CN1111305A

CN1111305A - Fibre treatment

Info

Publication number: CN1111305A
Application number: CN93119389A
Authority: CN
Inventors: 克里斯托弗·D·波特
Original assignee: Courtaulds Fibres Holdings Ltd
Current assignee: Lion True Fiber Co ltd; Lenzing AG; Courtaulds Fibres Holdings Ltd
Priority date: 1992-10-21
Filing date: 1993-10-21
Publication date: 1995-11-08
Anticipated expiration: 2013-10-21
Also published as: FI951888A0; GB9222059D0; AU5285193A; CZ97295A3; ATE173515T1; SK283618B6; TW230791B; CZ288615B6; CA2147350A1; ZA937646B; WO1994009191A1; RU2126464C1; IN187366B; TR28688A; CN1048533C; EP0665904B1; HUT69599A; PL308482A1; HU218349B; PL174026B1

Abstract

The fibrillation tendency of solvent-spun cellulose fiber is reduced by treating the previously dried fiber with a chemical reagent containing at least two functional groups which are reactive with cellulose and which are electrophilic carbon-carbon double bonds, particularly vinyl sulfone groups, or precursors thereof or electrophilic three-membered heterocyclic rings or precursors thereof. The chemical reagent is preferably colorless and is preferably applied to the fiber from aqueous solution. The fiber may be contained in a woven or knotted fabric.

Description

Fibre treatment

The present invention relates to improvement to the method that reduces Lyocell fibre fibrillation tendency.

Known, cellulose fibre can be clamp-oned coagulating bath and made by the cellulose solution that will be dissolved in appropriate solvent.An example of this method is at US-A-4, description arranged in 246,221, and content wherein is incorporated herein by reference.Cellulose is dissolved in appropriate solvent, as tertiary amine N-oxide, N-methylmorpholine N-oxide for example.Then, gained solution is clamp-oned in the water bath by suitable spinning head, obtained endless tow, desolvate to remove, then drying through washing.This kind method is called " solvent spinning ", and the cellulose fibre that makes thus is called " molten spinning " cellulose fibre.Lyocell fibre is different with the cellulose fibre that is made by other already known processes, and those technologies are, makes cellulosic soluble derivative earlier, decomposes then to form cellulose, for example viscose process again.

Fiber has the fibrillation tendency, and this tendency is more obvious when dampness is subjected to mechanical stress.When fibrillation occurred in fibre structure and longitudinally is damaged, this moment, tiny fibrillation broke away from from ground, fiber top, thereby made fiber and fabric, had filoplume shape outward appearance as woven or knit goods.The DYED FABRICS that contains fibrillating fibre easily presents " frost is white " and influences attractive in appearance.It is believed that this fibrillation phenomenon is that the mechanical friction that is subjected to of fiber is caused in swelling attitude processing procedure.Make fiber be subjected to mechanical friction inevitably as moistening processing procedures such as dyeing.In general, temperature is high more, the processing time is long more, and original fiber degree is also serious more.As if Lyocell fibre responsive especially to this friction, thereby than the cellulose fibre of other type easily fibrillable more.The present invention relates to processing, to reduce or to suppress its fibrillation and be inclined to Lyocell fibre.Yet have been found that some such processing methods can have a negative impact to the mechanical performance of fiber,, make tendering of fiber, or reduce the processing characteristics, particularly its stainability of fiber and fabric as obdurability and extensibility.Confirm that one can be reduced fibrillation tendency effectively can avoid the processing method of above-mentioned adverse effect again perhaps be difficult.

EP-A-538,977 have described the method for the Lyocell fibre of the low fibrillation tendency of preparation, and that is exactly with handling fiber with the chemical reagent of two to six senses of fiber-reactive.Document shows, unprocessed color with the fiber of handling is basic identical, and think, with the functional group of fibrin reaction be exactly that those are generally used for active group in the cellulosic chemically-reactive dyes, as the complete works of third edition volume of Kirk-Othmer chemical technology 8(1979, Wiley-Interscience) 3742392 pages are entitled as the example of being mentioned in " dyestuff, reactivity ".Think in these functional groups that example preferably has the reactive halogen atom on many azines ring, pyridazine for example, the fluorine on pyrimidine or the s-triazine ring, chlorine or bromine atom.Relevant other example has vinyl sulfone(Remzaol and parent thereof.EP-A-538, the used chemical reagent plain atom of many azines halogen in ring most importantly among 977 embodiment, as with unique functional group of fibrin reaction, but use a kind of commercial dye in an embodiment, then then a chlorine atom and a vinyl sulfone(Remzaol group on triazine ring, with this as its reactive group.

EP-A-2273091 has described a kind of method of making the rich and powerful viscose rayon fibre of low fibrillation tendency.This method is to handle the fiber of handling elementary gel state when rich fibre is made at least with crosslinking agent that contains two acrylamide groups and base catalyst.The fine elementary gelinite of this richness is one to have the high swell gel of 190-200% water absorption, and having only always, the rich and powerful viscose rayon fibre of undried just has so high water absorption.Water absorption is defined as the moisture in the per unit weight adiabatic drying material.As a comparison, the viscose rayon fibre crossed of common undried only has the water absorption of 120-150%.Three acryloyls-six hydrogen-the 1,3,5-triazines and the N that address among the FR-A-2273091, N '-methylene diacrylamine are the better examples of crosslinking agent.

On the one hand, the invention provides the manufacture method of the Lyocell fibre of low fibrillation tendency, wherein can handle fiber with the chemical reagent of the functional group of fibrin reaction with containing two or more, its characteristics are, the first dried fibres of going ahead of the rest, it two is that at least two functional groups with fibrin reaction containing in the reagent are selected from electrophilic carbon-to-carbon double bond and parent and electrophilic ternary heterocycle and parent thereof.

