Method for reducing the fibrillation tendency of lyocell fiber

Area techniques

This invention relates to methods of reducing the inclination of the lyocelových fibers to fibrillation.

The current state of the art

It is known that cellulose fibre can be produced by extruding a solution of cellulose in a suitable solvent in the coagulation bath. This method is referred to as a solvent-spinning, spinning of solvent and the produced cellulose fiber is known as cellulose fiber threads, spun in a solvent (solvent spun), or as lyocelové thread. Lyocelové fiber is distinguished from cellulose fibre made by other known procedures, which rely on the formation of a soluble chemical derivative of cellulose and its subsequent decomposition in the regeneration of the cellulose, e.g. viscose process. One example of a procedure for spinning of the solvent is described in US 4 246 221-A, the content of which is here incorporated as a reference. Cellulose is dissolved in a solvent, such as aqueous tertiary amino-N-oxide, for example N-methylmorfolino-N-oxide. The solution obtained is subsequently extruded through a suitable nozzle into an aqueous bath for the formation of assemblies of filaments, which is washed in water to remove the solvent and subsequently dried.

Fibres may exhibit a tendency to fibrillation, particularly if subjected to mechanical stress in the wet state. Vláknění is manifested, if they disrupt the structure of the fibers in the longitudinal direction so that the fibers begin to partially detach the delicate fibrily and give hair the appearance of thread and fabric, which contains, e.g., the fabric or pletenině. Dyed fabric containing fibrilovaná fiber tends to have a frosted appearance, which may be aesthetically undesirable. It is believed that such vláknění is due to the mechanical abrasion of the fibers during processing in a wet and swollen condition. Ways wet processing such as dyeing procedures, will inevitably expose the fibers to mechanical abrasion. Higher temperatures and longer processing times usually lead to a higher degree of fibrillation. Lyocelové thread to be particularly sensitive to such abrasion and is consequently often described as more susceptible to vláknění than other types of cellulosic fibers.

The presented invention relates to methods of adjustments lyocelového fibers so as to reduce or suppress his tendency to vláknění. However, it was found that some of these ways of processing may have an adverse effect on the mechanical properties of fibers, such as tenacity and extensibility, for example zkřehnutím fibers, or the processability of fibers and fabrics, especially his obarvitelnost. It can be difficult to establish the processing method that will guarantee the successful reduction of fibrilační tendency, and thus prevent these adverse effects.

EP-A-538 977 describes a method of manufacturing cellulose fiber with a reduced tendency to fibrillation by spinning from a solvent when the fiber is processed, a chemical agent with two to six functional groups reactive with cellulose. A chemical agent may be polyhalogenovaný polyazin or a compound containing polyazinový circle carrying two or more vinylsulfonových groups, or their precursors. The fiber may be treated in undried and or in a previously dried form of an aqueous solution of a chemical reagent, kteiý can be weakly alkaline by addition of sodium carbonate, sodium bicarbonate or sodium hydroxide. However, it was found that if the cellulose fiber threads, spun from the solvent is treated with a reagent of the type halogenovaného polyazinu, is obtained by reduction of the susceptibility to atrial fibrillation tend to lose, when fabric containing the treated fibre launders and cleans. Such agents react with cellulose with the formation of a multiple aromatic/aliphatic etherových groups, which are considered to be prone to chemical hydrolýzám in the course of processing and washing of the fabric. WO-A-94/24 343, published on 27. October 1994, describes a very similar procedure.

-1CZ 291981 B6

FR-a-2 273 091 describes a method of manufacturing the fiber of polynosic viscose rayon fibre with reduced tendency to fibrílaci, where the fiber is treated in the primary gel formulation of status characteristic for the production of polynosic viscose rayon is zesíťujícím reagent containing at least two akrylamidové groups and an alkaline catalyst at a temperature below 100 °C. Preferred examples of the 5 crosslinking agents are mentioned l,3,5-triakrylhexahydro-l,3,5-triazine and N,N-methylenbisakrylamid. The staining affinity of the fibers is not the following treatment should be modified. The procedure described in FR-a-2 273 091 has the drawback that there is required a processing time in the range of 5 to 15 minutes. Such a time is unacceptably long in the manufacture of fibers, when point velocities are commonly in the range of 10 to 100 m/min, especially if there is a thread processed in neřezané form such as chopped strands (tow, 10 also referred to as tow).

GB 0 953 171 describes the processing method of natural cellulose fibers or pre-dried regenerated cellulose fibers using chemical reagents, which may contain less than 2.1 akrylamidových groups in the molecule, for example MBA (N,N'-methylen15 bisakrylamid), or more than 2.1 akrylamidových groups in the molecule, for example, 1,3,5-triakryloylhexahydro-l,3,5-triazine (TAHT), without it turned out that is achieved any different results depending on the number of akrylamidových groups in the molecule.

FR 1 318 838 describes a method of processing knitted goods consisting wholly or partly 20 of the cellulosic or other polyhydroxylovaných polymemích fibers with widely diverse chemical agents, among which are included reagents containing less than 2.1 akrylamidových groups in the molecule and a reagent containing more than 2.1 akrylamidových groups in the molecule, without turned out that produces better results than previously. Because the material must be processed no longer a ring, it is necessary to have already been dried.

US 4 416 698 describes a method of producing shaped cellulosic articles, such as fibers shaped from a solution containing cellulose dissolved in a solvent for the cellulose comprising a tertiary amine-N-oxide and nerozpouštědlo for cellulose miscible with the tertiary amine-N-oxide, and then precipitation of the resulting solution to molding. Ν,Ν-Dimethylacetamid is mentioned as 30 possible nerozpouštědlo, but is not described processing of the created, but never not-dried fibers with any chemical agent.

