CN104358161A - Salt-free low-alkali cellulose fiber modified dyeing process - Google Patents

Abstract

The invention relates to a salt-free low-alkali cellulose fiber modified dyeing process, belonging to the technical field of textile dyeing. The process comprises the steps of cellulose fiber modification treatment, water washing treatment, dyeing and after-treatment, wherein in the step of cellulose fiber modification treatment, epoxy quaternary ammonium salt compounds and branched polyepichlorohydrin dimethylamine are adopted for modification treatment of cellulose fibers. The salt-free low-alkali cellulose fiber modified dyeing process has the beneficial technical effects that two kinds of specific modifiers are adopted, the synergistic effects of the modifiers are given play to and the specific dyeing steps are provided, so that the cellulose fibers achieve salt-free low-alkali dyeing in dyeing, have the effects of reducing pollution, saving the cost, simplifying the process and reducing the difficulty, have good modification and dyeing effects, and are suitable for large-scale industrial production.

Description

A kind of salt-free low alkali modification dyeing of cellulose fibre

Technical field

The present invention relates to a kind of dyeing of cellulose fibre, more particularly, the present invention relates to a kind of salt-free low alkali modification dyeing of cellulose fibre, belong to dope dyeing technical field.

Background technology

Traditional fibre cellulose fiber dyeing dye-uptake is generally at about 40-70%, and dye-uptake is low, and loose colour is many, in order to overcome electric charge obstacle in dyeing course, must add a large amount of inorganic salts, to improve dye-uptake in dye liquor; For reaching fixation object, the hydroxyl on cellulose needs ionization under strongly alkaline conditions, so the dyeing later stage, must add a large amount of soda ash in dye liquor.It is a difficult problem for puzzlement industry to the process of inorganic salts and alkali always, a large amount of inorganic salts that not only cannot reclaim but also be difficult to degrade enter rivers and lakes, severe contamination water quality, because salt has very high permeance property, make soil property salinization of soil around, become a difficult problem very thorny in environmental protection; In addition, in traditional salt, highly basic dye liquor, dye utilization rate is very low, and under highly basic, hydrolysis etc. occurs laking process, and cause a large amount of wastes of dyestuff, many deep-colour fabrics cannot reach requirement.Therefore, remained a large amount of dyestuffs, salt, alkali in the dyeing liquor of discharge, intractability is large, cost is high, is a difficult problem for puzzlement dyeing, is also the bottleneck of restriction dyeing development.

In order to solve the problem, the method adopted at present mainly contains two kinds:

One, direct high, low to the salt-dependent new dye of exploitation.As the low salt dyestuff of Sumifux Supra that SUMITOMO CHEMICAL company releases, during dyeing, inorganic salts consumption is traditional 1/3-1/2; The Remazol EF low-salt reactive dyes that Hirst company produces, during dyeing, the use amount of inorganic salts is 1/3 of conventional method; The Cibacron LS dyestuff that Clariant Corporation's Drimarene HF dyestuff and former vapour Bagong department release, salt dosage is the 1/4-1/2 of traditional handicraft; China's Shanghai Dyestuffs eight factory is also proposed EF low salt dyeing series dyes.Low salt dyestuff generally reduces sulfonic group, and improve fixation speed and degree of fixation by increasing active group number, dyestuff is direct strong.But existing new dye is also unsuccessful, this kind of dye activity and substantivity are too strong, are difficult to control dyeing kinetics, cause level-dyeing property poor; Dyestuff consumption is large, thus cause cost to increase and sewage treatment load large; The color fastness to light of coloured fibre and fabric is poor; Chromatogram is incomplete, dyestuff price is high; Only only reduce the consumption of inorganic salts and fail to cancel the use of inorganic salts, fundamentally not realizing salt-free dyeing; And the intermediate of the low salt dyestuff of part is large to equipment corrosion, itself does not also meet environmental requirement.These drawbacks hinder applying of low salt dyestuff.

Two, cation-modified process is carried out to fiber.Basic ideas are all by introducing cation group to fiber, and the electric charge eliminated between fiber and dyestuff hinders.

Adopting cation-modified method, is one of the new approaches and development trend that realize less salt or salt-free dyeing.The modifier adopted has following a few class:

1, a chloro-s-triazine quarternary ammonium salt compound.The hydroxyl of a chloro-s-triazine active group in this type of modifier easily and on cellulose fibre reacts, and makes cationization of pulp fiber.Representative is a chloro-s-triazine diquaternary amine modifier such as M. N. MICHEAL is when carrying out cation-modified as when catalyst to cotton fiber using 2-chloro-2-dimethylaminoethyl hydrochloride.Afterwards when dyeing to modified cotton fiber by REACTIVE DYES, adding zinc acetate and making color-fixing agent, the degree of fixation of REACTIVE DYES can be improved.For another example Chinese patent CN101747285A, which discloses a kind of preparation method of cationic grafting agent with multi-reactive groups, and this grafting agent is an a kind of chloro-s-triazine ammonium chloride derivative, for fabric graft modified, to improve Color.

2, cationic starch.Cationic starch is important Commercial starch, compares and is widely used as papermaking, weaving additive, oil drilling, sewage disposal or cosmetic industry.With the cation modifier of cationic starch as cotton fiber, fabric goes back to angle through modified dye level, color fastness to light and wrinkle and is all improved.Do comparatively system be M.Zhang etc., Main is, hydrolyzed starch and 2-hydroxypropyl-trimethyl ammonium chloride are carried out etherification reaction in the basic conditions, obtained cationic starch, then by pressure baking technique by cationic starch process on cotton fiber.Modified cotton fiber dyes under being the condition of 10g/l at salt-free and soda ash consumption, and dye-uptake and degree of fixation are all higher than traditional dyeing thing.

3, Chitosan-phospholipid complex.Shitosan is a kind of and polysaccharide macromolecule of obtaining deacetylated by chitin, and chitin is mainly derived from shrimp, crab shell, the therefore abundance of shitosan.The main distinction between shitosan and cellulosic molecule is that the hydroxyl at cellulose C-2 place is replaced by amino.In acid dye bath, the amino of shitosan can be protonated, positively charged, thus can play the effect of short dye.The research that domestic and international academia does this is more.Processing procedure is more loaded down with trivial details, again with chitin modified after being usually oxidized in advance by fiber, as cotton fiber is first oxidized with KIO4 by Yupaporn Kitkulnumchai etc., then carries out reduction amination with shitosan and boration sodium.When modified cotton fiber REACTIVE DYES dyes, when the consumption of dyestuff and the consumption of salt all reduce by half, the degree of fixation of degree of fixation and traditional dyeing is close.Shitosan can only dissolve in an acidic solution, and this has comparatively havoc to the coloured light of cellulosic fabrics intensity and follow-up DYED FABRICS, the oxidation carried out fabric before chitin modified, there is breakdown strength equally and controls the problem of difficulty.

