CN104831387A - Preparation process of extinction high-strength low-elongation viscose fiber - Google Patents
Preparation process of extinction high-strength low-elongation viscose fiber Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 50
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- 239000003513 alkali Substances 0.000 claims abstract description 154
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- 238000009987 spinning Methods 0.000 claims abstract description 79
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 54
- 238000000227 grinding Methods 0.000 claims abstract description 43
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- 238000006116 polymerization reaction Methods 0.000 claims abstract description 29
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- 238000004898 kneading Methods 0.000 claims abstract description 14
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- 238000005516 engineering process Methods 0.000 claims description 57
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- 238000004090 dissolution Methods 0.000 claims description 19
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- 210000000170 cell membrane Anatomy 0.000 description 3
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 3
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- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation process of delustering high-strength low-elongation viscose fibers, which comprises the steps of dipping pulp raw materials into alkali liquor, grinding to form slurry porridge, grinding, crushing and kneading the slurry porridge, adding pure oxygen for directional polymerization reduction, removing the alkali liquor to obtain alkali cellulose, yellowing and dissolving the alkali cellulose to obtain cellulose sulfonate solution, filtering, defoaming, ripening, spinning and stretching the cellulose sulfonate solution, and performing post-treatment to obtain the high-strength low-elongation viscose fibers. The viscose fiber prepared by the invention is a novel viscose fiber, has lower production cost than the existing modal, and has good economic and social benefits.
Description
Technical field
The present invention relates to viscose and preparation, particularly relate to the preparation technology of the high-strength flatness viscose of a kind of delustring, belong to textile fabric processing technique field.
Background technology
Current textile fiber material is mainly divided into the natural fabric raw material for representative such as cotton, numb, the petroleum base fibrous raw material being representative with terylene, acrylic fibers etc., and take natural cellulosic materials as the bio-based fibrous raw material such as viscose of raw material regeneration.At present, along with the anxiety of the rare of land resource and human resources, sown areas of cotton are in downward trend year by year, and cotton production can not meet the growing needs of people's living standard; And day by day reducing and continuous enhancing that people realize textiles comfortableness, functional, environment-friendly type along with petroleum reserves, more and more come into one's own with the viscose that recyclability resource is produced for raw material.For viscose, as natural regeneration fiber, the quality of its existing natural fabric, there is again excellent machinability, its structure composition is similar to cotton, not only there is hygroscopicity high, good permeability, comfortable and easy to wear, easy dyeing, the multifrequency natures such as heat-resisting quantity is strong, simultaneously, there is again the unexistent drapability of cotton and flexibility, certainly, due to these excellent properties that viscose possesses, development in recent years is very rapid, the particularly viscose scale of common variety expansion sharply, this phenomenon causes raw material supply anxiety, market harmful competition is fierce, meanwhile, more limit exploitation and the industrial upgrading of downstream new textile.
Based on above-mentioned situation, be the sustainable development promoting viscose industry, producing viscose that is differential, functionalization has become current industry and has newly marked.The production method of a patent document CN102296373A(superfine high-strength high-modulus viscose fiber, 2011.12.28) disclose a kind of viscose that a kind of even structure, fibre strength and modulus exceed conventional variety more than 50%, the fibre strength of obtained viscose be 0.44 ~ 0.78dtex, dry strong >=3.1cN/dtex(li ox/dtex), wet strong >=2.1cN/dtex, wet modulus >=0.5cN/dtex, whiteness >=82.0%.
The high white powerful fine denier viscose staple fiber of patent document CN1632189(mono-kind and production technology thereof, 2005.06.29) short rayon fiber that a kind of fiber number is thin, intensity is high is disclosed, compared with common viscose fiber, there is the advantages such as intensity is high, ABRASION RESISTANCE is strong, feel is fine and smooth, anti-fold, resistance to repeatedly distortion by the garment material of its processing, also can be used for weaving high grade yarn fabric products.
Patent document CN102251301A(production process of ultrafine-denier high-strength viscose fibers, 2011.11.23) disclose the preparation method of the viscose that a kind of fiber number is low, intensity is high, can obtain fiber number is the viscose that 1.11 dtexs and intensity are greater than 2.9 cN/dtex.
Only above-mentioned disclosed patent document can be known, for obtained differential, the viscose of functionalization, prior art is all that the mode by changing production technology realizes, wherein, include raw material, change of the shaping and technological parameter of viscose glue etc., the viscose obtained comparatively common viscose fiber has all carried out suitable optimization in fiber number and intensity, but for day by day fierce market competition, differential viscose does not meet exploitation and the industrial upgrading of downstream new textile to a greater extent, especially the same sky silk taking natural cellulosic materials as raw material and regenerate, model, the development of the fibrous raw materials such as copper ammonia fibre, the occupation rate of market of viscose is reduced increasingly.As: the preparation method of patent document CN101130885(fiber crops material viscose and the numb material viscose of preparation, 2008.02.27) a kind of viscose and the preparation technology thereof that utilize numb material plant production is disclosed, technique is simple, supplies consumption is low, and the numb material viscose produced has excellent whiteness, the performance such as intensity and elongate fiber, the numb material viscose prepared by this technique meets dry fracture strength >=1.820 cN/dtex, wet breaking strength >=1.12 cN/dtex, dry elongation at break >=15.4%, line density deviation ratio ± 6.00%, length variation rate ± 6.00%, overcut fibre rate≤1.0%, over-length fibre≤18.0mg/100g, fault≤11mg/100g, residual sulphur≤18.0mg/100g.
For Modal fibre, we know, Modal fibre is for raw material with European beech, be made through special spinning technique after making wooden slurries, equally with cotton belong to natural fabric raw material together, without any pollution in the whole production process of Modal fibre, its dry strong cohesiveness is bordering on terylene, wetting, it is many to improve than common viscose fiber by force, no matter be gloss, flexibility, hygroscopicity, dyeability, dyefastness is all better than Pure cotton Product, with the fabric that it is made, not show only a kind of silk face gloss, have more pleasant soft touch sensation and dangle sense and fabulous endurable performance, it is a kind of desirable environmental protection fiber cellulose fiber.But due to Modal fibre textile technology cost intensive, the model circulated on the market belongs to model and cotton blending substantially, or viscose glue (people is cotton) fiber is directly taken to pretend to be model.
For this reason, we need to find one to be different from natural fabric raw material and petroleum base fibrous raw material, performance is better than again the New Viscose Fibre of differential viscose, the requirement of people to natural prodcuts (as: Modal fibre) can not only be met, industrialized continuous production can also be applicable to, for enterprise brings larger economic benefit, certainly, this is also the inexorable trend of viscose industry energy sustainable development.
Summary of the invention
The object of the present invention is to provide the preparation technology of the high-strength flatness viscose of a kind of extinction type, the viscose that this technique obtains is different from traditional viscose product and cotton is fine, it is the tencel kind realized by technological innovation, there is the index system being different from common viscose fiber and Modal fibre, it is high-strength that its product not only shows Modal fibre, the fiber characteristics of flatness, also show more cotton fibre and the better skin-friendly of model, effectively can substitute existing Modal fibre, and production cost comparatively model is low, there is good economic and social benefit.
The present invention is achieved through the following technical solutions:
The preparation technology of the high-strength flatness viscose of a kind of delustring, it is characterized in that: pulp material be impregnated in alkali lye, after grinding, squeeze, pulverize, rubbing, adding pure oxygen orientation falls poly-, alkali cellulose is obtained after removing alkali lye, by this alkali cellulose through yellow, dissolve after obtained cellulose sulfonate solution, cellulose sulfonate solution more after filtration, deaeration, maturation, obtain high-strength flatness viscose after spinning drawing and post processing.
The present invention adopts the directed degrading and polymerizing technology of pure oxygen, add a certain amount of pure oxygen in the reactor, the alkali cellulose degree of polymerization is made to reduce to 400 ~ 600 by 650 ~ 1200, improve the purity of first fibre, reach 98.0 ~ 98.5%, can 2 ~ 3% be improved than traditional handicraft, orientation is fallen poly-fall more experienced than tradition and is gathered minimizing first fibre loss 3 ~ 5%, improve utilization rate of raw materials, saved production cost, and molecule falls poly-more even, abundant, effective.
Described pulp material comprises the one or more kinds of combinations in cotton pulp, bamboo pulp, wood pulp, jute pulp, when practical application, cotton pulp, bamboo pulp, wood pulp, jute pulp can mix in any proportion, and raw material sources are wide, and not high to the fine content requirement of first, effectively can reduce cost of material.
The degree of polymerization of described pulp material is 650 ~ 1200.
Using pulp as raw materials for production in the middle of preparation technology of the present invention, by viscose obtained after viscose glue preparation, spinning technique and post processing, in production process, still remain secondary response microscope sectional area, and the ectonexine area ratio at this interface is obviously different from the secondary response vestige of Modal fibre and common viscose fiber, ensure that this product has feature that is high-strength, flatness, also there is suitable water imbibition and significant fiber skin-friendly simultaneously.
Preparation technology's concrete steps of described extinction type high-strength flatness viscose are as follows:
A. being impregnated in by pulp material is equipped with in the treating tank of alkali lye, the slurry congee that concentration is 3 ~ 6% is made after being ground by grinder, when actual production, first pulp material is placed on and feeds on the machine dregs of rice, after setting certain rate of feeding (as 40kg/min), be added in treating tank, the object of grinding carries out shredding and dispersion by mechanism to fiber, thus improve cellulosic alkalization speed and alkalization rate again;
B. the slurry congee that steps A is obtained is delivered to squeezer, after squeezing, deliver to pulverizer pulverize, obtain alkali cellulose, this alkali cellulose is delivered to kneading machine, obtain the slurry congee that concentration is 30 ~ 40% after process, in this step, squeezing function removes unnecessary alkali lye, unnecessary alkali lye can be recycled, and processing mode reclaims alkali fiber after using the filter of filter screen 60 ~ 120 order, Zhen Kong Du – 0.4～– 0.1MPa to remove hemicellulose unnecessary in alkali lye
element, kneading machine uses twin screw device, can make fiber sub-wire, brooming, reach the effect destroying cellulose fibre cell membrane, remove the Small molecular in cellulose, thus improve fibrin reaction performance, improve cellulose in conjunction with alkali content, reach 6 ~ 8%(mass percent);
C, slurry congee obtained for step B is mixed with alkali lye after deliver to reactor, add pure oxygen in the reactor, fall poly-after obtain that the degree of polymerization is 400 ~ 600, the fine purity of first is the alkali cellulose of 98.0 ~ 98.5%, in this step, the object adding pure oxygen is that oxidation is fallen poly-, after falling and gathering, the alkali cellulose degree of polymerization reduces to 400 ~ 600 by 650 ~ 1200.