The essence of the invention

The object of this invention is a method of reducing the inclination of the lyocelového fibers to fibrílaci, whose essence lies in the fact that (1) the fiber in never nesušeném condition is applied an aqueous solution containing therein dissolved 40 inorganic principle and chemical reagent carrying more akrylamidových groups, while the average number of akrylamidových groups per molecule of chemical reagent in the solution is at least 2.1 and (2) filament, to which was applied a chemical agent, is heated to induce a reaction between the fibre and the chemical reagent.

An advantageous embodiment of the method according to this invention is that it is a chemical agent used in an amount in which the fiber after the reaction contains the thread of the fixed 0.25 to 1% by weight of the chemical reagent based on the weight of air dried fibers.

An advantageous embodiment of the method according to this invention is that it is a chemical agent used in an amount in which the fiber after the reaction contains the fiber fixed 0.4 to 0.8 % by weight of the chemical reagent based on the weight of air dried fibers.

-2GB 291981 B6

An advantageous embodiment of the method according to this invention is that it is a chemical agent used in an amount in which the average number of akrylamidových groups in the molecule is at least

2,5.

An advantageous embodiment of the method according to the invention lies in the fact that is uses a chemical reagent in the quantity in which the initial solution contains 5 to 50 grams per 1 liter of the chemical reagent.

An advantageous embodiment of the method according to the invention lies in the fact that as a chemical reagent used l,3,5-triakryloylhexahydro-l,3,5-triazine.

An advantageous embodiment of the method according to the invention lies in the fact that as inorganic bases used ortofosforečnanu sodium.

An advantageous embodiment of the method according to this invention is that it applies the solution at a pH in the range of 11 to 14.

An advantageous embodiment of the method according to the invention lies in the fact that it applies the solution, which further contains 10 to 50 grams per 1 liter of sodium sulphate, calculated as the decahydrate of sodium sulphate.

An advantageous embodiment of the method according to the invention lies in the fact that the temperature is in the warm-up stage in the range of from 80 to 100 °C.

An advantageous embodiment of the method according to the invention lies in the fact that the total residence time in the application and warm-up stage is shorter when the application and warm-up stage is less than 2 minutes.

What follows is a more detailed description of the invention in a broader context.

The expression fíbrilace indicates a tendency to vláknění.

As is evident from the above data, the subject of this invention allows to achieve a method of reducing the fibrilační tendency lyocelového fibers, which can be quickly carried out under the conditions of the production of the fibers. Another object of the invention is a method of reducing the tendency to fibrillation lyocelového fibers thus treated fiber keeps the resistance to fibrillation during subsequent wet processing, such as washing, dyeing and washing in laundries. According to this invention can be obtained lyocelové fiber is improved in staining.

Examples of suitable inorganic alkali include sodium hydroxide, sodium silicate and sodium phosphate (ortofosforečnan trojsodný), which is preferred. Can be used a mixture of principles, for example, sodium hydroxide and sodium phosphate.

The chemical reagent preferably bears three akrylamidové group (~NHCOCH=CH2 group), preferably a is l,3,5-triakryloylhexahydro-l,3,5-triazine. It is believed that the hydroxyl groups in the molecules of cellulose react michael's added with aktylamidovými groups of the chemical reagent, thereby zesíťují cellulose molecules. The solution may generally contain 5 to 50, preferably 10 to 20 grams per 1 liter of the chemical reagent. It was found that the chemical agents of this type tend to khydrolýze in an alkaline aqueous solution, especially at pH and during prolonged storage, or if used long application time. It was found that the excessive the degree of hydrolysis, where is the average number of akrylamidových groups in the molecule in the solution when applying to the fiber of less than about 2, is the protection against fibrillation, expected in the treatment of a chemical agent, a small, or missing. The average number of akiylamidových groups in the molecule solution can also be provided as a functionality of the reagent. Preferably is at least 2.2, more preferably at least 2.5. The reagent carrying three akrylamidové group is the desirable functionality of the reagent close to 3, but in fact may have a hydrolysis in a solution effect on the functionality of not higher than 2.9 or 2.7. Further

-3GB 291981 B6, it was found that chemical agents, which initially included only two akrylamidové group, have a worse success rate in reducing the inclination of the kfibrilaci than chemical reagents which initially contain three or more akrylamidových groups.

the pH of the Solution containing the principle and the chemical agent is preferably in the range of 11 to 14, more preferably in the range of 11.5 to 12.5. It was found that the rate of reaction may be undesirably slow if the pH is below the preferred range. Furthermore, it was found that lychlost hydrolysis of the functional groups in the chemical reagent may be undesirably accelerated, if the pH is above the preferred limit. The concentration of inorganic bases in the solution is selected so that the pH of the solution was at the desired value. The concentration of inorganic bases in the solution is usually in the range of from about 1 to 100 grams per 1 liter, preferably about 20 to about 50 grams per 1 liter of medium alkali, such as sodium phosphate, or about 2 to 10 grams per liter of hydroxide of alkaline metal, such as sodium hydroxide.

The thread treated in the manner according to the invention often contains 0.25 to 3% of the weight of the chemical reagent bonded (fixed) to the cellulose, based on the weight of the fibers dried in the air. The amount of fixed reagent can be determined e.g. by measuring the nitrogen content in the thread. Surprisingly, it was found that suitable protection against vláknění can be obtained with the content of the fixed reagent so low, such as 0.25 to 1 %. This is advantageous in that the chemical agents suitable for use according to the invention are often expensive, and so is the requirement to minimize the amount used. The content of the bound reagent in the range of 0.4 to 0.8 % figuring out an appropriate balance between the protection against fibrillation and the price. It was further found that a fiber treated in the manner according to the invention usually has a coloring affinity at least as high as this in the case of untreated fibers. It is essential that the processing of zesítěním generally reduces the dyeability of cellulosic fibers. Further, and surprisingly, it was found that the fiber containing 1 to 3% of the fixed reagent exhibits a advantageously higher dyeability some barvivý than the untreated fiber, for example certain direct and reactive barvivý. The invention further provides a method of increasing the staining lyocelového fibers, which consists in the fact that (1) is applied to the fibre in never nesušeném condition of the solution containing the code to dissolved inorganic principle and chemical reagent carrying more akrylamidových groups, and (2) thread, which was the chemical agent applied, it is heated to induce a reaction between the fibre and the chemical reagent, thereby to fixate on the filament of 1 to 3% by weight of the chemical reagent based on the weight of air dried fibers.