Surprisingly, select feature technology of the present invention for use, can reach any in the past known reduction fibrillation excellent results that processing method is beyond one's reach.These features are the selection of predrying fiber and the selection of electrophilic carbon-to-carbon double bond or electrophilic ternary heterocycle functional group.

On the other hand, the invention provides the manufacture method of the Lyocell fibre of low fibrillation tendency, wherein can handle fiber with the chemical reagent of the functional group of fibrin reaction with containing two or more, its characteristics are, first elder generation dried fibres, it two is reagent and fibrin reaction, forms at least two aliphatic ethers, and these aliphatic ethers are derived by the cellulose hydroxyl.

Better chemical reagent contain the electrophilic carbon-to-carbon double bond as with the functional group of fibrin reaction.The electrophilic carbon-to-carbon double bond is activated by the adding of nucleopilic reagent, and polarized by the replacement of at least one electron withdraw group.Cellulose contains hydroxyl, and the electrophilic carbon-to-carbon double bond in it and the chemical reagent forms ether by the Michael addition reaction.Generally, comparatively suitable by the electrophilic carbon-to-carbon double bond that electron-withdrawing group replaced.The example of suitable electron-withdrawing group comprises the carbonyl class, for example acid amides or ester group, and sulfuryl.The better example of this functional group comprises acrylamido and acrylate-based.Electrophilic carbon-to-carbon double bond parent comprises β-sulfuric acid ethyl sulfone and β-chloroethyl sulfuryl.Carbon-to-carbon double bond on the vinyl is better.The better example of this functional group is the ethene sulfuryl.Further replace on two keys and can reduce the reactivity of key when adding nucleopilic reagent, the hydroxyl in the cellulose and such reagent reacting are with formation-XCH ₂CH ₂The O-base, wherein X representative-CO-or-SO ₂-and so on electron-withdrawing group, oxygen atom is then from cellulosic hydroxyl.

Chemical reagent also can contain electrophilic ternary heterocycle as with the functional group of fibrin reaction.Its example is the aziridine ring, and wherein carbon atom does not preferably contain substituting group, and its nitrogen-atoms is best with the tertiary N atom.Aziridine ring reaction and beat it, formation-NHCH in hydroxyl in the cellulose and this reagent ₂CH ₂The O-base is so cellulose just links together by ether and reagent.The example of aziridine ring parent comprises 2-chloroethene amino, 2-sulfuric acid ethylamino, 2-chloro acetylamino and 2-chloroethyl-sulfonamido.

Therefore the chemically-resistant hydrolysis preferably under the condition of fabric processing and washing usually of key in the chemical reagent, contains vinyl sulfone(Remzaol or says that especially the chemical reagent of acrylamido functional group is more suitable.Functional group in the reagent can be identical or different.Except electrophilic carbon-to-carbon double bond functional group, chemical reagent can contain the functional group of one or more other types, as the reactive halogen atom on many azines ring.

The advantage of processing method of the present invention is that the key that forms between reagent and the cellulose is the chemically-resistant hydrolysis, the chemical hydrolysis that particularly anti-weak base causes under the condition of fabric processing and washing usually.These keys are aliphatic ether.Have been found that as EP-A-538 described in 977, Lyocell fibre is handled with many azine types of halo reagent, when the fabric of the fiber that contains processing like this stands concise and during washing, the effect that reduces the fibrillation tendency just is tending towards forfeiture.This reagent and fibrin reaction generate multiple aromatics/aliphatic ether, and such ether is considered to be easy to take place chemical hydrolysis in fabric processing and washing process.

Known, contain vinyl sulfone(Remzaol, the fibre-reactive dyes that particularly contains acrylamido is lower than those reactive acid chloride (imide chlorides), particularly dichlorotriazine and dichloro pyrimidine type chemically-reactive dyes with cellulosic reactivity.Thereby wondrous be this group than low reaction activity has height in the processing that reduces the fibrillation tendency validity.

This chemical reagent generally contains two to six, is three to six preferably, three or four often, common is three electrophilic carbon-to-carbon double bonds or ternary heterocycle or their parent as with the functional group of fibrin reaction.Chemical reagent preferably should contain at least one and have at least three, preferably also is the ring of three cellulose reactive functional groups.The example of this ring is many azines ring, for example diazine or triazine ring, and this ring also may be a halo.This reagent example preferably is three acryloyl Hexahydrotriazines (1,3,5-three acryloyl perhydro--carotene 1,3,5-triazines are abbreviated as TAHT), once is proposed as color-fixing agent in the past.Other example of this reagent comprise two molecule TAHT and a part can with the two sense reagent of TAHT reaction such as the product of aliphatic diol.Another example of this reagent is 2,4,6-three (1-aziridinyl)-1,3,5-triazines, and another example of this reagent is N, N '-methylene diacrylamine.

The solvent spun fibre of being handled by the inventive method has identical color basically with untreatment fiber.This can be colourless substantially by using, and the reagent that does not change its color in fiber treatment basically realizes, as TAHT.So the fiber of handling is can be any suitable becomes known for cellulose fibre, and the method for yarn or fabric dyes.

This chemical reagent preferably imposes on fiber with the form of its aqueous solution.This chemical reagent can contain one or more solubility groups to increase its solubility in water.The solubility group can be ion-type such as sulfonic group, or poly-(ethylene glycol) of nonionic such as low polymerization degree or poly-(propylene glycol) chain.Usually, nonionic solubility group is littler than ion-type person to the cellulose dyeing Effect on Performance, and therefore, they are more suitable.The solubility group can be connected on the chemical reagent by unsettled key, for example, is convenient to the key of hydrolysis after chemical reagent and cellulose fibre reaction.

The process of known preparation Lyocell fibre comprises the steps:

(ⅰ) cellulose is dissolved in solvent, particularly in tertiary amine N-oxide, forms solution, this solvent can be miscible with water;

(ⅱ) by the spinning head extrusion solution, form the fiber parent;

(ⅲ) this fiber parent is passed through a water bath at least, desolvate, form fiber, and wash it to remove; With

(ⅳ) dried fibres.