D. the alkali cellulose that step C is obtained is delivered to xanthating machine, in xanthating machine, add carbon disulfide, after yellow reaction, the cellulose sulfonate that yellow is obtained by reacting and dissolution with solvents, obtained concentration is the cellulose sulfonate solution of 9.0 ~ 10.0%;
E. by cellulose sulfonate solution obtained for step D after filtration, deaeration, after maturation, add delustering agent and obtain spinning solution, then the spinning solution that will obtain obtained viscose after spinning drawing and post processing.
In described steps A, described alkali lye is the sodium hydroxide solution of concentration 110 ~ 240g/L, and the temperature of steeping liquor is 30 ~ 60 DEG C, and dip time is 50 ~ 90min.When reality uses, concentration of lye is too high, and gained cellulose sulfonic acid fat solubility can reduce, viscose filtration difficulty; Concentration of lye is too low, and pulp material puffed degree is too high, squeezing difficulty; Temperature is too high, and cellulose falls poly-fast, accelerates side reaction, affects viscose filtration; Temperature is too low, and pulp puffed degree is high, squeezing difficulty.
To better implement the present invention, in described steps A, described grinder is located in the pipeline of connection treating tank and squeezer.
For reaching better alkalization rate, in described steps A, the temperature of described slurry congee is 30 ~ 60 DEG C, and the milling time of described grinder is 10 ~ 40s.
In the preparation field of viscose, material after slurry congee is squeezed by squeezer can be divided into two parts, a part is the unnecessary alkali lye being mingled with fiber and impurity, another part is the solid-state and liquid mixture having extruded excessive moisture, i.e. alkali cellulose, in described step B, the pressing temperature of described squeezer is 57 ~ 63 DEG C, squeezing multiple is 2.2 ~ 2.8.
Squeezing after dipping, unnecessary alkali lye, hemicellulose, impurity is extruded by pulp, improves alkali cellulose purity, and namely the degree of squeezing represents by dry pulp and mass ratio value before the quality after pulp squeezing and dipping with squeezing multiple; Alkali cellulose after squeezing is very tight, plate is hard, surface area diminishes, be unfavorable for the processing in later stage, the object pulverized is the bits shape making alkali cellulose become tiny, loose, increase surface area, be conducive to the uniformity of later stage operation processing, the constant volume weight of one of representation of degree of grinding alkali cellulose, referred to as degree of grinding in the present invention, after referring to that alkali cellulose is pulverized, the weight of unit volume, generally represents with g/L, and alkali cellulose crushing effect is better, then constant volume weight is less, and its surface area is larger.
In described step B, slurry congee is sent to pulverizer and pulverizes after squeezing, the degree of grinding of described pulverizer is 120 ~ 180g/L, by reasonably squeezing the adjustment of multiple and degree of grinding, the performance uniformity of alkali cellulose in post-production operation can be improved, prevent local from receiving strong extruding, thus hinder oxygen and enter, fall the speed of poly-step; The fine content of first of the alkali cellulose obtained after pulverizing is 29 ~ 31%, alkali content is 15 ~ 17%, and in alkali lye, half fine content controls within 10g/L.
Further, in described step C, described alkali lye is the sodium hydroxide solution of concentration 140 ~ 200g/l, and in reactor, the addition of pure oxygen is 2 ~ 10% of reactor volume, falls the poly-reaction time to control at 30 ~ 60min.
In described step D, the addition of carbon disulfide is 25 ~ 37% of the fine content of first in the alkali cellulose that obtains of step B, and when practical application, carbon disulfide addition is very few, yellow reaction not exclusively, filtration difficulty; Carbon disulfide addition is too high, and yellow overreact, accessory substance is more.
Further, in described step D, the described yellow reaction time controls at 45 ~ 50min, and yellow reaction temperature is 20 ~ 30 DEG C.
Further, in described step D, described dissolving is carried out mixing, stir and grinding at cellulose sulfonate and solvent, the sodium sulfite aqueous solution of described solvent comprises concentration to be 25 ~ 45 g/L sodium hydroxide solutions and concentration be 5 ~ 10 g/L.
In described step D, described solution temperature is 10 ~ 20 DEG C, and dissolution time is 30 ~ 50min.
In described step D, described delustering agent is titanium dioxide.
For further improving the product performance of viscose, the present invention also improves spinning drawing technique, comprise the high salt of low acid relax acid bath technique and high stretch to spin mould technique etc., be in particular in, described spinning drawing step is as follows:
F: by cellulose sulfonate solution after filtration, deaeration, deliver to spinning machine after maturation, after a bath, form tow by the shower nozzle extruding spinning thread of spinning machine, the coagulating bath that a described bath uses comprises the zinc sulfate of the sulfuric acid of 90 ~ 120g/L, the sodium sulphate of 220 ~ 280g/L and 8 ~ 15g/L;
G: the tow after a bath sends into two baths by one drawing machine, the coagulating bath that described two baths use comprises the sulfuric acid of 18 ~ 22g/L, and the degree of draft of described one drawing machine is 50 ~ 100%;
H: the tow after two baths sends into three baths by two road drawing machines, the coagulating bath that described three baths use comprises the sulfuric acid that pH value is 1 ~ 3, and the degree of draft of described two road drawing machines is 40 ~ 60%;
I: the tow after three baths delivers to post processing part by three road drawing machines, and the degree of draft of described three road drawing machines is 5 ~ 15%.
As mentioned above, the present invention adopts three bath wet spinning technology, viscose glue forms tow after draw-spinning process, ensure that the repeatedly reaction of fiber, in the process, fibre section can form secondary response microscope interface clearly, there is the characteristic improving fibre strength, increase fibrous absorbent speed and increasing fiber water-retaining property, in spinning technique, tow is stretched by one drawing machine, two road drawing machines, three road drawing machines, more be conducive to the fragility improving fiber, the degree of stretching of fiber is improved.
Described post processing comprises desulfurization that the tow that formed spinning drawing carries out, bleaches and oil, and the desulfurizing agent that described desulfurization uses is made up of the sodium carbonate of concentration to be the vulcanized sodium of 4 ~ 8g/L and concentration be 1 ~ 4g/L; The hydrogen peroxide that the bleaching agent that described bleaching uses is concentration 0.3 ~ 0.6g/L; The described finish addition used that oils is 7 ~ 9g/L, and after oiling, the pH value of tow is 6.5 ~ 7.
The present invention adopts gentle sulfur removal technology, the damage of product strength, degree of stretching is reduced, when reality uses, NaOH, the sodium sulfite of the more existing use of desulfurizing agent of vulcanized sodium and sodium carbonate composition are gentleer, the sulfuric acid brought from acid bath with tow in sodium carbonate energy, after sulfur removal technology, the pH value of adjustable tow is 8 ~ 11; Comparatively the bleaching agent such as clorox is gentleer for hydrogen peroxide bleaching agent, the pH value of viscose prepared by the present invention should control in 6.5 ~ 7 scopes, also by the mode adjust ph of washing, multiple-effect acid (organic acid), within the scope of this, the strength and elongation of viscose final product can not be affected, and strength and elongation is high.
Further, described desulfurization temperature is 50 ~ 55 DEG C, and desulfurization time is 2 ~ 3min; Described bleaching temperature is 50 ~ 55 DEG C, and bleaching time is 1 ~ 2min; The temperature of described finish is 50 ~ 55 DEG C.
In the present invention, described post processing also comprises oven dry, described oven dry is that desulfurization, the tow bleaching and obtain after oiling that the tow formed spinning drawing carries out makes to Tumble Dry, bake out temperature is 75 ~ 115 DEG C, after oven dry, obtain high-strength flatness viscose product, product regain controls 11 ~ 13.5%.
The delustring high-strength flatness viscose prepared by inventing described preparation technology meets following technical indicator:
Dry fracture strength >=3.10 cN/dtex;
Wet breaking strength >=1.60cN/dtex;
Intensity >=the 0.55cN/dtex needed for 5% percentage elongation is produced under wet condition,
Dry elongation at break 11.0 ~ 19.0%;
Wet elongation at break 16.0 ~ 21.0%;
Degree of crystallinity 40.0 ~ 45.0%;
Radial water swelling capacity 22 ~ 26%;
Dulling agent content 0.8 ~ 5%.
Further, the high-strength flatness viscose of described delustring also meets:
Whiteness >=85%;
Line density deviation ratio≤± 11.0%;
Residual sulphur≤12.0mg/100g;
Length variation rate≤± 11.0%;
Overcut fibre rate≤0.5%;
Over-length fibre≤4.0mg/100g;
Fault≤4.0mg/100g.
The present invention compared with prior art, has following beneficial effect:
(1) viscose that the present invention relates to is the tencel kind realized by technological innovation, belong to the great innovation of viscose staple fibre and cellulose fibre production technical field, this viscose is different from traditional viscose product and cotton is fine, there is the index system being different from common viscose fiber and Modal fibre, the intensity of fiber reaches more than 3.1cN/dtex, higher by about 30% than common bio-based staple fibre intensity, close to model, there is the high strength of Modal fibre, low elongation, degradable feature, make fabric not yielding, also there is more cotton fibre, the better hygroscopicity of model and gas permeability, and it is soft, smoothly, outward appearance is beautiful, can effectively substitute existing differential viscose, while raising viscose lower procedure processing characteristics, exploitation and the industrial upgrading of downstream new textile can also be promoted, there is good economic benefit and social benefit.