4, epoxy quaternary ammonium salt compound.This compounds comprises the chloropropylene oxide parent derivative of Glytac reagent containing epoxide group and Glytac reagent.Glytac reagent is due to containing epoxide group, and when carrying out modification with it to cellulose fibre, reactivity is high.But Glytac reagent is mainly used for textile printing and RESIN FINISH by current Research Literature both domestic and external, the modification really Glytac reagent being used for cellulose fibre salt-free dyeing is little.Peter J. etc. are in order to reduce the instability problem of system under the hydrolysis of epoxide and high temperature, during by Glytac agent modifier COTTON FABRIC, have employed and pad-cold batching process, 24h is deposited at normal temperatures afterwards by after the cotton plastic wraps after this PROCESS FOR TREATMENT, through several times washing, finally soak with spirit of vinegar to complete modification.Although the cotton fabric dyeing process after washing after the method process, friction and color fastness to light are basic and tradition has salt dyeing suitable, the cycle of whole processing procedure is quite very long numerous and diverse, poor controllability, also has no industrialization report.Some scholars are had to carry out modification with the chloropropylene oxide parent derivative of Glytac reagent to cotton fiber at present.Lili Wang etc. dry techniques by two bath pressures and prepare cationization cotton fiber, then dye under being the condition of 10g/l at the salt-free and consumption of soda ash by REACTIVE DYES.After dyeing, the degree of fixation of REACTIVE DYES is higher than adopting the degree of fixation of conventional method dyeing.The chloropropylene oxide parent derivative of the Glytac reagent of 35g/l and the NaOH of 15g/l such as M.Montazer first pad, then encase with plastic bag, and ambient temperatare puts 24h, soaks afterwards with spirit of vinegar.By the cotton fiber after the method process salt-free and the consumption of soda ash dyes under being the condition of 10g/l time, dye-uptake and degree of fixation are all improved.Wang Guangming, the chloropropylene oxide parent derivative of homemade for 15ml Glytac reagent and 2.5gNaOH are made into the 100ml aqueous solution by Liu Jinxi, two methods of rolling are soaked by modifier treatment on cotton fiber again with two, cotton fiber after process is dried at 75 DEG C, decatize 3 ~ 5min again, use hot water wash afterwards, finally wash with the acetic acid of 5g/l.Cotton fiber after cationization dyes under salt-free conditions, and dye-uptake and degree of fixation are all improved to some extent.According to the literature, the epoxide group of epoxies quarternary ammonium salt compound is easily hydrolyzed in the basic conditions, so modifier consumption is large, in order to head it off, have the polyepoxides of scholar's proposition high molecular as cation modifier, think that its substantivity is good, modifier consumption can reduce.So-called direct good, refer to modifier easily by fibers adsorption.High molecular modifier dissolubility is not good, although can be adsorbed to fabric face, the viscosity of modified system is large, is difficult to the uniformity ensureing modification, thus causes dyeing uneven.Meanwhile, the modifier diffusivity difference of high molecular is difficult to penetrate into fibrous inside, and most of modifier is deposited in fiber surface, although dye-uptake is high, degree of fixation is low; The CATION that surface sediment is too much, very large to dyestuff attraction during dyeing, cause dyeing speed too fast, cause upper dye uneven, " the look flower " of stained clot-h is cation-modified maximum problem, and client is difficult to accept, and therefore realizes industrialization and acquires a certain degree of difficulty.

In sum, existingly utilize single modifier to come modified fibre or fabric, then there is following problem in the salt-free dyeing technique of carrying out dyeing:

Although 1 can realize salt-free dyeing, alkali consumption is still higher, usually reaches 10g/L or more; And the colourity of dyeing residual liquid is also higher, still can pollute;

2, the modifying process before dyeing is loaded down with trivial details, and many operations can only complete in laboratory, is difficult to realize in actual production, and staining procedure also cannot coordinate modification procedure, can not be applicable to industrialization large-scale production;

3, Small molecular cation modifier substantivity is not good, consumption is very large, and the fiber after macromolecule cation modifier modification, the disadvantage such as easily occur during salt-free dyeing that look is heavy, look colored and COLOR FASTNESS is poor, more difficultly meet instructions for use, cause follow-up dyeing complicated like this, production difficulty is large, success rate is low, is more difficultly equally applicable to industrialization large-scale production.

Summary of the invention

The present invention is intended to solve in prior art to reduce the consumption of dyestuff, inorganic salts and alkali, after cellulose CSP process, then carry out the following problem that exists in the technique that dyes: alkali consumption is still comparatively large, and dyeing residual liquid colourity is higher, the waste water of discharging is difficult, pollutes; And existing salt-free low alkali modification dyeing can not be applicable to industrialization large-scale production.

The invention provides a kind of salt-free low alkali modification dyeing of cellulose fibre, salt-free low alkali dyeing can be realized, dye dosage reduces, dyeing residual liquid colourity can be made again to reduce, such residue wastewater is easy to process, greatly reduce the pollution of discharging and causing, and all right recycle of raffinate, reduce production cost; In addition, dyeing program of the present invention is simple, and execute-in-place difficulty is little, one-time success rate and production efficiency high, be applicable to industrialization large-scale production.

In order to realize foregoing invention object, its concrete technical scheme is as follows:

A salt-free low alkali modification dyeing for cellulose fibre, is characterized in that: comprise following processing step:

A, cellulose CSP process

Cellulose fibre is put into container, add water in container again, then with small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier two kinds of cation modifiers, modification is carried out to cellulose fibre, after modification completes, obtain modified cellulose fibre; Described small molecule quaternary ammonium salt cation modifier is epoxy quaternary ammonium salt compound, and described high molecular quaternary cation modifier is the poly-epoxychloropropane dimethylamine of branched chain type;

B, washing process

The modified cellulose fibre obtained through modification in steps A is carried out washing process;

C, dyeing

Put into dyeing container by step B through the modified cellulose fibre of washing process, add dye liquor and dye, then heat up, complete dyeing after continuing dyeing a period of time, obtain dyeing, modifying cellulose fiber peacekeeping dyeing residual liquid;

D, post processing

The dyeing, modifying cellulose fibre obtained by step C carries out washing process, then obtains finished product through oiling, drying.

Cellulose fibre of the present invention selects viscose fiber filament, viscose short fiber, model, sky silk, cotton fiber, yarn, fabric that aforementioned fibers cellulose fiber is made.

Above-mentioned yarn is cheese or reeled yarn.

The present invention in step, described modification is that cellulose fibre is put into container, then adds water in container, then adds the poly-epoxychloropropane dimethylamine of epoxy quaternary ammonium salt compound and branched chain type simultaneously, add NaOH after 5-10min, carry out modification; The time of modification is 40-70min, and in modification process, temperature controls as 60-90 DEG C.

The present invention in step, described modification is that cellulose fibre is put into container, add water in container again, then first add epoxy quaternary ammonium salt compound, after 5-10min, add NaOH, be warming up to 45-55 DEG C, reaction 10-15min, then add the poly-epoxychloropropane dimethylamine of branched chain type, add NaOH subsequently, be warming up to 65-85 DEG C, continue reaction; The total time of modification is 65-90min.

The present invention in step, described modification is that cellulose fibre is put into container, add water in container again, be warming up to 65-85 DEG C, then add the poly-epoxychloropropane dimethylamine of branched chain type, add NaOH subsequently, reaction 20-30min, is cooled to 45-55 DEG C, then adds epoxy quaternary ammonium salt compound, add NaOH after 5-10min, continue reaction; The total time of modification is 65-90min.

In above-mentioned modification, described programming rate is 1-2 DEG C/min.

In above-mentioned modification, bath raio is 1:4-1:16.

In above-mentioned modification, the ratio of the quality sum of described epoxy quaternary ammonium salt compound and the poly-epoxychloropropane dimethylamine of branched chain type and the quality of cellulose fibre is 0.02-0.2:1.

In above-mentioned modification, the mass ratio of described epoxy quaternary ammonium salt compound and the poly-epoxychloropropane dimethylamine of branched chain type is 4-3:1-2.

In above-mentioned modification, the ratio of the quality of described NaOH and the quality of modifier is 0.2-1:1.

In stepb, described washing process is that modified cellulose fibre is washed to pH=6.5-8 in the present invention.

In stepb, described washing process is specially in the present invention: first modified cellulose fibre is carried out overflow washing 5-10min, then adds the acetic acid neutralization of 0.5-1g/l, last overflow washing 5-10min.

The present invention is in step C, the described dye liquor that adds dyes, then heat up, complete dyeing and refer to after continuing dyeing a period of time: add dye liquor at 40 DEG C and dye being no more than, be warming up to 60-80 DEG C with the speed of 1-2 DEG C/min after 10-20min, after continuing dyeing 30-50min, complete dyeing.

The present invention, in step C or above-mentioned staining procedure, adds the sodium carbonate of 1-2g/l after described intensification.

The present invention is in step C, and described dye liquor concentration is 1-8%, and dye liquor addition is the 2-20% of modified cellulose fibre quality.

In step D, described washing process is specially in the present invention: first overflow washing 5-10 minute, then enters whole cylinder water, carries out reverse circulation washing, until clean.

In step D, described oiling is specially in the present invention: at 40-50 DEG C, carry out oiling treatment 20-30 minute.

