CN104911726B

CN104911726B - A kind of high-strength flatness viscose rayon of delustring superfine type and preparation method thereof

Info

Publication number: CN104911726B
Application number: CN201510276659.4A
Authority: CN
Inventors: 冯涛; 邓传东; 李蓉玲; 贺敏; 田启兵; 陈明付; 陈晓芳; 李春弟
Original assignee: Yibin Grace Group Co Ltd; Yibin Haisite Fiber Co Ltd
Current assignee: Yibin Grace Group Co Ltd; Yibin Haisite Fiber Co Ltd
Priority date: 2015-05-27
Filing date: 2015-05-27
Publication date: 2018-02-27
Anticipated expiration: 2035-05-27
Also published as: CN104911726A

Abstract

The invention discloses a kind of high-strength flatness viscose rayon of delustring superfine type, belong to textile fabric processing technique field.It is that pulp material obtains after impregnating, grind, squeezing crushing, rubbing, drop poly-, yellow, dissolving, filtering, deaeration, maturation, spinning drawing and post processing successively, and viscose rayon of the present invention possesses following technical indicator：0.8~1.11dtex of fiber number；The cN/dtex of dry fracture strength >=3.10；Wet breaking strength >=1.60cN/dtex；Intensity >=0.55cN/dtex needed for 5% elongation, dry elongation at break 11.0~19.0% are produced under wet condition；Wet elongation at break 16.0~21.0%；Crystallinity 40.0~45.0%；Radial water swelling capacity 22~26%；Dulling agent content 0.8~5%.The viscose rayon of the present invention is a kind of New Viscose Fibre, and the more existing Modal of production cost is lower, has good economic benefit and social benefit.

Description

A kind of high-strength flatness viscose rayon of delustring superfine type and preparation method thereof

Technical field

The present invention relates to viscose rayon and preparation, more particularly to a kind of high-strength flatness viscose rayon of delustring superfine type and its system Preparation Method, belong to textile fabric processing technique field.

Background technology

Textile fiber material is broadly divided into the natural fiber raw material for representative with cotton, fiber crops etc. at present, is with terylene, acrylic fibers etc. The petroleum base fibrous raw material of representative, and the bio-based fiber such as viscose rayon formed using natural cellulosic materials as raw material regeneration Raw material.At present, with rare and human resources the anxiety of land resource, sown areas of cotton are in downward trend year by year, cotton The product needs growing by people's living standard can not be met；And as the increasingly reduction and people of petroleum reserves are to weaving The continuous enhancing of product comfortableness, feature, environment-friendly type consciousness, the viscose rayon produced using recyclability resource as raw material is increasingly More is taken seriously.For viscose rayon, as natural regeneration fiber, the quality of its existing natural fiber, have again excellent Good machinability, its structure composition is similar to cotton, not only with hygroscopicity height, good permeability, comfortable and easy to wear, easy dyeing, resistance to The high temperatures multifrequency nature such as strong, meanwhile, there is the unexistent drapability of cotton and flexibility again, certainly, due to viscose rayon tool These standby excellent properties, develop very rapid, the particularly viscose rayon scale of common variety drastically swollen in recent years Swollen, this phenomenon causes raw material supply anxiety, and market harmful competition is fierce, at the same time, more limits downstream Novel Spinning The exploitation of fabric and industrial upgrading.

Based on the above situation, to promote the sustainable development of viscose rayon industry, differential, functionalization viscose rayon is produced Newly marked as current industry.Patent document CN102296373A（A kind of production method of superfine high-strength high-modulus viscose fiber, 2011.12.28）Disclose a kind of viscose glue fibre that a kind of even structure, fibre strength and modulus are higher by conventional variety more than 50% Dimension, the fibre strength of obtained viscose rayon are 0.44~0.78dtex, do strong >=3.1cN/dtex（Li ox/dtex）, it is wet strong >=2.1cN/dtex, wet modulus >=0.5cN/dtex, whiteness >=82.0%.

Patent document CN1632189（A kind of high white strength fine denier viscose staple fiber and its production technology, 2005.06.29） The short rayon fiber that a kind of fiber number is thin, intensity is high is disclosed, it is strong compared with having for common viscose fiber by the garment material of its processing Degree is high, wearability is strong, feel is fine and smooth, anti-fold, resistance to repeatedly deformation the advantages that, it may also be used for weaving high grade cotton yarn fabric products.

Patent document CN102251301A（A kind of production process of ultrafine-denier high-strength viscose fibers, 2011.11.23）Disclose A kind of preparation method for the viscose rayon that fiber number is low, intensity is high, fiber number can be obtained and be more than 2.9 cN/ for 1.11 dtexs and intensity Dtex viscose rayon.

Patent document only disclosed above can know that, for differential, functionalization viscose rayon is made, prior art is equal It is to be realized by way of changing production technology, wherein, include raw material, viscose glue shaping and its change of technological parameter Etc., the viscose rayon of acquisition has carried out appropriate optimization compared with common viscose fiber in fiber number and intensity, but for increasingly swashing For strong market competition, differential viscose rayon does not meet the exploitation and production of downstream new textile to a greater extent Industry upgrades, and it is former especially equally to regenerate the fibers such as the tencel formed, Modal, CUP using natural cellulosic materials as raw material The development of material so that the occupation rate of market of viscose rayon reduces increasingly.Such as：Patent document CN101130885（Numb material viscose rayon Preparation method and preparation numb material viscose rayon, 2008.02.27）It is fine to disclose a kind of viscose glue using numb material plant production Dimension and its preparation technology, technique is simple, and supplies consumption is low, and the numb material viscose rayon produced has excellent whiteness, intensity With the performance such as elongate fiber, the numb material viscose rayon prepared by the technique meets the cN/ of dry fracture strength >=1.820 Dtex, the cN/dtex of wet breaking strength >=1.12, dry elongation at break >=15.4%, line density deviation ratio ± 6.00%, length are inclined Rate ± 6.00%, overlength fiber rate≤1.0%, over-length fibre≤18.0mg/100g, fault≤11mg/100g, residual sulphur≤ 18.0mg/100g。

By taking Modal fibre as an example, it is known that Modal fibre is using European beech as raw material, after wooden slurries are made It is made by special spinning technique, belongs to natural fiber raw material together as cotton, the whole of Modal fibre produced There is no any pollution in journey, it dry by force close to terylene is wet to improve many than common viscose fiber by force, whether light Pool, flexibility, hygroscopicity, dyeability, dyefastness are superior to Pure cotton Product, the fabric made with it, not show only one Kind silk face gloss, feels with more pleasant soft touch and pendency feels and fabulous endurable performance, is a kind of preferable ring Protect fiber type cellulose fiber.But because Modal fibre textile technology is costly, the Modal to circulate on the market substantially belongs to Modal and cotton blend, or directly take viscose glue（People cotton）Fiber pretends to be Modal.

Therefore, we, which need to find one kind, is different from natural fiber raw material and petroleum base fibrous raw material, performance is again better than poor Not Hua viscose rayon New Viscose Fibre, people can not only be met to natural prodcuts（Such as：Modal fibre）Requirement, moreover it is possible to Suitable for industrialized continuous production, larger economic benefit is brought for enterprise, certainly, this is also that viscose rayon industry can continue The inexorable trend of development.

The content of the invention

It is an object of the invention to provide a kind of high-strength flatness viscose rayon of delustring superfine type, the viscose rayon is different from biography System viscose rayon product and cotton are fine, are the tencel kinds by technological innovation to realize, have and are different from common viscose glue fibre The index system of peacekeeping Modal fibre, its product not only show that Modal fibre is high-strength, fiber characteristics of flatness, go back table Reveal and Modal more preferable skin-friendly fine compared with cotton, can effectively substitute existing Modal fibre, and production cost more not generation You are low, has good economic and social benefit.

The present invention is achieved through the following technical solutions：A kind of high-strength flatness viscose rayon of delustring superfine type, it is slurry Dregs of rice raw material successively through impregnate, grind, squeeze crushing, rubbing, drop poly-, yellow, dissolving, filtering, deaeration, maturation, spinning drawing and Obtained after post processing, the high-strength flatness viscose rayon of delustring superfine type meets following technical indicator：

The dtex of fiber number 0.8~1.11；

The cN/dtex of dry fracture strength >=3.10；

Wet breaking strength >=1.60cN/dtex；

Intensity >=0.55cN/dtex needed for 5% elongation is produced under wet condition,

Dry elongation at break 11.0~19.0%；

Wet elongation at break 16.0~21.0%；

Crystallinity 40.0~45.0%；

Radial water swelling capacity 22~26%；

Dulling agent content 0.8~5%.