The wet fiber that step (ⅲ) obtains at last is called not dried fiber (never dried fibre), and its typical water absorption is 120-150%.Through the dried fiber typical case of step (ⅳ) water absorption is 60-80%.After the Lyocell fibre drying, that is after finishing, step (ⅳ) can handle it by the inventive method.

Process of the present invention can be carried out with the normal dyeing technology that chemically-reactive dyes dyes cellulose fibre, and wherein the using method of chemical reagent and chemically-reactive dyes are same or similar.This process can tow or staple fibre, and the form of yarn or woven fabric or knitted fabric is carried out.To the processing of fabric, generally should before any dyeing course, carry out, perhaps, more suitable is just to carry out when refining processing.Although also can carry out simultaneously or after dyeing, perhaps in concise or dyeing course, carry out with dyeing.The cellulose common dyes, for example direct or chemically-reactive dyes can be used for this dyeing course.Process of the present invention can use the dye bath that contains chemically-reactive dyes commonly used and this chemical reagent to carry out.Functional group in dyestuff and this reagent can be identical or different type.

Use process of the present invention under the situation of not obvious reduction fiber stainability, to reduce the fibrillation tendency of cellulose fibre.Have been found that the coloured fibre handled by the present invention or fabric can strip after dyeing again, and excessive fibrillation does not take place.Fiber or fabric are through still showing slight fibrillation tendency after the stronger chemical stripping treatment.

Under alkali condition, the electrophilic carbon-to-carbon double bond in the used chemical reagent of process of the present invention can with cellulose with the fastest speed responsing.Thereby, should use the weak alkaline aqueous solution of chemical reagent to handle solvent spun fibre, for example, by adding the alkaline aqueous solution that sodium carbonate (soda ash) or NaOH make.When using TAHT as chemical reagent, the pH of solution should be preferably 10.5-11.5 between 10-13.Perhaps,, that is, at first handle fiber, handle with this chemical reagent solution then, although it is not very desirable usually with weak base aqueous solution can use two step process to handle fiber.This alkali preliminary treatment of fiber or fabric is called on dyeing and adds alkali dyeing (presharpening) in advance.Can contain or not contain the alkaline agent of adding at used chemical reagent solution of second step of two step process.

Electrophilic base and cellulose in the chemical reagent can at room temperature react, but should be heated usually, so that make reaction reach the degree of basic need.For example, used reagent can be hot solution, perhaps, will soak the wet fiber of reagent solution and heat-treat or decatize, perhaps heats wet fiber to its drying.If fiber or fabric are carried out decatize, then should use low-pressure steam, for example under 100-110 ℃ temperature, steaming time can be 5-20 minute.

Behind chemical reagent and fibrin reaction, for any alkali that neutralizes and add, available weakly acidic aqueous solution washes fiber, for example uses the weak solution of acetic acid.

Handle fiber, can be the 0.1-10% of fibre weight with the consumption of this chemical reagent, be preferably 0.2-5%, more preferably 0.5-3% is preferably 1-2%.The reaction of chemical reagent and cellulose fibre should be controlled at the dyeing position consumption that makes on the cellulose fibre and be less than 10%, be less than 5% better, so that can carry out smoothly the dyeing of fiber with coloured dyestuff thereafter, the dyestuff of dyeing usefulness can be reactive, also can be non-reacted.

Process of the present invention can be applicable to the processing of knitted fabric or woven fabric fiber.Usually knitted fabric is easier to fibrillation than woven fabric.Can further process through the fabric that process of the present invention is handled, particularly dyeing processing, with the open width state or to the even more serious colouring method of fabric friction, for example rope dyeing comprises the jet dyeing processing.Knitted fabric is seldom processed with the open width form, and how to handle with rope form, and woven fabric is not processed with rope form with the open width form usually, to avoid producing unbecoming scratch and folding line.

The invention has the advantages that fiber or fabric can handle in the wet process of routine, and do not need to increase process time or step.The board time cost is the key factor of fiber or fabric processing charges, and may surpass the expense of used chemical substance.

Cellulose fibre is particularly handled to remove its surperficial fibrillation by the plain enzyme of fabric usable fibers that this fiber is made.Cellulase can aqueous solution form uses, and its concentration is 0.5-5%, is preferably 1%-3%(weight).The pH of solution can be in the scope of 4-6.Can contain nonionic detergent in the solution.Fabric can be handled down at 20 ℃-70 ℃, is preferably 40 ℃-65 ℃, and more preferably 50 ℃-60 ℃, the processing time is 15 minutes to 4 hours.This cellulose treatment method can be used for by the solvent spun fibre of the inventive method with the chemical reagent processing, the fibriilar removal of yarn and fabric.

The present invention is illustrated by following embodiment.The Lyocell fibre that uses at all occasions is Courtaulds Fibres Limited product, and its trade mark is " Tencel ".Determine the fibrillarity of material with following experimental technique 1, determine the fibrillation tendency of material with following experimental technique 2-4.

Determining of experimental technique 1(fibrillarity)

The standard that does not have definite fibrillation of the general approval in the whole world at present, and following method is used for determining fibrillation index (F.I.).A series of fibril content are assessed to many fiber samples that increase gradually by zero.Measure the full-length of each sample fiber then, and number goes out the number of fibrillation (from the tiny cilium of fibrous body upper fin) on the full-length.Measure every fibriilar length, and determine any number of each fiber, this any number is the product of fibril number and each fibril average length.Have that the fiber of high product value just is regarded as the most serious fiber of fibrillation, then its any fibrillation index promptly is decided to be 10.The fibrillation index of fibrillating fibre is not decided to be zero fully, and its fibrillation index of size that remaining fiber is counted arbitrarily according to micrometering is then evenly distributed successively by 0 to 10.