(2) compared with the model that viscose of the present invention is higher with performance indications, cost is lower, cause price lower than Modal fibre 4000 ~ 5000 yuan/ton, mainly contain the production cost that the following aspects reduces viscose of the present invention: a. is extensive in the raw material sources of viscose of the present invention, require low, (methylcellulose content is higher can to select raw material that methylcellulose content is lower, price is higher), one or more combination in available cotton pulp, bamboo pulp, wood pulp, jute pulp, Non-scale requirement; B., in present invention process process, comparatively conventional products is lower for the consumption of alkali; C. in the spinning process in present invention process step, the speed of spinning of spinning machine is 45 ~ 55m/min, faster than the 30m/min in model production process, and the acid bath composition optimized and draft process, the control of each working procedure parameter of overall balance can be accomplished, production efficiency is high, and energy consumption is low, thus reduces production cost.
(3) the present invention adopts three bath wet spinning technology, what coagulating bath adopted is the high salt of low acid, reaction condition is gentle, and viscose glue forms tow after draw-spinning process, ensure that the repeatedly reaction of fiber, viscose of the present invention has the secondary response interface different from common viscose fiber and Modal fibre, it should be noted that, secondary response interface is inhaled look ability difference according to fiber cross section to dyestuff and is formed, the i.e. cortex of fiber and sandwich layer, cortex is little to dyestuff suction look ability, dye partially shallow, sandwich layer is large to dyestuff suction look ability, color is partially dark, cortex has the higher degree of orientation, cortex is more, fracture strength is higher, and sandwich layer is more, water swelling capacity is higher, fibre section is done after dyed for fiber of the present invention, the fibre section of the viscose that the present invention relates to shows clear, obvious secondary response microscope sectional area, sandwich layer, cortex " area " ratio are (40 ~ 70): (30 ~ 60), ratio is moderate, and the sandwich layer of common viscose fiber and cortex " area " ratio are (90 ~ 95): (5 ~ 10), the inclined internal layer of ratio, therefore viscose of the present invention is compared with common viscose fiber, there is feature that is high-strength, flatness, also have suitable water imbibition, fiber skin-friendly has significant advantage simultaneously, do fibre section after Modal fibre dyeing, examine under a microscope, without secondary response interface, viscose of the present invention and Modal fibre are under equal dyeing condition, and viscose of the present invention inhales color depth than model, and dye-uptake is high, uniformity is better, and the COLOR FASTNESS of finished product is good.
(4) for guaranteeing that high-strength flatness viscose secondary response interface has suitable cortex, sandwich layer ratio, the present invention, from technology, has accomplished improvement acid bath technique, as reduced sulfuric acid concentration, sluggish, improves skin thickness; Change viscose glue index, as viscose ripening degree, the fine index such as content, alkali content of first, thus ensure that the fracture strength of viscose of the present invention is high.
(5) compared with adhering process of the prior art, the alkali cellulose hemicellulose level that the present invention obtains is low, control within 10g/L, we know: hemicellulose refers to that the degree of polymerization is at the beta cellulose of 50 ~ 200 and the gamma-cellulose of degree of polymerization < 50, as long as the impact of hemicellulose has the following aspects: a. affects the uniformity of alkali cellulose; B. ageing time is extended; C. the yellowing rate of hemicellulose is more fine than first fast, consumes a certain amount of carbon disulfide, causes alkali cellulose esterification to reduce, and the solubility of sulphonic acid ester reduces; D. affect the filtration of viscose glue, the solubility of sulphonic acid ester reduces, and the potential aldehyde radical of its end is oxidized to metal ion in carboxyl and ash content as ferrous ion, manganese ion, calcium ion, magnesium ion, form the complex compound that viscosity is extremely strong, cause viscose filtration difficulty, yield poorly; E. hemicellulose is more, and the physical and mechanical properties of viscose is poorer.The present invention passes through grinding mill, can grind the slurry congee sending into squeezer in advance, milling time is 10 ~ 40s, by the slurry congee after grinding with after squeezer squeezing, be separated and obtain mixed alkali liquor and alkali cellulose, containing hemicellulose and other impurity in mixed alkali liquor, pulverize through pulverizer, the multiple of squeezing is 2.2 ~ 2.8, degree of grinding is 120-180g/L, by mechanism, to improve the reactivity worth of slurry congee, ensure carrying out smoothly of viscose production.
(6) mixtures that the pulp material that the present invention uses can choose any one or both in cotton pulp, bamboo pulp, wood pulp, jute pulp above can be prepared in any proportion, raw material scope is widely applicable, technical requirement is prepared relatively low, and the cost of raw material is lower.
(7) in steps A of the present invention, alkali lye is the sodium hydroxide solution of concentration 110 ~ 240g/L, and the temperature of steeping liquor is 30 ~ 60 DEG C, and dip time is 50 ~ 90min.By rational optimum configurations, what guarantee was squeezed and filtered carries out smoothly; Concentration of lye is too high, and gained cellulose sulfonic acid fat solubility can reduce, viscose filtration difficulty; Concentration of lye is too low, and pulp material puffed degree is too high, squeezing difficulty; Temperature is too high, and cellulose falls poly-fast, accelerates side reaction, affects viscose filtration; Temperature is too low, and pulp puffed degree is high, squeezing difficulty.
(8) the present invention adopts multistage purification, as grinding, squeezing are pulverized, rubbed, alkali lye cascade utilization, as respectively before impregnation stage, rub the stage after add alkali lye, cellulose can not only be mentioned in conjunction with alkali content, reach the object of the comprehensive utilization ratio improving alkali lye, simultaneously, the input cost of auxiliary material alkali lye can also be effectively reduced, reduce the production cost of viscose.
(9) the present invention can obtain the alkali cellulose of the fine content 29 ~ 31% of first, alkali content 15 ~ 17% after pulverizing through grinding, squeezing, this alkali cellulose through rub, be oxidized fall poly-after can directly send into viscose production system, cellulose viscose manufacturing technique can adopt common process, after yellow acquisition viscose glue, then through filtration, maturation, deaeration, spinning to obtain viscose.
(10) in the present invention, alkali cellulose fiber processes through kneader twin screw device, make fiber sub-wire, brooming, reach the cell membrane destroying cellulose fibre, remove the Small molecular in cellulose, thus improve fibrin reaction performance, improve cellulose in conjunction with alkali content, reach 6 ~ 8%(mass percent).
(11) F step orientation of the present invention is fallen poly-: the alkali cellulose obtained by step D and concentration are the slurry congee that the alkali lye of 140 ~ 200g/L is mixed to form that concentration is 4 ~ 8%, slurry congee is delivered to orientation and falls poly-reactor, reaction time is 30 ~ 60min, after falling and gathering, the alkali cellulose degree of polymerization is made to reduce to 400 ~ 600 by 650 ~ 1200, the fine purity of first reaches 98.0 ~ 98.5%, can 2 ~ 3% be improved than traditional handicraft, orientation is fallen poly-fall more experienced than tradition and is gathered minimizing first fibre loss 3 ~ 5%, improve utilization rate of raw materials, save production cost, and molecule falls poly-more even, fully, effectively.
(12) draft process of the present invention, adopt high drawing-off technology step by step, a degree of draft is 50 ~ 100%, and drawing-off is too high, and lousiness is many, and drawing-off is too low, and intensity is low; Two degree of drafts are 40 ~ 60%; Three degree of drafts are that 5 ~ 15% drawing-offs are too high, and lousiness is many, and drawing-off is too low, and intensity declines, and by the control of rational degree of draft, improves the fragility of fiber, improves fibre strength, and reduce the amount of lousiness, improve the appearance property of product.
(13) NaOH of the more existing use of desulfurizing agent of vulcanized sodium and sodium carbonate composition in sulfur removal technology of the present invention, sodium sulfite are gentleer, the damage of fiber product intensity, degree of stretching can be made to reduce, and the sulfuric acid brought from acid bath with tow in sodium carbonate energy, after sulfur removal technology, the pH value of adjustable tow is 8 ~ 11.
(14) bleaching agent of the present invention's use is gentle, comparatively the bleaching agent such as clorox is gentleer to adopt hydrogen peroxide bleaching agent, the pH value of viscose prepared by the present invention should control in 6.5 ~ 7 scopes, also by the mode adjust ph of washing, multiple-effect acid (organic acid), within the scope of this, the strength and elongation of viscose final product can not be affected, and strength and elongation is high.
(15) the present invention is reasonable in design, in the production process of identical viscose product, the aspects such as comprehensive above-mentioned raw materials is chosen, preparation process amelioration, the production cost of the reduction viscose product of high degree, its price is low 4000 ~ 5000 yuan/ton compared with Modal fibre, significantly can reduce downstream raw material use cost, can be used for that family is spun, nonwoven fabric etc., particularly underwear and facial mask, hygenic towelette etc., for down-stream enterprises such as spinning, weave cotton cloth brings more high added value and wide market prospects, the market competitiveness of remarkable enterprise.
Accompanying drawing explanation
Fig. 1 is the fibre section cross section of the high-strength flatness viscose of extinction type of the present invention;
Fig. 2 is the fibre section cross section of model;
Fig. 3 is the fibre section cross section of sky silk.
Detailed description of the invention
Below goal of the invention of the present invention, technical scheme and beneficial effect are described in further detail.
It should be noted that, it is all exemplary for below describing in detail, be intended for the requested to provide further explanation of the invention, except as otherwise noted, all technology used herein and scientific terminology have the identical meanings usually understood with general technical staff of the technical field of the invention.
It silk, model, copper ammonia fibre, the fibrous raw materials such as viscose are all take natural cellulosic materials as the bio-based fibrous raw material that raw material regenerates, wherein, the highest with the occupation rate of market of viscose, but along with the viscose scale of common variety in recent years sharply expands, raw material supply is nervous, exploitation and the industrial upgrading of downstream new textile are progressively restricted, for overcoming this phenomenon, with patent document CN102296373A, CN1632189, CN102251301A is that a series of differential viscose of example is suggested, patented technology disclosed in it, this kind of differential viscose is all that the mode by changing production technology realizes, but for day by day fierce market competition, differential viscose does not meet exploitation and the industrial upgrading of downstream new textile to a greater extent, especially the same sky silk taking natural cellulosic materials as raw material and regenerate, model, the development of the fibrous raw materials such as copper ammonia fibre, the occupation rate of market of viscose is reduced increasingly.On this basis, the present invention proposes a kind of high-strength flatness viscose, this viscose product has product performance that is high-strength, flatness, and also have high-selenium corn characteristic, product skin-friendly outclass Modal fibre, is slightly better than cotton fiber simultaneously.