Described pulp material includes one or more kinds of combinations in cotton pulp, bamboo pulp, wood pulp, jute pulp, in reality When border is applied, cotton pulp, bamboo pulp, wood pulp, jute pulp can be mixed in any proportion, and raw material sources are wide, and to first fibre content requirement It is not high, it can effectively reduce cost of material.

The degree of polymerization of the pulp material is 650~1200.

Further preferably, described viscose rayon also meets following technical indicator：

Whiteness >=85%；

Line density deviation ratio≤± 11.0%；

Residual sulphur≤12.0mg/100g；

Length variation rate≤± 11.0%；

Overlength fiber rate≤0.5%；

Over-length fibre≤4.0mg/100g；

Fault≤4.0mg/100g.

Another object of the present invention is to provide a kind of preparation method of the high-strength flatness viscose rayon of delustring superfine type, the system Preparation Method is prepared by viscose glue using pulp as raw materials for production, viscose rayon, production process is made after spinning technique and post processing In, secondary response microscope sectional area is still remained, and the ectonexine area ratio at the interface is clearly distinguishable from Modal fibre With the secondary response vestige of common viscose fiber, it is ensured that the product has the characteristics of high-strength, flatness, while also has suitably Water imbibition and significant fiber skin-friendly.

The preparation method of the high-strength flatness viscose rayon of described delustring superfine type comprises the following steps that：

A. pulp material is impregnated in the treating tank equipped with alkali lye, it is 3~6% that concentration is made after being ground by grinder Congee is starched, in actual production, pulp material is firstly placed to feed on the machine dregs of rice, sets certain rate of feeding（Such as 40kg/min） Afterwards, add into treating tank, the purpose of grinding is to carry out shredding to fiber by mechanism and disperse, so as to improve fiber The alkalization speed and alkalization rate of element；

B. congee will be starched made from step A and delivers to squeezer, pulverizer is delivered to after squeezing and is crushed, obtains alkali fiber Element, the alkali cellulose is delivered into kneading machine, the slurry congee that concentration is 30~40% is obtained after processing, in this step, squeezing function is removed Remove unnecessary alkali lye, unnecessary alkali lye can recycle, processing mode be using the mesh of filter screen 60~120, vacuum -0.4~- 0.1MPa filter reclaims alkali fiber after removing hemicellulose unnecessary in alkali lyeElement, kneading machine uses twin screw device, can Make fiber sub-wire, brooming, have the function that to destroy cellulose fibre cell membrane, the small molecule in cellulose is removed, so as to improve Fibrin reaction performance, cellulose combination alkali content is improved, reaches 6~8%（Mass percent）；

C, it will be starched made from step B after congee mixes with alkali lye and deliver to reactor, added pure oxygen in the reactor, obtained after drop is poly- The alkali cellulose that the degree of polymerization is 400~600, first fibre purity is 98.0~98.5% is obtained, in this step, adds the purpose of pure oxygen It is that oxidation drop is poly-, after dropping and gathering, the alkali cellulose degree of polymerization is reduced to 400~600 by 650~1200.

D. alkali cellulose made from step C is delivered into xanthating machine, carbon disulfide is added in xanthating machine, reacted through yellow Afterwards, the cellulose sulfonate for yellow being reacted to obtain dissolves with solvent, and the cellulose sulfonate that concentration is 9.0~10.0% is made Solution；

E. by cellulose sulfonate solution made from step D is filtered, deaeration, after maturation, adds delustering agent and obtains spinning Stoste, then viscose rayon is made after spinning drawing and post processing in the spinning solution of acquisition.

In described step A, described alkali lye is 110~240g/L of concentration sodium hydroxide solution, steeping liquor Temperature is 30~60 DEG C, and dip time is 50~90min.In actual use, concentration of lye is too high, gained cellulose sulfonic acid fat Solubility can reduce, and viscose filtration is difficult；Concentration of lye is too low, and pulp material puffed degree is too high, and squeezing is difficult；Temperature is too high, Cellulose drop is poly- fast, accelerates side reaction, influences viscose filtration；Temperature is too low, and pulp puffed degree is high, and squeezing is difficult.

To better implement the present invention, in described step A, described grinder is located at connection treating tank and squeezer Pipeline in.

To reach more preferable alkalization rate, in described step A, the temperature of the slurry congee is 30~60 DEG C, the grinding The milling time of machine is 10~40s.

In the preparation field of viscose rayon, the material after slurry congee is squeezed by squeezer can be divided into two parts, and a part is It is mingled with the unnecessary alkali lye of fiber and impurity, another part is the mixture of the solid-state and liquid that have extruded excessive moisture, i.e. alkali Cellulose, in described step B, the pressing temperature of the squeezer is 57~63 DEG C, squeezing multiple is 2.2~2.8.

Squeezing is unnecessary alkali lye, hemicellulose, impurity to be extruded pulp after dipping, improves alkali cellulose purity, The degree of squeezing is represented with dry pulp before quality and the dipping that squeezing multiple is after being squeezed with pulp and mass ratio value；After squeezing Alkali cellulose it is very close, plate is hard, surface area diminishes, be unfavorable for the processing in later stage, the purpose of crushing be make alkali cellulose into For tiny, loose bits shape, surface area is increased, is advantageous to the uniformity of later stage process processing, the representation of degree of grinding One of alkali cellulose constant volume weight, the present invention in referred to as degree of grinding, refer to alkali cellulose crush after, the weight of unit volume Amount, is typically represented, alkali cellulose crushing effect is better, then constant volume weight is smaller, and its surface area is bigger with g/L.

In described step B, slurry congee is sent to pulverizer after squeezing and crushed, and the degree of grinding of the pulverizer is 120~180g/L, by the adjustment for reasonably squeezing multiple and degree of grinding, it is possible to increase alkali cellulose in post-production process Performance uniformity, prevent part from receiving strong extruding, enter so as to hinder oxygen, reduce the speed for dropping poly- step；Obtained after crushing Alkali cellulose first fibre content be 29~31%, alkali content be 15~17%, in alkali lye half fine content control 10g/L with It is interior.

Further, in described step C, described alkali lye is 140~200g/l of concentration sodium hydroxide solution, pure The 2~10% of the addition reactor volume of oxygen, poly- reaction time control drops in 30~60min.

In described step D, the addition of carbon disulfide be first fibre content in alkali cellulose made from step B 25~ 37%, in practical application, carbon disulfide addition is very few, yellow reaction is incomplete, filtration difficulty；Carbon disulfide addition mistake Height, yellow overreact, accessory substance are more.

Further, in described step D, the control of described yellow reaction time is in 45~50min, yellow reaction temperature Spend for 20~30 DEG C.

Further, in described step D, described dissolving is that cellulose sulfonate is mixed with solvent, is stirred Grinding is mixed and stirred, described solvent includes the sulfurous acid that concentration is 25~45 g/L sodium hydroxide solutions and concentration is 5~10 g/L Sodium water solution.

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 the further product performance for improving viscose rayon, the present invention is also improved spinning drawing technique, is wrapped Include low sour high salt and relax acid bath technique and high stretching spinning modeling technique etc., be in particular in, described spinning drawing step is as follows：

F：By cellulose sulfonate solution is filtered, deaeration, delivers to spinning-drawing machine after maturation, extruded and spun by the shower nozzle of spinning-drawing machine Silk thread forms tow after a bath, and coagulating bath that a bath uses includes 90~120g/L sulfuric acid, 220~280g/L The zinc sulfate of sodium sulphate and 8~15g/L；

G：Tow after a bath is sent into two baths by one of drafting machine, and the coagulating bath that two bath uses includes 18~22g/ L sulfuric acid, the degree of draft of one of drafting machine is 50~100%；

H：Tow after two baths is sent into three baths by two drafting machines, and it is 1 that the coagulating bath that three bath uses, which includes pH value, ~3 sulfuric acid, the degree of draft of two drafting machine is 40~60%；

I：Tow after three baths delivers to post processing part by three drafting machines, and the degree of draft of three drafting machine is 5 ~15%.

As described above, the present invention is formed tow after draw-spinning process, ensured using three bath wet spinning technologies, viscose glue More secondary responses of fiber, in the process, fibre section can form clearly secondary response microscope interface, have improve it is fine Intensity, increase fibrous absorbent speed and the characteristic for increasing fiber water-retaining property are tieed up, in spinning technique, tow passes through one of drawing-off Machine, two drafting machines, three drafting machines are stretched, and are more beneficial for improving the fragility of fiber, are improved the degree of stretching of fiber.