Then the fiber alignment of measuring is become the standard class chi.When determining the fibrillation index of any other fiber sample, 5 or 10 fibers to be examined under a microscope, direct and standard class fiber compares.The fibrillation exponential average of the every fiber that will relatively obtain then is the fibrillation index of sample.Be noted that and directly with the naked eye determine numerical value, and experienced fibre technology expert is always corresponding to the evaluation of fiber grade also in addition on average than fast a lot of times of measurement.

The fibrillation index of fabric, evaluation are to extract fiber out from fabric face, and then these fibers are evaluated.The F.I. of woven fabric will demonstrate unhandsome outward appearance as greater than 2.0-2.5.

Experimental technique 2(is concise, bleaching, dyeing)

(ⅰ) concise

The 1g fiber placed be about 25cm, diameter 4cm is in the stainless steel cylinder of the about 250ml of volume.Add 50ml commonly used contain the nonionic detergent of 2g/l Detergyl FS 955(available from ICI plc) the concise liquid of (Detergyl is a trade mark) and 2g/l sodium carbonate, the speed upside down turn that the cap nut of screwing on, the cylinder of building change with per minute 60 under 95 ℃ 60 minutes.Wash refined fiber with hot and cold water then.

(ⅱ) bleaching

In being arranged, the cylinder of fiber adds the 50ml liquid lime chloride, the hydrogen peroxide that wherein contains 15ml/l35%, 1g/l NaOH, 2g/lPrestogen PC(is available from the bleaching stibilizer of BASF AG) (Prestogen is a trade mark) and 0.5ml/l Irgalon PA(be available from the chelating agent of Ciba Geigy AG) (Irgalon is a trade mark), screw nut, rotating cylinder is 90 minutes under 95 ℃ of temperature.Use hot water and cold water flush bleached fiber then.

(ⅲ) dyeing

Add 50ml and contain 8%(o.w.f) the dark blue HER 150(of Procion chemically-reactive dyes) dyeing liquor of (Procion is the trade mark of ICI plc) and 55g/l glauber salt, cover tight round barrel cover, rotated 10 minutes down at 40 ℃.Be warming up to 80 ℃, add the sodium carbonate of capacity, make the concentration that reaches 20g/l.Cover tight cylinder once more, and roll was rotated 60 minutes.Water flushing fiber.Add 50ml then and contain the washing agent of 2ml/l Sandopur SR(available from Sandoz AG) solution of (Sandopur is a trade mark), cover tight cylinder, and in the time of 100 ℃ rotor 20 minutes, wash coloured fibre and drying then.Estimate its fibrillarity according to experimental technique 1.

Experimental technique 3(washing and drum dried)

Use typical home washing and rotary drum dryer (W/T circulation) to make fabric stand the hygrometric state rubbing action.With Daz(available from Procter ﹠amp; The house detergent of Gamble Limited) (Daz is a trade mark) solution was in 60 ℃ of laundering of textile fabrics 45 minutes.

Experimental technique 4(plunger)

If tested fiber sample is still without refining, then press earlier experimental technique 2(ⅰ) refining it.

The 0.5g fiber is cut into 5-6mm length, under the room temperature it is dispersed in the 500ml water, and place family expenses plunger (liquefier), under about 12000rpm rotating speed, started plunger 2 minutes.Collect fiber and drying then, and press experimental technique 1 definite its fibrillarity.Experimental technique 4 has more violent fibrillation condition than experimental technique 2.

The comparative example 1

With not dry Lyocell fibre (1.7dtex tow, 30cm is long) with containing N, the aqueous slkali (100ml) of N '-methylene diacrylamine (10g/l) and sodium sulphate (100g/l) pads processing under various condition, use the 0.1%(volume again) acetic acid flushing, and drying.Evaluate its F.I. according to test method 4.Various concrete treatment conditions and F.I. value list thereof are as follows:

Alkaline agent treatment conditions F.I. value

-be untreated 5.6 (4. piece average)

Na ₂CO ₃(20g/l) pad 3 * 5min 3.4

Na ₂CO ₃(20g/l) decatize 10min 4.8

Na ₂CO ₃(20g/l) decatize 20min 2.9

NaOH (20g/l) decatize 20min 4.4

Na ₂CO ₃(20g/l) handle 8min 3.5 for 70 ℃

The decatize condition is at 100 ℃, 98%R.H..When using NaOH as alkaline agent, fading of fiber.F.I. has the improvement of appropriateness in all cases.

The comparative example 2

With not dry Lyocell fibre (1.7dtex, 30cm is long) under different condition with containing TAHT(20g/l) aqueous slkali (100ml) pad processing, use the 0.1%(volume again) acetic acid flushing, and drying is determined its F.I. value according to test method 4.The various concrete treatment conditions and the F.I of gained are listed in the table below:

Alkaline agent Na ₂SO ₄Treatment conditions F.I.

--not handles 5.0

Na ₂CO ₃(20g/l)-decatize 20min 0.3

Na ₂CO ₃(20g/l)-and dry 2min in the time of 120 ℃, 0.3

Decatize 1min

NaOH (20g/l)-in the time of 40 ℃, pad 0.7

Na ₂CO ₃(10g/l) 75g/l decatize 20min 0.2

Na ₂CO ₃(10g/l) 75g/l dry 2min in the time of 120 ℃, 0.6

Decatize 1min

Na ₂CO ₃(10g/l) 50g/l decatize 20min 0.2

Na ₂CO ₃(10g/l) 50g/l dry 2min in the time of 120 ℃, 1.2

Decatize 1min

Na ₂CO ₃(10g/l)-not heat 3.2

Na ₂CO ₃(10g/l)-decatize 20min 0.1

Na ₂CO ₃(10g/l)-and dry 2min in the time of 120 ℃, 0.3

Decatize 1min

Under nearly all treatment conditions, F.I. is significantly improved.Yet be unacceptable desired heat time heating time on the tinuous production of making solvent spun fibre in these processing procedures.