Above-mentionedly oil in step, finish addition is the 0.5-3% of dyeing, modifying cellulose fibre quality.

The Advantageous Effects that the present invention brings:

1, the invention provides a kind of salt-free low alkali modification dyeing of cellulose fibre, solve in prior art and utilize single modifier to cellulose CSP, after carrying out salt-free dyeing again, chroma in waste water is comparatively large, and processing load is still comparatively large, and is not suitable for the problem of industrialization large-scale production.

Present invention employs specific small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier two class modifier, the i.e. poly-epoxychloropropane dimethylamine of epoxy quaternary ammonium salt compound and branched chain type, the effect of the cooperative effect of both performances, be equipped with specific staining procedure, achieve salt-free low alkali dyeing, do not need in dye liquor during dyeing to add inorganic salts (glauber salt or sodium chloride), alkali concn is the 4-10% of existing technique.When the modified cellulose fibre pH value obtained after modification of the present invention is in addition 6.5-8.5, Zeta electrode potential value is 10-30mV, and cationization is effective, and dye-uptake can bring up to more than 90%, or degree of fixation improves more than 30%.After dye-uptake improves, dye utilization rate increases substantially, and dyestuff consumption reduces about 30%, and dyeing waste-water discharge reduces 40-50%.Not containing inorganic salts in the dyeing residual liquid of discharge, only residual a small amount of dyestuff and alkali, wherein colourity is very low, and difficulty and the cost of process reduce greatly, decreases the pollution of discharging and causing, and dyeing residual liquid is close to achromaticity and clarification, can recycle, continue on for, in salt-free dyeing of the present invention, so both reducing the cost of dyeing and dyeing product, decrease again the generation of dyeing waste-water from source, in dyeing course, decrease the use of dyestuff and industrial chemicals.

In addition, the present invention adopts specific modifier and modification procedure, and with modification procedure supporting staining procedure, simplify existing loaded down with trivial details processing step, reduce execute-in-place difficulty, improve one-time success rate and production efficiency, solve the destruction of existing modified technique to fibre strength and coloured light, there is the problems such as aberration, look are spent, look heavy, ring dye, light fastness, COLOR FASTNESS and degree of fixation are not high after dyeing, be highly suitable for industrialization large-scale production.

2, the present invention adopts poly-epoxychloropropane dimethylamine two kinds of modifier of epoxy quaternary ammonium salt compound and branched chain type to carry out cation-modified to cellulose fibre, according to modification demand and the demand realizing industrialization large-scale production, two kinds of modifier are carried out rationally composite.Two kinds of modifier respectively have pluses and minuses, and composite mode of the present invention can make both have complementary advantages, and cooperatively interacts, and improves modification quality, and then improves follow-up dyeing quality.

Epoxy quaternary ammonium salt compound penetration is strong, so with it to cellulose CSP, can make fibrous inside cationization more fully, follow-up dye can enter fibrous inside, contaminates thoroughly and evenly.But micromolecular substantivity is poor, facile hydrolysis, consumption are large.The poly-epoxychloropropane dimethylamine substantivity of branched chain type is good, good stability, and consumption is few, but poor permeability, be unfavorable for the inside penetrating into fiber, modification mainly concentrates on the top layer of fiber.During dyeing, due to the Coulomb repulsion that fibrous inside modification causes not, dyestuff can only concentrate on the many surfaces of cations.Cause the too much dyestuff of surface sediment, Shade of Dyed Textiles is not bright-coloured, fibrous inside contaminates not good, occurs ring dye phenomenon.The present invention is by the poly-epoxychloropropane dimethylamine compound use of epoxy quaternary ammonium salt compound and branched chain type, the consumption of small molecule-modified dose and total consumption of modifier can be reduced greatly, and can ensure that the inside and outside of cellulose fibre can obtain uniform cation modifying, follow-up dyeing is when identical dye-uptake, obtain darker Color, the problem such as avoid that look is heavy, look colored and COLOR FASTNESS is poor, is applicable to large-scale industrial production.

3, small molecule quaternary ammonium salt cation modifier of the present invention is epoxy quaternary ammonium salt compound.The present invention selects specific small molecule quaternary ammonium salt cation modifier, this modifier contains quaternary ammonium salt cationic and reactive group, can react well with the hydroxyl on cellulose fibre in the basic conditions, thus cellulose fibre is become positively charged lotus, improve the affinity between cellulose fibre and dyestuff and reactivity, modifier is more easily combined with cellulosic molecule, is beneficial on dyestuff and contaminates on fiber, improve dye-uptake, decrease the consumption of dyestuff.

4, high molecular quaternary cation modifier of the present invention is branched chain type poly-epoxychloropropane dimethylamine.Branched chain type Polyamide-Polyamsne-Epichlorohydrin belongs to reactive polymer class modifier, and its reactive group can form covalent bond with hydroxyl reaction on cellulose fibre in the basic conditions, thus cellulose fibre is become positively charged lotus.So backbone chain type Polyamide-Polyamsne-Epichlorohydrin can be combined preferably with cellulose fibre, make positive charge on fiber band, improve the affinity between fiber and dyestuff, be beneficial on dyestuff and contaminate on fiber, improve dye-uptake, decrease the consumption of dyestuff.

5, the present invention adopts three kinds of modes adding modifier, these three kinds of feed postition can both play two kinds of modifier advantage separately, the total consumption of modifier is all less than the single modifier consumption added in prior art, and dye-uptake is higher than the mode of modifier single in prior art, colourless heavy look flower, dye level is even.Namely the first feed postition adds two kinds of modifier simultaneously, and this modification mode processing step is simple, is easy to operate and control; The second feed postition for first to add small molecule quaternary ammonium salt cation modifier, then adds high molecular quaternary cation modifier, and this modification mode is optimum to the modified effect of cellulose fibre inside, and level-dyeing property is best; The third feed postition for first to add high molecular quaternary cation modifier, then adds small molecule quaternary ammonium salt cation modifier, and this modification mode can reach identical dye level well, and the dyestuff of needs is minimum.

Specifically:

1) namely the first feed postition adds two kinds of modifier simultaneously, small molecule-modified dose spreads to fiber surface with macromolecule modifier simultaneously, there is a competitive reaction process, small molecule-modified dose of diffusion velocity is fast, macromolecule modifier molecular diffusion rates is slow, reach the object of fibrous inside and surface all being carried out to modification, this modification mode processing step is simple, is easy to operate and control simultaneously;

2) the second feed postition is for first to add small molecule-modified dose, by adsorbing in advance and controlling programming rate, suppress hydrolysis as far as possible, small molecule-modified dose is not only carried out modification to fiber surface, fibrous inside can also be diffused into, thus it is more even with inter-modification to fiber surface, add macromolecule modifier again, mainly further modification is carried out to fiber surface, macromolecule modifier good stability, utilization rate is high, mainly concentrate on fiber surface, adopt less amount just can reach high surface modification effect, this modification mode is optimum to the modified effect of cellulose fibre inside, during follow-up dyeing, level-dyeing property is best,

3) the third feed postition is for first to add macromolecule modifier, then adds small molecule-modified dose.First add macromolecule modifier and mainly modification is carried out to fiber surface, add small molecule-modified dose again, small molecule-modified dose of part is diffused into fibrous inside, part small molecule-modified dose of impact being subject to macromolecule modifier concentrates on fiber surface, modification is carried out to fiber surface, the dyestuff that the modified fibre that this mode obtains needs when obtaining identical dye level is minimum, and without the heavy phenomenon of the look pattern of single macromolecule modified existence.