The aqueous solution used in the method according to the invention may optionally contain sodium sulphate, preferably in a concentration in the range of 10 to 50 grams per 1 liter, calculated as anhydrous salt. It was found that the addition of sodium sulfate can increase the efficiency and/or speed of reaction of the chemical reagent with the cellulose.

The method according to the invention can be carried out by extrusion lyocelového fibers through an aqueous circulating bath containing an inorganic principle and chemical reagent. The chemical agent must be capable of hydrolysis in such a circulating water bath and the volume of the bath there is preferably as small as possible. Alternatively, a separate solution of the inorganic alkali and the chemical reagent is to be mixed shortly before use to the thread, and can be on the thread applied, for example, impregnation or spraying. In another case they may be of such separated solutions applied to the fiber individually. In this method, which is preferred, can be on the thread applied the first solution, for example in a circulating bath or by impregnation or by spraying, preferably followed by a squeezing to the extrusion of the excess liquid, and the second solution is then applied to the fiber, for example, impregnation or spraying. Separate solutions can be applied to the thread one way or the other. If you used sodium sulfate, then, may be the sodium sulfate contained in one or the other of the separate solutions. The temperature of the solution is generally chosen having regard to the requirement that the chemical reagent is applied to the fibre in the dissolved state and is often in the range of from ambient temperature to 60 °C.

-4GB 291981 B6

It was found that after applying the solution of the chemical reagent on the fiber will be the pH of the liquid in contact with the fiber generally lower than the pH of the solution prior to the application due to the ústrojnému the effect of carboxyl groups present usually in the molecules of cellulose. At the same time, if applied to the fiber separate solutions of the inorganic bases and the chemical reagent, the pH of the liquid in contact with the fiber is not necessarily in the range preferred for a separate solution before application to the fiber. When used this way, then the pH of an aqueous solution containing an inorganic principle and chemical reagent carrying more akrylamidových groups, as described above, is defined as the pH of the mixture of separate solutions, in the proportions in which they are applied.

After applying the inorganic bases and the chemical reagent in aqueous solution on the fiber is wet the fiber subjected to fixačnímu step to run the reaction between the fibre and the chemical reagent. For the temperature of the heat treatment is considered to be the maximum temperature reached during the fixation.. it is Usually at least about 50 °C, can be at least about 80 °C, and may be about 100 °C, or above about 140 °C. Fiber, which solution is applied, is preferably heated above the temperature of the coating, for example steaming or by microwaves, thereby to induce reaction between the cellulose and the chemical reagent. Dry heating is usually less preferred. The overall processing time (application plus fixation) is usually shorter than 3 minutes, preferably shorter than 2 minutes, even more preferably below 1 minute. In particular, this short processing time is an advantage of the invention. Another advantage of the invention is the effective use of chemical reagents.

After treatment with an alkaline solution of the chemical reagent in a manner according to the invention of the fiber can be washed and dried. A washing stage involves is preferably washing with dilute aqueous acid so that the pH of dried fibers was in the range of from about 4.5 to about to 6.5.

The invention further provides a method of manufacturing a lyocelového fibers with reduced tendency to fibrillation, which includes the steps of:

(a) dissolving cellulose in a solvent to form a solution, the solvent is miscible with water, (b) extruding the solution through a nozzle to form precursor fibers, (c) the passage of the precursor fibers at least one aqueous bath to remove the solvent and the formation of fibers, (d) applying an aqueous solution which contains an inorganic principle and chemical reagent carrying more akrylamidových groups in aqueous solution, the average number of akiylamidových groups per molecule of chemical reagent in the solution is at least 2.1, the on the fiber, (e) heating the fibers to a temperature at least 50 °C, to indukovala reaction between the chemical reagent and the fibre, (f) washing the fiber, and (g) drying the fiber.

The thread at the end of step (c) and in the years of (d) and (e) is undried and fiber, and generally has a range of receiving water in the range of 120 to 150 %.

The invention further describes a method of reducing fibrilační tendency lyocelového fibers, consisting in the fact that the thread handles in the nesušeném state at a temperature of at least about 50 °C with an inorganic principle and a chemical reagent bearing at least three akrylamidové group in an aqueous solution, wherein the pH of the solution before applying on the fiber is in the range of 11.5 to 14, preferably 11,75 to 12.5.

-5GB 291981 B6

The advantage of this invention is that it can be implemented in the production of lyocelového fibers at operating speeds, it can be said on the fibrous koudelné the yarn in the extended form. The thread is protected against fibrillation at an early state, especially before the wet processing of the dried lyocelového fibers or fabrics made with it, such as knitted fabrics or woven fabrics. These wet processing methods include washing, dyeing and cleaning.

The invention is illustrated by the following examples. The degree of fibrillation of the materials may be determined by the procedure described hereinafter, the testing Method 1, and the propensity for fibrillation using the techniques described hereinafter, the testing Method 2 or 2A.

Method of testing 1 (Determination of fibrillation)

For the determination of the fibrillation is not generally acceptable standard, the following procedure is used to determine the fibrilačního index (F.I.). Was indentifikována a series of fiber samples with zero and increasing degrees of fibrillation. Measure the standard length of the fibers of each sample and calculates the number of fibrils (fine side hair protruding from the main body of the fibre) along the standard length. Measure the length of each fibrily and for each fiber provides a certain number, which is the number of fibrils multiplied by the average length of each fibrily. Fiber shows the highest value of this specified number is considered as a maximum vlákněné fiber and shall be marked with the fibrilačním index 10. Completely nezvlákněné thread is marked fibrilačním index equal to 0 and the remaining fibres odstupňují from 0 to 10 based on the microscopically measured arbitrary numbers.