High-strength flatness viscose of the present invention is in fiber forming process, maintain exclusive fibre structure, there is the feature of high-tenacity, its dry fracture strength improves about 25% with wet breaking strength compared with common viscose fiber, with differential viscose, also there is obvious difference, as can be seen from product index, the product index of high-strength flatness viscose meets: fiber number 0.88 ~ 1.67 dtex, dry fracture strength >=3.10 cN/dtex, wet breaking strength >=1.60cN/dtex, and differential viscose records CN102296373A with patent document, CN1632189, CN102251301A is example, its product index is as follows: CN102296373A meets fiber number 0.44 ~ 0.78dtex, dry fracture strength >=3.10 cN/dtex, wet breaking strength >=2.1cN/dtex, CN1632189 meets fiber number 0.90 ~ 1.40dtex, dry fracture strength >=2.50 cN/dtex, wet breaking strength >=1.20cN/dtex, CN102251301A meets fiber number 1.11 dtex, intensity >=2.9 cN/dtex, and as can be seen from These parameters, the fibre strength of the high-strength flatness viscose that the present invention relates to obviously is better than existing differential viscose.
High-strength flatness viscose the present invention obtained is compared with Modal fibre, sky silk more respectively, and alignments is as follows:
By high-strength flatness viscose, Modal fibre, fibre section is done after it silk dyes respectively, its fibre section is amplified 2000 times under the microscope observe, as shown in Figures 1 to 3, Fig. 1 is the fibre section cross section of the high-strength flatness viscose of the present invention, as shown in Figure 1, after the dyed process of high-strength flatness viscose that the present invention relates to, its fibrocortex, the color of sandwich layer shows shallow respectively, dark difference, differ greatly, cortex is partially shallow, sandwich layer is obviously partially dark, there is secondary response interface clearly, ratio is moderate, ensure that this product has high-strength, the feature of flatness, also there is suitable water imbibition simultaneously, fiber skin-friendly has significant advantage, wherein, sandwich layer: " area " ratio of cortex is 40 ~ 70:30 ~ 60.
Fig. 2 is the fibre section sectional view of Modal fibre, as shown in Figure 2, after the dyed process of Modal fibre, its fibrocortex is dark with the color of sandwich layer, shallow consistent, and without obvious secondary interface, this products characteristics enhances the hydrophobicity of fiber, water suction rate variance, thus its skin-friendly is deteriorated.
Fig. 3 is the fibre section sectional view of sky silk, as shown in Figure 3, after the dyed process of it silk, its fibrocortex is dark with the color of sandwich layer, shallow consistent, without obvious secondary interface, this products characteristics has concurrently outside the advantages such as the excellent hygroscopicity of plain edition viscose, soft and smooth elegant property, comfortableness, overcomes common viscose fiber brute force low, especially wet defect low by force, its brute force is almost close with terylene.
Just because of the above-mentioned characteristic of product, determine the extinction type high-strength flatness viscose that the present invention obtains and meet following index:
Dry fracture strength >=3.10 cN/dtex, wet breaking strength >=1.60cN/dtex,
Intensity >=the 0.55cN/dtex needed for 5% percentage elongation is produced under wet condition,
Dry elongation at break 11.0 ~ 19.0%, wet elongation at break 16.0 ~ 21.0%,
Dulling agent content 0.8 ~ 5%, whiteness >=85%, radial water swelling capacity 22 ~ 26%,
Line density deviation ratio≤± 11.0%, residual sulphur≤12.0mg/100g,
Length variation rate≤± 11.0%, overcut fibre rate≤0.5%,
Over-length fibre≤4.0mg/100g, fault≤4.0mg/100g.
These parameters is applicable to the mensuration that linear density range is the viscose of the high-strength flatness of 0.8dtex ~ 1.67dtex, the assay method of dry fracture strength is GB/T 14337, the assay method of wet breaking strength is GB/T 14337, the intensity produced under wet condition needed for 5% percentage elongation is completed by GB/T 14337, the assay method of dry elongation at break is GB/T 14337, the assay method of wet elongation at break is GB/T 14337, the assay method of line density deviation ratio is GB/T 14335, the assay method of residual sulphur is FZ/T 50014, the assay method of length variation rate is GB/T 14336, the assay method of overcut fibre rate is GB/T 14336, the assay method of over-length fibre is GB/T 14336, the assay method of fault is GB/T 14339, the assay method of whiteness is FZ/T 50013, the assay method of radial water swelling capacity is GB/T 6503.
Enumerate explanation the specific embodiment of the present invention with several exemplary embodiments below, certainly, protection scope of the present invention is not limited to following examples.
Embodiment 1
The preparation technology of the high-strength flatness viscose of a kind of delustring, pulp material be impregnated in alkali lye, after grinding, squeeze, pulverize, rubbing, adding pure oxygen orientation falls poly-, alkali cellulose is obtained after removing alkali lye, by this alkali cellulose through yellow, dissolve after obtained cellulose sulfonate solution, cellulose sulfonate solution more after filtration, deaeration, maturation, obtain high-strength flatness viscose after spinning drawing and post processing.The viscose obtained by the present embodiment meets following technical indicator:
Dry fracture strength >=3.10 cN/dtex;
Wet breaking strength >=1.60cN/dtex;
Intensity >=the 0.55cN/dtex needed for 5% percentage elongation is produced under wet condition,
Dry elongation at break 11.0 ~ 19.0%;
Wet elongation at break 16.0 ~ 21.0%;
Radial water swelling capacity 22 ~ 26%;
Dulling agent content 0.8 ~ 5%.
Embodiment 2
The difference of the present embodiment and embodiment 1 is, the viscose obtained according to embodiment 1 technique also meets:
Whiteness >=85%;
Line density deviation ratio≤± 11.0%;
Residual sulphur≤12.0mg/100g;
Length variation rate≤± 11.0%;
Overcut fibre rate≤0.5%;
Over-length fibre≤4.0mg/100g;
Fault≤4.0mg/100g.
Embodiment 3
A preparation technology for the high-strength flatness viscose of delustring, step is as follows:
A. first pulp material is placed on and feeds on the machine dregs of rice, setting rate of feeding is after 40kg/min, raw material is joined in treating tank, the slurry congee that concentration is 3% is made after grinder grinding, wherein, the object of grinding carries out shredding and dispersion by mechanism to fiber, thus improve cellulosic alkalization speed and alkalization rate;
B. the slurry congee that steps A is obtained is delivered to squeezer, after squeezing, deliver to pulverizer pulverize, obtain alkali cellulose, this alkali cellulose is delivered to kneading machine, obtain the slurry congee that concentration is 30% after process, in this step, squeezing function removes unnecessary alkali lye, unnecessary alkali lye can be recycled, and processing mode reclaims alkali fiber after using the filter of filter screen 60 order, Zhen Kong Du – 0.4MPa to remove hemicellulose unnecessary in alkali lye
element, kneading machine uses twin screw device, can make fiber sub-wire, brooming, reaches the effect destroying cellulose fibre cell membrane, removes the Small molecular in cellulose, thus improves fibrin reaction performance, improves cellulose in conjunction with alkali content, reaches 6%;
C, slurry congee obtained for step B mix with alkali lye after deliver to reactor, add pure oxygen in the reactor, fall poly-after obtain that the degree of polymerization is 400, first fibre purity is the alkali cellulose of 98.0%, in this step, the object adding pure oxygen be oxidized fall poly-.
D. the alkali cellulose that step C is obtained is delivered to xanthating machine, in xanthating machine, add carbon disulfide, after yellow reaction, the cellulose sulfonate that yellow is obtained by reacting and dissolution with solvents, obtained concentration is the cellulose sulfonate solution of 9.0%;
E. by cellulose sulfonate solution obtained for step D after filtration, deaeration, after maturation, add delustering agent and obtain spinning solution, then the spinning solution that will obtain obtained viscose after spinning drawing and post processing.
In the present embodiment, pulp material is cotton pulp.
Embodiment 4
A preparation technology for the high-strength flatness viscose of delustring, step is as follows:
A: be impregnated in by pulp material and be equipped with in the treating tank of alkali lye, makes the slurry congee that concentration is 3.5% by grinder after being ground;
B: squeezer delivered to by the slurry congee that steps A is obtained, delivers to pulverizer and pulverizes after squeezing, obtains alkali cellulose, this alkali cellulose is delivered to kneading machine, obtains the slurry congee that concentration is 32% after process;
C: deliver to reactor after mix with alkali lye by slurry congee obtained for step B, add pure oxygen in the reactor, fall poly-after the acquisition degree of polymerization be 450, first fibre purity is the alkali cellulose of 98.5%;
D: the alkali cellulose that step C is obtained delivers to xanthating machine, adds carbon disulfide in xanthating machine, after yellow reaction, the cellulose sulfonate that chrysanthemum is obtained by reacting and dissolution with solvents, obtained concentration is the cellulose sulfonate solution of 10.0%;
E: by cellulose sulfonate solution obtained for step D after filtration, deaeration, after maturation, add delustering agent and obtain spinning solution, then the spinning solution that will obtain obtained viscose after spinning drawing and post processing.
In above-mentioned steps A, pulp material is the mixture of cotton pulp, bamboo pulp, wood pulp and jute pulp, and the degree of polymerization is 1100, and mixed proportion is 3:2:1:1; Described alkali lye is NaOH, and its concentration is 120g/L, and dipping temperature is 35 DEG C, and dip time is 65min; Described grinder is located in the pipeline of connection treating tank and squeezer, and after grinding, the temperature of slurry congee is 35 DEG C, and the time of grinding is 35s.
