CN104358159B

CN104358159B - A kind of salt-free low alkali circulating dyeing process of cellulose fibre

Info

Publication number: CN104358159B
Application number: CN201410689106.7A
Authority: CN
Inventors: 廖周荣; 段太刚; 贾卫平; 何大雄; 汤伟; 黄金洪; 张海; 刘志军
Original assignee: Sichuan Yibin Huimei Line Industry Co Ltd
Current assignee: Beijing culture science and technology finance leasing Limited by Share Ltd
Priority date: 2014-11-26
Filing date: 2014-11-26
Publication date: 2016-07-13
Anticipated expiration: 2034-11-26
Also published as: CN104358159A

Abstract

The present invention relates to the salt-free low alkali circulating dyeing process of a kind of cellulose fibre, belong to dope dyeing technical field.The present invention includes cellulose CSP process, washing process and dyeing cycle step, and wherein cellulose CSP processes and adopts small molecule quaternary ammonium salt cation modifying agent and high molecular quaternary cation modifier to be modified cellulose fibre processing.The present invention adopts specific two kinds of modifying agent, play the effect of both cooperative effects, it is equipped with specific staining procedure, make cellulose fibre realize the dyeing of salt-free low alkali in dyeing, reduce and pollute, save cost, and Simplified flowsheet, reduce difficulty, modified good with Color, it is adaptable to industrialization large-scale production.Owing to dyeing residual liquid of the present invention is close to achromaticity and clarification, it is possible to recycle, continue on in the salt-free dyeing of the present invention, and owing to dyeing residual liquid is close to achromaticity and clarification, so in dyeing cycle, it is possible to the dyestuff continuing with different colours is circulated dyeing.

Description

A kind of salt-free low alkali circulating dyeing process of cellulose fibre

Technical field

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

Background technology

Traditional fibre cellulose fiber dyeing dye-uptake is typically in about 40-70%, and dye-uptake is low, and loose colour is many, in order to overcome electric charge obstacle in dyeing course, it is necessary to add substantial amounts of inorganic salt in dye liquor, to improve dye-uptake；For reaching fixation purpose, the hydroxyl on cellulose needs ionizing under strongly alkaline conditions, so the dyeing later stage, must be added to substantial amounts of soda in dye liquor.The process of inorganic salt and alkali is always up perplexing a difficult problem for industry; a large amount of inorganic salts that not only cannot reclaim but also be difficult to degrade enter rivers and lakes, and severe contamination water quality, owing to salt has significantly high permeance property; make soil property salinization of soil around, become a difficult problem very thorny in environmental conservation；Additionally, dye utilization rate is very low in traditional salt, highly basic dye liquor, and laking process generation hydrolysis etc. under highly basic, causing a large amount of wastes of dyestuff, many deep-colour fabrics are unable to reach requirement.Therefore, having remained substantial amounts of dyestuff, salt, alkali in the dyeing liquor of discharge, intractability is big, cost is high, is a difficult problem for puzzlement dyeing, is also the bottleneck of restriction dyeing development.

In order to solve the problems referred to above, the method adopted at present mainly has two kinds:

One, the direct new dye high, salt-dependent is low of exploitation.Such as the low salt dyestuff of SumifuxSupra that SUMITOMO CHEMICAL company releases, during dyeing, inorganic salt consumption is traditional 1/3-1/2；The RemazolEF low-salt reactive dyes that Hirst company produces, during dyeing make consumption be traditional method the 1/3 of inorganic salt；The CibacronLS dyestuff that Clariant Corporation DrimareneHF 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, improves fixation speed and degree of fixation by increasing active group number, and dyestuff is direct strong.But existing new dye is also unsuccessful, and this kind of dye activity and substantivity are too strong, it is difficult to control dyeing kinetics, cause level-dyeing property poor；Dyestuff consumption is big, and thus resulting in cost increases big with sewage treatment load；The color fastness to light of coloured fibre and fabric is poor；Chromatograph is incomplete, dyestuff price is high；It is only the use decreasing the consumption of inorganic salt and failing to cancel inorganic salt, it does not have fundamentally realize salt-free dyeing；And the intermediate of the low salt dyestuff of part is big to equipment corrosion, itself does not also meet environmental requirement.These drawbacks hinder the popularization and application of low salt dyestuff.

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

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

1, a chloro-s-triazine quarternary ammonium salt compound.The chloro-s-triazine active group in this type of modifying agent hydroxyl easily and on cellulose fibre reacts, and makes cationization of pulp fiber.Representative is that cotton fiber is carried out cation-modified with a chloro-s-triazine diquaternary amine modifying agent by M.N.MICHEAL etc. when using 2-chloro-2-dimethylaminoethyl hydrochlorate as catalyst.Afterwards when modified cotton fiber being dyeed with reactive dye, add zinc acetate and make color fixing agent, it is possible to improve the degree of fixation of reactive dye.For another example Chinese patent CN101747285A, the preparation method which disclosing a kind of cationic grafting agent with multi-reactive groups, this grafting agent is an a kind of chloro-s-triazine ammonium chloride derivant, 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 cationic starch cation modifier as cotton fiber, fabric dye level after modified, color fastness to light and wrinkle go back to angle and are all improved.That be made comparatively system is M.Zhang etc., and Main is, hydrolysis starch and 2-hydroxypropyl-trimethyl ammonium chloride are carried out etherification reaction in the basic conditions, prepares cationic starch, then is processed on cotton fiber by cationic starch by pressure baking technique.Modified cotton fiber is salt-free and dye when soda consumption is 10g/l, and dye-uptake and degree of fixation are all higher than traditional dyeing thing.

3, Chitosan-phospholipid complex.Chitosan is polysaccharide macromolecule that is a kind of deacetylated by chitin and that obtain, and chitin is mainly derived from shrimp, Carapax Eriocheir sinensis, the therefore abundance of chitosan.The hydroxyl differring primarily in that cellulose C-2 place between chitosan and cellulosic molecule is replaced by amino.In acid dye bath, the amino of chitosan can protonate, positively charged, such that it is able to play the effect of short dye.The research that this is done by domestic and international academia is more.Processing procedure is comparatively laborious, again with chitin modified after generally being aoxidized in advance by fiber, is first aoxidized by cotton fiber with KIO4 such as YupapornKitkulnumchai etc., then carries out reduction amination with chitosan and boration sodium.When modified cotton fiber reactive dye dye, when the consumption of dyestuff and the consumption of salt all reduce by half, degree of fixation is close with the degree of fixation of traditional dyeing.Chitosan is only dissolve in acid solution, and the coloured light of cellulosic fabrics intensity and follow-up dyed fabric is had relatively havoc by this, oxidation fabric carried out before chitin modified, equally exists breakdown strength and the problem controlling difficulty.