Measured fiber is then used to create a standard scale of quality. To determine the fibrilačního index any further sample of the fibers is five or ten fibres visually compare under a microscope with a standard scale fibers. Visually a set number for each thread are then averaged and the obtained fibrilační index of the sample in the test. It is necessary to take into account that the visual determination and the determination of the diameter is many times quicker than measurement, and it was found that the technologists who are experts in the field of fibres, agree in their assessments of the fibers.

Fabrics containing fibers with F.Also. 2 and more generally have frosted’ appearance. In the fabric, including washed fabrics, it is for fiber, the required F-value.Also. 1 or less, preferably 0.5 or less.

Method of test 2 (action of inducing fibrillation)

A) Treatment of the washing. 1 g of the fiber is inserted into the cylinder from stainless steel, approximately 25 cm long with a diameter of 4 cm, containing approximately 250 ml. Add 50 ml of a conventional laundry detergent containing 2g/l Detergylu FS955 (anionický detergent available from ICI plc) (Detergyl is a trade mark) and 2 g/1 of sodium carbonate, affix with screw cap and an enclosed cylinder, alternately turning at 60 převaleních per minute for 60 minutes at 95 °C. The washed fiber is then rinsed in hot and cold water.

B) Processing in mísičce. 0.5 g of washed fibers neřezaného on a length of 5-6 mm and dispersed in 500 ml of water at ambient temperature is inserted into the home mísičky (zkapalňovač) and mísidlo running 2 minutes at approximately 12 000 rpm. The fibers are then collected and dried and determined the degree of the lamps method of testing 1.

The testing method 2A (action of inducing fibrillation)

The procedure is the same as in method 2, but with the omission of washing (And).

Method testing 3 (Processing of fibers)

The following general procedure is used for determination of the conditions of processing of the fibers. A solution of cellulose in aqueous N-methylmorfolino-N-oxide (NMMO) was extruded into an aqueous coagulation bath

-6CZ 291981 B6 that the emergence of a 1.7 decitex lyocelových fílamentů, which promývaly water until they were basically free

NMMO. These never undried and filaments or fibers were vířeny in a hot aqueous bath containing l,3,5-triakryloylhexahydro-l,3,5-triazine (TAHT), and the principle, as stated above, rinsed

0.5 ml/1 aqueous acetic acid and dried.

Method of test 4 (Processing of fibers)

The following general procedure is used for determination of the conditions of processing of the fibers. A solution of cellulose in aqueous processing of fibers. A solution of cellulose in aqueous N-methylmetfolino-N-oxide (NMMO) was extruded into an aqueous coagulation bath to form a 1.7 decitex lyocelových fílamentů, which promývaly water, until they were essentially free of NMMO. These never undried and filaments were pushed through the through the application unit containing a l,3,5-triakryloylhexahydro-l,3,5-triazine (TAHT), and the principle, and in some cases sodium sulphate. Filaments were then wrung out by squeezing prior to the passage of steam a device for fixation of TAHT on the thread. The course of the deposition was in the range of 1 to 2 minutes, if not stated otherwise. Filaments were then washed in water to remove all unwanted used chemicals.

Method of test 5 (Measurement of the concentration and functionality of TAHT)

The following procedure shall be used to establish the average number of akiylamidových groups in the molecule (functionality) in an aqueous solution which comprises TAHT and its hydrolysis products, as well as to determine the concentration of TAHT in these solutions. It was found that the UV spectrum of TAHT shows absorption peaks at 195 and 230 nm and UV spectrum of its hydrolysis products at 195 nm. The measurement of absorbance is normally carried out using a solution containing 5 to 20 mg/1 TAHT at a path length of 10 nm. More concentrated solutions can be before the measurement, the diluted water. The concentration of TAHT in an aqueous solution can be determined by comparing the absorbance measured at 230 nm against a calibration curve obtained using a solution of known concentration in clean water. Experimentally it was found that the average functionality of the solution which comprises TAHT and its hydrolysis products can be estimated using the equation:

F = (AND₂₃₀/And₁₉₅-0,057)/0,1423, where F stands for functionality and₂₃about and And₁₉₅ mean absorbance measured at 230 and 195 nm.

The concentration and the functionality of the other chemical reagents bearing more akrylamidových groups can be determined experimentally experimental procedures based on a similar method.

Example 1

Never undried and lyocelové filaments (of 1.7 dtex) were processed by the test method 4. Filaments (134 g/min) were pressed through an aqueous bath containing l,3,5-triakiylhexahydro-l,3,5-triazine (TAHT), sodium sulphate (nominally 20 g/1) and sodium phosphate (trisodium phosphate TSP). This bath was maintained at steady-state (at a concentration of TAHT 10,8 - 16,0 g/1, a TSP concentration of 15.8 to 20.5 g/1, a temperature of 46 to 51 °C and a pH of 11.6 to 12.0) by adding solid TAHT (of 3.4 gl/min) and TSP (5.8 g/min) and a solution of sodium hydroxide (5% solution) into the circulating fluid by using in-line vysocestřihového mixer/pump. (The functionality TAHT was determined by the method of testing 5). Then there was a thread quite clearly pressing before the action of saturated steam for 2 minutes. Then it was a thread promyto and dried and determined the slope to fíbrilaci test methods 1 and 2. The amount of cloth TAHT it was determined by the Kjeldahl analysis of nitrogen.

The results obtained are in table 1.