6, the present invention adds in the mode of two kinds of modifier simultaneously, and the time of modification is 40-70min, and in modification process, temperature controls as 60-90 DEG C.The present invention selects the specific modification time, can meet multiple modifier composite after modification requirement, make reaction more abundant, and modification efficiency can be ensured.The present invention selects specific modification temperature, can meet multiple modifier composite after modification requirement, make reaction more abundant, and can ensure that the cost of modification is lower.In general, under certain condition, modification time is long, temperature is high, modifier and cellulose fibre react more abundant, the cations of cellulose fibre is just more, modified effect is better, and the dye-uptake of follow-up dyeing is also just higher, but temperature reaches the sufficient reacting of the agent of certain value post-modification and cellulose fibre, modified effect is tending towards constant, because modifier of the present invention forms with macromolecule modifier is composite by small molecule-modified dose, if long for small molecule-modified dose of time, temperature is too high, hydrolysis is many, and modified effect is not just very desirable.So the combination of the present invention's modification time of selecting and modification temperature can either ensure two kinds of modifier composite after and cellulose fibre fully react, combine well, can not make again small molecule-modified dose hydrolyzed many, thus obtain a good modified effect.

7, the present invention's preferred the second modification mode is for first to add small molecule quaternary ammonium salt cation modifier, then adds high molecular quaternary cation modifier, and adopts specific process parameter control.Small molecular class modifier reactivity is large, and the required activation energy of reaction is low, just have higher reaction rate at a lower reaction temperature, and the higher hydrolysis rate of temperature is also larger, so reaction should choose lower temperature; And high score subclass modifier due to molecular structure larger, the required activation energy of reaction is relatively high, can obtain higher diffusion, seepage velocity and reaction rate at relatively high temperatures, and not facile hydrolysis, so reaction can be carried out at relatively high temperatures.

The process of the second way first adds small molecule-modified dose, allow it be adsorbed onto fully on cellulose fibre and spread to fibrous inside, after 5-10min, add NaOH, be warming up to 45-55 DEG C, reaction 10-15min, at this moment be adsorbed on fiber surface and inner modifier and fiber to react in the basic conditions, form covalent bond, small molecule-modified dose that now dissolves in water owing to having carried out pre-absorption compares less, thus can reduce by small molecule-modified dose of hydrolysis in the solution, improve the effective rate of utilization of small molecule-modified dose, improve the amount that modifier is combined with fiber.And then add macromolecule modifier, add NaOH subsequently, be warming up to 65-85 DEG C, continuing reaction to modification total time is 65-90min, and modifier and fiber are fully reacted.

So, the mode of temperature-gradient method and the control of special parameter, small molecule-modified dose and cellulosic reaction can be ensured at relatively low temperature, make on cellulose fibre with more CATION, after Small molecular is combined with fiber substantially, macromolecule cation modifier dissolves at a higher temperature and spreads or is conducive to the combination with fiber with fiber-reactive, this ensure that two kinds of modifier can with cellulose fibre sufficient reacting, improve modification quality, reduce modification cost.

8, the present invention's the third modification mode preferred is for first to add high molecular quaternary cation modifier, then adds small molecule quaternary ammonium salt cation modifier, and adopts specific process parameter control.Small molecular class modifier reactivity is large, and the required activation energy of reaction is low, just have higher reaction rate at a lower reaction temperature, and the higher hydrolysis rate of temperature is also larger, so react temperature required lower; And high score subclass modifier is larger due to molecular structure, not easily spreads and permeate, the required activation energy of reaction is relatively high, and not facile hydrolysis, better reaction effect can be obtained at relatively high temperatures, so reaction can be carried out at relatively high temperatures.

The process of the third mode is first warming up to 65-85 DEG C, then macromolecule modifier is added, add NaOH subsequently, reaction 20-30min, fast cooling is to 45-55 DEG C, add small molecule quaternary ammonium salt cation modifier again, add NaOH after 5-10min, continuing reaction to modification total time is 65-90min.This mode considers macromolecule modifier to be needed to dissolve at relatively high temperatures, spread, permeate or react, simultaneously in order to suppress micromolecular hydrolysis, so add small molecule-modified dose again after the temperature of modified system being reduced.

So, the mode of temperature-gradient method and the control of special parameter, small molecule-modified dose and cellulosic reaction can be ensured at relatively low temperature, make on cellulose fibre with more CATION, high molecular weight reactive carries out at relatively high temperatures, ensure that the combination of macromolecule and fiber, this ensure that two kinds of modifier can with cellulose fibre sufficient reacting, improve modification quality, reduce modification cost.

9, the present invention is preferred, and in modification, programming rate is 1-2 DEG C/min.Select this velocity interval, modified-reaction speed can be reduced, make modification more even, so also can make modified cellulose fibre in follow-up dyeing on contaminate more even.In addition, hydrolysis can be suppressed to a certain extent, improve the effective rate of utilization of modifier.

10, bath raio of the present invention is preferably 1:4-1:16.The scope control of this bath raio mass ratio between cellulose fibre and water, can ensure best modified effect and the cost of the best, reduce the difficulty of modification, improve the success rate of modification within the scope of this.

11, the ratio of the preferred modifier total amount of the present invention and cellulose fibre quality is 0.02-0.2:1.Above-mentioned amount ranges can adapt to the requirement of multiple condition and multiple dyestuff, high at dye-uptake, dye dosage is few, under the light-colored prerequisite of dyeing residual liquid, reduce the consumption of modifier, thus on the basis ensureing the dyeing quality in follow-up dyeing, reduce modification cost and modification difficulty.

12, the present invention preferably controls the mass ratio of the poly-epoxychloropropane dimethylamine of epoxy quarternary ammonium salt compound and branched chain type is 4-3:1-2.

First, the present invention controls the amount of small molecule-modified dose all the time higher than the amount of macromolecule modifier.Because the permeability of small molecule-modified dose is better, modification can be more thorough, and namely small molecule-modified dose is carried out modification mainly for fibrous inside, and aequum is larger.The substantivity of macromolecule modifier is good, and chemical stability is good, and mainly for fiber surface and top layer modification, aequum is less.

Secondly, the present invention controls again the concrete proportion of two kinds of modifier consumptions, has so just carried out effective complementation by small molecule-modified dose with the pluses and minuses of macromolecule modifier and has coordinated, having taken into account the action character of two kinds of modifier.With the preferred ratio of the present invention carry out composite after, reach same dye level, required modifier consumption is less, and dyestuff addition also declines thereupon, greatly reduces production cost.And follow-up dyeing evenly, color is more bright-coloured, also can effectively prevent modification from just concentrating on fiber surface, occur during dyeing dye not thoroughly, the generation of the problems such as look flower (dyeing uneven), look sink, COLOR FASTNESS difference.

13, the addition of the preferred NaOH of the present invention is 0.2-1 times of modifier.In modified-reaction system of the present invention, need to add NaOH, make reaction environment be alkalescence, NaOH makes that cellulose fibre expansion modifiers is easier permeates to fibrous inside in addition, modification is more abundant, and cellulose CATION degree is higher, and the dye-uptake of follow-up dyeing is also just higher.But the addition of NaOH too much can cause dyeing during follow-up dyeing uneven.The present invention first solves the uneven problem of modification, have employed specific addition amount of sodium hydroxide, by modified-reaction speeds control to an optimum range, makes modification more even, and then makes follow-up dyeing more even.

14, the present invention washes and pickling processes modified cellulose fibre, is washed till by modified cellulose fibre neutral to alkalescent, is conducive to follow-up dyeing.The present invention preferably washes the modifier wash clean that processing mode can effectively will not be combined with fiber with washing treatment process parameter, prevents modifier to be present in equipment with free state, avoids dyestuff to flocculate.

15, the present invention is preferred, the described dye liquor that adds dyes, then heat up, complete dyeing and refer to after continuing dyeing a period of time: add dye liquor at 40 DEG C and dye being no more than, be warming up to 60-80 DEG C with the speed of 1-2 DEG C/min after 10-20min, after continuing dyeing 30-50min, complete dyeing.Above-mentioned concrete staining procedure matches with aforementioned modified step, and simplify dyeing step, dyeing time is short, and efficiency is high, and technological operation is simple, can ensure even to improve dyeing quality when using some sensitive colors to dye.Be no more than 40 DEG C to add dye liquor and can prevent under the high temperature conditions dyestuff contaminating too fast, cause look flower; Controlling programming rate is 1-2 DEG C/min, and can ensure under each thermograde, the every aspect cellulose fibre in cylinder is heated evenly, and dyestuff can above be contaminated uniformly, not easily look flower.