4, epoxy quaternary ammonium salt compound.This compounds includes the chloropropylene oxide parent derivant of the Glytac reagent containing epoxide group and Glytac reagent.Glytac reagent is owing to containing epoxide group, when cellulose fibre being modified with it, reactivity is high.But Glytac reagent is mainly used for textile printing and resin finishing by current Research Literature both domestic and external, really Glytac reagent is used for the modified little of cellulose fibre salt-free dyeing.PeterJ. the instability problem of system under the hydrolysis in order to reduce epoxide and high temperature is waited, during with Glytac agent modifier bafta, have employed and pad-cold batching process, 24h is deposited at normal temperatures afterwards after the cotton plastic wraps after this PROCESS FOR TREATMENT, wash through several times, finally soak to complete to modifiy with spirit of vinegar.Although washing after the cotton fabric dyeing process after the method process, friction and color fastness to light are basic and tradition has salt dyeing suitable, but the cycle of whole processing procedure is quite very long numerous and diverse, poor controllability, also has no industrialization and reports.Some scholars are had by the chloropropylene oxide parent derivant of Glytac reagent, cotton fiber to be modified at present.LiliWang etc. dry technique by two bath pressures and prepare cationization cotton fiber, then dye when salt-free and soda consumption is 10g/l with reactive dye.After dyeing, the degree of fixation of reactive dye is higher than the degree of fixation adopting traditional method dyeing.The chloropropylene oxide parent derivant 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 with spirit of vinegar afterwards.When cotton fiber after being processed by the method is dyeed when salt-free and soda consumption is 10g/l, dye-uptake and degree of fixation are all improved.Wang Guangming, the chloropropylene oxide parent derivant of homemade for 15ml Glytac reagent is made into 100ml aqueous solution with 2.5gNaOH by Liu Jinxi, two methods rolled are soaked by modifier treatment to cotton fiber again with two, cotton fiber after process is dried at 75 DEG C, decatize 3～5min again, afterwards by hot water wash, 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 amount of modifier is big, in order to solve this problem, there is the polyepoxides of scholar's proposition high molecular as cation modifier, it is believed that its substantivity is good, and amount of modifier can reduce.So-called direct good, refer to that modifying agent is easily by fibers adsorption.High molecular modifying agent dissolubility is not good, although fabric face can be adsorbed to, but the viscosity of modified system is big, it is difficult to ensure modified uniformity, thus causing dyeing uneven.Meanwhile, the modifying agent diffusivity difference of high molecular is difficult to penetrate into fibrous inside, and major part modifying agent is deposited in fiber surface, although dye-uptake is high, but degree of fixation is low；The cation that surface sediment is too much, during dyeing, dyestuff captivation is very big, cause dyeing speed too fast, cause upper dye uneven, " the color 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, existing utilize single modifying agent to come modified fibre or fabric, then the salt-free dyeing technique carrying out dyeing there is problems in that

Although 1 can realize salt-free dyeing, but alkali consumption is still higher, generally reach 10g/L or more than；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 at laboratory, is difficult in actual production, and staining procedure also cannot coordinate modification procedure, it is impossible to suitable in industrialization large-scale production；

3, little molecular cation modifying agent substantivity is not good, consumption is very big, and the fiber after macromolecule cation modifier modification, easily occur during salt-free dyeing that color is heavy, the disadvantage such as color flower and color fastness difference, more difficult meeting instructions for use, so cause follow-up dyeing complicated, production difficulty is big, success rate is low, more difficult equally suitable in industrialization large-scale production.

Summary of the invention

Present invention seek to address that in prior art to reduce the consumption of dyestuff, inorganic salt and alkali, after cellulose CSP is processed, then carry out the problems with existed in the technique that dyes: alkali consumption is still relatively big, and dyeing residual liquid colourity is higher, the waste water discharged is difficult, pollutes；And existing salt-free low alkali modification dyeing is not applied for industrialization large-scale production.

The present invention provides the salt-free low alkali circulating dyeing process of a kind of cellulose fibre, the dyeing of salt-free low alkali can be realized, dye dosage reduces, dyeing residual liquid colourity can be made again to reduce, such residue wastewater is easily handled, greatly reduce the pollution that discharge causes, and residual liquid can also recycle, reduce production cost；It addition, the dyeing program of the present invention is simple, execute-in-place difficulty is little, and one-time success rate and production efficiency are high, it is adaptable to industrialization large-scale production.

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

A kind of salt-free low alkali circulating dyeing process of cellulose fibre, it is characterised in that: comprise the following steps that:

A, cellulose CSP process

Being put in container by cellulose fibre, then add water in container, then be modified processing to cellulose fibre with modifier A and two kinds of quaternary ammonium salt cationic modifying agent of modifying agent B, modification obtains modified cellulose fibre after completing；Described modifier A is small molecule quaternary ammonium salt cation modifying agent, and described modifying agent B is high molecular quaternary cation modifier；

B, washing process

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

C, dyeing cycle

The modified cellulose fibre processed through washing in step B is put in the first dyeing container, dye, obtain dyeing, modifying cellulose fiber peacekeeping dyeing residual liquid, dyeing residual liquid is pumped into equipped with in the second dyeing container of modified cellulose fibre, again the dyeing, modifying cellulose fibre in the first dyeing container is washed and oiling treatment, take out；After second dyeing container has dyeed, then the dyeing, modifying cellulose fibre in the second dyeing container is washed and oiling treatment, take out；Putting into modified cellulose fibre in the first dyeing container, the dyeing residual liquid in the second dyeing container pumps in the first dyeing container；First dyeing container and the second dyeing container are circulated dyeing in the manner described above, obtain finished product after the dyeing, modifying cellulose fibre of washing process and oiling treatment is dried.

Cellulose fibre of the present invention selects viscose fiber filament, the short fibre of viscose rayon, Modal, tencel, cotton fiber, yarn that aforementioned fibers cellulose fiber is made, fabric.

Above-mentioned yarn is cheese or reeled yarn.

In step, described small molecule quaternary ammonium salt cation modifying agent is epoxy quaternary ammonium salt compound, the chloropropylene oxide parent derivant of epoxy quaternary ammonium salt, 3-acrylamide-2-hydroxypropyl-trimethyl ammonium chloride, azetidinium compound or chloro Triazine quarternary ammonium salt compound to the present invention.

In step, described high molecular quaternary cation modifier is poly-epoxychloropropane dimethylamine, Polyamide-Polyamsne-Epichlorohydrin, PAMC compounds or cationic starch to the present invention.

The present invention is in step, described modification is to be put in container by cellulose fibre, then adds water in container, is then simultaneously introduced small molecule quaternary ammonium salt cation modifying agent and high molecular quaternary cation modifier, add sodium hydroxide after 5-10min, be modified processing；The time of modification is 40-70min, and in modification process, temperature controls as 60-90 DEG C.

The present invention is in step, described modification is to put in container by cellulose fibre, add water in container again, be then initially charged small molecule quaternary ammonium salt cation modifying agent, after 5-10min, add sodium hydroxide, it is warming up to 45-55 DEG C, reaction 10-15min, adds high molecular quaternary cation modifier, is subsequently added sodium hydroxide, it is warming up to 65-85 DEG C, continues reaction；The total time of modification is 65-90min.

The present invention is in step, described modification is to put in container by cellulose fibre, add water in container again, be warming up to 65-85 DEG C, be subsequently adding high molecular quaternary cation modifier, it is subsequently added sodium hydroxide, reaction 20-30min, is cooled to 45-55 DEG C, adds small molecule quaternary ammonium salt cation modifying agent, add sodium hydroxide 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 of described small molecule quaternary ammonium salt cation modifying agent and the quality sum of high molecular quaternary cation modifier and cellulose fibre is 0.02-0.2:1.