-7GB 291981 B6

Table 1

<td>run time, minutes</td><td>the functionality of the</td><td>TAHT % owf</td><td>fibrilační index</td>

<td> 0</td><td> 2,53</td><td> 0,6</td><td> 0,3</td>

<td> 40</td><td> 2,42</td><td> 0,8</td><td> 0,1</td>

<td> 80</td><td> 2,43</td><td> 0,9</td><td> 0,3</td>

<td> 120</td><td> 2,36</td><td> 0,7</td><td> 0,5</td>

<td> 160</td><td> 2,60</td><td> 0,7</td><td> 0,5</td>

(owf = on weight of fibre, the weight of the fibers, e.g. the weight of air dried fibers)

As is evident, a very good straight up protection from vlákněním was achieved under processing conditions with the levels of fixed TAHT as low as 0.6 %.

Example 2

Different principles

Was used test method 4, the water bath contained TAHT (15 g/1) and various alkali. Details are in table 2.

Table 2

<td>principle, g/1</td><td>PH</td><td>TAHT % on w / w. fibers</td><td>fixation efficiency %</td>

<td>sodium phosphate 20 g/1</td><td> 11,79</td><td> 0,71</td><td> 63</td>

<td>sodium hydroxide 5 g/1</td><td> 11,46</td><td> 1,03</td><td> 77</td>

<td>metakřemičitan chloride 10 g/1</td><td> 11,77</td><td> 0,66</td><td> 57</td>

<td>metakřemičitan chloride 20 g/1 and sodium sulphate 20 g/1</td><td> 12,6</td><td> 1,01</td><td> 100</td>

There is evidence that in the method according to the invention can be used a number of principles. The fixing efficiency is the ratio of chemical reagent bound to the air dried fiber to the amount present in the fibre after the application step.

Example 3

Was used test method 3, the bath contained 40 g/1 TAHT and 30 g/1 TSP (ortofosforečnan hydroxide) at 80 °C for 30 seconds. In one series of experiments contained a bath in addition 50 g/1 the decahydrate of sodium sulphate (Glauberova salt). The thread will then process another 30 seconds in various ways as listed in table 3. Vláknění was induced by test procedure 2 and examined the test way 1.

The results are shown in table 3:

-8CZ 291981 B6

Table 3

<td rowspan="2">Processing</td><td colspan="2">TAHT % in proc. of the form</td><td rowspan="2">F.Also.</td>

<td>0g/lNa₂SO₄</td><td>50g/lNa₂SO₄</td>

<td>control</td><td> 0,00</td><td> 0,00</td><td> 6,4</td>

<td>the surrounding</td><td> 2,68</td><td> 3,49</td><td> 0,0</td>

<td>110 °C oven</td><td> 3,52</td><td> 4,77</td><td> 0,0</td>

<td>98 °C/100 % R.H. steam</td><td> 4,26</td><td> 5,64</td><td> 0,0</td>

(R.H. = relative humidity)

Zero fíbrilace was detected in this experiment when using TAHT, no matter was used sodium sulphate or not. The addition of sodium sulfate increased the degree of fixation of TAHT.

Example 4

Aqueous solution containing 40 g/1 TAHT and an inorganic alkali was filled with not undried and lyocelové fiber at 80 °C and the fiber was treated at 98 °C/100% relative. humidity for a period of 1 minute, are flushed with 0.5 ml/1 aqueous acetic acid and dried. Vláknění was induced by test procedure 2 and set the test way 1.

The results are shown in table 4:

Table 4

<td>the principle of</td><td>concentration g/i</td><td>PH</td><td>On₂SO₄g/1</td><td>TAHT</td><td>F.Also.</td>

<td>kostrol.</td><td></td><td> —</td><td> —</td><td> 0,00</td><td> 6,2</td>

<td>TSP</td><td> 30</td><td> 11,9</td><td> 0</td><td> 2,65</td><td> 1,0</td>

<td>TSP</td><td> 30</td><td> -</td><td> 50</td><td> 3,13</td><td> 0,2</td>

<td>NaOH</td><td> 10</td><td> 13,4</td><td> 0</td><td> 2,70</td><td> 0,0</td>

<td>NaOH</td><td> 20</td><td> 13,7</td><td> 0</td><td> 2,54</td><td> 0,6</td>

In all cases it was found an excellent reduction in tendency to vláknění.

Example 5

The use of sodium hydroxide. Was used test method 4, a water bath at 50 °C contained TAHT (15 g/1) and sodium hydroxide in different concentrations (as indicated in table 5).

-9CZ 291981 B6

Table 5

<td>sodium hydroxide g/1</td><td>TAHT, % on w / w. fibers</td><td>fixation efficiency, %</td>

<td> 2</td><td> 0,25</td><td> 28</td>

<td> 3</td><td> 0,42</td><td> 63</td>

<td> 3,5</td><td> 0,51</td><td> 61</td>

<td> 4</td><td> 0,55</td><td> 74</td>

<td> 4,5</td><td> 0,74</td><td> 74</td>

<td> 5</td><td> 0,73</td><td> 64</td>

<td> 6</td><td> 0,53</td><td> 64</td>

Example 6

Never undried and lyocelové filaments (of 1.7 dtex) were dragged (134 g/min) through an aqueous bath (temperature 52 to 56 °C, pH 12,0-12,4) containing l,3,5-triakryloylhexahydro-l,3,5-triazine (TAHT) (iniciačně 17 g/1), sodium sulphate (iniciačně 17 g/1) and sodium hydroxide (iniciačně 3.5 g/1). Solid reagent and a solution of sodium hydroxide were added to the circulating fluid during the test, in order to maintain constant conditions in addition to the caused by the hydrolysis of TAHT. The functionality of TAHT in the solution was measured by the test way 5. The fiber was then drained by pressing before processing the saturated steam for 2 minutes. Then it was a thread promyto and dried and subjected to vláknění test way 1 and 2. The level of fixation of TAHT was determined Kjeldahovou analysis of nitrogen. The results are shown in table 6.