16, the present invention is preferred, adds the sodium carbonate of 1-2g/l in step C after heating up.Due to aforesaid modification procedure, now only with the sodium carbonate adding trace, can production cost be reduced, can pollution be reduced again.In addition, above-mentioned preferred addition scope can be consolidated under stable alkali condition, and modified cellulose fibre and dyestuff generation chemical reaction, finally make dyestuff go up firmly on modified cellulose fibre.

17, the present invention is in step C, and described dye liquor concentration is 1-8%, and dye liquor addition is the 2-20% of modified cellulose fibre quality.The control of above-mentioned concentration and addition can prevent dyeization, and simultaneously production control cost.

18, the present invention in step D, and described cleaning with the dyeing, modifying cellulose fibre that step C obtains by water is specially: first overflow washing 5-10 minute, then enter whole cylinder water, carries out reverse circulation washing, until clean.Alkalescence can be gradually become neutral by above-mentioned washing treatment step specifically fast, and a small amount of loose colour can be washed away simultaneously.

Detailed description of the invention

embodiment 1

Cellulose dyeing technique:

A salt-free low alkali modification dyeing for cellulose fibre, comprises following processing step:

A, cellulose CSP process

Cellulose fibre is put into container, add water in container again, then with small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier two kinds of cation modifiers, modification is carried out to cellulose fibre, after modification completes, obtain modified cellulose fibre; Described small molecule quaternary ammonium salt cation modifier is epoxy quaternary ammonium salt compound, and described high molecular quaternary cation modifier is the poly-epoxychloropropane dimethylamine of branched chain type;

B, washing process

The modified cellulose fibre obtained through modification in steps A is carried out washing process;

C, dyeing

Put into dyeing container by step B through the modified cellulose fibre of washing process, add dye liquor and dye, then heat up, complete dyeing after continuing dyeing a period of time, obtain dyeing, modifying cellulose fiber peacekeeping dyeing residual liquid;

D, post processing

The dyeing, modifying cellulose fibre obtained by step C carries out washing process, then obtains finished product through oiling, drying.

Above-mentioned technique is dyeing of the present invention, and wherein steps A obtains the modified cellulose fibre of nitrogen content 0.2-0.43%, and this fiber is when pH value is 6.5-8.5, and Zeta electrode potential value is 5-26mV.Because small molecule quaternary ammonium salt cation modifier molecules amount is little, can not only be adsorbed on fiber surface can also spread to fibrous inside, and high molecular quaternary cation modifier molecular weight is large, is mainly adsorbed on fiber surface, more difficultly spreads to fibrous inside.But small molecule quaternary ammonium salt cation modifier is direct poor, is easily hydrolyzed.The present invention is by two kinds of quaternary ammonium salt cationic modifier compound uses, modification is carried out to cellulose fibre, work in coordination, while its advantage of respective performance, play cooperative effect effect, make cation modifying better effects if, modification is more even, and simplify modification procedure, be suitable for industrialization large-scale production.Be equipped with specific staining procedure and post-processing step further subsequently, modified effect can be shown in dyeing course completely, its dyeing quality improves, and staining procedure is simple to operation, and dyeing cost reduces, and is applicable to industrialization large-scale production.

embodiment 2

Cellulose dyeing technique:

A salt-free low alkali modification dyeing for cellulose fibre, comprises following processing step:

A, cellulose CSP process

Cellulose fibre is put into container, add water in container again, then with small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier two kinds of cation modifiers, modification is carried out to cellulose fibre, after modification completes, obtain modified cellulose fibre; Described small molecule quaternary ammonium salt cation modifier is epoxy quaternary ammonium salt compound, and described high molecular quaternary cation modifier is the poly-epoxychloropropane dimethylamine of branched chain type;

B, washing process

The modified cellulose fibre obtained through modification in steps A is carried out washing process;

C, dyeing

Put into dyeing container by step B through the modified cellulose fibre of washing process, add dye liquor and dye, then heat up, complete dyeing after continuing dyeing a period of time, obtain dyeing, modifying cellulose fiber peacekeeping dyeing residual liquid;

D, post processing

The dyeing, modifying cellulose fibre obtained by step C carries out washing process, then obtains finished product through oiling, drying.

Described cellulose fibre selects viscose fiber filament, viscose short fiber, model, sky silk, cotton fiber, yarn, fabric that aforementioned fibers cellulose fiber is made.

Dyeing of the present invention is applicable to the cellulose fibre of all kinds, also comprises the yarn (skein or cheese form) that these cellulose fibres are twisted, or the fabric that these cellulose fibres are made (cloth etc.).

embodiment 3

Small molecule quaternary ammonium salt cation modifier of the present invention is epoxy quaternary ammonium salt compound;

High molecular quaternary cation modifier of the present invention is branched chain type poly-epoxychloropropane dimethylamine.

Epoxy quaternary ammonium salt compound:

The poly-epoxychloropropane dimethylamine of branched chain type:

embodiment 4

The modified technique of cellulose fibre:

The first modification mode:

Cellulose fibre is put into container, add water in container again, then with small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier two kinds of cation modifiers, modification is carried out to cellulose fibre, after modification completes, obtain modified cellulose fibre; Described small molecule quaternary ammonium salt cation modifier is epoxy quaternary ammonium salt compound, and described high molecular quaternary cation modifier is the poly-epoxychloropropane dimethylamine of branched chain type.

Concrete modification is: cellulose fibre is put into container, then adds water in container, then adds the poly-epoxychloropropane dimethylamine of epoxy quaternary ammonium salt compound and branched chain type simultaneously, adds NaOH after 10min, carries out modification; The time of modification is 40min, and in modification process, temperature controls is 90 DEG C.

embodiment 5

The modified technique of cellulose fibre:

The first modification mode:

Cellulose fibre is put into container, add water in container again, then with small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier two kinds of cation modifiers, modification is carried out to cellulose fibre, after modification completes, obtain modified cellulose fibre; Described small molecule quaternary ammonium salt cation modifier is epoxy quaternary ammonium salt compound, and described high molecular quaternary cation modifier is the poly-epoxychloropropane dimethylamine of branched chain type.

Concrete modification is: cellulose fibre is put into container, then adds water in container, then adds the poly-epoxychloropropane dimethylamine of epoxy quaternary ammonium salt compound and branched chain type simultaneously, adds NaOH after 5min, carries out modification; The time of modification is 70min, and in modification process, temperature controls is 60 DEG C.

embodiment 6

The modified technique of cellulose fibre:

The first modification mode:

Cellulose fibre is put into container, add water in container again, then with small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier two kinds of cation modifiers, modification is carried out to cellulose fibre, after modification completes, obtain modified cellulose fibre; Described small molecule quaternary ammonium salt cation modifier is epoxy quaternary ammonium salt compound, and described high molecular quaternary cation modifier is the poly-epoxychloropropane dimethylamine of branched chain type.

Concrete modification is: cellulose fibre is put into container, then adds water in container, then adds the poly-epoxychloropropane dimethylamine of epoxy quaternary ammonium salt compound and branched chain type simultaneously, adds NaOH after 8min, carries out modification; The time of modification is 60min, and in modification process, temperature controls is 70 DEG C.

embodiment 7

The modified technique of cellulose fibre:

The first modification mode:

Cellulose fibre is put into container, add water in container again, then with small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier two kinds of cation modifiers, modification is carried out to cellulose fibre, after modification completes, obtain modified cellulose fibre; Described small molecule quaternary ammonium salt cation modifier is epoxy quaternary ammonium salt compound, and described high molecular quaternary cation modifier is the poly-epoxychloropropane dimethylamine of branched chain type.

Concrete modification is: cellulose fibre is put into container, then adds water in container, then adds the poly-epoxychloropropane dimethylamine of epoxy quaternary ammonium salt compound and branched chain type simultaneously, adds NaOH after 5min, carries out modification; The time of modification is 87min, and in modification process, temperature controls is 62 DEG C.

embodiment 8

The modified technique of cellulose fibre:

The second modification mode:

Cellulose fibre is put into container, add water in container again, then with small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier two kinds of cation modifiers, modification is carried out to cellulose fibre, after modification completes, obtain modified cellulose fibre; Described small molecule quaternary ammonium salt cation modifier is epoxy quaternary ammonium salt compound, and described high molecular quaternary cation modifier is the poly-epoxychloropropane dimethylamine of branched chain type.