Described post processing includes the desulfurization of the tow progress formed to spinning drawing, bleaches and oil, and the desulfurization makes The sodium carbonate that the vulcanized sodium and concentration that desulfurizing agent is 4~8g/L by concentration are 1~4g/L forms；It is described to bleach the drift used The hydrogen peroxide that white agent is 0.3~0.6g/L of concentration；The finish addition used that oils is 7~9g/L, tow after oiling PH value is 6.5~7.

The present invention uses gentle sulfur removal technology, reduces the damage of product strength, degree of stretching, in actual use, vulcanization The more existing sodium hydroxide used of desulfurizing agent, the sodium sulfite of sodium and sodium carbonate composition are gentleer, and sodium carbonate can neutralize tow The sulfuric acid brought from acid bath, after sulfur removal technology, the pH value of tow is can adjust 8~11；Hydrogen peroxide bleaching agent is compared with sodium hypochlorite Gentleer Deng bleaching agent, the pH value of viscose rayon prepared by the present invention should be controlled in the range of 6.5~7, can also by washing, Multiple-effect acid（Organic acid）Mode adjust pH value, within the range, the strength and elongation of viscose final product is unaffected, Qiang Shen Degree 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, bleaching time is 1~2min；The temperature of the finish is 50~55 DEG C.

In the present invention, described post processing also includes drying, and described drying is that the tow formed to spinning drawing enters Capable desulfurization, the tow bleached and obtained after oiling use drying machine drying, and drying temperature is 75~115 DEG C, after drying, is obtained High-strength flatness viscose rayon product, product regain are controlled 11~13.5%.

The present invention compared with prior art, has the advantages that：

（1）Viscose rayon of the present invention is the tencel kind to realize by technological innovation, and it is short to belong to viscose glue The great innovation of fiber and cellulose fibre production technical field, the viscose rayon are different from traditional viscose rayon product and cotton Fibre, having and be different from common viscose fiber and the index system of Modal fibre, the intensity of fiber reaches more than 3.1cN/dtex, It is higher by 30% or so than common bio-based chopped fiber intensity, close to Modal, the high intensity with Modal fibre, low elongation, The characteristics of degradable so that fabric is unlikely to deform, and also has, Modal more preferable hygroscopicity fine compared with cotton and gas permeability, and feel Softness, smoothly, outward appearance are beautiful, can effectively substitute existing differential viscose rayon, add improving viscose rayon lower procedure While work performance, moreover it is possible to promote exploitation and the industrial upgrading of downstream new textile, there is good economic benefit and society Benefit.

（2）For the viscose rayon of the present invention compared with the higher Modal of performance indications, cost is lower, causes price than not generation Your fiber is low 4000~5000 yuan/ton, mainly there is the production cost that the following aspects reduces viscose rayon of the present invention：A. in The raw material sources of viscose rayon of the present invention are extensive, it is desirable to and it is low, the relatively low raw material of methylcellulose content may be selected（Methylcellulose contains Amount is higher, and price is higher）, combination more than one or both of cotton pulp, bamboo pulp, wood pulp, jute pulp, Non-scale requirement can be used； B. during present invention process, the more conventional product of dosage of alkali is lower；C. in the spinning process in present invention process step, spinning The spinning speed of machine is 45~55m/min, than the 30m/min in Modal production process faster, and the acid bath composition optimized and drawing-off Technique, the control of each working procedure parameter of overall balance can be accomplished, production efficiency is high, and energy consumption is low, so as to reduce production cost.

（3）The present invention is using three bath wet spinning technologies, and using low sour high salt, reaction condition is gentle for coagulating bath, and Viscose glue forms tow after draw-spinning process, ensure that more secondary responses of fiber, viscose rayon of the invention have with it is common The viscose rayon secondary response interface different with Modal fibre is, it is necessary to which explanation, secondary response interface are horizontal according to fiber Section inhales what color ability was differently formed to dyestuff, i.e. the cortex and sandwich layer of fiber, and cortex is small to dyestuff suction color ability, and dyeing is inclined Shallow, sandwich layer is big to dyestuff suction color ability, and color is partially deep, and cortex has the higher degree of orientation, and cortex is more, and fracture strength is higher, And sandwich layer is more, water swelling capacity is higher；By fiber of the present invention it is dyed after do fibre section, viscose rayon of the present invention Fibre section is shown 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 the viscose rayon of the present invention has the characteristics of high-strength, flatness, while also have compared with common viscose fiber There is appropriate water imbibition, fiber skin-friendly has significant advantage；Fibre section is done after Modal fibre dyeing, is seen under the microscope Examine, no secondary response interface, for viscose rayon of the invention with Modal fibre under equal dyeing condition, viscose glue of the invention is fine Dimension inhales color depth than Modal, and dye-uptake is high, and uniformity is more preferable, and the good color fastness of finished product.

（4）To ensure that high-strength flatness viscose rayon secondary response interface has suitable cortex, a sandwich layer ratio, the present invention from Technology is set out, and has accomplished improvement acid bath technique, such as reduces sulfuric acid concentration, and reaction is slow, improves skin thickness；Change viscose glue Index, such as viscose ripening degree, first fibre content, alkali content index, so as to ensure that the fracture strength of viscose rayon of the present invention height.

（5）Compared with adhering process of the prior art, alkali cellulose hemicellulose level produced by the present invention is low, control Within 10g/L, it is understood that：Hemicellulose refers to the degree of polymerization in 50~200 beta cellulose and degree of polymerization ＜ 50 gamma fiber Element, as long as the influence of hemicellulose has the following aspects：A. the uniformity of alkali cellulose is influenceed；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, sulphonic acid ester Solubility reduces；D. the filtering of viscose glue is influenceed, the solubility of sulphonic acid ester reduces, and the potential aldehyde radical in its end is oxidized to carboxyl and ash Metal ion in point is such as：Ferrous ion, manganese ion, calcium ion, magnesium ion, the extremely strong complex compound of viscosity is formed, causes viscose glue Filtration difficulty, yield poorly；E. hemicellulose is more, and the physical and mechanical properties of viscose rayon is poorer.The present invention, can by grinding mill The slurry congee for being sent into squeezer is ground in advance, milling time is 10~40s, and the slurry congee after grinding is squeezed with squeezer Afterwards, separation obtains mixed alkali liquor and alkali cellulose, contains hemicellulose and other impurities in mixed alkali liquor, through pulverizer powder Broken, the multiple of squeezing is 2.2~2.8, degree of grinding 120-180g/L, by mechanism, to improve the reactivity worth for starching congee, Ensure being smoothed out for viscose rayon production.

（6）The pulp material that the present invention uses can choose any one in cotton pulp, bamboo pulp, wood pulp, jute pulp or both with On mixture can be prepared in any proportion, raw material scope is widely applicable, and technical requirements prepare relatively low, raw material Cost is relatively low.

（7）In step A of the present invention, alkali lye is 110~240g/L of concentration sodium hydroxide solution, and the temperature of steeping liquor is 30~60 DEG C, dip time is 50~90min.By rational parameter setting, ensure to squeeze and that filters is smoothed out；Alkali lye Excessive concentration, gained cellulose sulfonic acid fat solubility can reduce, and viscose filtration is difficult；Concentration of lye is too low, and pulp material is expanded Height is spent, squeezing is difficult；Temperature is too high, and cellulose drop is poly- fast, accelerates side reaction, influences viscose filtration；Temperature is too low, and pulp is swollen Change degree is high, and squeezing is difficult.

（8）The present invention uses multistage purification, and such as grinding, squeezing crush, rubbing, alkali lye cascade utilization, are such as impregnating respectively Before stage, rubbing add alkali lye after the stage, cellulose combination alkali content can not only be mentioned, reach improve alkali lye comprehensive utilization ratio Purpose, simultaneously, moreover it is possible to effectively reduce the input cost of auxiliary material alkali lye, reduce the production cost of viscose rayon.

（9）The present invention is ground, squeezing can obtain first fibre content 29~31%, the alkali fiber of alkali content 15~17% after crushing Element, the alkali cellulose can be sent directly into viscose rayon production system after rubbing, aoxidizing drop and gather, and cellulose viscose manufacturing technique can be adopted With common process, after obtaining viscose glue such as yellow, then by filtering, maturation, deaeration, spinning to obtain viscose rayon.

（10）In the present invention, alkali cellulose fiber is handled through kneader twin screw device, makes fiber sub-wire, broom Change, reach the cell membrane for destroying cellulose fibre, remove the small molecule in cellulose, so as to improve fibrin reaction performance, carry High-cellulose combination alkali content, reaches 6~8%（Mass percent）.