Embodiment 5
A preparation technology for the high-strength flatness viscose of delustring, step is as follows:
A: be impregnated in by pulp material and be equipped with in the treating tank of alkali lye, makes the slurry congee that concentration is 4% by grinder after being ground;
B: squeezer delivered to by the slurry congee that steps A is obtained, delivers to pulverizer and pulverizes after squeezing, obtains alkali cellulose, this alkali cellulose is delivered to kneading machine, obtains the slurry congee that concentration is 35% after process;
C: deliver to reactor after mix with alkali lye by slurry congee obtained for step B, add pure oxygen in the reactor, fall poly-after the acquisition degree of polymerization be 500, first fibre purity is the alkali cellulose of 98.2%;
D: the alkali cellulose that step C is obtained delivers to xanthating machine, adds carbon disulfide in xanthating machine, after yellow reaction, the cellulose sulfonate that chrysanthemum is obtained by reacting and dissolution with solvents, obtained concentration is the cellulose sulfonate solution of 9.5%;
E: by cellulose sulfonate solution obtained for step D after filtration, deaeration, after maturation, add delustering agent and obtain spinning solution, then the spinning solution that will obtain obtained viscose after spinning drawing and post processing.
In the present embodiment steps A, pulp material is the mixture of wood pulp and jute pulp, and mixed proportion is 3:1, and the degree of polymerization is 1000.
In the present embodiment steps A, described alkali lye is NaOH, and its concentration is 110g/L, and dipping temperature is 30 DEG C, and dip time is 50min.
Embodiment 6
A preparation technology for the high-strength flatness viscose of delustring, step is as follows:
A: be impregnated in by pulp material and be equipped with in the treating tank of alkali lye, makes the slurry congee that concentration is 4% by grinder after being ground;
B: squeezer delivered to by the slurry congee that steps A is obtained, delivers to pulverizer and pulverizes after squeezing, obtains alkali cellulose, this alkali cellulose is delivered to kneading machine, obtains the slurry congee that concentration is 38% after process;
C: deliver to reactor after mix with alkali lye by slurry congee obtained for step B, add pure oxygen in the reactor, fall poly-after the acquisition degree of polymerization be 550, first fibre purity is the alkali cellulose of 98.3%;
D: the alkali cellulose that step C is obtained delivers to xanthating machine, adds carbon disulfide in xanthating machine, after yellow reaction, the cellulose sulfonate that chrysanthemum is obtained by reacting and dissolution with solvents, obtained concentration is the cellulose sulfonate solution of 9.6%;
E: by cellulose sulfonate solution obtained for step D after filtration, deaeration, after maturation, add delustering agent and obtain spinning solution, then the spinning solution that will obtain obtained viscose after spinning drawing and post processing.
In above-mentioned steps A, pulp material is the mixture of bamboo pulp, wood pulp and jute pulp, and the degree of polymerization is 900, and mixed proportion is 3:1:1; Described alkali lye is NaOH, and its concentration is 240g/L, and dipping temperature is 60 DEG C, and dip time is 90min; Described grinder is located in the pipeline of connection treating tank and squeezer, and after grinding, the temperature of slurry congee is 30 DEG C, and the time of grinding is 10s.
Embodiment 7
A preparation technology for the high-strength flatness viscose of delustring, step is as follows
A: be impregnated in by pulp material and be equipped with in the treating tank of alkali lye, makes the slurry congee that concentration is 6% by grinder after being ground;
B: squeezer delivered to by the slurry congee that steps A is obtained, delivers to pulverizer and pulverizes after squeezing, obtains alkali cellulose, this alkali cellulose is delivered to kneading machine, obtains the slurry congee that concentration is 40% after process;
C: deliver to reactor after mix with alkali lye by slurry congee obtained for step B, add pure oxygen in the reactor, fall poly-after the acquisition degree of polymerization be 600, first fibre purity is the alkali cellulose of 98.5%;
D: the alkali cellulose that step C is obtained delivers to xanthating machine, adds carbon disulfide in xanthating machine, after yellow reaction, the cellulose sulfonate that chrysanthemum is obtained by reacting and dissolution with solvents, obtained concentration is the cellulose sulfonate solution of 10.0%;
E: by cellulose sulfonate solution obtained for step D after filtration, deaeration, after maturation, add delustering agent and obtain spinning solution, then the spinning solution that will obtain obtained viscose after spinning drawing and post processing.
In the present embodiment, pulp material is bamboo pulp, and its degree of polymerization is 800.
In above-mentioned steps A, described alkali lye is NaOH, and its concentration is 200g/L, and dipping temperature is 40 DEG C, and dip time is 60min; Described grinder is located in the pipeline of connection treating tank and squeezer, and after grinding, the temperature of slurry congee is 60 DEG C, and the time of grinding is 40s.
In above-mentioned steps B, the pressing temperature of squeezer 57 DEG C, squeezing multiple is 2.2 times, and the degree of grinding of pulverizer is 120 g/L.
Embodiment 8
The difference of the present embodiment and embodiment 4 is: in step, and pulp material is the mixture of cotton pulp, bamboo pulp, wood pulp and jute pulp, and the degree of polymerization is 1200, and mixed proportion is 2:3:1:1; In stepb, the pressing temperature of described squeezer is 63 DEG C, squeezing multiple is 2.8.By reasonably squeezing the adjustment of multiple and degree of grinding, the performance uniformity of alkali cellulose in post-production operation can be improved, preventing local from receiving strong extruding, thus hindering oxygen and enter, falling the speed of poly-step.
In step C, described alkali lye is the sodium hydroxide solution of concentration 140g/ L, and in reactor, the addition of pure oxygen is 2%, falls the poly-reaction time to control at 30min.
Embodiment 9
A preparation technology for the high-strength flatness viscose of delustring, comprises the following steps:
A: be impregnated in by pulp material and be equipped with in the treating tank of alkali lye, makes the slurry congee that concentration is 4% by grinder after being ground;
B: squeezer delivered to by the slurry congee that steps A is obtained, delivers to pulverizer and pulverizes after squeezing, obtains alkali cellulose, this alkali cellulose is delivered to kneading machine, obtains the slurry congee that concentration is 32% after process;
C: deliver to reactor after mix with alkali lye by slurry congee obtained for step B, add pure oxygen in the reactor, fall poly-after the acquisition degree of polymerization be 600, first fibre purity is the alkali cellulose of 98.0%;
D: the alkali cellulose that step C is obtained delivers to xanthating machine, adds carbon disulfide in xanthating machine, after yellow reaction, the cellulose sulfonate that chrysanthemum is obtained by reacting and dissolution with solvents, obtained concentration is the cellulose sulfonate solution of 9.6%;
E: by cellulose sulfonate solution obtained for step D after filtration, deaeration, after maturation, add delustering agent and obtain spinning solution, then the spinning solution that will obtain obtained viscose after spinning drawing and post processing.
In above-mentioned steps A, pulp material is the mixture of cotton pulp, bamboo pulp, wood pulp and jute pulp, and the degree of polymerization is 1100, and mixed proportion is 3:2:1:1; Described alkali lye is NaOH, and its concentration is 180g/L, and dipping temperature is 50 DEG C, and dip time is 55min; Described grinder is located in the pipeline of connection treating tank and squeezer, and after grinding, the temperature of slurry congee is 45 DEG C, and the time of grinding is 20s; In stepb, the pressing temperature of described squeezer is 60 DEG C, squeezing multiple is 2.6 times, and the degree of grinding of pulverizer is 160g/L; In step C, described alkali lye is the sodium hydroxide solution of concentration 200g/ L, and in reactor, the addition of pure oxygen is 10%, falls the poly-reaction time to control at 60min.
In the step D of the present embodiment, the addition of carbon disulfide is 25% of the fine content of first in the alkali cellulose that obtains of step B; The described yellow reaction time controls at 45min, yellow reaction temperature is 20 DEG C, described dissolving is carried out mixing, stir and grinding at cellulose sulfonate and solvent, the sodium sulfite aqueous solution of described solvent comprises concentration to be 25g/L sodium hydroxide solution and concentration be 5 g/L, described solution temperature is 10 DEG C, and dissolution time is 30min.
Embodiment 10
The difference of the present embodiment and embodiment 9 is: in step C, and described alkali lye is the sodium hydroxide solution of concentration 140g/ L, and in reactor, the addition of pure oxygen is 5%, falls the poly-reaction time to control at 45min.
In the step D of the present embodiment, the addition of carbon disulfide is 37% of the fine content of first in the alkali cellulose that obtains of step B; The described yellow reaction time controls at 50min, yellow reaction temperature is 30 DEG C, described dissolving is carried out mixing, stir and grinding at cellulose sulfonate and solvent, the sodium sulfite aqueous solution of described solvent comprises concentration to be 45g/L sodium hydroxide solution and concentration be 10 g/L, described solution temperature is 20 DEG C, and dissolution time is 50min.
Embodiment 11
The difference of the present embodiment and embodiment 8 is: in step C, and described alkali lye is the sodium hydroxide solution of concentration 160g/ L; In step D, the addition of carbon disulfide is 30% of the fine content of first in the alkali cellulose that obtains of step B; The described yellow reaction time controls at 48min, yellow reaction temperature is 26 DEG C, described dissolving is carried out mixing, stir and grinding at cellulose sulfonate and solvent, it be 30g/L sodium hydroxide solution and concentration is the sodium sulfite aqueous solution of 8g/L that described solvent comprises concentration, described solution temperature is 15 DEG C, and dissolution time is 44min.
The present embodiment selects titanium dioxide to make delustering agent.
Embodiment 12
The difference of the present embodiment and embodiment 9 is: in steps A, and pulp material is the mixture of cotton pulp, bamboo pulp, wood pulp and jute pulp, and the degree of polymerization is 1000, and mixed proportion is 4:2:1:1.