Concrete modification is: cellulose fibre is put into container, add water in container again, then epoxy quaternary ammonium salt compound is first added, add NaOH after 10min, be warming up to 50 DEG C, reaction 15min, add the poly-epoxychloropropane dimethylamine of branched chain type again, add NaOH subsequently, be warming up to 75 DEG C, continue reaction; The total time of modification is 80min.

embodiment 9

The modified technique of cellulose fibre:

The second modification mode:

Cellulose fibre is put into container, add water in container again, then with small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier two kinds of cation modifiers, modification is carried out to cellulose fibre, after modification completes, obtain modified cellulose fibre; Described small molecule quaternary ammonium salt cation modifier is epoxy quaternary ammonium salt compound, and described high molecular quaternary cation modifier is the poly-epoxychloropropane dimethylamine of branched chain type.

Concrete modification is: cellulose fibre is put into container, add water in container again, then epoxy quaternary ammonium salt compound is first added, add NaOH after 5min, be warming up to 45 DEG C, reaction 10min, add the poly-epoxychloropropane dimethylamine of branched chain type again, add NaOH subsequently, be warming up to 65 DEG C, continue reaction; The total time of modification is 90min.

embodiment 10

The modified technique of cellulose fibre:

The second modification mode:

Cellulose fibre is put into container, add water in container again, then with small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier two kinds of cation modifiers, modification is carried out to cellulose fibre, after modification completes, obtain modified cellulose fibre; Described small molecule quaternary ammonium salt cation modifier is epoxy quaternary ammonium salt compound, and described high molecular quaternary cation modifier is the poly-epoxychloropropane dimethylamine of branched chain type.

Concrete modification is: cellulose fibre is put into container, add water in container again, then epoxy quaternary ammonium salt compound is first added, add NaOH after 7min, be warming up to 55 DEG C, reaction 13min, add the poly-epoxychloropropane dimethylamine of branched chain type again, add NaOH subsequently, be warming up to 80 DEG C, continue reaction; The total time of modification is 78min.

embodiment 11

The modified technique of cellulose fibre:

The second modification mode:

Cellulose fibre is put into container, add water in container again, then with small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier two kinds of cation modifiers, modification is carried out to cellulose fibre, after modification completes, obtain modified cellulose fibre; Described small molecule quaternary ammonium salt cation modifier is epoxy quaternary ammonium salt compound, and described high molecular quaternary cation modifier is the poly-epoxychloropropane dimethylamine of branched chain type.

Concrete modification is: cellulose fibre is put into container, add water in container again, then epoxy quaternary ammonium salt compound is first added, add NaOH after 6min, be warming up to 50 DEG C, reaction 15min, add the poly-epoxychloropropane dimethylamine of branched chain type again, add NaOH subsequently, be warming up to 85 DEG C, continue reaction; The total time of modification is 65min.

embodiment 12

The modified technique of cellulose fibre:

The third modification mode:

Cellulose fibre is put into container, add water in container again, then with small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier two kinds of cation modifiers, modification is carried out to cellulose fibre, after modification completes, obtain modified cellulose fibre; Described small molecule quaternary ammonium salt cation modifier is epoxy quaternary ammonium salt compound, and described high molecular quaternary cation modifier is the poly-epoxychloropropane dimethylamine of branched chain type.

Concrete modification is: cellulose fibre is put into container, add water in container again, be warming up to 75 DEG C, then add the poly-epoxychloropropane dimethylamine of branched chain type, add NaOH subsequently, reaction 25min, be cooled to 50 DEG C, add epoxy quaternary ammonium salt compound again, after 7min, add NaOH, continue reaction; The total time of modification is 80min.

embodiment 13

The modified technique of cellulose fibre:

The third modification mode:

Cellulose fibre is put into container, add water in container again, then with small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier two kinds of cation modifiers, modification is carried out to cellulose fibre, after modification completes, obtain modified cellulose fibre; Described small molecule quaternary ammonium salt cation modifier is epoxy quaternary ammonium salt compound, and described high molecular quaternary cation modifier is the poly-epoxychloropropane dimethylamine of branched chain type.

Concrete modification is: cellulose fibre is put into container, add water in container again, be warming up to 85 DEG C, then add the poly-epoxychloropropane dimethylamine of branched chain type, add NaOH subsequently, reaction 20min, be cooled to 55 DEG C, add epoxy quaternary ammonium salt compound again, after 5min, add NaOH, continue reaction; The total time of modification is 65min.

embodiment 14

The modified technique of cellulose fibre:

The third modification mode:

Cellulose fibre is put into container, add water in container again, then with small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier two kinds of cation modifiers, modification is carried out to cellulose fibre, after modification completes, obtain modified cellulose fibre; Described small molecule quaternary ammonium salt cation modifier is epoxy quaternary ammonium salt compound, and described high molecular quaternary cation modifier is the poly-epoxychloropropane dimethylamine of branched chain type.

Concrete modification is: cellulose fibre is put into container, add water in container again, be warming up to 65 DEG C, then add the poly-epoxychloropropane dimethylamine of branched chain type, add NaOH subsequently, reaction 30min, be cooled to 45 DEG C, add epoxy quaternary ammonium salt compound again, after 10min, add NaOH, continue reaction; The total time of modification is 88min.

embodiment 15

The modified technique of cellulose fibre:

The third modification mode:

Cellulose fibre is put into container, add water in container again, then with small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier two kinds of cation modifiers, modification is carried out to cellulose fibre, after modification completes, obtain modified cellulose fibre; Described small molecule quaternary ammonium salt cation modifier is epoxy quaternary ammonium salt compound, and described high molecular quaternary cation modifier is the poly-epoxychloropropane dimethylamine of branched chain type.

Concrete modification is: cellulose fibre is put into container, add water in container again, be warming up to 65 DEG C, then add the poly-epoxychloropropane dimethylamine of branched chain type, add NaOH subsequently, reaction 20min, be cooled to 55 DEG C, add epoxy quaternary ammonium salt compound again, after 5min, add NaOH, continue reaction; The total time of modification is 90min.

embodiment 16

The modifying processing step of cellulose fibre:

On the basis of embodiment 8-15, in modification:

Described programming rate is 1 DEG C/min, 1.5 DEG C/min or 2 DEG C/min, and the total time according to modification is selected.Described cooling is for drop to assigned temperature fast.

On the basis of embodiment 4-15, in modification:

Bath raio is 1:4.Bath raio is the mass ratio of cellulose fibre and water.

The ratio of the quality sum of described epoxy quaternary ammonium salt compound and the poly-epoxychloropropane dimethylamine of branched chain type and the quality of cellulose fibre is 0.02:1.

The mass ratio of described epoxy quaternary ammonium salt compound and the poly-epoxychloropropane dimethylamine of branched chain type is 3:1.

The ratio of the quality of described NaOH and the quality of modifier is 0.2:1.In the first modification mode, namely represent the quality of NaOH, with the ratio of small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier quality summation; In the second and the third modification mode, namely the quality of NaOH is represented, with the ratio of small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier quality summation, also represent the amount adding NaOH after adding small molecule quaternary ammonium salt cation modifier or high molecular quaternary cation modifier.

embodiment 17

The modifying processing step of cellulose fibre:

On the basis of embodiment 8-15, in modification:

Described programming rate is 1 DEG C/min, 1.5 DEG C/min or 2 DEG C/min, and the total time according to modification is selected.Described cooling is for drop to assigned temperature fast.

On the basis of embodiment 4-15, in modification:

Bath raio is 1:16.Bath raio is the mass ratio of cellulose fibre and water.

The ratio of the quality sum of described epoxy quaternary ammonium salt compound and the poly-epoxychloropropane dimethylamine of branched chain type and the quality of cellulose fibre is 0.2:1.