（11）The F-step orientation drop of the present invention is poly-：The alkali cellulose that step D is obtained is 140~200g/L's with concentration Alkali lye is mixed to form the slurry congee that concentration is 4~8%, and slurry congee is delivered into orientation drops poly- reactor, and the reaction time is 30~60min, After dropping and gathering, the alkali cellulose degree of polymerization is set to be reduced to 400~600 by 650~1200, first fibre purity reaches 98.0~98.5%, than passing System technique can improve 2~3%, and the poly- drop more experienced than tradition of orientation drop is poly- to reduce the fine loss 3~5% of first, improves utilization rate of raw materials, Production cost is saved, and molecule drop is poly- more uniformly, abundant, effective.

（12）The draft process of the present invention, high drawing-off technology, a degree of draft are 50~100% step by step for use, and drawing-off is too high, Lousiness is more, and drawing-off is too low, low intensity；Two degree of drafts are 40~60%；Three degree of drafts are that 5~15% drawing-offs are too high, and lousiness is more, drawing-off Too low, intensity declines, and by the control of rational degree of draft, improves the fragility of fiber, improves fibre strength, and reduce hair The amount of silk, improve the appearance property of product.

（13）The present invention sulfur removal technology in vulcanized sodium and sodium carbonate composition the more existing sodium hydroxide used of desulfurizing agent, Sodium sulfite is gentleer, can reduce the damage of fiber product intensity, degree of stretching, and sodium carbonate can neutralize tow from acid bath The sulfuric acid brought, after sulfur removal technology, the pH value of tow is can adjust 8~11.

（14）The bleaching agent that the present invention uses is gentle, is more heated compared with bleaching agents such as sodium hypochlorite using hydrogen peroxide bleaching agent With the pH value of viscose rayon prepared by the present invention should be controlled in the range of 6.5~7, can also pass through washing, multiple-effect acid（Organic acid） Mode adjust pH value, within the range, the strength and elongation of viscose final product is unaffected, and strength and elongation is high.

（15）The present invention is reasonable in design, and in the production process of identical viscose rayon product, summary raw material is chosen, system Standby process modification etc., the production cost of the reduction viscose rayon product of high degree, its price is compared with Modal fibre Low 4000~5000 yuan/ton, downstream raw material use cost can be greatly lowered, available for home textile, non-woven fabrics etc., particularly underwear And facial mask, hygenic towelette etc., to spin, weave cotton cloth etc., down-stream enterprise brings more high added value and wide market prospects, significantly carries Rise the market competitiveness of enterprise.

Brief description of the drawings

Fig. 1 is the fibre section cross section of the high-strength flatness viscose rayon of delustring superfine type of the present invention；

Fig. 2 is the fibre section cross section of Modal；

Fig. 3 is the fibre section cross section of tencel.

Embodiment

Goal of the invention, technical scheme and the beneficial effect of the present invention are described in further detail below.

It is noted that described further below is all exemplary, it is intended to which the required present invention is provided further Bright, unless otherwise indicated, all technologies used herein and scientific terminology are with the common skill with the technical field of the invention The identical meanings that art personnel are generally understood that.

The fibrous raw materials such as tencel, Modal, CUP, viscose rayon are regenerated by raw material of natural cellulosic materials The bio-based fibrous raw material formed, wherein, with the occupation rate of market highest of viscose rayon, but it is viscous with common variety in recent years Glue fiber scale is drastically expanded, and raw material supply is nervous, and the exploitation of downstream new textile and industrial upgrading are progressively restricted, To overcome this phenomenon, a series of difference by taking patent document CN102296373A, CN1632189, CN102251301A as an example Change viscose rayon to be suggested, from its disclosed patented technology, this kind of differential viscose rayon is to produce work by changing The mode of skill realizes, but for increasingly fierce market competition, and differential viscose rayon is not to a greater extent The exploitation for meeting downstream new textile and industrial upgrading, especially equally using natural cellulosic materials as raw material regeneration form Tencel, Modal, the fibrous raw material such as CUP development so that the occupation rate of market of viscose rayon reduces increasingly.Herein On the basis of, the present invention proposes a kind of high-strength flatness viscose rayon, and the viscose rayon product has high-strength, flatness product special Property, while also there is high-selenium corn characteristic, product skin-friendly outclass Modal fibre, slightly better than cotton fiber.

The high-strength flatness viscose rayon of delustring superfine type of the present invention maintains exclusive fibre in fiber forming process Structure is tieed up, there is the characteristics of high-tenacity, its dry fracture strength and wet breaking strength improve 25% left side compared with common viscose fiber The right side, also there is significant difference with differential viscose rayon, from product index as can be seen that the product of high-strength flatness viscose rayon refers to Mark meets：0.8~1.110dtex of fiber number, does the cN/dtex of fracture strength >=3.20, wet breaking strength >=1.60cN/dtex, and So that patent document records CN102296373A, CN1632189, CN102251301A as an example, its product refers to differential viscose rayon Mark is as follows：CN102296373A meets the cN/dtex of 0.44~0.78dtex of fiber number, dry fracture strength >=3.10, wet breaking strength ≥2.1cN/dtex；CN1632189 meets the cN/dtex of 0.90~1.40dtex of fiber number, dry fracture strength >=2.50, wet fracture Intensity >=1.20cN/dtex；CN102251301A meets the cN/dtex of the dtex of fiber number 1.11, intensity >=2.9, from These parameters As can be seen that the fibre strength of the high-strength flatness viscose rayon of delustring superfine type of the present invention be substantially better than it is existing differential Viscose rayon.

The high-strength flatness viscose rayon of delustring superfine type of the present invention is compared with Modal fibre, tencel respectively again Right, alignments are as follows：

Fibre section is done after high-strength flatness viscose rayon, Modal fibre, tencel are dyed respectively, its fibre section is existed Amplify 2000 times under microscope to be observed, as shown in Figures 1 to 3, Fig. 1 is the high-strength flatness viscose rayon of delustring superfine type of the present invention Fibre section cross section, as shown in figure 1, after the high-strength dyed processing of flatness viscose rayon of the present invention, its fiber sheath Layer, the color of sandwich layer show shallow, deep difference respectively, differ greatly, and cortex is partially shallow, and sandwich layer is substantially partially deep, and it is clear to exist Secondary response interface, ratio is moderate, it is ensured that the product has the characteristics of high-strength, flatness, while also has appropriate water suction Property, fiber skin-friendly have 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 Fig. 2 after the dyed processing of Modal fibre, its Fibrocortex is deep, shallow consistent with the color of sandwich layer, and without obvious secondary interface, the products characteristics enhance the hydrophobicity of fiber, inhales Water rate is poor, so that its skin-friendly is deteriorated.

Fig. 3 is the fibre section sectional view of tencel, as shown in figure 3, after the dyed processing of tencel, its fibrocortex and sandwich layer Color it is deep, shallow consistent, without obvious secondary interface, the products characteristics have the excellent hygroscopicity of plain edition viscose rayon, soft and smooth concurrently Outside the advantages that elegant property, comfortableness, it is low to overcome common viscose fiber strength, it is especially wet strong low the defects of, its strength is several It is close with terylene.

Just because of the above-mentioned characteristic of product, determine that the high-strength flatness viscose rayon of delustring superfine type of the present invention is expired It is enough lower index：

The dtex of fiber number 0.8~1.11,

The cN/dtex of dry fracture strength >=3.10, wet breaking strength >=1.60cN/dtex,

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%, overlength fiber rate≤0.5%,

Over-length fibre≤4.0mg/100g, fault≤4.0mg/100g.

In These parameters, the assay method for doing fracture strength is GB/T 14337, and the assay method of wet breaking strength is GB/ T 14337, the intensity produced needed for 5% elongation under wet condition are completed by GB/T 14337, the survey of dry elongation at break The method of determining is GB/T 14337, and the assay method of wet elongation at break is GB/T 14337, the assay method of line density deviation ratio It is GB/T 14335, the assay method of residual sulphur is FZ/T 50014, and the assay method of length variation rate is GB/T 14336, overlength The assay method of fiber rate is GB/T 14336, and the assay method of over-length fibre is GB/T 14336, and the assay method of fault is GB/T 14339, the assay method of whiteness is FZ/T 50013, and the assay method of radial water swelling capacity is GB/T 6503.

The embodiment of the explanation present invention, certainly, protection of the invention are enumerated with several exemplary embodiments below Scope is not limited to following examples.