In above-mentioned modification, described small molecule quaternary ammonium salt cation modifying agent and the mass ratio of high molecular quaternary cation modifier are 4-3:1-2.

In above-mentioned modification, the ratio of the quality of described sodium hydroxide and the quality of modifying agent is 0.2-1:1.

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

In stepb, described washing processes particularly as follows: modified cellulose fibre first carries out overflow washing 5-10min the present invention, and the acetic acid adding 0.5-1g/l neutralizes, last overflow washing 5-10min.

The present invention is in step C, and described dyeing refers to: adds dye liquor at less than 40 DEG C and dyes, is warming up to 60-80 DEG C with the speed of 1-2 DEG C/min after 10-20min, completes dyeing after continuing dyeing 30-50min.

The sodium carbonate of 1-2g/l is added after intensification of the present invention.

Dye liquor concentration of the present invention is 1-8%, and dye liquor addition is the 2-20% of modified cellulose fibre quality.

The present invention is in step C, and described washing processes particularly as follows: first overflow is washed 5-10 minute, then enters whole cylinder water, carries out reverse circulation washing, until cleaning.

The present invention is in step C, and described oils particularly as follows: carry out oiling treatment 20-30 minute at 40-50 DEG C.

Above-mentioned oiling in step, oil preparation addition is the 0.5-3% of dyeing, modifying cellulose fibre quality.

The Advantageous Effects that the present invention brings:

1, the invention provides the salt-free low alkali circulating dyeing process of a kind of cellulose fibre, solve and prior art utilizes single modifying agent to cellulose CSP, after carrying out salt-free dyeing again, chroma in waste water is relatively big, processes load still relatively big, and the problem being not suitable for industrialization large-scale production.

Present invention employs specific small molecule quaternary ammonium salt cation modifying agent and high molecular quaternary cation modifier two class modifying agent, play the effect of both cooperative effects, it is equipped with specific staining procedure, achieve the dyeing of salt-free low alkali, not needing in dye liquor during dyeing to add inorganic salt (Matrii Sulfas Exsiccatus or sodium chloride), alkali concn is the 4-10% of existing technique.When the modified cellulose fibre pH value additionally obtained after the modification of the present invention is 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%.Without inorganic salt in the dyeing residual liquid of discharge, only remaining a small amount of dyestuff and alkali, wherein colourity is very low, and difficulty and the cost of process are substantially reduced, and decreases the pollution that discharge causes.

Additionally, the present invention adopts specific modifying agent and modification procedure, and the staining procedure supporting with modification 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 existing modified technique destruction to fibre strength and coloured light, occur after dyeing that aberration, color flower, color be heavy, ring dye, light fastness, color fastness and the problem such as degree of fixation is not high, be highly suitable for industrialization large-scale production.

Finally, due to dyeing residual liquid of the present invention is close to achromaticity and clarification, it is possible to recycle, continue on in the salt-free dyeing of the present invention.The present invention adopts two dyeing containers being interconnected, and controls the flowing of dyeing residual liquid, and residual liquid need not discharge, and recycles continuously between two dyeing containers, it is achieved the salt-free low alkali circulation continuous dyeing of cellulose fibre.Owing to dyeing residual liquid is close to achromaticity and clarification, so in dyeing cycle, the dyestuff that can continue with different colours is circulated dyeing, so both reduce the cost of dyeing and dyeing product, decrease again the generation of dyeing waste-water from source, dyeing course decreases the use of dyestuff and industrial chemicals.

2, the present invention adopts small molecule quaternary ammonium salt cation modifying agent and two kinds of modifying agent of high molecular quaternary cation modifier to carry out cation-modified to cellulose fibre, according to modified demand and the demand realizing industrialization large-scale production, two kinds of modifying agent are carried out rationally composite.Two kinds of modifying agent are respectively arranged with pluses and minuses, and the composite mode of the present invention can make both have complementary advantages, and cooperates, and improve modified quality, and then improve follow-up dyeing quality.

Small molecule-modified dose of permeability is strong, so with it to cellulose CSP, it is possible to making fibrous inside cationization more fully, follow-up dye can enter fibrous inside, contaminate thoroughly and uniformly.But micromolecular substantivity is poor, facile hydrolysis, consumption are big.Macromolecule modifier substantivity is good, good stability, and consumption is few, but poor permeability, it is unfavorable for penetrating into the inside of fiber, the modified top layer being concentrated mainly on fiber.During dyeing, due to the modified Coulomb repulsion caused not of fibrous inside, dyestuff can only concentrate on the surface that cations is many.Causing the too much dyestuff of surface sediment, Shade of Dyed Textiles is not bright-coloured, fibrous inside contaminates not good, ring dye phenomenon occurs.The present invention is by small molecule-modified dose and macromolecule modifier compound use, the consumption of small molecule-modified dose and total consumption of modifying agent can be reduced greatly, and ensure that the inside and outside of cellulose fibre can obtain uniform cation modifying, follow-up dyeing is when identical dye-uptake, obtain deeper of Color, avoid that color is heavy, the problem such as color flower and color fastness difference, it is adaptable to large-scale industrial production.

3, small molecule quaternary ammonium salt cation modifying agent of the present invention is epoxy quaternary ammonium salt compound, the chloropropylene oxide parent derivant of epoxy quaternary ammonium salt, 3-acrylamide-2-hydroxypropyl-trimethyl ammonium chloride, azetidinium Chloride or chloro Triazine quarternary ammonium salt compound.The present invention selects specific small molecule quaternary ammonium salt cation modifying agent, all contain quaternary ammonium salt cationic and reactive group, can react well with the hydroxyl on cellulose fibre in the basic conditions, the lotus so that cellulose fibre becomes positively charged, improve the affinity between cellulose fibre and dyestuff and reactivity, modifying agent is easier to be 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 poly-epoxychloropropane dimethylamine, Polyamide-Polyamsne-Epichlorohydrin, PAMC compounds or cationic starch.The present invention selects specific high molecular quaternary cation modifier, wherein poly-epoxychloropropane dimethylamine, Polyamide-Polyamsne-Epichlorohydrin belong to reactive polymer class modifying agent, its reactive group can form covalent bond, the lotus so that cellulose fibre becomes positively charged with hydroxyl reaction on cellulose fibre in the basic conditions；PAMC compounds and cationic starch broadly fall into non-reacted high score subclass modifying agent, it is all anchor on cellulose fibre by physisorption, the lotus so that cellulose fibre becomes positively charged, in PAMC compounds molecular structure containing a large amount of amide groups can and fiber on form hydrogen bond action between hydroxyl, and cationic starch is close with cellulose fibre molecular structure, and starch also contains great amount of hydroxy group can with on cellulose fibre hydroxyl formed hydrogen bond action, so these high molecular quaternary cation modifiers also are able to be combined preferably with cellulose fibre, fiber is made to become positively charged lotus, improve the affinity between fiber and dyestuff, it is beneficial on dyestuff and contaminates on fiber, improve dye-uptake, decrease the consumption of dyestuff.