In step e, described spinning drawing concrete steps are as follows:
F: by cellulose sulfonate solution after filtration, deaeration, deliver to spinning machine after maturation, after a bath, form tow by the shower nozzle extruding spinning thread of spinning machine, the coagulating bath that a described bath uses comprises the zinc sulfate of the sulfuric acid of 90g/L, the sodium sulphate of 220g/L and 8g/L;
G: the tow after a bath sends into two baths by one drawing machine, the coagulating bath that described two baths use comprises the sulfuric acid of 18g/L, and the degree of draft of described one drawing machine is 50%;
H: the tow after two baths sends into three baths by two road drawing machines, the coagulating bath that described three baths use comprises the sulfuric acid that pH value is 1, and the degree of draft of described two road drawing machines is 40%;
I: the tow after three baths delivers to post processing part by three road drawing machines, and the degree of draft of described three road drawing machines is 5%.
Embodiment 13
The difference of the present embodiment and embodiment 9 is: in step C, and described alkali lye is the sodium hydroxide solution of concentration 190g/ L, and in reactor, the addition of pure oxygen is 3%, falls the poly-reaction time to control at 50min.
In step e, described spinning drawing concrete steps are as follows:
F: by cellulose sulfonate solution after filtration, deaeration, deliver to spinning machine after maturation, after a bath, form tow by the shower nozzle extruding spinning thread of spinning machine, the coagulating bath that a described bath uses comprises the zinc sulfate of the sulfuric acid of 120g/L, the sodium sulphate of 280g/L and 15g/L;
G: the tow after a bath sends into two baths by one drawing machine, the coagulating bath that described two baths use comprises the sulfuric acid of 18 ~ 22g/L, and the degree of draft of described one drawing machine is 60%;
H: the tow after two baths sends into three baths by two road drawing machines, the coagulating bath that described three baths use comprises the sulfuric acid that pH value is 3, and the degree of draft of described two road drawing machines is 45%;
I: the tow after three baths delivers to post processing part by three road drawing machines, and the degree of draft of described three road drawing machines is 8%.
In the present embodiment, a described bath temperature is 40 DEG C, two bath temperatures are 80 DEG C, three bath temperatures are 80 DEG C.
Embodiment 14
The difference of the present embodiment and embodiment 13 is: in step e, and described rear operation comprises desulfurization, bleaches and oil, and the desulfurizing agent that described desulfurization uses is made up of the sodium carbonate of concentration to be the vulcanized sodium of 4g/L and concentration be 4g/L; The hydrogen peroxide that the bleaching agent that described bleaching uses is concentration 0.3g/L; The described finish addition used that oils is 7g/L, and after oiling, the pH value of tow is 6.5.
Described spinning drawing step is as follows:
F: by cellulose sulfonate solution after filtration, deaeration, deliver to spinning machine after maturation, after a bath, form tow by the shower nozzle extruding spinning thread of spinning machine, the coagulating bath that a described bath uses comprises the zinc sulfate of the sulfuric acid of 100g/L, the sodium sulphate of 250g/L and 10g/L;
G: the tow after a bath sends into two baths by one drawing machine, the coagulating bath that described two baths use comprises the sulfuric acid of 20g/L, and the degree of draft of described one drawing machine is 80%;
H: the tow after two baths sends into three baths by two road drawing machines, the coagulating bath that described three baths use comprises the sulfuric acid that pH value is 2, and the degree of draft of described two road drawing machines is 50%;
I: the tow after three baths delivers to post processing part by three road drawing machines, and the degree of draft of described three road drawing machines is 10%.
A described bath temperature is 50 DEG C, two bath temperatures are 85 DEG C, three bath temperatures are 80 DEG C.
Embodiment 15
The difference of the present embodiment and embodiment 12 is: in described spinning drawing step, and a described bath temperature is 44 DEG C, two bath temperatures are 90 DEG C, three bath temperatures are 90 DEG C; The desulfurizing agent that described desulfurization uses is that the vulcanized sodium of 8g/L and the sodium carbonate of concentration 1g/L form by concentration; The hydrogen peroxide that the bleaching agent that described bleaching uses is concentration 0.6g/L; The described finish addition used that oils is 9g/L, and after oiling, the pH value of tow is 7; Described desulfurization temperature is 50 DEG C, and desulfurization time is 3min; Described bleaching temperature is 50 DEG C, and bleaching time is 2min; The temperature of described finish is 50 DEG C.
Embodiment 16
A preparation technology for the high-strength flatness viscose of delustring, comprises the following steps:
A: pulp material be impregnated in and be equipped with in the treating tank of alkali lye, described pulp material is the mixture of cotton pulp, bamboo pulp, wood pulp and jute pulp, and the degree of polymerization is 1100, and mixed proportion is 3:2:1:1; The concentration of alkali lye is 180g/L, and temperature is 50 DEG C, and dip time is 55min; Through grinder grinding after dipping, milling time is 20s, and making concentration after grinding is 4%, and temperature is the slurry congee of 45 DEG C;
B: squeezer delivered to by the slurry congee that steps A is obtained, and pressing temperature is 60 DEG C, squeezing multiple is 2.6 times, after squeezing, deliver to pulverizer pulverize, degree of grinding is 120g/L, obtains alkali cellulose, this alkali cellulose is delivered to kneading machine, after process, obtains the slurry congee that concentration is 35%;
C: the slurry congee obtained by step B and concentration are deliver to reactor after the alkali lye of 190g/L mixes, and add the pure oxygen of 2% in the reactor, obtains after falling poly-50min that the degree of polymerization is 450, the fine purity of first is the alkali cellulose of 98.1%;
D: the alkali cellulose that step C is obtained delivers to xanthating machine, the carbon disulfide of 35% of the fine content of first in the alkali cellulose that step B obtains is added in xanthating machine, at 20 DEG C after yellow 45min, the cellulose sulfonate that yellow is obtained by reacting and dissolution with solvents, NaOH and the concentration of described solvent to be concentration be 25g/L are the sodium sulfite aqueous solution of 5g/L, the temperature of dissolving is 10 DEG C, and dissolution time is 30min, and obtained concentration is the cellulose sulfonate solution of 9.5%;
E: by cellulose sulfonate solution obtained for step D after filtration, deaeration, after maturation, add a certain amount of delustering agent, titanium dioxide selected by the delustering agent of the present embodiment, obtains spinning solution after stirring;
F: by cellulose sulfonate solution after filtration, deaeration, deliver to spinning machine after maturation, after a bath, tow is formed by the shower nozzle extruding spinning thread of spinning machine, the temperature of a described bath is 42 DEG C, and the coagulating bath of use comprises the sulfuric acid of 120g/L, the sodium sulphate of 280g/L and the zinc sulfate of 15g/L;
G: the tow after a bath sends into two baths by one drawing machine, the temperature of described two baths is 80 DEG C, and the coagulating bath of use comprises the sulfuric acid of 20g/L, and the degree of draft of described one drawing machine is 60%;
H: the tow after two baths sends into three baths by two road drawing machines, the temperature of three described baths is 80 DEG C, and the coagulating bath of use comprises the sulfuric acid that pH value is 2, and the degree of draft of described two road drawing machines is 45%;
I: the tow after three baths delivers to post processing part by three road drawing machines, and the degree of draft of described three road drawing machines is 8%.
The post processing of the present embodiment comprises desulfurization, bleaches and oil and dry.The desulfurizing agent that described desulfurization uses is made up of the sodium carbonate of concentration to be the vulcanized sodium of 5g/L and concentration be 2g/L, and desulfurization temperature is 55 DEG C, and desulfurization time is 3min; The hydrogen peroxide that the bleaching agent that described bleaching uses is concentration 0.5g/L, bleaching temperature is 55 DEG C, and bleaching time is 1min; The described finish addition used that oils is 8g/L, and after oiling, the pH value of tow is 7, and the temperature of finish is 55 DEG C; It is that desulfurization, the tow bleaching and obtain after oiling that the tow formed spinning drawing carries out makes to Tumble Dry that described post processing is dried, and bake out temperature is 115 DEG C, after oven dry, obtains extinction type high-strength flatness viscose product.
Embodiment 17
A preparation technology for the high-strength flatness viscose of delustring, comprises the following steps:
A: pulp material be impregnated in and be equipped with in the treating tank of alkali lye, the concentration of alkali lye is 120g/L, and temperature is 40 DEG C, and dip time is 60min; Through grinder grinding after dipping, milling time is 15s, and making concentration after grinding is 4%, and temperature is the slurry congee of 45 DEG C;
B: squeezer delivered to by the slurry congee that steps A is obtained, and pressing temperature is 60 DEG C, squeezing multiple is 2.6 times, after squeezing, deliver to pulverizer pulverize, degree of grinding is 180g/L, obtains alkali cellulose, this alkali cellulose is delivered to kneading machine, after process, obtains the slurry congee that concentration is 32%;
C: the slurry congee obtained by step B and concentration are deliver to reactor after the alkali lye of 150g/L mixes, and add the pure oxygen of 10% in the reactor, obtains after falling poly-40min that the degree of polymerization is 600, the fine purity of first is the alkali cellulose of 98%;
D: the alkali cellulose that step C is obtained delivers to xanthating machine, the carbon disulfide of 32% of the fine content of first in the alkali cellulose that step B obtains is added in xanthating machine, at 26 DEG C after yellow 48min, the cellulose sulfonate that yellow is obtained by reacting and dissolution with solvents, NaOH and the concentration of described solvent to be concentration be 35g/L are the sodium sulfite aqueous solution of 8g/L, the temperature of dissolving is 15 DEG C, and dissolution time is 40min, and obtained concentration is the cellulose sulfonate solution of 9.6%;
E: by cellulose sulfonate solution obtained for step D after filtration, deaeration, after maturation, add a certain amount of delustering agent, titanium dioxide selected by the delustering agent of the present embodiment, obtains spinning solution after stirring;
F: by cellulose sulfonate solution after filtration, deaeration, deliver to spinning machine after maturation, after a bath, tow is formed by the shower nozzle extruding spinning thread of spinning machine, the temperature of a described bath is 40 DEG C, and the coagulating bath of use comprises the sulfuric acid of 120g/L, the sodium sulphate of 280g/L and the zinc sulfate of 15g/L;
G: the tow after a bath sends into two baths by one drawing machine, the temperature of described two baths is 80 DEG C, and the coagulating bath of use comprises the sulfuric acid of 19g/L, and the degree of draft of described one drawing machine is 60%;
H: the tow after two baths sends into three baths by two road drawing machines, the temperature of three described baths is 80 DEG C, and the coagulating bath of use comprises the sulfuric acid that pH value is 2, and the degree of draft of described two road drawing machines is 45%;
I: the tow after three baths delivers to post processing part by three road drawing machines, and the degree of draft of described three road drawing machines is 8%.