The mass ratio of described epoxy quaternary ammonium salt compound and the poly-epoxychloropropane dimethylamine of branched chain type is 4:2.

The ratio of the quality of described NaOH and the quality of modifier is 1:1.In the first modification mode, namely represent the quality of NaOH, with the ratio of small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier quality summation; In the second and the third modification mode, namely the quality of NaOH is represented, with the ratio of small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier quality summation, also represent the amount adding NaOH after adding small molecule quaternary ammonium salt cation modifier or high molecular quaternary cation modifier.

embodiment 18

The modifying processing step of cellulose fibre:

On the basis of embodiment 8-15, in modification:

Described programming rate is 1 DEG C/min, 1.5 DEG C/min or 2 DEG C/min, and the total time according to modification is selected.Described cooling is for drop to assigned temperature fast.

On the basis of embodiment 4-15, in modification:

Bath raio is 1:10.Bath raio is the mass ratio of cellulose fibre and water.

The ratio of the quality sum of described epoxy quaternary ammonium salt compound and the poly-epoxychloropropane dimethylamine of branched chain type and the quality of cellulose fibre is 0.11:1.

The mass ratio of described epoxy quaternary ammonium salt compound and the poly-epoxychloropropane dimethylamine of branched chain type is 3.5:1.5.

The ratio of the quality of described NaOH and the quality of modifier is 0.6:1.In the first modification mode, namely represent the quality of NaOH, with the ratio of small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier quality summation; In the second and the third modification mode, namely the quality of NaOH is represented, with the ratio of small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier quality summation, also represent the amount adding NaOH after adding small molecule quaternary ammonium salt cation modifier or high molecular quaternary cation modifier.

embodiment 19

The modifying processing step of cellulose fibre:

On the basis of embodiment 8-15, in modification:

Described programming rate is 1 DEG C/min, 1.5 DEG C/min or 2 DEG C/min, and the total time according to modification is selected.Described cooling is for drop to assigned temperature fast.

On the basis of embodiment 4-15, in modification:

Bath raio is 1:12.Bath raio is the mass ratio of cellulose fibre and water.

The ratio of the quality sum of described epoxy quaternary ammonium salt compound and the poly-epoxychloropropane dimethylamine of branched chain type and the quality of cellulose fibre is 0.05:1.

The mass ratio of described epoxy quaternary ammonium salt compound and the poly-epoxychloropropane dimethylamine of branched chain type is 3.2:1.8.

The ratio of the quality of described NaOH and the quality of modifier is 0.8:1.In the first modification mode, namely represent the quality of NaOH, with the ratio of small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier quality summation; In the second and the third modification mode, namely the quality of NaOH is represented, with the ratio of small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier quality summation, also represent the amount adding NaOH after adding small molecule quaternary ammonium salt cation modifier or high molecular quaternary cation modifier.

embodiment 20

The washing treatment step of cellulose fibre:

Modified cellulose fibre carries out washing process after modification completes, and modified cellulose fibre is washed to pH=6.5.

Preferably, washing process is specially: first modified cellulose fibre is carried out overflow washing 5min, then adds the acetic acid neutralization of 0.5g/l, last overflow washing 5min.

embodiment 21

The washing treatment step of cellulose fibre:

Modified cellulose fibre carries out washing process after modification completes, and modified cellulose fibre is washed to pH=8.

Preferably, washing process is specially: first modified cellulose fibre is carried out overflow washing 10min, then adds the acetic acid neutralization of 1g/l, last overflow washing 10min.

embodiment 22

The washing treatment step of cellulose fibre:

Modified cellulose fibre carries out washing process after modification completes, and modified cellulose fibre is washed to pH=7.25.

Preferably, washing process is specially: first modified cellulose fibre is carried out overflow washing 6min, then adds the acetic acid neutralization of 0.6g/l, last overflow washing 8min.

embodiment 23

The washing treatment step of cellulose fibre:

Modified cellulose fibre carries out washing process after modification completes, and modified cellulose fibre is washed to pH=7.

Preferably, washing process is specially: first modified cellulose fibre is carried out overflow washing 8min, then adds the acetic acid neutralization of 0.8g/l, last overflow washing 6min.

embodiment 24

The dyeing of cellulose fibre and post-processing step:

The present invention is in step C, the described dye liquor that adds dyes, and then heats up, and completes dyeing and refers to: at 25 DEG C, add dye liquor dye after continuing dyeing a period of time, be warming up to 60 DEG C with the speed of 1 DEG C/min after 10min, after continuing dyeing 30min, complete dyeing.

The present invention, in step C or above-mentioned staining procedure, adds the sodium carbonate of 1g/l after described intensification.

The present invention is in step C, and described dye liquor concentration is 1%, and dye liquor addition is 2% of modified cellulose fibre quality.

In step D, described washing process is specially: first overflow washes 5 minutes in the present invention, then enters whole cylinder water, carries out reverse circulation washing, until clean.

In step D, described oiling is specially in the present invention: at 40 DEG C, carry out oiling treatment 20 minutes.

Above-mentionedly oil in step, finish addition is 0.5% of dyeing, modifying cellulose fibre quality.

embodiment 25

The dyeing of cellulose fibre and post-processing step:

The present invention is in step C, the described dye liquor that adds dyes, and then heats up, and completes dyeing and refers to: at 40 DEG C, add dye liquor dye after continuing dyeing a period of time, be warming up to 80 DEG C with the speed of 2 DEG C/min after 20min, after continuing dyeing 50min, complete dyeing.

The present invention, in step C or above-mentioned staining procedure, adds the sodium carbonate of 2g/l after described intensification.

The present invention is in step C, and described dye liquor concentration is 8%, and dye liquor addition is 20% of modified cellulose fibre quality.

In step D, described washing process is specially: first overflow washes 10 minutes in the present invention, then enters whole cylinder water, carries out reverse circulation washing, until clean.

In step D, described oiling is specially in the present invention: at 50 DEG C, carry out oiling treatment 30 minutes.

Above-mentionedly oil in step, finish addition is 3% of dyeing, modifying cellulose fibre quality.

embodiment 26

The dyeing of cellulose fibre and post-processing step:

The present invention is in step C, the described dye liquor that adds dyes, and then heats up, and completes dyeing and refers to: at 30 DEG C, add dye liquor dye after continuing dyeing a period of time, be warming up to 70 DEG C with the speed of 1.5 DEG C/min after 15min, after continuing dyeing 40min, complete dyeing.

The present invention, in step C or above-mentioned staining procedure, adds the sodium carbonate of 1.5g/l after described intensification.

The present invention is in step C, and described dye liquor concentration is 4.5%, and dye liquor addition is 11% of modified cellulose fibre quality.

In step D, described washing process is specially: first overflow washes 7.5 minutes in the present invention, then enters whole cylinder water, carries out reverse circulation washing, until clean.

In step D, described oiling is specially in the present invention: at 45 DEG C, carry out oiling treatment 25 minutes.

Above-mentionedly oil in step, finish addition is 1.75% of dyeing, modifying cellulose fibre quality.

embodiment 27

The dyeing of cellulose fibre and post-processing step:

The present invention is in step C, the described dye liquor that adds dyes, and then heats up, and completes dyeing and refers to: at 36 DEG C, add dye liquor dye after continuing dyeing a period of time, be warming up to 66 DEG C with the speed of 1.8 DEG C/min after 12min, after continuing dyeing 32min, complete dyeing.

The present invention, in step C or above-mentioned staining procedure, adds the sodium carbonate of 1.1g/l after described intensification.

The present invention is in step C, and described dye liquor concentration is 6.5%, and dye liquor addition is 5.3% of modified cellulose fibre quality.

In step D, described washing process is specially: first overflow washes 8 minutes in the present invention, then enters whole cylinder water, carries out reverse circulation washing, until clean.

In step D, described oiling is specially in the present invention: at 47 DEG C, carry out oiling treatment 27 minutes.