5, the present invention adopts three kinds of modes adding modifying agent, these three feed postition can both play two kinds of respective advantages of modifying agent, the total consumption of modifying agent is less than the single amount of modifier added in prior art, and dye-uptake is higher than the mode of single modifying agent in prior art, colourless heavy color flower, dye level is uniform.Namely the first feed postition is simultaneously introduced two kinds of modifying agent, and this modification mode processing step is simple, it is easy to operation and control；The second feed postition, for being initially charged small molecule quaternary ammonium salt cation modifying agent, adds high molecular quaternary cation modifier, and this modification mode is optimum to the modified effect within cellulose fibre, and level-dyeing property is best；The third feed postition, for being initially charged high molecular quaternary cation modifier, adds small molecule quaternary ammonium salt cation modifying agent, and this modification mode can be properly arrived at identical dye level, it is necessary to dyestuff minimum.

Specifically:

1) namely the first feed postition is simultaneously introduced two kinds of modifying agent, 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, reaching the purpose that fibrous inside and surface are all modified, this modification mode processing step is simple simultaneously, it is easy to operation and control；

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

3) the third feed postition is for being initially charged macromolecule modifier, adds small molecule-modified dose.It is initially charged macromolecule modifier mainly fiber surface to be modified, add small molecule-modified dose, small molecule-modified dose of part is diffused into fibrous inside, small molecule-modified dose of impact being subject to macromolecule modifier of part concentrates on fiber surface, fiber surface is modified, the dyestuff that the modified fibre that this mode prepares needs when obtaining identical dye level is minimum, and without the heavy phenomenon of the color pattern of single macromolecule modified existence.

6, the present invention is simultaneously introduced in the mode of two kinds of modifying agent, 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, it is possible to meet multiple modifying agent composite after modification requirement, make reaction more abundant, and ensure that modification efficiency.The present invention selects specific modification temperature, it is possible to meet multiple modifying agent composite after modification requirement, make reaction more abundant, and ensure that the less costly of modification.In general, under certain condition, modification time is long, temperature is high, modifying agent and cellulose fibre reaction are 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 the reaction that temperature reaches certain value post-modification agent and cellulose fibre is abundant, modified effect tends to constant, owing to the modifying agent of the present invention is to be formed 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 just less desirable.So modification time of selecting of the present invention and the combination of modification temperature can either ensure that two kinds of modifying agent fully react with cellulose fibre after composite, combine well, will not make again small molecule-modified dose hydrolyzed many, thus obtaining a good modified effect.

7, currently preferred the second modification mode is for being initially charged small molecule quaternary ammonium salt cation modifying agent, adds high molecular quaternary cation modifier, and adopts specific process parameter control.Little molecule class modifying agent reactivity is big, and the required activation energy of reaction is low, just has higher reaction rate at a lower reaction temperature, and the more high hydrolysis rate of temperature is also more big, so reaction should choose relatively low temperature；And high score subclass modifying agent is relatively larger due to molecular structure, the required activation energy of reaction is of a relatively high, can obtain higher diffusion, seepage velocity and reaction rate at relatively high temperatures, and not facile hydrolysis, so reaction can carry out at relatively high temperatures.

The process of the second way is to be initially charged small molecule-modified dose, allow it be adsorbed onto on cellulose fibre fully and spread to fibrous inside, after 5-10min, add sodium hydroxide, it is warming up to 45-55 DEG C, reaction 10-15min, at this moment it is adsorbed on fiber surface and internal modifying agent reacts in the basic conditions with fiber, form covalent bond, small molecule-modified dose owing to having carried out dissolving in preadsorption now water compares less, such that it is able to 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 modifying agent is combined with fiber.Then adding macromolecule modifier, be subsequently added sodium hydroxide, be warming up to 65-85 DEG C, continuing reaction to modified total time is 65-90min, and the agent of making property and fiber fully react.

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 little molecule is substantially combined with fiber, macromolecule cation modifying agent dissolves at a higher temperature and spreads or is conducive to the combination with fiber with fiber-reactive, this ensure that two kinds of modifying agent can react abundant with cellulose fibre, improve modified quality, reduce modified cost.

8, the third modification mode currently preferred is for being initially charged high molecular quaternary cation modifier, adds small molecule quaternary ammonium salt cation modifying agent, and adopts specific process parameter control.Little molecule class modifying agent reactivity is big, and the required activation energy of reaction is low, just has higher reaction rate at a lower reaction temperature, and the more high hydrolysis rate of temperature is also more big, so reacting temperature required relatively low；And high score subclass modifying agent is relatively larger due to molecular structure, not easily diffusion and infiltration, the required activation energy of reaction is of a relatively high, and not facile hydrolysis, can obtain better reaction effect at relatively high temperatures, so reaction can carry out at relatively high temperatures.

The process of the third mode is first to be warming up to 65-85 DEG C, it is subsequently adding macromolecule modifier, it is subsequently added sodium hydroxide, reaction 20-30min, fast cooling is to 45-55 DEG C, adding small molecule quaternary ammonium salt cation modifying agent, add sodium hydroxide after 5-10min, continuing reaction to modified 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 adding small molecule-modified dose 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, it is ensured that macromolecule and the combination of fiber, this ensure that two kinds of modifying agent can react abundant with cellulose fibre, improve modified quality, reduce modified cost.

9, currently preferred, in modification, programming rate is 1-2 DEG C/min.Select this velocity interval, it is possible to reduce modified-reaction speed, make modification more uniform, so it is also possible that modified cellulose fibre in follow-up dyeing on contaminate more uniform.Furthermore it is possible to suppress hydrolysis to a certain extent, improve the effective rate of utilization of modifying agent.

10, the 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, ensure that the cost of the modified effect of the best and the best within the scope of this, reduces the difficulty of modification, improve the success rate of modification.

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

12, the mass ratio of currently preferred control small molecule quaternary ammonium salt cation modifying agent and high molecular quaternary cation modifier is 4-3:1-2.

First, the present invention controls the amount of small molecule-modified dose and is consistently higher than the amount of macromolecule modifier.Because the permeability of small molecule-modified dose is better, modified meeting is more thorough, and namely small molecule-modified dose is modified mainly for fibrous inside, and aequum is bigger.The substantivity of macromolecule modifier is good, and chemical stability is good, modifiies mainly for fiber surface and top layer, and aequum is less.

Secondly, the present invention controls again the concrete proportion of two kinds of amount of modifier, has thus 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 modifying agent.With currently preferred ratio carry out composite after, reach same dye level, required amount of modifier is less, and dyestuff addition also declines therewith, greatly reduces production cost.And follow-up dyeing is evenly, color is more bright-coloured, it is also possible to effectively prevent from modified just concentrating on fiber surface, occur during dyeing dye not thoroughly, the generation of the problems such as heavy, the color fastness difference of color flower (dyeing uneven), color.

13, the addition of currently preferred sodium hydroxide is 0.2-1 times of modifying agent.In the modified-reaction system of the present invention, it is necessary to add sodium hydroxide, making reaction environment is alkalescence, additionally sodium hydroxide makes cellulose fibre expansion modifiers be easier to permeate to fibrous inside, modified more abundant, cellulose cation degree is higher, and the dye-uptake of follow-up dyeing is also just higher.But the addition of sodium hydroxide too much can cause follow-up dyeing time dye uneven.The present invention first solves modified uneven problem, have employed specific addition amount of sodium hydroxide, by modified-reaction speed controlling a to optimum range, makes modified more uniform, and then makes follow-up dyeing more uniform.