Embodiment 1

The high-strength flatness viscose rayon of delustring superfine type that the present embodiment is related to be by pulp material successively through impregnating, grinding, Squeezing is crushed, crumpled, drop is gathered, obtained from after yellow, dissolving, filtering, deaeration, maturation, spinning drawing and post processing, through surveying Fixed, the high-strength flatness viscose rayon meets：

The dtex of fiber number 0.8~1.11；

The cN/dtex of dry fracture strength >=3.10；

Wet breaking strength >=1.60cN/dtex；

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 present embodiment and the difference of embodiment 1 are：The high-strength flatness viscose rayon of delustring superfine type that the present embodiment is related to Also meet：

Whiteness >=85%；

Line density deviation ratio≤± 11.0%；

Residual sulphur≤12.0mg/100g；

Length variation rate≤± 11.0%；

Overlength fiber rate≤0.5%；

Over-length fibre≤4.0mg/100g；

Fault≤4.0mg/100g.

Embodiment 3

A kind of preparation method of the high-strength flatness viscose rayon of delustring superfine type, step are as follows：

A：Pulp material is impregnated in the treating tank equipped with alkali lye, the slurry that concentration is 3% is made after being ground by grinder Congee；

B：Squeezer is delivered to by congee is starched made from step A, pulverizer is delivered to after squeezing and is crushed, obtains alkali fiber Element, the alkali cellulose is delivered into kneading machine, the slurry congee that concentration is 30% is obtained after processing；

C：Reactor is delivered to by being starched made from step B after congee mixes with alkali lye, pure oxygen is added in the reactor, is obtained after drop is poly- Obtain the alkali cellulose that the degree of polymerization is 400, first fibre purity is 98.0%；

D：Alkali cellulose made from step C is delivered into xanthating machine, carbon disulfide is added in xanthating machine, is reacted through yellow Afterwards, the cellulose sulfonate for yellow being reacted to obtain dissolves with solvent, and the cellulose sulfonate solution that concentration is 10.0% is made；

E：By cellulose sulfonate solution made from step D is filtered, deaeration, after maturation, the delustering agent of addition is spun Silk stock solution, then viscose rayon is made after spinning drawing and post processing in the spinning solution of acquisition.

In the present embodiment, pulp material is bamboo pulp.

After testing, the viscose rayon obtained by the present embodiment meets the high-strength flatness viscose rayon of superfine type of the present invention Product performance.

Embodiment 4

A：Pulp material is impregnated in the treating tank equipped with alkali lye, the slurry that concentration is 6% is made after being ground by grinder Congee；

B：Squeezer is delivered to by congee is starched made from step A, pulverizer is delivered to after squeezing and is crushed, obtains alkali fiber Element, the alkali cellulose is delivered into kneading machine, the slurry congee that concentration is 40% is obtained after processing；

C：Reactor is delivered to by being starched made from step B after congee mixes with alkali lye, pure oxygen is added in the reactor, is obtained after drop is poly- Obtain the alkali cellulose that the degree of polymerization is 600, first fibre purity is 98.5%；

D：Alkali cellulose made from step C is delivered into xanthating machine, carbon disulfide is added in xanthating machine, is reacted through yellow Afterwards, the cellulose sulfonate for yellow being reacted to obtain dissolves with solvent, and the cellulose sulfonate solution that concentration is 9.0% is made；

In the present embodiment, pulp material is the mixture of cotton pulp and bamboo pulp, mixed proportion 1:2, the polymerization of pulp material Spend for 700.

In the present embodiment step A,

Described alkali lye is concentration 110g/L sodium hydroxide solution, and the temperature of steeping liquor is 30 DEG C, and dip time is 50min；Described grinder is in the pipeline of connection treating tank and squeezer.

Embodiment 5

A：Pulp material is impregnated in the treating tank equipped with alkali lye, the slurry that concentration is 4% is made after being ground by grinder Congee；

B：Squeezer is delivered to by congee is starched made from step A, pulverizer is delivered to after squeezing and is crushed, obtains alkali fiber Element, the alkali cellulose is delivered into kneading machine, the slurry congee that concentration is 36% is obtained after processing；

C：Reactor is delivered to by being starched made from step B after congee mixes with alkali lye, pure oxygen is added in the reactor, is obtained after drop is poly- Obtain the alkali cellulose that the degree of polymerization is 500, first fibre purity is 98.2%；

D：Alkali cellulose made from step C is delivered into xanthating machine, carbon disulfide is added in xanthating machine, is reacted through yellow Afterwards, the cellulose sulfonate for yellow being reacted to obtain dissolves with solvent, and the cellulose sulfonate solution that concentration is 9.6% is made；

In the present embodiment, pulp material be cotton pulp, bamboo pulp and wood pulp mixture, mixed proportion 2：1:4, pulp polymerization Spend for 1200, in described step A, alkali lye is concentration 240g/L sodium hydroxide solution, and the temperature of steeping liquor is 60 DEG C, Dip time is 90min；The temperature of the slurry congee is 30 DEG C, and the milling time of the grinder is 10s.

Embodiment 6

A：Pulp material is impregnated in the treating tank equipped with alkali lye, the slurry that concentration is 5% is made after being ground by grinder Congee；

B：Squeezer is delivered to by congee is starched made from step A, pulverizer is delivered to after squeezing and is crushed, obtains alkali fiber Element, the alkali cellulose is delivered into kneading machine, the slurry congee that concentration is 32% is obtained after processing；

C：Reactor is delivered to by being starched made from step B after congee mixes with alkali lye, pure oxygen is added in the reactor, is obtained after drop is poly- Obtain the alkali cellulose that the degree of polymerization is 450, first fibre purity is 98.4%；

D：Alkali cellulose made from step C is delivered into xanthating machine, carbon disulfide is added in xanthating machine, is reacted through yellow Afterwards, the cellulose sulfonate for yellow being reacted to obtain dissolves with solvent, and the cellulose sulfonate solution that concentration is 9.8% is made；

In the present embodiment, pulp material is the mixture of cotton pulp, bamboo pulp, wood pulp and jute pulp, mixed proportion 2:1:1:1, Pulp polymer is 650；In step A, described alkali lye is concentration 150g/L sodium hydroxide solution, and the temperature of steeping liquor is 45 DEG C, dip time 60min；The temperature of the slurry congee is 60 DEG C, and the milling time of the grinder is 40s.

Embodiment 7

The present embodiment and the difference of embodiment 6 are：Pulp is wood pulp, the degree of polymerization 700；Congee is starched described in step A Temperature is 45 DEG C, and the milling time of the grinder is 60s.

Embodiment 8

The present embodiment and the difference of embodiment 5 are：In step B, the pressing temperature of the squeezer is 57 DEG C, pressed It is 2.2 to squeeze multiple, and degree of grinding is 120 g/L, by the adjustment for reasonably squeezing multiple and degree of grinding, it is possible to increase post-production The performance uniformity of alkali cellulose in process, prevent part from receiving strong extruding, enter so as to hinder oxygen, reduce and drop poly- step Speed.

Embodiment 9

The present embodiment and the difference of embodiment 6 are：In step, pulp material is cotton pulp, bamboo pulp, wood pulp and jute pulp Mixture, the degree of polymerization 1200, mixed proportion 2：3：1：1；In stepb, the pressing temperature of the squeezer be 63 DEG C, It is 2.8 to squeeze multiple, and degree of grinding is 180 g/L；In described step C, described alkali lye is concentration 140g/ L hydroxide Sodium solution, the addition of pure oxygen is 2% in reactor, drops poly- reaction time control in 30min.

Embodiment 10

The present embodiment and the difference of embodiment 6 are：

In stepb, the pressing temperature of the squeezer be 60 DEG C, squeezing multiple be 2.5, degree of grinding is 160 g/L； In described step C, described alkali lye is concentration 180g/ L sodium hydroxide solution, and the addition of pure oxygen is in reactor 10%, poly- reaction time control is dropped in 60min；In described step D, the addition of carbon disulfide is that alkali made from step B is fine The 25% of first fibre content in dimension element；In 45min, yellow reaction temperature is 20 DEG C for described yellow reaction time control.

Embodiment 11

The present embodiment and the difference of embodiment 6 are：In step C, described alkali lye is concentration 160g/ L sodium hydroxide Solution, the addition of pure oxygen is 6% in reactor, drops poly- reaction time control in 40min；In step D, the addition of carbon disulfide Measure as 37% of first fibre content in alkali cellulose made from step B；Described yellow reaction time control is anti-in 50min, yellow It is 30 DEG C to answer temperature, and described dissolving is that cellulose sulfonate is mixed, stirred and ground with solvent, described solvent bag The sodium sulfite aqueous solution that concentration is 25g/L sodium hydroxide solutions and concentration is 5g/L is included, described solution temperature is 10 DEG C, molten The solution time is 30min.