The comparative example 3

Three kinds of not dry Lyocell fibre samples are handled in the following manner with TAHT solution.Press experimental technique 2 refinings then, bleaching and dyeing are promptly pressed experimental technique 4 and are measured its F.I. value after each procedure of processing.

Sample 1 is to contain TAHT(20g/l), Na ₃PO ₄(10g/l) and Na ₂SO ₄Solution (25g/l) pads processing, then in 70 ℃ of heating 6 minutes.

Sample 2 is to contain TAHT(30g/l), urea (100g/l) and Na ₂CO ₃Solution (10g/l) pads processing, then in 100 ℃ of decatizes 20 minutes.

Earlier with sample 3 in 70 ℃ to contain Na ₂CO ₃Solution (2g/l) pads processing, and then to contain TAHT(20g/l), Na ₂CO ₃(8g/l) and Na ₂SO ₄Solution (25g/l) pads processing in 70 ℃.

The F.I. mean value that obtains is as follows, is the number of times of every kind of sample repeated experiments in the bracket.

Behind the refining after bleaching poststaining

Sample 1 0.1 (2) 0.5 (3) 0.2 (3)

Sample 2 0.5 (3) 1.7 (3) 2.2 (3)

Sample 3 2.4 (3) 2.4 (3) 2.6 (3)

Although sample 1 demonstrates good result, be unacceptable its desired heat time heating time in the production line of making solvent spun fibre.

Embodiment 1

The Lyocell fibre fabric (with the 20tex yarn that the ring spinning method is spun into, is made into 123gm by the 1.7dtex fiber again ^-2The normal structure fabric) with containing TAHT(20g/l), Na ₂CO ₃(10g/l) and Na ₂SO ₄The aqueous solution (25g/l) pads and heats 15 minutes (sample 1) in 70 ℃.Except not adding the TAHT, handle control sample with identical method.With another fabric sample with containing TAHT(20g/l) and aqueous solution NaOH(20g/l) pads and in 30 minutes (sample 2) of 40 ℃ of heating.With following condition fabric sample is dyeed then.In the dye bath with 25 ℃ of sample immersions, this bath contain the dark blue H4R(fabric of Procion heavy 4%) (available from the chloro-s-triazine type chemically-reactive dyes of ICI plc) (Procion is a trade mark), Matexil PAL(3g/l) (available from mild oxidation agent-nitrobenzene-sulfonic acid of ICI plc) (Matexil is a trade mark) and Depsolube ACA(1g/l) (the alkali stable lubricants that is used for jet dyeing that provides by ICI plc) (Depsolube is a trade mark).Be warming up to 80 ℃, the NaCl with time-division three addings capacity makes the concentration that reaches 70g/l.Be incubated 20 minutes, in 10 minutes, add the Na of q.s ₂CO ₃, make the concentration that reaches 20g/l, continue insulation 60 minutes.Laundering of textile fabrics under the boiling condition, was soaped 20 minutes with soap flakes solution (2g/l) then.Dyeing also wash the fabric of drying and drying 5 times in rotary drum dryer, measure its F.I. value, result's following (mean value of twice experiment):

Contrast 3.7

Sample 1 0.8

Sample 2 1.8

(make 20tex yarn circle tricot, 193gm with identical method processing and dyeing Lyocell fibre knitted fabric by the spinning of 1.7dtex fibrous airstream ^-2), after two and four washings and drum dried, measuring its F.I., the result is as follows:

2 times 4 times

Control sample 1 3.6 4.8

Sample 1 0.0 0.1

Sample 2 1.3 2.6

Embodiment 2

The sort of solvent-spun cellulose woven fabric that embodiment 1 is used with the open width form with containing Detergyl(2g/l), alkali (2g/l), TAHT(20g/l) and Na ₂SO ₄Solution refining (25g/l), and in 95 ℃ of heating 1 hour.The nitrogen content of refining and dry back fiber is measured it by the Kjeldahl method, and the gained result represents with TAHT content (weight) in the fabric.Handle fabric sample in the same way, but do not add TAHT, in contrast.Use the red 3BL(of direct dyes (shine jail dimension) then available from Ciba-Geigy AG) (shine the jail dimension and be trade mark) dye on reel dye machine with the rope form form.Condition is as follows, fiber is immersed 50 ℃ contain dyestuff (the 4%(weight of fabric)) dye bath in, in 30 minutes, be warming up to 100 ℃, kept the Na of adding capacity 15 minutes ₂SO ₄, make the concentration that reaches 20g/l, continue insulation 45 minutes, then washing and drying.Repeated washing and drum dried fabric sample are measured its F.I. after each washing is dry then, and the gained result is as follows:

Alkaline agent TAHT% washing and drum dried number of times

0 1 2 3 4 5

Contrast--3.3 3.9 5.4 4.9 5.6 6.5

Sample 1 Na ₂CO ₃2.88 0.0 0.2 0.1 0.0 0.0 0.0

Sample 2 Na ₂CO ₃2.40 0.2 0.0 0.0 0.0 0.0 0.2

Sample 3 NaOH 5.28 0.1 0.0 0.0 0.0 0.0 0.0

The color of sample 3 is light than other samples, it is believed that, that is because this sample contains excessive TAHT.