14, modified cellulose fibre is washed and pickling processes by the present invention, is washed till by modified cellulose fibre neutral to alkalescence, is conducive to follow-up dyeing.Currently preferred washing processing mode and washing process the modifying agent wash clean that technological parameter can effectively will not be combined with fiber, it is prevented that modifying agent is present in equipment with free state, it is to avoid dyestuff flocculates.

15, currently preferred, described addition dye liquor dyes, and then heats up, and completes dyeing and refers to after continuing dyeing a period of time: adding dye liquor at less than 40 DEG C dyes, it is warming up to 60-80 DEG C with the speed of 1-2 DEG C/min after 10-20min, after continuing dyeing 30-50min, completes dyeing.Above-mentioned concrete staining procedure matches with aforementioned modified step, simplifies dyeing step, and dyeing time is short, and efficiency is high, and technological operation is simple, uses some sensitive colors to ensure that when dyeing and even improves dyeing quality.Add dye liquors less than 40 DEG C and be possible to prevent under the high temperature conditions dyestuff to contaminate too fast, cause color flower；Controlling programming rate is 1-2 DEG C/min, it is possible to ensureing under each thermograde, the every aspect cellulose fibre in cylinder is heated evenly, and makes dyestuff upper uniformly to contaminate, not easily color flower.

16, currently preferred, add the sodium carbonate of 1-2g/l after step C heats up.Due to aforesaid modification procedure, now only with the sodium carbonate adding trace, production cost can be reduced, pollution can be reduced again.It addition, the above-mentioned weight range that is preferably added can be consolidated under stable alkali condition, 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 is prevented from dyeization, and controls production cost simultaneously.

18, the present invention is in step D, and the described dyeing, modifying cellulose fibre obtained by step C with water cleans particularly as follows: first overflow is washed 5-10 minute, then enters whole cylinder water, carries out reverse circulation washing, until cleaning.Above-mentioned concrete washing processes step quickly can gradually become neutral by alkalescence, and can be washed away by a small amount of loose colour simultaneously.

Detailed description of the invention

Embodiment 1

Cellulose dyeing technique:

The salt-free low alkali circulating dyeing process of a kind of cellulose fibre, comprises the following steps that:

A, cellulose CSP process

B, washing process

C, dyeing cycle

Above-mentioned technique is the dyeing of the present invention, and wherein step A obtains pH value when being 6.5-8.5, and Zeta electrode potential value is the modified cellulose fibre of-10～30mV.Owing to 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 big, is mainly adsorbed on fiber surface, it is more difficult to spread to fibrous inside.But, small molecule quaternary ammonium salt cation modifying agent substantivity is poor, it is easy to hydrolysis.The present invention is by two kinds of quaternary ammonium salt cationic modifying agent compound uses, cellulose fibre is modified, work in coordination, each play while its advantage, play cooperative effect effect so that cation modifying better effects if, modified more uniform, and simplify modification procedure, it is suitable for industrialization large-scale production.Being equipped with specific staining procedure and post-processing step subsequently further, it is possible to shown completely in dyeing course by modified effect, its dyeing quality improves, and staining procedure is simple to operation, and dyeing cost reduces, it is adaptable to industrialization large-scale production.Owing to dyeing residual liquid is close to achromaticity and clarification, so being circulated dyeing, and the dyestuff of different colours can be used continuously.

Embodiment 2

Cellulose dyeing technique:

A, cellulose CSP process

B, washing process

C, dyeing cycle

The dyeing of the present invention is applicable to the cellulose fibre of all kinds, also includes 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

Cellulose dyeing technique:

A, cellulose CSP process

B, washing process

C, dyeing cycle

Wherein small molecule quaternary ammonium salt cation modifying agent selects epoxy quaternary ammonium salt compound, the chloropropylene oxide parent derivant of epoxy quaternary ammonium salt, 3-acrylamide-2-hydroxypropyl-trimethyl ammonium chloride, azetidinium Chloride or chloro Triazine quarternary ammonium salt compound.

Wherein high molecular quaternary cation modifier selects poly-epoxychloropropane dimethylamine, Polyamide-Polyamsne-Epichlorohydrin, PAMC compounds or cationic starch.

In the dyeing of cellulose fibre of the present invention, the composite modifier of modification procedure is the combination of any one small molecule quaternary ammonium salt cation modifying agent above-mentioned and any one high molecular quaternary cation modifier.

Embodiment 4

Cellulose dyeing technique:

A, cellulose CSP process

Cellulose fibre is put in container, add water in container again, then being modified processing to cellulose fibre with small molecule quaternary ammonium salt cation modifying agent and two kinds of cation modifiers of high molecular quaternary cation modifier, modification obtains modified cellulose fibre after completing；The described chloropropylene oxide parent derivant that small molecule quaternary ammonium salt cation modifying agent is epoxy quaternary ammonium salt, the described poly-epoxychloropropane dimethylamine that high molecular quaternary cation modifier is backbone chain type；

B, washing process

C, dyeing cycle

Above-mentioned technique is the dyeing of the present invention, and wherein step A obtains the modified cellulose fibre of nitrogen content 0.16-0.38%, and this fiber is when pH value is 6.5-8.5, and Zeta electrode potential value is 5-26mV.

Embodiment 5

Cellulose dyeing technique:

A, cellulose CSP process

Cellulose fibre is put in container, add water in container again, then being modified processing to cellulose fibre with small molecule quaternary ammonium salt cation modifying agent and two kinds of cation modifiers of high molecular quaternary cation modifier, modification obtains modified cellulose fibre after completing；Described small molecule quaternary ammonium salt cation modifying agent is epoxy quaternary ammonium salt compound, the described poly-epoxychloropropane dimethylamine that high molecular quaternary cation modifier is branched chain type；

B, washing process

C, dyeing cycle

Above-mentioned technique is the dyeing of the present invention, and wherein step 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.

Embodiment 6

Cellulose dyeing technique:

A, cellulose CSP process

Cellulose fibre is put in container, add water in container again, then being modified processing to cellulose fibre with small molecule quaternary ammonium salt cation modifying agent and two kinds of cation modifiers of high molecular quaternary cation modifier, modification obtains modified cellulose fibre after completing；Described small molecule quaternary ammonium salt cation modifying agent is azetidinium compound, and described high molecular quaternary cation modifier is Polyamide-Polyamsne-Epichlorohydrin；

B, washing process

C, dyeing cycle

Above-mentioned technique is the dyeing of the present invention, and wherein step A obtains pH value when being 6.5-8.5, and Zeta electrode potential value is the modified cellulose fibre of 0-20mV.

Embodiment 7

Cellulose dyeing technique:

A, cellulose CSP process

Cellulose fibre is put in container, add water in container again, then being modified processing to cellulose fibre with small molecule quaternary ammonium salt cation modifying agent and two kinds of cation modifiers of high molecular quaternary cation modifier, modification obtains modified cellulose fibre after completing；Described small molecule quaternary ammonium salt cation modifying agent is chloro Triazine quarternary ammonium salt compound, and described high molecular quaternary cation modifier is poly-epoxychloropropane dimethylamine；

B, washing process

C, dyeing cycle

Above-mentioned technique is the dyeing of the present invention, and wherein step A obtains pH value when being 6.5-8.5, and Zeta electrode potential value is the modified cellulose fibre of 0-15mV.