The post processing of the present embodiment comprises desulfurization, bleaches and oil and dry.The desulfurizing agent that described desulfurization uses is made up of the sodium carbonate of concentration to be the vulcanized sodium of 6g/L and concentration be 3g/L, and desulfurization temperature is 52 DEG C, and desulfurization time is 2.5min; The hydrogen peroxide that the bleaching agent that described bleaching uses is concentration 0.5g/L, bleaching temperature is 50 DEG C, and bleaching time is 2min; The described finish addition used that oils is 9g/L, and after oiling, the pH value of tow is 7, and the temperature of finish is 53 DEG C; It is that desulfurization, the tow bleaching and obtain after oiling that the tow formed spinning drawing carries out makes to Tumble Dry that described post processing is dried, and bake out temperature is 75 DEG C, after oven dry, obtains extinction type high-strength flatness viscose product.
In steps A, described pulp material is the mixture of cotton pulp, bamboo pulp, wood pulp and jute pulp, and the degree of polymerization is 1200, and mixed proportion is 1:2:4:1.
Embodiment 18
A preparation technology for the high-strength flatness viscose of delustring, comprises the following steps:
A: pulp material be impregnated in and be equipped with in the treating tank of alkali lye, the concentration of alkali lye is 120g/L, and temperature is 40 DEG C, and dip time is 60min; Through grinder grinding after dipping, milling time is 15s, and making concentration after grinding is 4%, and temperature is the slurry congee of 45 DEG C;
B: squeezer delivered to by the slurry congee that steps A is obtained, and pressing temperature is 60 DEG C, squeezing multiple is 2.6 times, after squeezing, deliver to pulverizer pulverize, degree of grinding is 130g/L, obtains alkali cellulose, this alkali cellulose is delivered to kneading machine, after process, obtains the slurry congee that concentration is 35%;
C: the slurry congee obtained by step B and concentration are deliver to reactor after the alkali lye of 150g/L mixes, and add the pure oxygen of 5% in the reactor, obtains after falling poly-40min that the degree of polymerization is 450, the fine purity of first is the alkali cellulose of 98.1%;
D: the alkali cellulose that step C is obtained delivers to xanthating machine, the carbon disulfide of 35% of the fine content of first in the alkali cellulose that step B obtains is added in xanthating machine, at 26 DEG C after yellow 48min, the cellulose sulfonate that yellow is obtained by reacting and dissolution with solvents, NaOH and the concentration of described solvent to be concentration be 35g/L are the sodium sulfite aqueous solution of 8g/L, the temperature of dissolving is 15 DEG C, and dissolution time is 40min, and obtained concentration is the cellulose sulfonate solution of 9.5%;
E: by cellulose sulfonate solution obtained for step D after filtration, deaeration, after maturation, add a certain amount of delustering agent, titanium dioxide selected by the delustering agent of the present embodiment, obtains spinning solution after stirring;
F: by cellulose sulfonate solution after filtration, deaeration, deliver to spinning machine after maturation, after a bath, tow is formed by the shower nozzle extruding spinning thread of spinning machine, the temperature of a described bath is 42 DEG C, and the coagulating bath of use comprises the sulfuric acid of 100g/L, the sodium sulphate of 230g/L and the zinc sulfate of 10g/L;
G: the tow after a bath sends into two baths by one drawing machine, the temperature of described two baths is 85 DEG C, and the coagulating bath of use comprises the sulfuric acid of 20g/L, and the degree of draft of described one drawing machine is 100%;
H: the tow after two baths sends into three baths by two road drawing machines, the temperature of three described baths is 87 DEG C, and the coagulating bath of use comprises the sulfuric acid that pH value is 2, and the degree of draft of described two road drawing machines is 60%;
I: the tow after three baths delivers to post processing part by three road drawing machines, and the degree of draft of described three road drawing machines is 15%.
The post processing of the present embodiment comprises desulfurization, bleaches and oil and dry.The desulfurizing agent that described desulfurization uses is made up of the sodium carbonate of concentration to be the vulcanized sodium of 5g/L and concentration be 2g/L, and desulfurization temperature is 55 DEG C, and desulfurization time is 2min; The hydrogen peroxide that the bleaching agent that described bleaching uses is concentration 0.5g/L, bleaching temperature is 52 DEG C, and bleaching time is 1min; The described finish addition used that oils is 8g/L, and after oiling, the pH value of tow is 7, and the temperature of finish is 53 DEG C; It is that desulfurization, the tow bleaching and obtain after oiling that the tow formed spinning drawing carries out makes to Tumble Dry that described post processing is dried, and bake out temperature is 95 DEG C, after oven dry, obtains extinction type high-strength flatness viscose product.
In steps A, described pulp material is the mixture of cotton pulp, bamboo pulp, wood pulp and jute pulp, and the degree of polymerization is 650, and mixed proportion is 1:1:2:1.
The viscose that embodiment 3 ~ 18 obtains is detected, indicator-specific statistics is as follows, wherein embodiment 3 ~ 10 is in table 1, embodiment 11 ~ 18 is in table 2, the desired value of the viscose of embodiment 3 ~ 18 is averaged, then is compared in table 3 with Modal fibre, differential viscose (CN102296373A documents 1, CN1632189 documents 2, CN102251301A documents 3) and the test index of common viscose fiber respectively by this mean value.
Table 1:
Table 2:
Table 3:
From table 1, table 2, the viscose product that embodiment 4,5,6 prepares mainly applies to tight SEILE textile field, produces high sth. made by twisting, high grade yarn product, and with the high domain requirements such as high sth. made by twisting that are applicable to of product strength for feature; The viscose product that embodiment 10,11,12,13,14,15,16,17,18 prepares mainly applies to produce underwear, high-grade shuttle-woven fabric field, and with product feel silk sliding softness, comfortable pro-skin, and finished textile product good stability of the dimension is feature; The viscose product that embodiment 8,9,10 prepares mainly applies to jean field, and with bright, soft, and little of feature with finished textile product modification.
Choose arbitrarily extinction type high-strength flatness viscose product obtained in embodiment 3 ~ 18, as embodiment 16, microscope sectional drawing is carried out to its fibre section, can find, its cross section remains with reacts vestige clearly, and the color of its fibrocortex, sandwich layer shows shallow, dark difference respectively, cortex is obviously partially shallow, sandwich layer is partially dark, (internal layer+middle level): outer field " area " ratio is 60:37, belongs to sandwich layer: cortex=(40 ~ 70): in the scope of (30 ~ 60).
Known by his-and-hers watches 3 data analysis, the high-strength flatness viscose obtained according to preparation technology of the present invention has and is different from common viscose fiber, the index system of differential viscose and Modal fibre, the dry fracture strength of viscose of the present invention and wet breaking strength are apparently higher than common viscose fiber, and percentage elongation is starkly lower than common viscose fiber, arranged by technological parameter, viscose of the present invention is made to have obvious secondary response interface, thus ensure that the characteristic of the high-strength flatness suitable with model, and its radial water swelling capacity is higher than Modal fibre, there is the hygroscopicity higher than model, therefore skin-friendly comparatively Modal fibre is good, viscose of the present invention is a kind of novel viscose, effectively can substitute existing Modal fibre and common viscose fiber, and production cost is lower, has good economic and social benefit.
The above is only preferred embodiment of the present invention, and not do any pro forma restriction to the present invention, every any simple modification, equivalent variations done above embodiment according to technical spirit of the present invention, all falls within protection scope of the present invention.
Claims (21)
1. the preparation technology of the high-strength flatness viscose of delustring, it is characterized in that: pulp material be impregnated in alkali lye, after grinding, squeeze, pulverize, rubbing, adding pure oxygen orientation falls poly-, alkali cellulose is obtained after removing alkali lye, by this alkali cellulose through yellow, dissolve after obtained cellulose sulfonate solution, cellulose sulfonate solution more after filtration, deaeration, maturation, obtain high-strength flatness viscose after spinning drawing and post processing.
2. the preparation technology of the high-strength flatness viscose of delustring according to claim 1, is characterized in that: described pulp material comprises the one or more kinds of combinations in cotton pulp, bamboo pulp, wood pulp, jute pulp.
3. the preparation technology of the high-strength flatness viscose of delustring according to claim 1, is characterized in that: the degree of polymerization of described pulp material is 650 ~ 1200.
4. the preparation technology of the high-strength flatness viscose of delustring according to claim 1, is characterized in that:
The step of described preparation technology is as follows:
A: be impregnated in by pulp material and be equipped with in the treating tank of alkali lye, makes the slurry congee that concentration is 3 ~ 6% by grinder after being ground;
B: squeezer delivered to by the slurry congee that steps A is obtained, delivers to pulverizer and pulverizes after squeezing, obtains alkali cellulose, this alkali cellulose is delivered to kneading machine, obtains the slurry congee that concentration is 30 ~ 40% after process;
C: deliver to reactor after mix with alkali lye by slurry congee obtained for step B, add pure oxygen in the reactor, fall poly-after the acquisition degree of polymerization be 400 ~ 600, first fibre purity is the alkali cellulose of 98.0 ~ 98.5%;
D: the alkali cellulose that step C is obtained delivers to xanthating machine, adds carbon disulfide in xanthating machine, after yellow reaction, the cellulose sulfonate that yellow is obtained by reacting and dissolution with solvents, obtained concentration is the cellulose sulfonate solution of 9.0 ~ 10.0%;
E: by cellulose sulfonate solution obtained for step D after filtration, deaeration, after maturation, the delustering agent added obtains spinning solution, then the spinning solution that will obtain obtained viscose after spinning drawing and post processing.
