated to 75 ℃ under nitrogen.Add 6 gram glucose, continue heating 30 minutes at 85 ℃.Gained solution obtains 101.0 gram dye solutions through 11 centimetres of Fischer filter paper filterings, and through potentiometric determination, sulfide content is 1.18% with the 0.2N cuprammonium sulfate, and pH value is 11.6.

Example 4

With 200 gram sulphur black 2(CI 53195) mixture of filter cake and 2 premium on currency at room temperature stirred 30 minutes, and filtered then.With 16 liters of tap water at 50 ℃ of filter wash cakes.Because the existence of a small amount of soluble dye, finally wash electrical conductivity of water and be 300 gemmhos/centimetre.Obtain 165.9 gram filter cakes, wherein solid accounts for 60.1%.

The filter cake that 46.6 grams are prepared above mixes with 20 gram aqueous sodium hydroxide solutions (50%) and 15 gram water, heats 40 minutes under nitrogen at 90 ℃.Obtain the stable liquid dye preparation of 80 grams, through potentiometric determination, its sulfide content is 7.94% with the 0.2N cuprammonium sulfate, and pH value is 11.4.

Example 5

With 963 gram SULPHUR BLUE BRN 150 7(CI 53440) the sulfuration body and the mixture of 2000 gram water blew 14 hours at 85 ℃, be 0 up to sulfide content, dyestuff is separated out fully.Filter the slurry of gained, at 50 ℃ of filter wash cakes, add 100 gram S-WATs with 3 premium on currency, the gained mixture heats 2 hours with further realization desulfidation at 72 ℃, filters then.With 10 premium on currency at 50 ℃ of filter wash cakes.Output 533 grams.

With 77 solids contents that make above of gram is that 91.7% filter cake, 30 gram Diethylene Glycols, 25 gram aqueous sodium hydroxide solutions (50%) and 50 restrain water and mix, and is heated to 88 ℃ under nitrogen.Add 20 gram glucose, continue heating 20 minutes.Obtain 200 gram liquid dye preparations, through potentiometric determination, wherein sulfide content is 5.15% with the 0.2N cuprammonium sulfate, and PH is 11.1.

Example 6

250 parts of sulfuration body crude products according to the sulfur green dyestuff of United States Patent (USP) 3338918 examples 1 preparation mix with 488 parts of water, blow 2 hours at 88 ℃, are chilled to 45 ℃, filter.Filter cake with 12000 parts from the beginning the washing, up to washing water be clarifying and specific conductivity be 110 gemmhos/centimetre.Obtain the filter cake of 55 parts of weight, solids content is 43.2%.

6.5 the sodium hydroxide solution of the filter cake that part prepares above, 2.0 parts of water, 2.0 parts of Diethylene Glycols and 2.2 part 50% mixes, and is heated to 78 ℃ under nitrogen.Add 1.2 parts of glucose in the mixture, stirred 30 minutes at 85 ℃.Gained liquid obtains 13.7 parts of green liquid dye formulations through 11 centimetres Fischer filter paper filtering, and its PH is 11.5, and through potentiometric determination, sulfide content is 4.2% with the 0.2N cuprammonium sulfate.

Example 7

78 gram pentanoic and the right-nitrophenols of 71 grams obtain corresponding indophenols 0-5 ℃ of reaction.It is restrained reaction of Salmon-Saxl in 67 gram sodium sulphite (60%) and 100 under 110 ℃ of boilings.The blue look thioxine dyes (SULPHUR BLUE BRN 150 13, CI 53450) that generates adds 180 gram sodium hydroxide (50%) and 215 and restrains glucose with 1250 gram water dilutions, at 70 ℃ with mixture heating up 15 minutes.Obtaining sodium sulfide content is 1.5 to 2.5%(iodometric determinations) stable prereduction thioxine dyes preparation.

Example 8

Right-the hydroxy diphenylamine of 325 grams restrains reaction of Salmon-Saxl at 120 ℃ with 383 gram sodium sulphite (60%) and 490, generates reddish-brown thioxine dyes (sulfur brown 96).When finishing, vulcanization reaction adds 770 gram water, 268 gram sodium hydroxide (50%) and 156 gram glucose.Mixture is observed the reduction fully of dyestuff 80-85 ℃ of heating 30 minutes.Sulfide content is the 2-3%(iodometric determination in the liquid preparation that obtains).