Embodiment 8

Cellulose dyeing technique:

A, cellulose CSP process

Cellulose fibre is put in container, add water in container again, then being modified processing to cellulose fibre with small molecule quaternary ammonium salt cation modifying agent and two kinds of cation modifiers of high molecular quaternary cation modifier, modification obtains modified cellulose fibre after completing；Described small molecule quaternary ammonium salt cation modifying agent is epoxy quaternary ammonium salt compound, and described high molecular quaternary cation modifier is cationic starch；

B, washing process

C, dyeing cycle

Embodiment 9

Cellulose dyeing technique:

A, cellulose CSP process

Cellulose fibre is put in container, add water in container again, then being modified processing to cellulose fibre with small molecule quaternary ammonium salt cation modifying agent and two kinds of cation modifiers of high molecular quaternary cation modifier, modification obtains modified cellulose fibre after completing；Described small molecule quaternary ammonium salt cation modifying agent is 3-acrylamide-2-hydroxypropyl-trimethyl ammonium chloride, and described high molecular quaternary cation modifier is Polyamide-Polyamsne-Epichlorohydrin；

B, washing process

C, dyeing cycle

Above-mentioned technique is the dyeing of the present invention, and wherein step A obtains pH value when being 6.5-8.5, and Zeta electrode potential value is the modified cellulose fibre of-5～15mV.

Embodiment 10

Cellulose dyeing technique:

A, cellulose CSP process

Cellulose fibre is put in container, add water in container again, then being modified processing to cellulose fibre with small molecule quaternary ammonium salt cation modifying agent and two kinds of cation modifiers of high molecular quaternary cation modifier, modification obtains modified cellulose fibre after completing；Described small molecule quaternary ammonium salt cation modifying agent is 3-acrylamide-2-hydroxypropyl-trimethyl ammonium chloride, and described high molecular quaternary cation modifier is PAMC compounds；

B, washing process

C, dyeing cycle

Above-mentioned technique is the dyeing of the present invention, and wherein step A obtains pH value when being 6.5-8.5, and Zeta electrode potential value is the modified cellulose fibre of-8～5mV.

Embodiment 11

Cellulose dyeing technique:

A, cellulose CSP process

Cellulose fibre is put in container, add water in container again, then being modified processing to cellulose fibre with small molecule quaternary ammonium salt cation modifying agent and two kinds of cation modifiers of high molecular quaternary cation modifier, modification obtains modified cellulose fibre after completing；The described chloropropylene oxide parent derivant that small molecule quaternary ammonium salt cation modifying agent is epoxy quaternary ammonium salt, described high molecular quaternary cation modifier is cationic starch；

B, washing process

C, dyeing cycle

Embodiment 12

Cellulose dyeing technique:

A, cellulose CSP process

Cellulose fibre is put in container, add water in container again, then being modified processing to cellulose fibre with small molecule quaternary ammonium salt cation modifying agent and two kinds of cation modifiers of high molecular quaternary cation modifier, modification obtains modified cellulose fibre after completing；Described small molecule quaternary ammonium salt cation modifying agent is epoxy quaternary ammonium salt compound, and described high molecular quaternary cation modifier is PAMC compounds；

B, washing process

C, dyeing cycle

Above-mentioned technique is the dyeing of the present invention, and wherein step A obtains pH value when being 6.5-8.5, and Zeta electrode potential value is the modified cellulose fibre of 0-25mV.

Embodiment 13

The modifier A of the present invention is small molecule quaternary ammonium salt cation modifying agent: epoxy quaternary ammonium salt compound, the chloropropylene oxide parent derivant of epoxy quaternary ammonium salt, 3-acrylamide-2-hydroxypropyl-trimethyl ammonium chloride, azetidinium compound or chloro Triazine quarternary ammonium salt compound；

The modifying agent B of the present invention is high molecular quaternary cation modifier: poly-epoxychloropropane dimethylamine, Polyamide-Polyamsne-Epichlorohydrin, PAMC compounds or cationic starch.

Epoxy quaternary ammonium salt compound:

The chloropropylene oxide parent derivant of epoxy quaternary ammonium salt:

3-acrylamide-2-hydroxypropyl-trimethyl ammonium chloride:

Azetidinium compound:

Chloro Triazine quarternary ammonium salt compound:

Poly-epoxychloropropane dimethylamine:

1) backbone chain type

2) branched chain type

Polyamide-Polyamsne-Epichlorohydrin:

PAMC compounds:

Cationic starch:

Embodiment 14

The modified technique of cellulose fibre:

The first modification mode:

Being put in container by cellulose fibre, then add water in container, then be modified processing to cellulose fibre with modifier A and two kinds of quaternary ammonium salt cationic modifying agent of modifying agent B, modification obtains modified cellulose fibre after completing；Described modifier A is small molecule quaternary ammonium salt cation modifying agent, and described modifying agent B is high molecular quaternary cation modifier.

Concrete modification is: put in container by cellulose fibre, then adds water in container, is then simultaneously introduced small molecule quaternary ammonium salt cation modifying agent and high molecular quaternary cation modifier, adds sodium hydroxide after 10min, is modified processing；The time of modification is 40min, and in modification process, temperature controls is 90 DEG C.

Embodiment 15

The modifying processing step of cellulose fibre:

The first modification mode:

Concrete modification is: put in container by cellulose fibre, then adds water in container, is then simultaneously introduced small molecule quaternary ammonium salt cation modifying agent and high molecular quaternary cation modifier, adds sodium hydroxide after 5min, is modified processing；The time of modification is 70min, and in modification process, temperature controls is 60 DEG C.

Embodiment 16

The modifying processing step of cellulose fibre:

The first modification mode:

Concrete modification is: put in container by cellulose fibre, then adds water in container, is then simultaneously introduced small molecule quaternary ammonium salt cation modifying agent and high molecular quaternary cation modifier, adds sodium hydroxide after 8min, is modified processing；The time of modification is 60min, and in modification process, temperature controls is 70 DEG C.

Embodiment 17

The modifying processing step of cellulose fibre:

The first modification mode:

Concrete modification is: put in container by cellulose fibre, then adds water in container, is then simultaneously introduced small molecule quaternary ammonium salt cation modifying agent and high molecular quaternary cation modifier, adds sodium hydroxide after 5min, is modified processing；The time of modification is 87min, and in modification process, temperature controls is 62 DEG C.

Embodiment 18

The modifying processing step of cellulose fibre:

The second modification mode:

Concrete modification is: put into by cellulose fibre in container, add water in container again, then small molecule quaternary ammonium salt cation modifying agent it is initially charged, add sodium hydroxide after 10min, be warming up to 50 DEG C, react 15min, add high molecular quaternary cation modifier, it is subsequently added sodium hydroxide, is warming up to 75 DEG C, continue reaction；The total time of modification is 80min.

Embodiment 19

The modifying processing step of cellulose fibre:

The second modification mode:

Concrete modification is: put into by cellulose fibre in container, add water in container again, then small molecule quaternary ammonium salt cation modifying agent it is initially charged, add sodium hydroxide after 5min, be warming up to 45 DEG C, react 10min, add high molecular quaternary cation modifier, it is subsequently added sodium hydroxide, is warming up to 65 DEG C, continue reaction；The total time of modification is 90min.