Table 6

<td>run time minutes</td><td>the functionality of the</td><td>PH</td><td>TAHT % on w / w. fibers</td><td>F.Also.</td>

<td> 0</td><td> —</td><td> 12,3</td><td> 2,11</td><td> 0,0</td>

<td> 10</td><td> 2,2</td><td> 12,4</td><td> 2,54</td><td> 0,0</td>

<td> 20</td><td> —</td><td> 12,2</td><td> 1,88</td><td> 0,4</td>

<td> 30</td><td> 1,6</td><td> 12,2</td><td> 1,84</td><td> 2,1</td>

<td> 40</td><td> —</td><td> 12,2</td><td> 1,87</td><td> 1,7</td>

<td> 50</td><td> 1,2</td><td> 12,1</td><td> 1,10</td><td> -</td>

<td> 60</td><td> —</td><td> 12,2</td><td> 1,10</td><td> 4,9</td>

<td> 70</td><td> 0,8</td><td> 12,1</td><td> —</td><td> —</td>

<td> 80</td><td> —</td><td> 12,1</td><td> 0,97</td><td> 5,4</td>

<td> 90</td><td> 0,6</td><td> 12,1</td><td> -</td><td> -</td>

<td> 100</td><td> -</td><td> 12,0</td><td> 1,01</td><td> 4,9</td>

Under these conditions, TAHT subjects after the first few minutes in a bath of excessive hydrolysis, therefore, samples with a longer period of run time represent the comparative samples. Protection against vláknění, provided treatment, fades with increasing duration of the run. Fibrilační index of subsequent samples is unacceptably high, even though the thread has been fixed a considerable amount of TAHT. We can assume that even less protection will be provided by the low TAHT fixation levels (less than 1%) required for commercial reasons.

Example 7

This example was designed to tent the influence of time of steaming. After the test method 4 was followed using a solution processing, containing TAHT (15 g/1) and sodium phosphate (20 g/1). The results are shown in table 7:

-10CZ 291981 B6

Table 7

<td>the period of steaming, seconds</td><td>fixation efficiency, %</td>

<td> 60</td><td> 48</td>

<td> 77</td><td> 55</td>

<td> 92</td><td> 62</td>

<td> 108</td><td> 65</td>

<td> 126</td><td> 65</td>

The results prove that under the conditions used in this processing was fastening the efficiency of the same level at the time of processing steam for about 90 s and higher. The shorter the fusing time is reached the rapid preheat treatment koudelné yarn before the steam treatment, or use of microwaves.

Example 8

Fixation using microwaves. Was used test method 4, sTAHT (15 g/1) and ammonium phosphate (20 g/1) at 50 °C. Samples were processed in batches and fixed after different times using a 700 W microwave oven, instead of the treatment of the steam. The results are shown in table 8.

Table 8

<td>time microwaves seconds</td><td>TAHT % on w / w. fibers</td><td>fusing efficiency</td><td>fibrils. index</td>

<td> 15</td><td> 0,2</td><td> 21</td><td> 1,8</td>

<td> 30</td><td> 0,5</td><td> 54</td><td> 1,9</td>

<td> 50</td><td> 0,4</td><td> 36</td><td> 1,2</td>

<td> 60</td><td> 0,6</td><td> 66</td><td> 0,1</td>

<td>60 (repeat)</td><td> 1,0</td><td> 97</td><td> 0,0</td>

<td> 180</td><td> 1,1</td><td> 100</td><td> 0,0</td>

Excellent protection from vlákněním was achieved with the amount of fixed TAHT as low as 0.6 % w / w. fibers.

Example 9

After the test method 4 was followed using an aqueous solution of TAHT and sodium phosphate, when used as a raw material TAHT, sodium phosphate and sodium hydroxide to ensure a steady state with regard to concentration and pH (12,8-13,9 g/1 TAHT, 20,3-26,0 g/1 TSP, pH 11,7911,95) under the conditions set out to minimise hydrolysis of TAHT.

Fiber, on which was applied the solution, it was towed through the press cylinder to push out the excess fluid, zkadeřeno passage through the tamping chamber and composed into the steam box (J-box). The first steam hose was connected to the steam box 7.5 minutes after the start of the trial and the second hose was watered 14 minutes after the initiation of the experiment. After a 20-minute phone course was the temperature inside the steam box consistently about 100 °C, measured termoelektrickým article in different places. The residence time of the fiber in the steam box was about 10 to 15 minutes. The results of the samples of fibers obtained in variously long run times after the system has been stabilized, are given in table 9.

Table 9

<td>running time minutes</td><td>TAHT, % on w / w. fibers</td><td>fixation efficiency, %</td><td>fibrils. index</td>

<td> 20</td><td> 1,07</td><td> 83</td><td> 0,8</td>

<td> 25</td><td> 1,07</td><td> 74</td><td> 0,3</td>

<td> 27,5</td><td> 0,90</td><td> 71</td><td> 0,9</td>

<td> 30</td><td> 0,88</td><td> 81</td><td> 1,3</td>

Example 10

Never has not dried fibre was treated with TAHT test manner 3, when using the concentration range of the solution TAHT that provide the level of TAHT fixed on fibre. Processing is carried out using a John Jeffries Hank Dyer with 20 g/1 TSP at a temperature of 80 °C and a ratio of a spa 20 : 1 for 30 minutes. The physical properties of the treated fibres are given in table 10.

Table 10

<td>TAHT% in the solution</td><td>TAHT % owf</td><td>the absorption of water %</td><td colspan="2">specific strength cN/tex</td><td colspan="2">elongation to rupture %</td>

<td></td><td></td><td></td><td>moist</td><td>dry</td><td>moist</td><td>dry</td>

<td> —</td><td> —</td><td> 61</td><td> 35,3</td><td> 40,3</td><td> 15,6</td><td> 13,7</td>

<td> 1,25</td><td> 0,42</td><td> 64</td><td> 31,2</td><td> 40,3</td><td> 15,0</td><td> 12,9</td>

<td> 2,4</td><td> 0,97</td><td> 72</td><td> 27,7</td><td> 38,6</td><td> 11,9</td><td> 13,5</td>

<td> 4,5</td><td> 1,93</td><td> 81</td><td> 26,1</td><td> 38,8</td><td> 11,0</td><td> 11,2</td>

owf' = on the weight of the fibers

The results show a small reduction of the specific strength and expansion with the increasing value of TAHT. This reduction is considered acceptable in textile applications. Noticeably rises the imbibition water with the rising level of fixation of TAHT. This may indicate that cross-linking of fibers in the swollen state increases the ability of the dried fibers absorb water, when it is again dipped. This ability to control the absorption of water is an advantage of this invention.