Embodiment 12

A kind of preparation method of the high-strength flatness viscose fiber of extinction type, comprises the following steps：

C：Reactor is delivered to by being starched made from step B after congee mixes with alkali lye, pure oxygen is added in the reactor, is obtained after drop is poly- Obtain the alkali cellulose that the degree of polymerization is 600, first fibre purity is 98.0%；

D：Alkali cellulose made from step C is delivered into xanthating machine, carbon disulfide is added in xanthating machine, is reacted through yellow Afterwards, the cellulose sulfonate for chrysanthemum being reacted to obtain dissolves with solvent, and the cellulose sulfonate solution that concentration is 9.6% is made；

E：By cellulose sulfonate solution made from step D is filtered, deaeration, after maturation, adds delustering agent and obtains spinning Stoste, then viscose rayon is made after spinning drawing and post processing in the spinning solution of acquisition.

In above-mentioned steps A, pulp material is the mixture of cotton pulp, bamboo pulp, wood pulp and jute pulp, the degree of polymerization 1100, is mixed Ratio is 3：2：1：1；Described alkali lye is sodium hydroxide, and its concentration is 180g/L, and dipping temperature is 50 DEG C, and dip time is 55min；Described grinder is in the pipeline of connection treating tank and squeezer, and the temperature that congee is starched after grinding is 45 DEG C, grinding Time be 20s；In stepb, the pressing temperature of the squeezer be 60 DEG C, squeezing multiple be 2.6 times, the crushing of pulverizer Spend for 160g/L；In step C, described alkali lye is concentration 200g/ L sodium hydroxide solution, the addition of pure oxygen in reactor For 10%, poly- reaction time control drops in 60min.

In the step D of the present embodiment, the addition of carbon disulfide is first fibre content in alkali cellulose made from step B 25%；Described yellow reaction time control is 21 DEG C in 46min, yellow reaction temperature, and described dissolving is by cellulose sulphur Acid esters is mixed with solvent, stirred and ground, and described solvent is 26g/L sodium hydroxide solutions including concentration and concentration is 6 G/L sodium sulfite aqueous solution, described solution temperature are 10 DEG C, dissolution time 35min.

In the present embodiment, pulp material is the mixture of cotton pulp, bamboo pulp, wood pulp and jute pulp, the degree of polymerization 1000, mixing ratio Example is 4：2：1：1.

In step D, described spinning drawing comprises the following steps that：

F：By cellulose sulfonate solution is filtered, deaeration, delivers to spinning-drawing machine after maturation, extruded and spun by the shower nozzle of spinning-drawing machine Silk thread forms tow after a bath, the coagulating bath that a bath uses include 90g/L sulfuric acid, 220g/L sodium sulphate and 8g/L zinc sulfate；In step D, the addition of carbon disulfide is 25% of first fibre content in alkali cellulose made from step B；Institute In 46min, yellow reaction temperature is 21 DEG C for the yellow reaction time control stated, described dissolving be by cellulose sulfonate with it is molten Agent is mixed, stirred and ground, and described solvent includes the Asia that concentration is 26g/L sodium hydroxide solutions and concentration is 6 g/L Aqueous sodium persulfate solution, described solution temperature are 10 DEG C, dissolution time 35min.

G：Tow after a bath is sent into two baths by one of drafting machine, and the coagulating bath that two bath uses includes 18g/L's Sulfuric acid, the degree of draft of one of drafting machine is 50%；

H：Tow after two baths is sent into three baths by two drafting machines, and it is 1 that the coagulating bath that three bath uses, which includes pH value, Sulfuric acid, the degree of draft of two drafting machine is 40%；

I：Tow after three baths delivers to post processing part by three drafting machines, and the degree of draft of three drafting machine is 5%。

Embodiment 13

The present embodiment and the difference of embodiment 12 are：

In step C, described alkali lye is concentration 190g/ L sodium hydroxide solution, and the addition of pure oxygen is in reactor 3%, poly- reaction time control is dropped in 50min；In step D, the addition of carbon disulfide is first in alkali cellulose made from step B The 30% of fine content；In 50min, yellow reaction temperature is 30 DEG C for described yellow reaction time control, described dissolving be by Cellulose sulfonate is mixed with solvent, stirred and ground, described solvent include concentration be 45g/L sodium hydroxide solutions and Concentration is 10 g/L sodium sulfite aqueous solution, and described solution temperature is 20 DEG C, dissolution time 50min.

In step E, described spinning drawing comprises the following steps that：

F：By cellulose sulfonate solution is filtered, deaeration, delivers to spinning-drawing machine after maturation, extruded and spun by the shower nozzle of spinning-drawing machine Silk thread forms tow after a bath, the coagulating bath that a bath uses include 120g/L sulfuric acid, 280g/L sodium sulphate and 15g/L zinc sulfate；

G：Tow after a bath is sent into two baths by one of drafting machine, and the coagulating bath that two bath uses includes 18~22g/ L sulfuric acid, the degree of draft of one of drafting machine is 60%；

H：Tow after two baths is sent into three baths by two drafting machines, and it is 3 that the coagulating bath that three bath uses, which includes pH value, Sulfuric acid, the degree of draft of two drafting machine is 45%；

I：Tow after three baths delivers to post processing part by three drafting machines, and the degree of draft of three drafting machine 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 present embodiment and the difference of embodiment example 13 are：In step E, described rear process include desulfurization, bleaching and on Oil, the sodium carbonate that the vulcanized sodium and concentration that the desulfurizing agent that the desulfurization uses is 4g/L by concentration are 4g/L form；The bleaching The bleaching agent used is concentration 0.3g/L hydrogen peroxide；The finish addition used that oils is 7g/L, tow after oiling PH value is 6.5.

Described spinning drawing step is as follows：

F：By cellulose sulfonate solution is filtered, deaeration, delivers to spinning-drawing machine after maturation, extruded and spun by the shower nozzle of spinning-drawing machine Silk thread forms tow after a bath, the coagulating bath that a bath uses include 100g/L sulfuric acid, 250g/L sodium sulphate and 10g/L zinc sulfate；

G：Tow after a bath is sent into two baths by one of drafting machine, and the coagulating bath that two bath uses includes 20g/L's Sulfuric acid, the degree of draft of one of drafting machine is 80%；

H：Tow after two baths is sent into three baths by two drafting machines, and it is 2 that the coagulating bath that three bath uses, which includes pH value, Sulfuric acid, the degree of draft of two drafting machine is 50%；

I：Tow after three baths delivers to post processing part by three drafting machines, and the degree of draft of three drafting machine 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 present embodiment and the difference of embodiment 13 are：In described spinning drawing step, a described bath temperature is 44 DEG C, two bath temperatures be 90 DEG C, three bath temperatures be 90 DEG C；The desulfurizing agent that the desulfurization uses by concentration be 8g/L vulcanized sodium and Concentration 1g/L sodium carbonate composition；The hydrogen peroxide bleached the bleaching agent used and be concentration 0.6g/L；It is described to oil what is used Finish addition is 9g/L, and the pH value of tow is 7 after oiling；Described desulfurization temperature is 50 DEG C, desulfurization time 3min；It is described Bleaching temperature be 50 DEG C, bleaching time 2min；The temperature of the finish is 50 DEG C.