Embodiment 20

The modifying processing step of cellulose fibre:

The second modification mode:

Concrete modification is: put into by cellulose fibre in container, add water in container again, then small molecule quaternary ammonium salt cation modifying agent it is initially charged, add sodium hydroxide after 7min, be warming up to 55 DEG C, react 13min, add high molecular quaternary cation modifier, it is subsequently added sodium hydroxide, is warming up to 80 DEG C, continue reaction；The total time of modification is 78min.

Embodiment 21

The modifying processing step of cellulose fibre:

The second modification mode:

Concrete modification is: put into by cellulose fibre in container, add water in container again, then small molecule quaternary ammonium salt cation modifying agent it is initially charged, add sodium hydroxide after 6min, be warming up to 50 DEG C, react 15min, add high molecular quaternary cation modifier, it is subsequently added sodium hydroxide, is warming up to 85 DEG C, continue reaction；The total time of modification is 65min.

Embodiment 22

The modifying processing step of cellulose fibre:

The third modification mode:

Concrete modification is: put into by cellulose fibre in container, add water in container again, it is warming up to 75 DEG C, it is subsequently adding high molecular quaternary cation modifier, is subsequently added sodium hydroxide, react 25min, it is cooled to 50 DEG C, add small molecule quaternary ammonium salt cation modifying agent, add sodium hydroxide after 7min, continue reaction；The total time of modification is 80min.

Embodiment 23

The modifying processing step of cellulose fibre:

The third modification mode:

Concrete modification is: put into by cellulose fibre in container, add water in container again, it is warming up to 85 DEG C, it is subsequently adding high molecular quaternary cation modifier, is subsequently added sodium hydroxide, react 20min, it is cooled to 55 DEG C, add small molecule quaternary ammonium salt cation modifying agent, add sodium hydroxide after 5min, continue reaction；The total time of modification is 65min.

Embodiment 24

The modifying processing step of cellulose fibre:

The third modification mode:

Concrete modification is: put into by cellulose fibre in container, add water in container again, it is warming up to 65 DEG C, it is subsequently adding high molecular quaternary cation modifier, is subsequently added sodium hydroxide, react 30min, it is cooled to 45 DEG C, add small molecule quaternary ammonium salt cation modifying agent, add sodium hydroxide after 10min, continue reaction；The total time of modification is 88min.

Embodiment 25

The modifying processing step of cellulose fibre:

The third modification mode:

Concrete modification is: put into by cellulose fibre in container, add water in container again, it is warming up to 65 DEG C, it is subsequently adding high molecular quaternary cation modifier, is subsequently added sodium hydroxide, react 20min, it is cooled to 55 DEG C, add small molecule quaternary ammonium salt cation modifying agent, add sodium hydroxide after 5min, continue reaction；The total time of modification is 90min.

Embodiment 26

The modifying processing step of cellulose fibre:

On the basis of embodiment 18-25, in modification:

Described programming rate is 1 DEG C/min, 1.5 DEG C/min or 2 DEG C/min, selects according to the total time of modification.Described cooling is for quickly dropping to assigned temperature.

On the basis of embodiment 14-25, in modification:

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

The ratio of the quality of described small molecule quaternary ammonium salt cation modifying agent and the quality sum of high molecular quaternary cation modifier and cellulose fibre is 0.02:1.

Described small molecule quaternary ammonium salt cation modifying agent and the mass ratio of high molecular quaternary cation modifier are 3:1.

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

Embodiment 27

The modifying processing step of cellulose fibre:

On the basis of embodiment 18-25, in modification:

On the basis of embodiment 14-25, in modification:

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

The ratio of the quality of described small molecule quaternary ammonium salt cation modifying agent and the quality sum of high molecular quaternary cation modifier and cellulose fibre is 0.2:1.

Described small molecule quaternary ammonium salt cation modifying agent and the mass ratio of high molecular quaternary cation modifier are 4:2.

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

Embodiment 28

The modifying processing step of cellulose fibre:

On the basis of embodiment 18-25, in modification:

On the basis of embodiment 14-25, in modification:

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

The ratio of the quality of described small molecule quaternary ammonium salt cation modifying agent and the quality sum of high molecular quaternary cation modifier and cellulose fibre is 0.11:1.

Described small molecule quaternary ammonium salt cation modifying agent and the mass ratio of high molecular quaternary cation modifier are 3.5:1.5.

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

Embodiment 29

The modifying processing step of cellulose fibre:

On the basis of embodiment 18-25, in modification:

On the basis of embodiment 14-25, in modification:

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

The ratio of the quality of described small molecule quaternary ammonium salt cation modifying agent and the quality sum of high molecular quaternary cation modifier and cellulose fibre is 0.05:1.

Described small molecule quaternary ammonium salt cation modifying agent and the mass ratio of high molecular quaternary cation modifier are 3.2:1.8.

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

Embodiment 30

The washing of cellulose fibre processes step:

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

Preferably, washing processes particularly as follows: modified cellulose fibre first carries out overflow washing 5min, and the acetic acid adding 0.5g/l neutralizes, last overflow washing 5min.

Embodiment 31

The washing of cellulose fibre processes step:

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

Preferably, washing processes particularly as follows: modified cellulose fibre first carries out overflow washing 10min, and the acetic acid adding 1g/l neutralizes, last overflow washing 10min.

Embodiment 32

The washing of cellulose fibre processes step:

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

Preferably, washing processes particularly as follows: modified cellulose fibre first carries out overflow washing 6min, and the acetic acid adding 0.6g/l neutralizes, last overflow washing 8min.

Embodiment 33

The washing of cellulose fibre processes step:

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

Preferably, washing processes particularly as follows: modified cellulose fibre first carries out overflow washing 8min, and the acetic acid adding 0.8g/l neutralizes, last overflow washing 6min.

Embodiment 34

The dyeing of cellulose fibre and post-processing step:

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

The sodium carbonate of 1g/l is added after intensification of the present invention.

Dye liquor concentration of the present invention is 1%, and dye liquor addition is the 2% of modified cellulose fibre quality.

The present invention is in step C, and described washing processes particularly as follows: first overflow is washed 5 minutes, then enters whole cylinder water, carries out reverse circulation washing, until cleaning.

The present invention is in step C, and described oils particularly as follows: carry out oiling treatment at 40 DEG C 20 minutes.

Above-mentioned oiling in step, oil preparation addition is the 0.5% of dyeing, modifying cellulose fibre quality.

Embodiment 35

The dyeing of cellulose fibre and post-processing step:

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

The sodium carbonate of 2g/l is added after intensification of the present invention.

Dye liquor concentration of the present invention is 8%, and dye liquor addition is the 20% of modified cellulose fibre quality.

The present invention is in step C, and described washing processes particularly as follows: first overflow is washed 10 minutes, then enters whole cylinder water, carries out reverse circulation washing, until cleaning.

The present invention is in step C, and described oils particularly as follows: carry out oiling treatment at 50 DEG C 30 minutes.

Above-mentioned oiling in step, oil preparation addition is the 3% of dyeing, modifying cellulose fibre quality.

Embodiment 36

The dyeing of cellulose fibre and post-processing step:

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

The sodium carbonate of 1.5g/l is added after intensification of the present invention.

Dye liquor concentration of the present invention is 4.5%, and dye liquor addition is the 11% of modified cellulose fibre quality.