Embodiment 3

The sort of solvent-spun cellulose staple fibre woven fabric that embodiment 1 is used with the open width form with containing Detergyl(2g/l) and Na ₂CO ₃Solution (2g/l) was in 95 ℃ of refinings 1 hour.Then fabric is stood a series of processing with the rope form form on reel dye machine.At first with containing TAHT(20g/l), Na ₂CO ₃(2g/l) and Na ₂SO ₄Solution (30g/l) was handled 10 minutes in 20 ℃.Then, add the dichloro one fluorine pyrimidine chemically-reactive dyes of the cotton beautiful orange K 3R(of black pigment used by women in ancient times to paint their eyebrows of capacity available from Sandoz AG) (black pigment used by women in ancient times to paint their eyebrows cotton beautiful be trade mark), make the 4%(weight that reaches fiber) concentration.After 10 minutes, in 30 minutes, dye bath is warming up to 50 ℃, and in the time of 50 ℃, continues to keep 20 minutes.Add Na then ₂CO ₃(18g/l), continue and in the time of 50 ℃ to handle 60 minutes.Fabric is through soaping and drying.Except not adding TAHT, handle control sample with identical method.Then fabric sample is repeated washing and drum dried processing, it is as follows to record F.I. result:

Washing and drum dried number of times

0 1 2 3 4 5

Contrast 1.5 3.7 3.5 3.7 4.8 5.0

Sample 3.1 1.2 0.5 0.4 0.6 0.4

Embodiment 4

The sort of Lyocell fibre fabric sample that embodiment 1 is used is with containing TAHT(20g/l), Detergyl(2g/l), Na ₂CO ₃(2g/l) and Na ₂SO ₄Solution (20g/l) was in 95 ℃ of refinings 1 hour.Except not adding the TAHT, with identical method refining control sample.Refining can the open width form carried out on reel dye machine on the dye jigger or with the rope form form.Sample dyes with following method on reel dye machine with the rope form form then.Dye bath contains the simple function group chemically-reactive dyes of the green H4G(of Procion available from ICI plc) (the 4%(weight of fabric)), Depsolube ACA(1g/l) (the alkali stable lubricants that is used for jet dyeing that provides by ICI plc) (Depsolube is a trade mark) and Matexil PAL(mild oxidation agent-nitrobenzene-sulfonic acid-as the textile auxiliary that prevents reducing dyes) (Matexil is the trade mark of ICI plc) (3g/l).Fabric passed through 10 minutes in dye bath in 20 ℃, temperature was risen to 80 ℃ then, simultaneously, added NaCl(70g/l in batches); 80 ℃ of insulations 20 minutes; In 10 minutes, add Na ₂CO ₃(20g/l); 80 ℃ of insulations 60 minutes.Then, the washing fabric and to contain Sandopur SR(2g/l) processing of (available from the washing agent of Sandoz AG) (Sandopur is a trade mark) bathes and soaped 20 minutes at 95 ℃.Make fabric stand repeated washing and drum dried processing then, the F.I. result of acquisition is as follows:

Fabric fine purifiation TAHT washing and rotary drum-dry number of times

0 1 2 3 4 5

Woven dye jigger does not have 2.7 2.1 3.6 4.3 5.3 4.8

Woven dye jigger has 0.0 0.0 0.0 0.0 0.0 0.0

Woven capstan winch does not have 1.5 3.0 3.1 3.8 4.6 5.3

Woven capstan winch has 0.4 0.0 0.0 0.0 0.0 2.5

Knitting capstan winch does not have 1.4 3.9 4.2 4.9 4.2 5.1

Knitting capstan winch has 0.0 0.0 0.0 0.0 0.0 0.0

(it is believed that the result of gained is unusual to woven fabric using the TAHT refining and handle afterwards through 5 washings and drum dried).

Embodiment 5

The single knitting fabric of Lyocell fibre is handled on jet dyeing machine fully.The processing conditions of such machine is the harshest in whole processing conditions, thereby can cause heavy wear.Fabric is earlier with containing TAHT(20g/l), Na ₂SO ₄(25g/l), Depsolube ACA(1g/l), Na ₂CO ₃(2g/l) and Sandopur SR(2g/l) body lotion in 50 ℃ of refinings 10 minutes.Be warming up to 95 ℃, and be incubated 60 minutes.Use hot water drip washing fabric then.Then with containing Na ₂SO ₄(70g/l) and Tebolan UF(3g/l) body lotion of (available from the non-ionic lubricant of German Dr.Th Bohme KG) (Tebolan is a trade mark) handled fabrics 15 minutes at 25 ℃, afterwards, in 10 minutes, in bathing, add the red HE-7B(fabric of Procion heavy 4%) (available from two-chlorotriazine type chemically-reactive dyes of ICI plc).Be warming up to 80 ℃ and kept this temperature 20 minutes.In 10 minutes, add Na ₂CO ₃(2g/l), and fabric turned round in machine 1 hour, afterwards, drip washing and soap boiling fabric.Calculate fabric by its nitrogen content (measuring) and contain 5.16%(weight by the Kjeldahl method) TAHT.The F.I. value that is exposed to that side fabric of nozzle is 0.2, and still keeps this value constant after 35 washings and drum dried processing.The fabric limit of nozzle side is subjected to the most violent effect, and clothes are inwardly made with this limit usually.

Embodiment 6

The Lyocell fibre woven fabric (is spun into the 20tex yarn by 1.7dtex fibrous ring ingot, makes 115gm again ^-2Elementary organization's fabric) with containing TAHT(20g/l), Detergyl(2g/l), Na ₂CO ₃(2g/l) and Na ₂SO ₄Solution refining treatment (25g/l) 1 hour.Except not adding the TAHT, with identical method refining control sample.Fabric sample is with the 4%(weight of Procion palm fibre H3R(fabric then)) (available from the chlorotriazine chemically-reactive dyes of ICI plc) (Procion is a trade mark) dye with following method.Fabric is with containing dyestuff, Matexil PAL(3g/l) and Depsolube ACA(1g/l) solution in 25 ℃ of processing.Be warming up to 80 ℃, add NaCl in three batches simultaneously, reach the concentration of 70g/l.80 ℃ of insulations 20 minutes, afterwards, in 10 minutes, add Na ₂CO ₃Reach the total concentration of 22g/l.Continue dyeing 60 minutes, simultaneously, to dye bath and fabric sampling and analyze it.Dyestuff total amount on each sample of two kinds of fabrics is determined it by the Q value.Comparison process fabric and control fabric get Q=100.2%(standard=100%).