Example 11

Undried and lyocelové fibre was treated with TAHT test way 4 (of 2.1 - 1.5 g/1 TAHT, namely 20 g/1 TSP, pH 11,84-11,49) to ensure the samples of fibers containing 1,6-2,0% fixed TAHT. These samples were converted to yarn and the yarn was thin on the fabric. These fabric samples and untreated control samples were dyed with direct barvivý under the following conditions:

The ratio of bath 10:1, the temperature of the bath 50 °C, amount of dye 3 % on weight of fiber (% owf). Immersion of the fabric into the dyeing bath was 10 minutes. Was added NaC14g/l, left for 10 minutes. The temperature was raised to 95 °C for 30 minutes, was added NaCl to provide a total of 20 g/1, the course of 30 minutes. Cooling to 80 °C for 10 minutes, left 15 minutes. The fabric was flushed through with hot and cold water, coiled and dried.

During the staining procedure, samples were taken in dyeing bath and analyzed by visible spectroscopy is the determination of the amount of the adopted colorants on a thread. The results are expressed as

-12CZ 291981 B6 percentage loss of dye in the bath in comparison with its original amount, are listed in table 11.

Table 11

<td>coloring</td><td colspan="2">Solofenyl Orange ARL</td><td colspan="2">Solofenyl Violet4HL</td><td colspan="2">Solar Black G</td><td colspan="2">Solar Green HL</td>

<td>time min</td><td>nezprac.</td><td>proc.</td><td>nezprac.</td><td>proc.</td><td>nezprac.</td><td>proc.</td><td>nezprac.</td><td>proc.</td>

<td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td><td> 0</td>

<td> 10</td><td> 0</td><td> 25</td><td> 5</td><td> 8</td><td> 4</td><td> 0</td><td> 0</td><td> 10</td>

<td> 20</td><td> 0</td><td> 11</td><td> 10</td><td> 10</td><td> 13</td><td> 0</td><td> 0</td><td> 20</td>

<td> 50</td><td> 24</td><td> 26</td><td> 69</td><td> 61</td><td> 58</td><td> 54</td><td> 33</td><td> 63</td>

<td> 90</td><td> 30</td><td> 52</td><td> 58</td><td> 90</td><td> 65</td><td> 64</td><td> 36</td><td> 61</td>

<td> 115</td><td> 34</td><td> 74</td><td> 62</td><td> 90</td><td> 64</td><td> 66</td><td> 61</td><td> 84</td>

In these and other experiments was the rate of loss of dye in untreated and treated lyocell similar. The main differences were in the saturation of the hue. In many cases, the dyed treated lyocell on a deeper shade (absorbed more colors) than the untreated lyocell. This is advantageous both in terms of cost savings, so for colouring sytějšími shades.

The saturation of the shades can be described quantitatively using the relative values of color saturation (Q-values). The Q-value is the relative depth of color of the sample against a specific standard sample, whose color saturation is given a value of 100. The saturation of the color of the surface is expressed as the integral of K/S in the range of 400 to 700 nm, where Kje absorption coefficient and S is the coefficient of variance. K/S can be calculated from the values of reflectance of the surface at a certain wavelength. Integrals of K/S is proportional to the ratio of the amount of dye in the fabric. Compared the colors of the fabrics dyed a single color is usually a difference of 5 % or more in the Q-value of visibly different to the naked eye. Q-values are listed in table 12 and are presented for samples processed TAHT due to the corresponding untreated samples. The amount received of the dye indicates the ratio of the dye in the fiber to the amount originally present in the dye bath.

Table 12

<td rowspan="2"></td><td colspan="2">received dye %</td><td>relative. value-Q %</td>

<td>nezprac.</td><td>TAHT proc.</td><td></td>

<td>Solar Red B</td><td> 72</td><td> 58</td><td> 111</td>

<td>Solofenyl Violet 4BL</td><td> 58</td><td> 90</td><td> 138</td>

<td>Solar Bleck G</td><td> 65</td><td> 64</td><td> 102</td>

<td>Solar Green BL</td><td> 36</td><td> 61</td><td> 153</td>

<td>Solofenyl Orange ARL</td><td> 30</td><td> 53</td><td> 132</td>

<td>Solofenyl Blue AGFL</td><td> 64</td><td> 78</td><td> 113</td>

It is obvious that in a few cases are a slam dunk lyocelové fiber treated in accordance with the procedure according to the invention on a deeper shade than the untreated fiber, which usually corresponds to the absorption of a larger amount of dye.

-13CZ 291981 B6

Example 12

Never undried and lyocelové fiber in the form of koudelné yarn was processed TAHT test procedure 3 to ensure the samples with different content of TAHT fixed on fibre. Dried lyocelové fibre was treated with TAHT in an analogous procedure. Processing was carried out using a John Jeffries Hank Dyer, 20 g/1 TSP, at a temperature of 80 °C in a ratio of bath 20 : 1 for 30 minutes. Then samples were stained with Direct Green 26 (1 % on weight of fibers) and the dyed samples were then compared to determine the Q-values against the raw preliminarily dried lyocelovým koudelím as standard.

The results are shown in table 13.