Embodiment 16

A：Pulp material is impregnated in the treating tank equipped with alkali lye, described pulp material be cotton pulp, bamboo pulp, wood pulp and The mixture of jute pulp, the degree of polymerization 1100, mixed proportion 3：2：1：1；The concentration of alkali lye is 180g/L, and temperature is 50 DEG C, leaching The stain time is 55min；Ground after dipping through grinder, milling time 20s, it is 4% that concentration is made after grinding, and temperature is 45 DEG C Slurry congee；

B：Congee will be starched made from step A and delivers to squeezer, pressing temperature is 60 DEG C, and squeezing multiple is 2.6 times, after squeezing Deliver to pulverizer to be crushed, degree of grinding 120g/L, obtain alkali cellulose, the alkali cellulose is delivered into kneading machine, after processing Obtain the slurry congee that concentration is 35%；

C：Reactor is delivered to after the alkali lye for congee being starched made from step B with concentration is 190g/L is mixed, is added in the reactor 2% pure oxygen, drop obtain after poly- 50min the degree of polymerization be 450, the alkali cellulose that first fibre purity is 98.1%；

D：Alkali cellulose made from step C is delivered into xanthating machine, added in xanthating machine in alkali cellulose made from step B 35% carbon disulfide of first fibre content, at 20 DEG C after yellow 45min, by yellow react obtained cellulose sulfonate with it is molten Agent is dissolved, the sodium sulfite aqueous solution that described solvent is the sodium hydroxide that concentration is 25g/L and concentration is 5g/L, the temperature of dissolving Spend for 10 DEG C, dissolution time 30min, the cellulose sulfonate solution that concentration is 9.5% is made；

E：By cellulose sulfonate solution made from step D is filtered, deaeration, after maturation, adds a certain amount of delustering agent, The delustering agent of the present embodiment selects titanium dioxide, and spinning solution is obtained after stirring；

F：By cellulose sulfonate solution is filtered, deaeration, delivers to spinning-drawing machine after maturation, extruded and spun by the shower nozzle of spinning-drawing machine Silk thread forms tow after a bath, and the temperature of a bath is 42 DEG C, sulfuric acid of the coagulating bath used including 120g/L, 280g/L sodium sulphate and 15g/L zinc sulfate；

G：Tow after a bath is sent into two baths by one of drafting machine, and the temperature of two bath is 80 DEG C, the solidification used Bath includes 20g/L sulfuric acid, and the degree of draft of one of drafting machine is 60%；

H：Tow after two baths is sent into three baths by two drafting machines, and the temperature of described three baths is 80 DEG C, and what is used is solidifying Gu bath includes the sulfuric acid that pH value is 2, the degree of draft of two drafting machine is 45%；

The post processing of the present embodiment includes desulfurization, bleaches and oil and dry.The desulfurizing agent that described desulfurization uses is by dense The sodium carbonate composition for being 2g/L for 5g/L vulcanized sodium and concentration is spent, desulfurization temperature is 55 DEG C, desulfurization time 3min；The drift The bleaching agent used in vain is concentration 0.5g/L hydrogen peroxide, and bleaching temperature is 55 DEG C, bleaching time 1min；The use that oils Finish addition be 8g/L, the pH value of tow is 7 after oiling, and the temperature of finish is 55 DEG C；Described post processing drying is pair The desulfurization for the tow progress that spinning drawing is formed, the tow bleached and obtained after oiling use drying machine drying, and drying temperature is 115 DEG C, after drying, obtain the high-strength flatness viscose fiber product of extinction type.

Embodiment 17

A：Pulp material is impregnated in the treating tank equipped with alkali lye, the concentration of alkali lye is 120g/L, and temperature is 40 DEG C, leaching The stain time is 60min；Ground after dipping through grinder, milling time 15s, it is 4% that concentration is made after grinding, and temperature is 45 DEG C Slurry congee；

B：Congee will be starched made from step A and delivers to squeezer, pressing temperature is 60 DEG C, and squeezing multiple is 2.6 times, after squeezing Deliver to pulverizer to be crushed, degree of grinding 180g/L, obtain alkali cellulose, the alkali cellulose is delivered into kneading machine, after processing Obtain the slurry congee that concentration is 32%；

C：Reactor is delivered to after the alkali lye for congee being starched made from step B with concentration is 150g/L is mixed, is added in the reactor Enter 10% pure oxygen, drop obtain after poly- 40min the degree of polymerization be 600, the alkali cellulose that first fibre purity is 98%；

D：Alkali cellulose made from step C is delivered into xanthating machine, added in xanthating machine in alkali cellulose made from step B 32% carbon disulfide of first fibre content, at 26 DEG C after yellow 48min, by yellow react obtained cellulose sulfonate with it is molten Agent is dissolved, the sodium sulfite aqueous solution that described solvent is the sodium hydroxide that concentration is 35g/L and concentration is 8g/L, the temperature of dissolving Spend for 15 DEG C, dissolution time 40min, the cellulose sulfonate solution that concentration is 9.6% is made；

F：By cellulose sulfonate solution is filtered, deaeration, delivers to spinning-drawing machine after maturation, extruded and spun by the shower nozzle of spinning-drawing machine Silk thread forms tow after a bath, and the temperature of a bath is 40 DEG C, sulfuric acid of the coagulating bath used including 120g/L, 280g/L sodium sulphate and 15g/L zinc sulfate；

G：Tow after a bath is sent into two baths by one of drafting machine, and the temperature of two bath is 80 DEG C, the solidification used Bath includes 19g/L sulfuric acid, and the degree of draft of one of drafting machine is 60%；

The post processing of the present embodiment includes desulfurization, bleaches and oil and dry.The desulfurizing agent that described desulfurization uses is by dense The sodium carbonate composition for being 3g/L for 6g/L vulcanized sodium and concentration is spent, desulfurization temperature is 52 DEG C, desulfurization time 2.5min；It is described The hydrogen peroxide that the bleaching agent used is concentration 0.5g/L is bleached, bleaching temperature is 50 DEG C, bleaching time 2min；Described oil makes Finish addition is 9g/L, and the pH value of tow is 7 after oiling, and the temperature of finish is 53 DEG C；Described post processing is dried The desulfurization carried out to the tow that spinning drawing is formed, the tow bleached and obtained after oiling use drying machine drying, drying temperature For 75 DEG C, after drying, the high-strength flatness viscose fiber product of extinction type is obtained.

In step A, the pulp material is the mixture of cotton pulp, bamboo pulp, wood pulp and jute pulp, the degree of polymerization 1200, is mixed Ratio is 1：2：4：1.

Embodiment 18

B：Congee will be starched made from step A and delivers to squeezer, pressing temperature is 60 DEG C, and squeezing multiple is 2.6 times, after squeezing Deliver to pulverizer to be crushed, degree of grinding 130g/L, obtain alkali cellulose, the alkali cellulose is delivered into kneading machine, after processing Obtain the slurry congee that concentration is 35%；

C：Reactor is delivered to after the alkali lye for congee being starched made from step B with concentration is 150g/L is mixed, is added in the reactor Enter 5% pure oxygen, drop obtain after poly- 40min the degree of polymerization be 450, the alkali cellulose that first fibre purity is 98.1%；

D：Alkali cellulose made from step C is delivered into xanthating machine, added in xanthating machine in alkali cellulose made from step B 35% carbon disulfide of first fibre content, at 26 DEG C after yellow 48min, by yellow react obtained cellulose sulfonate with it is molten Agent is dissolved, the sodium sulfite aqueous solution that described solvent is the sodium hydroxide that concentration is 35g/L and concentration is 8g/L, the temperature of dissolving Spend for 15 DEG C, dissolution time 40min, the cellulose sulfonate solution that concentration is 9.5% is made；

F：By cellulose sulfonate solution is filtered, deaeration, delivers to spinning-drawing machine after maturation, extruded and spun by the shower nozzle of spinning-drawing machine Silk thread forms tow after a bath, and the temperature of a bath is 42 DEG C, sulfuric acid of the coagulating bath used including 100g/L, 230g/L sodium sulphate and 10g/L zinc sulfate；

G：Tow after a bath is sent into two baths by one of drafting machine, and the temperature of two bath is 85 DEG C, the solidification used Bath includes 20g/L sulfuric acid, and the degree of draft of one of drafting machine is 100%；

H：Tow after two baths is sent into three baths by two drafting machines, and the temperature of described three baths is 87 DEG C, and what is used is solidifying Gu bath includes the sulfuric acid that pH value is 2, the degree of draft of two drafting machine is 60%；

I：Tow after three baths delivers to post processing part by three drafting machines, and the degree of draft of three drafting machine is 15%。

The post processing of the present embodiment includes desulfurization, bleaches and oil and dry.The desulfurizing agent that described desulfurization uses is by dense The sodium carbonate composition for being 2g/L for 5g/L vulcanized sodium and concentration is spent, desulfurization temperature is 55 DEG C, desulfurization time 2min；The drift The bleaching agent used in vain is concentration 0.5g/L hydrogen peroxide, and bleaching temperature is 52 DEG C, bleaching time 1min；The use that oils Finish addition be 8g/L, the pH value of tow is 7 after oiling, and the temperature of finish is 53 DEG C；Described post processing drying is pair The desulfurization for the tow progress that spinning drawing is formed, the tow bleached and obtained after oiling use drying machine drying, and drying temperature is 95 DEG C, after drying, obtain the high-strength flatness viscose fiber product of extinction type.

In step A, the pulp material is the mixture of cotton pulp, bamboo pulp, wood pulp and jute pulp, the degree of polymerization 650, mixing ratio Example is 1：1：2：1.