Above-mentionedly oil in step, finish addition is 1% of dyeing, modifying cellulose fibre quality.

embodiment 28

The modified impact on the basic index of cellulose fibre of cellulose fibre:

1, spun rayon yarn's (specification: R30S/2) of making of cellulose fibre

1) openpore:

2) modified:

3) after dyeing (blueness):

2, viscose fiber monofilament (specification: 300D/1)

1) openpore:

2) modified:

3) after dyeing (rose):

3, floss silk (specification: 120D/2)

1) openpore:

2) modified:

3) after dyeing (yellow):

4, loose fine (specification: 1.5D*38mm)

1) openpore:

2) modified:

3) after dyeing (black):

Conclusion: after above table shows various cellulose CSP and dyeing, the change of its basic index is little, illustrate and adopt modified technique of the present invention, and the composite modifier selected to cellulose fibre carry out modified and dyeing after, the basic index of cellulose fibre itself does not have too large change, can keep index and its quality of cellulose fibre itself.

embodiment 29

The Color of modified cellulose fibre:

1,3RS Huang (1%)

2,3RS Huang (2%)

3,3RS Huang (3%)

4,3BSN red (1%)

5,3BSN red (2%)

6,3BSN red (3%)

7, CGF emerald green blue (1%)

8, CGF emerald green blue (2%)

9, CGF emerald green blue (3%)

10, LC-G black (1%)

11, LC-G black (2%)

12, LC-G black (3%)

Conclusion: after above table shows the dyeing of various cellulose CSP, different modification mode and standard sample contrast, and the contrast between different modification mode, can find out the depth after the dyeing of different modification mode, coloured light is partial to.As a whole, adopting the modified cellulose fibre that composite modifier of the present invention and modification mode obtain, being applicable to most of dyestuff when dyeing, Color is better, meets the requirement of industrialization large-scale production.

embodiment 30

After the modification of and coloration of modified cellulose fibre raffinate and tradition not after modification of and coloration raffinate compare:

Conclusion: the indices of modification of and coloration raffinate is better than the tradition not indices of raffinate after modification of and coloration greatly, part index number is within the scope of direct discharge standard, part index number processes a little and just can reach standard, and from the indices of raffinate after modification of and coloration, raffinate can direct reuse.

Claims (19)

1. a salt-free low alkali modification dyeing for cellulose fibre, is characterized in that: comprise following processing step:

A, cellulose CSP process

Cellulose fibre is put into container, add water in container again, then with small molecule quaternary ammonium salt cation modifier and high molecular quaternary cation modifier two kinds of cation modifiers, modification is carried out to cellulose fibre, after modification completes, obtain modified cellulose fibre; Described small molecule quaternary ammonium salt cation modifier is epoxy quaternary ammonium salt compound, and described high molecular quaternary cation modifier is the poly-epoxychloropropane dimethylamine of branched chain type;

B, washing process

The modified cellulose fibre obtained through modification in steps A is carried out washing process;

C, dyeing

Put into dyeing container by step B through the modified cellulose fibre of washing process, add dye liquor and dye, then heat up, complete dyeing after continuing dyeing a period of time, obtain dyeing, modifying cellulose fiber peacekeeping dyeing residual liquid;

D, post processing

The dyeing, modifying cellulose fibre obtained by step C with water is cleaned, and then obtains finished product through oiling, drying.

2. the salt-free low alkali modification dyeing of a kind of cellulose fibre according to claim 1, it is characterized in that: cellulose fibre selects viscose fiber filament, viscose short fiber, model, sky silk, cotton fiber, yarn, fabric that aforementioned fibers cellulose fiber is made.

3. the salt-free low alkali modification dyeing of a kind of cellulose fibre according to claim 2, is characterized in that: described yarn is cheese or reeled yarn.

4. the salt-free low alkali modification dyeing of a kind of cellulose fibre according to claim 1, it is characterized in that: in step, described modification is that cellulose fibre is put into container, add water in container again, then add the poly-epoxychloropropane dimethylamine of epoxy quaternary ammonium salt compound and branched chain type simultaneously, add NaOH after 5-10min, carry out modification; The time of modification is 40-70min, and in modification process, temperature controls as 60-90 DEG C.

5. the salt-free low alkali modification dyeing of a kind of cellulose fibre according to claim 1, it is characterized in that: in step, described modification is that cellulose fibre is put into container, then adds water in container, then epoxy quaternary ammonium salt compound is first added, add NaOH after 5-10min, be warming up to 45-55 DEG C, reaction 10-15min, add the poly-epoxychloropropane dimethylamine of branched chain type again, add NaOH subsequently, be warming up to 65-85 DEG C, continue reaction; The total time of modification is 65-90min.

6. the salt-free low alkali modification dyeing of a kind of cellulose fibre according to claim 1, it is characterized in that: in step, described modification is that cellulose fibre is put into container, then adds water in container, be warming up to 65-85 DEG C, then add the poly-epoxychloropropane dimethylamine of branched chain type, add NaOH subsequently, reaction 20-30min, be cooled to 45-55 DEG C, add epoxy quaternary ammonium salt compound again, after 5-10min, add NaOH, continue reaction; The total time of modification is 65-90min.

7. the salt-free low alkali modification dyeing of a kind of cellulose fibre according to claim 5 or 6, is characterized in that: described programming rate is 1-2 DEG C/min.

8. the salt-free low alkali modification dyeing of a kind of cellulose fibre according to claim 4,5 or 6, is characterized in that: in modification, bath raio is 1:4-1:16.

9. the salt-free low alkali modification dyeing of a kind of cellulose fibre according to claim 4,5 or 6, it is characterized in that: in modification, the ratio of the quality sum of described epoxy quaternary ammonium salt compound and the poly-epoxychloropropane dimethylamine of branched chain type and the quality of cellulose fibre is 0.02-0.2:1.

10. the salt-free low alkali modification dyeing of a kind of cellulose fibre according to claim 4,5 or 6, is characterized in that: in modification, and the mass ratio of described epoxy quaternary ammonium salt compound and the poly-epoxychloropropane dimethylamine of branched chain type is 4-3:1-2.

The salt-free low alkali modification dyeing of 11. a kind of cellulose fibres according to claim 4,5 or 6, it is characterized in that: in modification, the ratio of the quality of described NaOH and the quality of modifier is 0.2-1:1.

The salt-free low alkali modification dyeing of 12. a kind of cellulose fibres according to claim 1, is characterized in that: in stepb, described washing process is that modified cellulose fibre is washed to pH=6.5-8.

The salt-free low alkali modification dyeing of 13. a kind of cellulose fibres according to claim 1 or 12, it is characterized in that: in stepb, described washing process is specially: first modified cellulose fibre is carried out overflow washing 5-10min, add the acetic acid neutralization of 0.5-1g/l again, last overflow washing 5-10min.

The salt-free low alkali modification dyeing of 14. a kind of cellulose fibres according to claim 1, it is characterized in that: in step C, the described dye liquor that adds dyes, then heat up, complete dyeing and refer to after continuing dyeing a period of time: add dye liquor at 40 DEG C and dye being no more than, be warming up to 60-80 DEG C with the speed of 1-2 DEG C/min after 10-20min, after continuing dyeing 30-50min, complete dyeing.

The salt-free low alkali modification dyeing of 15. a kind of cellulose fibres according to claim 1 or 14, is characterized in that: the sodium carbonate adding 1-2g/l after described intensification.

The salt-free low alkali modification dyeing of 16. a kind of cellulose fibres according to claim 1, it is characterized in that: in step C, described dye liquor concentration is 1-8%, dye liquor addition is the 2-20% of modified cellulose fibre quality.

The salt-free low alkali modification dyeing of 17. a kind of cellulose fibres according to claim 1, it is characterized in that: in step D, described washing process is specially: first overflow washing 5-10 minute, then enters whole cylinder water, carry out reverse circulation washing, until clean.

The salt-free low alkali modification dyeing of 18. a kind of cellulose fibres according to claim 1, it is characterized in that: in step D, described oiling is specially: at 40-50 DEG C, carry out oiling treatment 20-30 minute.

The salt-free low alkali modification dyeing of 19. a kind of cellulose fibres according to claim 18, is characterized in that: finish addition is the 0.5-3% of dyeing, modifying cellulose fibre quality.