Table 13

<td rowspan="2">TAHT day. g/1</td><td rowspan="2">TAHT fix. %</td><td colspan="2">The relative Q-values</td>

<td>undried and</td><td>dried</td>

<td> 0,5</td><td> 0,10</td><td></td><td> 98</td>

<td> 0,5</td><td> 0,13</td><td> 100</td><td></td>

<td> 1,0</td><td> 0,27</td><td></td><td> 99</td>

<td> 1,0</td><td> 0,38</td><td> 102</td><td></td>

<td> 2,0</td><td> 0,64</td><td></td><td> 100</td>

<td> 2,0</td><td> 0,84</td><td> 100</td><td></td>

<td> 4,0</td><td> 1,77</td><td></td><td> 97</td>

<td> 4,0</td><td> 1,83</td><td> 108</td><td></td>

<td> 5,0</td><td> 2,02</td><td></td><td> 96</td>

<td> 5,0</td><td> 2,19</td><td> 106</td><td></td>

<td> 7,0</td><td> 2,65</td><td></td><td> 101</td>

<td> 7,0</td><td> 3,59</td><td> 105</td><td></td>

<td> 10,0</td><td> 3,99</td><td></td><td> 93</td>

<td> 10,0</td><td> 5,48</td><td> 107</td><td></td>

All dried fibres processed TAHT is colored paler saturation than TAHT-processed never nesušená fibers. Also all processed TAHT in a never nesušeném state is colored more deeply than the untreated control samples.

Example 13

Undried and lyocelové fibre was treated with TAHT test way 4 (of 2.1 - 1.5 g/1 TAHTm, namely 20 g/1 TSP, pH 11,84-11,49) to ensure the samples of fibers containing 1,6-2,0% fixed TAHT. These samples were předeny on the yarn and the yarn was woven to the fabric. These samples of the fabric and the fabric made of untreated lyocelového fibers were dyed with a variety of reactive dyes. The mode of dyeing was as follows:

Start at 25 °C with color (1.1% of the paint on the weight of the fibers)

The course of the 10 minutes Sample 1

The rise at 80 °C for 30 minutes, the addition To the₂SO4 in doses of Sample 2

The course of 20 minutes, the addition To the₂CO3 after 10 minutes Sample of 3

The course of the 15 minutes Sample of 4

The course of the 45 minutes Sample 5

-14CZ 291981 B6

Fabric samples were taken at different times, washed in cold water and cleaned of soap.

The content of the dye in various spa was set visible spectroscopy. The percentage loss of dye from the dyeing bath into the fiber was determined from the amount of paint that remained in the dye bath and it is marked as exhaustion. Percent dye in the fiber after washing, which remained in the fiber after odmýdlení, was determined by measuring the relative colour intensity using visible spectroscopy.

The results are shown in table 14.

Table 14

<td rowspan="2">sample no.</td><td rowspan="2">time min.</td><td colspan="2">exhaustion %</td><td colspan="2">fixation %</td>

<td>controls.</td><td>proc TAHT</td><td>controls.</td><td>proc TAHT</td>

<td colspan="6">Procion Yellow HE4R</td>

<td> 1</td><td> 10</td><td> 6</td><td> 13</td><td> 1</td><td> 2</td>

<td> 2</td><td> 40</td><td> 66</td><td> 90</td><td> 13</td><td> 9</td>

<td> 3</td><td> 60</td><td> 75</td><td> 94</td><td> 21</td><td> 17</td>

<td> 4</td><td> 85</td><td> 80</td><td> 96</td><td> 77</td><td> 97</td>

<td> 5</td><td> 130</td><td> 75</td><td> 97</td><td> 74</td><td> 85</td>

<td colspan="6">Procion Red HE7B</td>

<td> 1</td><td> 10</td><td> 6</td><td> 19</td><td> 1</td><td> 2</td>

<td> 2</td><td> 40</td><td> 68</td><td> 79</td><td> 19</td><td> 13</td>

<td> 3</td><td> 60</td><td> 69</td><td> 83</td><td> 21</td><td> 23</td>

<td> 4</td><td> 85</td><td> 72</td><td> 88</td><td> 69</td><td> 85</td>

<td> 5</td><td> 130</td><td> 76</td><td> 94</td><td> 73</td><td> 80</td>

The results when using Procin Yellow HE4R and Procion Red HE7B are typical. (Procion is a trade mark of ICI plc). A number of exhaustion were faster for the fabric processed TAHT and exhaustion continued to a higher level. The extent of fixation of the colors was similar in the two fabrics, but the level of fixation in the fabric processed TAHT was higher than that in the control lyocelové fabric.

Thus the TAHT-treated fabric exhibits a higher efficiency in the applied staining than the control. Furthermore, it is fabric, processed TAHT, dyed to a deeper shade than the control. From the point of view of a much faster depletion in textiles, processed TAHT may consider shorter cycles of staining.

Example 14

A solution of cellulose in aqueous N-methylmorfolino-N-oxide (NMMO) is extruded into an aqueous coagulation bath to form a 1.7-dtex lyocelových fiber, which is washed with water, until they are basically deprived of the N-methylmorfolino-N-oxide. On this never nasušená fibers was applied an aqueous solution containing 10 g/1 Ν,Ν'-methylene-bisakiylamidu (MBA), 20 g/1 of sodium carbonate and 100 g/1 sodium sulphate. The fibers odmačkají to remove the surplus fluid, heat up (in different ways, as is evident from the following data) for the fixation of the N,N'-methylene-bisakrylamidu, washed with dilute acetic acid to remove any unwanted chemicals and dried. The tendency to fibrillation of the processed fibers is measured using test methods 2 and reaches to the following results:

<td>Fastening step</td><td>F.Also. (average of 4 determinations)</td>

<td>neošetřeno, control determinations (without an MBA)</td><td> 5,6</td>

<td>steaming (100 °C, a relative humidity of 98 %, duration 10 min)</td><td> 4,8</td>

<td>steaming (100 °C, a relative humidity of 98 %, duration 20 min)</td><td> 2,9</td>

<td>heating (70 °C, 8 min)</td><td> 3,5</td>

-15CZ 291981 B6