5. want the high-strength flatness viscose of the delustring described in 4 preparation technology according to right, it is characterized in that: in described steps A, described alkali lye is the sodium hydroxide solution of concentration 110 ~ 240g/L, and the temperature of steeping liquor is 30 ~ 60 DEG C, and dip time is 50 ~ 90min.
6. the preparation technology of the high-strength flatness viscose of delustring according to claim 4, is characterized in that: in described steps A, and described grinder is located in the pipeline of connection treating tank and squeezer.
7. the preparation technology of the high-strength flatness viscose of delustring according to claim 4, is characterized in that: in described steps A, and the temperature of described slurry congee is 30 ~ 60 DEG C, and the milling time of described grinder is 10 ~ 40s.
8. the preparation technology of the high-strength flatness viscose of delustring according to claim 4, is characterized in that: in described step B, and the pressing temperature of described squeezer is 57 ~ 63 DEG C, squeezing multiple is 2.2 ~ 2.8.
9. the preparation technology of the high-strength flatness viscose of delustring according to claim 4, is characterized in that: in described step B, and the degree of grinding of described pulverizer is 120 ~ 180g/L.
10. the preparation technology of the high-strength flatness viscose of delustring according to claim 4, it is characterized in that: in described step C, described alkali lye is the sodium hydroxide solution of concentration 140 ~ 200g/ L, in reactor, the addition of pure oxygen is 2 ~ 10%, falls the poly-reaction time to control at 30 ~ 60min.
The preparation technology of the high-strength flatness viscose of 11. delustring according to claim 4, is characterized in that: in described step D, and the addition of carbon disulfide is 25 ~ 37% of the fine content of first in the alkali cellulose that obtains of step B.
The preparation technology of the high-strength flatness viscose of 12. delustring according to claim 4, it is characterized in that: in described step D, the described yellow reaction time controls at 45 ~ 50min, and yellow reaction temperature is 20 ~ 30 DEG C.
The preparation technology of the high-strength flatness viscose of 13. delustring according to claim 4, it is characterized in that: in described step D, described dissolving is carried out mixing, stir and grinding at cellulose sulfonate and solvent, the sodium sulfite aqueous solution of described solvent comprises concentration to be 25 ~ 45 g/L sodium hydroxide solutions and concentration be 5 ~ 10 g/L.
The preparation technology of the high-strength flatness viscose of 14. delustring according to claim 4, it is characterized in that: in described step D, described solution temperature is 10 ~ 20 DEG C, and dissolution time is 30 ~ 50min.
The preparation technology of the high-strength flatness viscose of 15. delustring according to claim 4, it is characterized in that: in described step e, described delustering agent is titanium dioxide.
The preparation technology of the high-strength flatness viscose of 16. delustring according to claim 4, is characterized in that: described spinning drawing step is as follows:
F: by cellulose sulfonate solution after filtration, deaeration, deliver to spinning machine after maturation, after a bath, form tow by the shower nozzle extruding spinning thread of spinning machine, the coagulating bath that a described bath uses comprises the zinc sulfate of the sulfuric acid of 90 ~ 120g/L, the sodium sulphate of 220 ~ 280g/L and 8 ~ 15g/L;
G: the tow after a bath sends into two baths by one drawing machine, the coagulating bath that described two baths use comprises the sulfuric acid of 18 ~ 22g/L, and the degree of draft of described one drawing machine is 50 ~ 100%;
H: the tow after two baths sends into three baths by two road drawing machines, the coagulating bath that described three baths use comprises the sulfuric acid that pH value is 1 ~ 3, and the degree of draft of described two road drawing machines is 40 ~ 60%;
I: the tow after three baths delivers to post processing part by three road drawing machines, and the degree of draft of described three road drawing machines is 5 ~ 15%.
The preparation technology of the high-strength flatness viscose of 17. delustring according to claim 16, is characterized in that: in described spinning drawing step, a described bath temperature is 40 ~ 50 DEG C, two bath temperatures are 80 ~ 90 DEG C, three bath temperatures are 80 ~ 90 DEG C.
The preparation technology of the high-strength flatness viscose of 18. delustring according to claim 4, it is characterized in that: described post processing comprises desulfurization that the tow that formed spinning drawing carries out, bleaches and oil, the desulfurizing agent that described desulfurization uses is made up of the sodium carbonate of concentration to be the vulcanized sodium of 4 ~ 8g/L and concentration be 1 ~ 4g/L; The hydrogen peroxide that the bleaching agent that described bleaching uses is concentration 0.3 ~ 0.6g/L; The described finish addition used that oils is 7 ~ 9g/L, and after oiling, the pH value of tow is 6.5 ~ 7.
The preparation technology of the high-strength flatness viscose of 19. delustring according to claim 18, it is characterized in that: described desulfurization temperature is 50 ~ 55 DEG C, desulfurization time is 2 ~ 3min; Described bleaching temperature is 50 ~ 55 DEG C, and bleaching time is 1 ~ 2min; The temperature of described finish is 50 ~ 55 DEG C.
The preparation technology of the high-strength flatness viscose of 20. delustring according to claim 18, it is characterized in that: described post processing also comprises oven dry, bake out temperature is 75 ~ 115 DEG C, after oven dry, obtains described delustring high-strength flatness viscose product.
The preparation technology of the high-strength flatness viscose of 21. delustring according to claim 1, is characterized in that: described delustring high-strength flatness viscose meets following technical indicator:
Dry fracture strength >=3.10 cN/dtex;
Wet breaking strength >=1.60cN/dtex;
Intensity >=the 0.55cN/dtex needed for 5% percentage elongation is produced under wet condition,
Dry elongation at break 11.0 ~ 19.0%;
Wet elongation at break 16.0 ~ 21.0%;
Degree of crystallinity 40.0 ~ 45.0%;
Radial water swelling capacity 22 ~ 26%;
Dulling agent content 0.8 ~ 5%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016188274A1 (en) * | 2015-05-27 | 2016-12-01 | 宜宾丝丽雅集团有限公司 | Matte high-strength, low-stretch viscose fiber and manufacturing method therefor |
| CN109610064A (en) * | 2019-02-15 | 2019-04-12 | 宜宾惠美精纺科技股份有限公司 | A kind of scribbled and preparation method |
| CN109778332A (en) * | 2019-01-03 | 2019-05-21 | 杭州优标科技有限公司 | A kind of preparation method of mascara regenerated celulose fibre |
| CN111206290A (en) * | 2020-02-28 | 2020-05-29 | 上海棉芙生物科技有限公司 | Making method of beautiful sesame fiber |
| CN113388908A (en) * | 2021-06-15 | 2021-09-14 | 赛得利(江苏)纤维有限公司 | Production process of stock solution viscose |
| CN113474375A (en) * | 2019-02-22 | 2021-10-01 | 巴斯夫欧洲公司 | Method for producing viscose solution, viscose solution produced thereby and method for producing viscose fibers |
| CN115772233A (en) * | 2022-11-22 | 2023-03-10 | 宜宾丝丽雅集团有限公司 | Defoaming process and system for producing regenerated cellulose based on low-temperature alkali urea method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289761A (en) * | 2008-06-10 | 2008-10-22 | 宜宾长毅浆粕有限责任公司 | Process for preparing dissolved pulp by oxidative decomposition of paper pulp |
| CN101603210A (en) * | 2008-06-10 | 2009-12-16 | 宜宾海丝特纤维有限责任公司 | String is made the production method of viscose |
| CN101851802A (en) * | 2010-05-24 | 2010-10-06 | 杭州奥通科技有限公司 | Method for producing functional high wet modulus fiber by using hemp-containing pulp |
| CN103556261A (en) * | 2013-10-31 | 2014-02-05 | 宜宾海丝特纤维有限责任公司 | Extinction bamboo charcoal viscose fiber and preparation method thereof |
-
2015
- 2015-05-27 CN CN201510276132.1A patent/CN104831387A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289761A (en) * | 2008-06-10 | 2008-10-22 | 宜宾长毅浆粕有限责任公司 | Process for preparing dissolved pulp by oxidative decomposition of paper pulp |
| CN101603210A (en) * | 2008-06-10 | 2009-12-16 | 宜宾海丝特纤维有限责任公司 | String is made the production method of viscose |
| CN101851802A (en) * | 2010-05-24 | 2010-10-06 | 杭州奥通科技有限公司 | Method for producing functional high wet modulus fiber by using hemp-containing pulp |
| CN103556261A (en) * | 2013-10-31 | 2014-02-05 | 宜宾海丝特纤维有限责任公司 | Extinction bamboo charcoal viscose fiber and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016188274A1 (en) * | 2015-05-27 | 2016-12-01 | 宜宾丝丽雅集团有限公司 | Matte high-strength, low-stretch viscose fiber and manufacturing method therefor |
| CN109778332A (en) * | 2019-01-03 | 2019-05-21 | 杭州优标科技有限公司 | A kind of preparation method of mascara regenerated celulose fibre |
| CN109610064A (en) * | 2019-02-15 | 2019-04-12 | 宜宾惠美精纺科技股份有限公司 | A kind of scribbled and preparation method |
| CN113474375A (en) * | 2019-02-22 | 2021-10-01 | 巴斯夫欧洲公司 | Method for producing viscose solution, viscose solution produced thereby and method for producing viscose fibers |
| CN113474375B (en) * | 2019-02-22 | 2023-09-29 | 巴斯夫欧洲公司 | Method for producing viscose solution, viscose solution produced thereby and method for producing viscose fibers |
| CN111206290A (en) * | 2020-02-28 | 2020-05-29 | 上海棉芙生物科技有限公司 | Making method of beautiful sesame fiber |
| CN113388908A (en) * | 2021-06-15 | 2021-09-14 | 赛得利(江苏)纤维有限公司 | Production process of stock solution viscose |
| CN115772233A (en) * | 2022-11-22 | 2023-03-10 | 宜宾丝丽雅集团有限公司 | Defoaming process and system for producing regenerated cellulose based on low-temperature alkali urea method |
| CN115772233B (en) * | 2022-11-22 | 2024-02-27 | 宜宾丝丽雅集团有限公司 | Defoaming process and system for producing regenerated cellulose based on low-temperature alkali urea method |
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