Example 9

73.5 the gram p-phenylenediamine, the mixture of 43.5 gram meta-toluenediamines and 12 gram para-aminophenols and 242 gram sulphur generate a pausiaceous dyestuff (sulfur green 16) 250-300 ℃ of reaction 26 hours.Dyestuff is dissolved in the 366 gram sodium hydroxide (50%).In solution, be blown into air and carry out desulfurization, be lower than 2% up to sodium sulfide content.Under 80 ℃, heat and add 110 gram glucose and 163 gram sodium hydroxide (50%), obtain the liquid preparation of the low vat of sulfide content.

Application example A

10 grams stir together by the dye solution and the 50 gram water of example 1 preparation, up to forming clear soln.The NaOH solution that adds 8 gram glucose, 4 grams 50% in this solution, water that 10 grams are added and the anionic phosphoric acid ester of 0.5 gram permeate agent EH().After the mixed solution of gained stirred 5 minutes, add water and be diluted to 133 milliliters.

The above dye solution that makes is heated to 43 ℃, and impouring is dyed in the pot.The jean of pre-bleaching is carried out pad dyeing by dyeing solution, and making wet pickup is 70-80%, 101-103 ℃ of 60 seconds of decatize, uses warm tap water rinsing then.

Add 7.5 gram hydrogen peroxide (35% solution) and 7.5 gram Glacial acetic acid in enough water, making cumulative volume is 1 liter, forms an oxidizing solution.This solution is heated to 60 ℃, drops into the above-mentioned pollutant that dyed, in 30 seconds of stirred solution, use warm tap water that the pollutant rinsing is clean and dry then.

Application example B

Following percentage number average is benchmark with the fabric weight.

Cotton goods are added in the dye bath of liquid dye preparation of the example 7 that contains 1% commodity wetting agent, 5% sodium hydroxide (50%), 6% glucose and 4%.Bath raio is 10: 1.The temperature of dye bath is risen to 90-95 ℃, in 15 minutes, divide three parts to be added in the dye bath in the sodium sulfate of 20-40% then.Continue dyeing 45 minutes at 90-95 ℃.After this dye bath is chilled to 70 ℃, the fabric that rinsing was dyed is up to clarification of water.

Hydrogen peroxide with 2% (35% solution) and 2% acetic acid (80%) are added in the enough water, constitute a bath raio and be 10: 1 oxidizing solution.Fabric is added in the bath, handled 20 minutes at 50 ℃.

After the rinsing with the commodity soaping agent of 2% polyacrylate based in 80 ℃ of fabrics 15 minutes soaped, rinsing and dry then.

Claims (12)

1, a kind of liquid dye preparation, said preparation contain the dyestuff that is reduced into colorless form of at least 8% (weight); The alkali of 1 to 17% (weight); A kind of reductive agent of this dyestuff, this reductive agent are selected from a kind of sulfide and a kind of reducing sugar that forms or result from sulfuration on the spot; And optional a kind of non-ionic hydrotropic agent, the inorganic sulphide total amount in the said preparation is no more than 3% of said preparation gross weight.

2, according to the liquid dye preparation of claim 1, said preparation contains a kind of reducing sugar as reductive agent, and its content is total formulation weight amount 1 to 25%.

3, according to the liquid dye preparation of claim 1, its mineral sulfates content is less than 3%(weight).

4, according to the liquid dye preparation of claim 1, remove the sulfuration beyond the region of objective existence, it does not contain other inorganic salt in fact.

5, the method for the liquid preparation of the described reductive colorless form of preparation claim 1 thioxine dyes, comprise thioxine dyes is reduced in alkaline aqueous medium, its pH scope is 9-14, the temperature that adopts is 60-110 ℃, contain a kind of reducing sugar in this medium or form or result from the sulfide of sulfuration on the spot, as the reductive agent of this thioxine dyes.

6, according to the method for claim 5, wherein in this alkaline aqueous solution medium, do not add the sulfide reductive agent.

7, according to the method for claim 5, wherein in the alkaline aqueous solution medium reducing sugar is arranged.

8, according to the method for claim 5, wherein this thioxine dyes is used in water medium or the alkaline medium a kind of organic sulfur product oxidation is obtained.

9, according to the method for claim 5, wherein the alkaline aqueous solution medium also contains a kind of non-ionic hydrotropic agent.

10, according to the method for claim 5, also comprise the step of washing thioxine dyes, so that before this dyestuff is added to alkaline aqueous medium, remove inorganic salt earlier.

11, according to the method for claim 5, wherein this reducing sugar is selected from arabinose, ribose, wood sugar, glucose, fructose, seminose, semi-lactosi, sucrose, lactose, maltose and cellobiose.

12, the purposes of the described preparation of claim 1 comprises said preparation is applied to and desires to dye on the textiles, dyes or stamp.