Benchmark sample treatment samples

Time bathe in dyestuff on the dyestuff fabric in the dye bath on the dyestuff fabric

(minute)

0 100 - 100 -

15 15.4 87.3 22.7 84.8

30 12.6 92.7 16.8 95.7

45 11.1 95.8 13.9 95.3

60 13.0 100 10.1 100

Numerical expression in " dyestuff in the bath " hurdle be initial in bath the percentage of amount of dye, the numerical value " dyestuff on the fabric " hurdle in is for appointing the percentage of Q value after 60 minutes calmly.

As can be seen, it is gratifying handling coloration of textile materials speed.

Embodiment 7

With the Lyocell fibre woven fabric with containing TAHT(20g/l), Detergyl(2g/l), Na ₂CO ₃(2g/l) and Na ₂SO ₄Solution refining (25g/l) 1 hour.Except not adding the TAHT, with identical method refining control sample.To handle with direct or chemically-reactive dyes then and control sample dyeing; Carry out stripping treatment again; Redye with aforementioned dyestuff again; Handle through a series of washing and rotary drum-drying (w/T).Measure the fibrillation index behind each treatment step.

Following two kinds of methods are used for textile dyeing:

Direct dyes, neutral bath method: at room temperature with textile impregnation in the 4%(weight that contains the purple F2BLL(fabric of sharp top grade of sunset)) (available from Bayer AG) (sunset sharp be trade mark) and Na ₂SO ₄In the solution (18g/l); In 45 minutes, be warming up to 97 ℃; Be incubated 1 hour; Flushing and drying.

Chemically-reactive dyes, standard method: with textile impregnation in the 4%(weight that contains the red MX-8B(fabric of Procion)) in 45 ℃ the solution of (available from ICI plc) (Procion is a trade mark); Be incubated 10 minutes; Add the NaCl of capacity, make the concentration that reaches 60g/l; Be incubated 30 minutes; The Na that adds capacity ₂CO ₃, make the concentration that reaches 5g/l, be incubated 30 minutes; Flushing; With 100 ℃ of soap boilings of soap flakes solution (2g/l) 15 minutes; Dry.

Following three kinds of methods are used for stripping of fabric; In each case, finish afterflush and dry fabric in stripping treatment:

Method A: under 100 ℃ of conditions with containing Na ₂CO ₃(6g/l) and the solution-treated fabric of sodium hydrogensulfite (6g/l) 1 hour.

Method B: handled fabric 20 minutes with cold liquor natrii hypochloritis (10g/l), add the sodium hydrogensulfite of capacity or hypo solution (2.5g/l) then to decompose remaining hypochlorite.

Method C: then use method B behind the method A.

Gained F.I. the results are shown in following table:

Direct dyes:

Redye back 1 washing after method is stripped behind the refining poststaining to wash for/5 times/

The drum dried drum dried

To 2.2 1.8 A 1.0 2.4 7.2 9.2 in the same old way

B 2.8 3.8 6.0 8.8

C 1.6 3.2 6.2 8.8

Treated sample 1.2 0.6 A 2.2 0.4 0.4 0.6

B 2.2 1.8 0.2 0.4

C 2.4 0.4 0.4 0.4

Chemically-reactive dyes:

The drum dried drum dried

To 2.2 2.0 A 2.0 1.6 2.8 7.6 in the same old way

B 1.0 2.6 3.0 7.0

C 0.4 0.8 2.8 8.2

Treated sample 1.2 0.4 A 0.4 0.8 0.4 0.2

B 0.2 1.6 0.6 0.2

C 0.8 0.4 0.2 0.2

As can be seen, compare with control sample in each case, the fibrillation of fabric tendency demonstrates sizable reduction after redying.

Embodiment 8

Embodiment 1 used the sort of solvent spun fibre cellulose fabric use is contained TAHT(10g/l), Detergyl FS 955(2g/l), Na ₂SO ₄(5g/l) with the solution of alkaline agent under different pH values, 95 ℃ of following refinings 1 hour.In the time of 95 ℃, use and contain Detergyl(2g/l) and Na ₂CO ₃Solution refining control sample (2g/l) 1 hour.Body lotion is 10: 1 with the ratio of fabric.Then in the time of 25 ℃ with containing the 4%(weight of the red HE-7B(fabric of Procion)) (available from ICI plc), Matexil PAL(3g/l) and Depsolube ACA(1g/l) the solution-treated sample; In 30 minutes, temperature is risen to 80 ℃, add the NaCl of capacity simultaneously, make to reach 70g/l concentration; Be incubated 20 minutes; The Na that adds capacity ₂CO ₃, make to reach 20g/l concentration; Kept temperature 60 minutes; Then drip washing and in the time of 95 ℃ with soap fabric 20 minutes of Sandopur SR solution (2g/l).Body lotion is 70: 1 with the ratio of fabric.Dry fabric stands 5 washings and drum dried is handled.The fibrillation index of working sample is by its nitrogen content of Kjeldahl assay and with the TAHT content of this calculation sample.Gained the results are shown in following table:

Alkaline agent pH TAHT% F.I.

- - - 7.2

NaHCO ₃(3g/l) 8.3 0.14 6.2

NaHCO ₃(10g/l) 8.45 0.17 6.3

NaHCO ₃(10g/l)+ 9.0 0.39 5.5

Na ₂CO ₃(1.02g/l)

Na ₂CO ₃(0.5g/l) 10.25 0.92 1.2

Na ₂CO ₃(2g/l) 10.77 2.23 0.1

Na ₂CO ₃(10g/l) 11.19 2.87 0.1

Na ₃PO ₄(1g/l) 11.53 1.85 0.3

Na ₃PO ₄(10g/l) 12.03 2.74 1.9

NaOH(3g/l) 12.53 1.70 0.8

As can be seen, the pH that bathes when refining is greater than 10 the time, and the fixed amount of TAHT is just bigger, and the fibrillation tendency is just lower, when pH can obtain the F.I. result of the best during for 10.5-11.5.