The viscose rayon that embodiment 3~18 obtains is detected, indicator-specific statistics is as follows, and wherein embodiment 3~10 is shown in Table 1, embodiment 11~18 is shown in Table 2, and the desired value of the viscose rayon of embodiment 3~18 is averaged, then by the average value respectively with Modal fibre, differential viscose rayon（CN102296373A documents 1, CN1632189 documents 2, CN102251301A documents 3）And the test index of common viscose fiber is compared and is shown in Table 3.

Table 1：

Table 2：

Table 3：

Product produced by the present invention, can be divided into different credit ratings, such as embodiment 4 by the data drawn from table 1, table 2 For certified products, embodiment 7 is Grade A, and embodiment 10 is high-class product, by different application field point, as embodiment 16,18 is real The viscose rayon product prepared mainly applies to close SEILE textile field, produces high sth. made by twisting, high grade cotton yarn product, and strong with product The high domain requirements such as high sth. made by twisting that are applied to of degree are characterized；The viscose rayon product that embodiment 14,15 prepares mainly applies to give birth to Underwear, high-grade shuttle-woven fabric field are produced, and soft, comfortable pro-skin, and finished textile product dimensional stability are slided with product feel silk It is characterized well；The viscose rayon product that embodiment 12,13,17 prepares mainly applies to denim fabric field, and with it is bright, Softness, and characterized by finished textile product modification is small.

It is any to choose the high-strength flatness viscose rayon product of delustring superfine type being prepared in embodiment 3~18, such as implement Example 13, microscope sectional drawing is carried out to its fibre section, it is possible to find, its section, which remains with, clearly reacts vestige, its fibrocortex, The color of sandwich layer shows shallow, deep difference respectively, and cortex is substantially partially shallow, and sandwich layer is partially deep,（Internal layer+middle level）：" the face of outer layer Product " ratio is 58：37, belong to sandwich layer：Cortex=（40~70）：（30~60）In the range of.

By to the data analysis of table 3, high-strength flatness viscose rayon of the invention have be different from common viscose fiber, The index system of differential viscose rayon and Modal fibre, the dry fracture strength and wet breaking strength of viscose rayon of the present invention are bright It is aobvious to be higher than common viscose fiber, and elongation is significantly lower than common viscose fiber, is set by technological parameter so that it is of the invention Viscose rayon has obvious secondary response interface, so as to ensure that the characteristic of the high-strength flatness suitable with Modal, and its footpath It is higher than Modal fibre to water swelling capacity, there is the hygroscopicity higher than Modal, therefore skin-friendly is good compared with Modal fibre；This hair Bright viscose rayon is a kind of new viscose rayon, can effectively substitute existing Modal fibre and common viscose fiber, And production cost is lower, there is good economic and social benefit.

It is described above, be only presently preferred embodiments of the present invention, any formal limitation not done to the present invention, it is every according to Any simply modification, the equivalent variations made according to the technical spirit of the present invention to above example, each fall within the protection of the present invention Within the scope of.

Claims

A kind of 1. high-strength flatness viscose rayon of delustring superfine type, it is characterised in that：By pulp material successively through impregnating, grinding, pressing Squeeze and crush, crumple, dropping and gather, obtain high-strength flatness viscose glue after yellow, dissolving, filtering, deaeration, maturation, spinning drawing and post processing Fiber, the fiber meet：

0.8~1.11dtex of fiber number；

The cN/dtex of dry fracture strength >=3.10；

1.6~1.78cN/dtex of wet breaking strength；

The intensity ＞ 0.55cN/dtex needed for 5% elongation are produced under wet condition,

Dry elongation at break 11.0~19.0%；

Wet elongation at break 16.2~21.0%；

Crystallinity 40.0~45.0%；

Radial water swelling capacity 22~26%；

Dulling agent content 0.8~5%；

The high-strength flatness viscose glue preparation process is as follows：

A：Pulp material is impregnated in the treating tank equipped with alkali lye, the slurry congee that concentration is 3~6% is made after being ground by grinder；

B：Squeezer is delivered to by congee is starched made from step A, pulverizer is delivered to after squeezing and is crushed, obtains alkali cellulose, will The alkali cellulose delivers to kneading machine, and the slurry congee that concentration is 30~40% is obtained after processing；

C：Reactor is delivered to by being starched made from step B after congee mixes with alkali lye, pure oxygen is added in the reactor, is gathered after drop is poly- It is right be 400~600, the alkali cellulose that first fibre purity is 98.0~98.5%；

D：Alkali cellulose made from step C is delivered into xanthating machine, carbon disulfide is added in xanthating machine, will after yellow is reacted The cellulose sulfonate that yellow reacts to obtain dissolves with solvent, and the cellulose sulfonate solution that concentration is 9.0~10.0% is made；

E：By cellulose sulfonate solution made from step D is filtered, deaeration, after maturation, the delustering agent of addition obtains spinning original Liquid, then viscose rayon is made after spinning drawing and post processing in the spinning solution of acquisition；

Described spinning drawing step is as follows：

F：It is thin by the shower nozzle extruding spinning of spinning-drawing machine by cellulose sulfonate solution is filtered, deaeration, delivers to spinning-drawing machine after maturation Tow is formed after flowing through a bath, the coagulating bath that a bath uses includes 90~120g/L sulfuric acid, 220~280g/L sulfuric acid The zinc sulfate of sodium and 8~15g/L；

G：Tow after a bath is sent into two baths by one of drafting machine, and the coagulating bath that two bath uses includes 18~22g/L's Sulfuric acid, the degree of draft of one of drafting machine is 50~100%；

H：Tow after two baths is sent into three baths by two drafting machines, and it is 1~3 that the coagulating bath that three bath uses, which includes pH value, Sulfuric acid, the degree of draft of two drafting machine is 40~60%；

I：Tow after three baths delivers to post processing part by three drafting machines, the degree of draft of three drafting machine for 5~ 15%；

In described step A, described alkali lye be 110~240g/L of concentration sodium hydroxide solution, the temperature of steeping liquor For 30~60 DEG C, dip time is 50~90min；

In described step B, the pressing temperature of the squeezer is 57~63 DEG C, squeezing multiple is 2.2~2.8；

In described step B, the degree of grinding of the pulverizer is 120~180g/L；

In described step C, described alkali lye is 140~200g/ of concentration L sodium hydroxide solution, pure oxygen in reactor Addition is 2~10%, drops poly- reaction time control in 30~60min；

The pulp be cotton pulp, bamboo pulp and wood pulp mixture, mixed proportion 2：1:4, the pulp degree of polymerization is 1200；

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 Spend for 80~90 DEG C；

In described step A, the temperature of the slurry congee is 30~60 DEG C, and the milling time of the grinder is 10~40s；

In described step D, the addition of carbon disulfide be first fibre content in alkali cellulose made from step B 25~ 37%；

In described step D, for the control of described yellow reaction time in 45~50min, yellow reaction temperature is 20~30 DEG C；

In described step D, described dissolving is that cellulose sulfonate is mixed, stirred and ground with solvent, described Solvent include concentration is 25~45 g/L sodium hydroxide solutions and concentration is 5~10 g/L sodium sulfite aqueous solution；

In described step D, described solution temperature is 10~20 DEG C, and dissolution time is 30~50min.
2. the preparation method of the high-strength flatness viscose rayon of delustring superfine type according to claim 1, it is characterised in that：Institute In the step A stated, described grinder is in the pipeline of connection treating tank and squeezer.
3. the preparation method of the high-strength flatness viscose rayon of delustring superfine type according to claim 1, it is characterised in that：Institute In the step E stated, described delustering agent is titanium dioxide.
4. the preparation method of the high-strength flatness viscose rayon of delustring superfine type according to claim 1, it is characterised in that：It is described Post processing include carrying out the tow that spinning drawing is formed desulfurization, bleach and oil, the desulfurizing agent that the desulfurization uses by The sodium carbonate composition that the vulcanized sodium and concentration that concentration is 4~8g/L are 1~4g/L；The bleaching agent used of bleaching is concentration 0.3~0.6g/L hydrogen peroxide；The finish addition used that oils is 7~9g/L, after oiling the pH value of tow be 6.5~ 7。
5. the preparation method of the high-strength flatness viscose rayon of delustring superfine type according to claim 4, it is characterised in that：It is described Desulfurization temperature be 50~55 DEG C, desulfurization time is 2~3min；Described bleaching temperature be 50~55 DEG C, bleaching time be 1~ 2min；The temperature of the finish is 50~55 DEG C.
6. the preparation method of the high-strength flatness viscose rayon of delustring superfine type according to claim 4, it is characterised in that：It is described Post processing also include drying, drying temperature is 75~115 DEG C, after drying, obtains the described high-strength flatness of delustring superfine type and glues Glue fiber product.