The present invention is in step C, and described washing processes particularly as follows: first overflow is washed 7.5 minutes, then enters whole cylinder water, carries out reverse circulation washing, until cleaning.

The present invention is in step C, and described oils particularly as follows: carry out oiling treatment at 45 DEG C 25 minutes.

Above-mentioned oiling in step, oil preparation addition is the 1.75% of dyeing, modifying cellulose fibre quality.

Embodiment 37

The dyeing of cellulose fibre and post-processing step:

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

The sodium carbonate of 1.1g/l is added after intensification of the present invention.

Dye liquor concentration of the present invention is 6.5%, and dye liquor addition is the 5.3% of modified cellulose fibre quality.

The present invention is in step C, and described washing processes particularly as follows: first overflow is washed 8 minutes, then enters whole cylinder water, carries out reverse circulation washing, until cleaning.

The present invention is in step C, and described oils particularly as follows: carry out oiling treatment at 47 DEG C 27 minutes.

Above-mentioned oiling in step, oil preparation addition is the 1% of dyeing, modifying cellulose fibre quality.

Embodiment 38

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

1, the spun rayon yarn (specification: R30S/2) that cellulose fibre is made

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, dissipate 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 to adopt modified technique of the present invention, and cellulose fibre is modified afterwards and after dyeing by the composite modifier selected, the basic index of cellulose fibre itself does not have too big change, it is possible to keep index and its quality of cellulose fibre itself.

Embodiment 39

The Color of modified cellulose fibre:

1,3RS yellow (1%)

2,3RS yellow (2%)

3,3RS yellow (3%)

4,3BSN red (1%)

5,3BSN red (2%)

6,3BSN red (3%)

7, CGF kingfisher blue (1%)

8, CGF kingfisher blue (2%)

9, CGF kingfisher 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, it can be seen that the depth after different modification mode dyeing, coloured light is partial to.As a whole, the modified cellulose fibre that the composite modifier of the employing present invention and modification mode obtain, it is applicable to most of dyestuffs when dyeing, Color is better, meets the requirement of industrialization large-scale production.

Embodiment 40

After the modification of and coloration of modified cellulose fibre, after residual liquid and tradition not modification of and coloration, residual liquid compares:

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

Claims

1. the salt-free low alkali circulating dyeing process of a cellulose fibre, it is characterised in that: comprise the following steps that:

A, cellulose CSP process

B, washing process

C, dyeing cycle

2. the salt-free low alkali circulating dyeing process of a kind of cellulose fibre according to claim 1, it is characterized in that: in step, described small molecule quaternary ammonium salt cation modifying agent is epoxy quaternary ammonium salt compound, the chloropropylene oxide parent derivant of epoxy quaternary ammonium salt, 3-acrylamide-2-hydroxypropyl-trimethyl ammonium chloride, azetidinium compound or chloro Triazine quarternary ammonium salt compound.

3. the salt-free low alkali circulating dyeing process of a kind of cellulose fibre according to claim 1, it is characterized in that: in step, described high molecular quaternary cation modifier is poly-epoxychloropropane dimethylamine, Polyamide-Polyamsne-Epichlorohydrin, PAMC compounds or cationic starch.

4. the salt-free low alkali circulating dyeing process of a kind of cellulose fibre according to claim 1, it is characterized in that: in step, described modification is to put in container by cellulose fibre, add water in container again, then small molecule quaternary ammonium salt cation modifying agent and high molecular quaternary cation modifier it are simultaneously introduced, add sodium hydroxide after 5-10min, be modified processing；The time of modification is 40-70min, and in modification process, temperature controls as 60-90 DEG C.

5. the salt-free low alkali circulating dyeing process of a kind of cellulose fibre according to claim 1, it is characterized in that: in step, described modification is to be put in container by cellulose fibre, then adds water in container, then small molecule quaternary ammonium salt cation modifying agent it is initially charged, add sodium hydroxide after 5-10min, be warming up to 45-55 DEG C, react 10-15min, add high molecular quaternary cation modifier, it is subsequently added sodium hydroxide, is warming up to 65-85 DEG C, continue reaction；The total time of modification is 65-90min.

6. the salt-free low alkali circulating dyeing process of a kind of cellulose fibre according to claim 1, it is characterized in that: in step, described modification is to be put in container by cellulose fibre, then adds water in container, it is warming up to 65-85 DEG C, it is subsequently adding high molecular quaternary cation modifier, is subsequently added sodium hydroxide, react 20-30min, it is cooled to 45-55 DEG C, add small molecule quaternary ammonium salt cation modifying agent, add sodium hydroxide after 5-10min, continue reaction；The total time of modification is 65-90min.

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

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

9. the salt-free low alkali circulating dyeing process 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 of described small molecule quaternary ammonium salt cation modifying agent and the quality sum of high molecular quaternary cation modifier and cellulose fibre is 0.02-0.2:1.

10. the salt-free low alkali circulating dyeing process of a kind of cellulose fibre according to claim 4,5 or 6, it is characterized in that: in modification, described small molecule quaternary ammonium salt cation modifying agent and the mass ratio of high molecular quaternary cation modifier are 4-3:1-2.

11. the salt-free low alkali circulating dyeing process of a kind of cellulose fibre according to claim 4,5 or 6, it is characterised in that: in modification, the ratio of the quality of described sodium hydroxide and the quality of modifying agent is 0.2-1:1.

12. the salt-free low alkali circulating dyeing process of a kind of cellulose fibre according to claim 1, it is characterised in that: in stepb, it is that modified cellulose fibre is washed to pH=6.5-8 that described washing processes.

13. the salt-free low alkali circulating dyeing process of a kind of cellulose fibre according to claim 1 or 12, it is characterized in that: in stepb, described washing processes particularly as follows: modified cellulose fibre first carries out overflow washing 5-10min, the acetic acid adding 0.5-1g/l neutralizes, last overflow washing 5-10min.

14. the salt-free low alkali circulating dyeing process of a kind of cellulose fibre according to claim 1, it is characterized in that: in step C, described dyeing refers to: adds dye liquor at less than 40 DEG C and dyes, it is warming up to 60-80 DEG C with the speed of 1-2 DEG C/min after 10-20min, after continuing dyeing 30-50min, completes dyeing.

15. the salt-free low alkali circulating dyeing process of a kind of cellulose fibre according to claim 14, it is characterised in that: add the sodium carbonate of 1-2g/l after described intensification.

16. the salt-free low alkali circulating dyeing process of a kind of cellulose fibre according to claim 15, it is characterised in that: in step C, described dye liquor concentration is 1-8%, and dye liquor addition is the 2-20% of modified cellulose fibre quality.

17. the salt-free low alkali circulating dyeing process of a kind of cellulose fibre according to claim 1, it is characterised in that: in step C, described washing processes particularly as follows: first overflow is washed 5-10 minute, then enters whole cylinder water, carries out reverse circulation washing, until cleaning.

18. the salt-free low alkali circulating dyeing process of a kind of cellulose fibre according to claim 1, it is characterised in that: in step C, described oils particularly as follows: carry out oiling treatment 20-30 minute at 40-50 DEG C.

19. the salt-free low alkali circulating dyeing process of a kind of cellulose fibre according to claim 18, it is characterised in that: oil preparation addition is the 0.5-3% of dyeing, modifying cellulose fibre quality.