Embodiment 9

In the time of 95 ℃, the woven or knitted fabric of the sort of solvent-spun cellulose that embodiment 1 is used on reel dye machine with containing the different amounts of TAHT(), Detergyl(2g/l), Na ₂CO ₃(10g/l) and Na ₂SO ₄Solution-treated (5g/l) 1 hour.In the time of 95 ℃ with containing Detergyl(2g/l) and Na ₂CO ₃Solution refining control sample (2g/l) 1 hour.Solution is 15: 1 with the ratio of fabric.Press embodiment 8 described method stained specimens with the red HE-7B of Procion then, and obtain following F.I. result through disposable washing and drum dried processing:

TAHT woven fabric knit goods

g/l

Behind the W/T poststaining of dyeing back behind the W/T

The F.I. of F.I. of F.I. of F.I.

- 2.2 3.4 3.0 3.0

1 1.4 2.0 1.8 2.2

2 1.0 1.2 1.4 1.8

5 1.0 1.0 0.2 0.6

As can be seen, even in the occasion of minimum TAHT concentration, the fibrillation tendency also significantly decreases.

Embodiment 10

In the time of 95 ℃, the sort of solvent-spun cellulose woven fabric that embodiment 1 is used is with containing HAHT(20g/l), Detergyl(2g/l), Na ₂CO ₃(2g/l) and Na ₂SO ₄Solution refining (25g/l) 1 hour.Except not adding the TAHT, with identical method refining control sample, then in the time of 50 ℃, fabric sample be impregnated in contain hydrogen peroxide (every liter contains 35% hydrogen peroxide 15ml), Prestogen PC(1g/l) (available from the bleaching stibilizer of BASF AG) (Prestogen is a trade mark), Trilon C(0.5g/l) bleaches in (Trilon is the trade mark of BASF AG) and solution NaOH(1g/l), after the dipping, temperature is risen to 85 ℃ and kept 60 minutes, then that sample wash is clean.Sample is dyeed with Procion palm fibre H3R by embodiment 6 described methods then.After the washing of different number of times and drum dried are handled, just following F.I. result:

W/T (washing/rotary drum) number of times

0 1 2 3 4 5

To in the same old way 4.5 4.5 4.7 5.1 6.5 4.9

Treatment samples 0.5 0.0 0.0 0.3 0.4 0.0

As can be seen, the effect of handling the reduction fibrillation tendency obtained with TAHT does not disappear because of bleaching.

Embodiment 11

Embodiment 1 used the sort of solvent-spun cellulose woven fabric packed into to be contained in the dyeing machine of handle bathing, and this bath is one to contain the aqueous solution of anion or non-ionic lubricant, 50 ℃ of temperature.With fabric by this bath in case moistening it, in bath, add TAHT(4g/l then), then add Na again ₂CO ₃(10g/l) and Na ₂SO ₄(5g/l), make pH reach 10.5-11.5.To bathe temperature rise to 95 ℃, fabric turns round in bath unceasingly simultaneously, keeps this temperature 1 hour.Such treatment conditions can produce good fixation rate and anti-fibrillation effect.TAHT target fixed amount is greater than 1% of fabric weight, and better the person is 1.2-1.5%.Fabric obtains the effect of low fibrillation tendency through soaping and drying then.

Claims

1, a kind of manufacturing has the method for the Lyocell fibre of low fibrillation tendency, wherein Lyocell fibre is with containing two or more chemical reagent processing with the functional group of fibrin reaction, it is characterized in that, pending fiber elder generation drying, chemical reagent contain be selected from electrophilic carbon-to-carbon double bond and parent and electrophilic ternary heterocycle and the parent thereof at least two groups as with the functional group of fibrin reaction.

2, a kind of manufacturing has the method for the Lyocell fibre of low fibrillation tendency, wherein Lyocell fibre is with containing two or more chemical reagent processing with the functional group of fibrin reaction, it is characterized in that, the first drying of pending fiber, chemical reagent and fibrin reaction form at least two aliphatic ethers.

As the method for claim 1 or 2, it is characterized in that 3, chemical reagent contains the functional group of an acrylamido or acrylate-based conduct and fibrin reaction at least.

4, as the method for claim 1 or 2, it is characterized in that, chemical reagent contain at least ethene sulfuryl as with the functional group of fibrin reaction.

5, the method for each claim as described above is characterized in that, chemical reagent contains two to six functional groups with fibrin reaction.

6, the method for each claim as described above is characterized in that chemical reagent contains a ring at least, connects three functional groups with fibrin reaction on this ring at least.

7, method as claimed in claim 6 is characterized in that, chemical reagent is three acryloyl Hexahydrotriazines.

8, method as claimed in claim 3 is characterized in that, chemical reagent is N, N '-methylene diacrylamine.

9, the method for each claim as described above is characterized in that, handles fiber with the aqueous solution of chemical reagent.

10, method as claimed in claim 9 is characterized in that, the aqueous solution is alkalescent.

11, the method for each claim as described above is characterized in that, will be based on the 0.2-5%(weight of fibre weight) chemical reagent and fiber-reactive handle fiber.

12, as the method for claim 11, it is characterized in that, will be based on the 1-2%(weight of fibre weight) chemical reagent and fiber-reactive handle fiber.

13, the method for each claim as described above is characterized in that processed fiber is present in the woven fabric.

As the method for each claim among the claim 1-12, it is characterized in that 14, processed fiber is present in the knit goods.

As the method for claim 14, it is characterized in that 15, knit goods is handled with chemical reagent with the rope form form.

16, the method for each claim as described above is characterized in that, the fiber after handling is further dyeed.

17, the method for each claim as described above is characterized in that chemical reagent is colourless basically.

18, the method for each claim as described above is characterized in that, fiber before handling with chemical reagent with have identical color afterwards basically.

19, the method for each claim as described above is characterized in that, clamp-ons water bath by the solution that cellulose is dissolved in tertiary amine N-oxide, and washing is dry then, prepares pending fiber.