AT513426A1 - Spun-dyed modal fiber, its use and process for its preparation - Google Patents

Abstract

The present invention relates to a spun-dyed regenerated cellulosic fiber which achieves the definition of a modal, its use for the production of yarns and fabrics, for textile and technical applications, and a process for the production of these fibers. The spun-dyed modal fibers of the invention are suitable for textile applications in technical fields such as e.g. Automotive textiles, furniture, carpets, curtains & transport textiles. The fibers meet all requirements for fibers for technical textiles, such as, for example, high strength in the wet state, high fastness to rubbing in the wet state, high heat-light fastness and also the requirements of industrial laundry. The fibers can be made in a wide range of titers depending on the product use. The invention thus enables the use of cellulosic fibers in all areas in which spin-dyed viscose fibers are not used. Likewise, the spun-dyed modal fibers according to the invention are suitable both for the clothing sector and for home textiles.

Description

1 i-btr-dülc: 14:11 From: LHla ff-HtNIWfcbtN'WlBi + 4JS fb <d Ml ddf4B Hn: + 4J 1 bbb b.b'Jb · * # ·····

Lenzing AG, PL0529

Solnna-stained modal fiber, using it as well as methods of making same

The present invention relates to spun-dyed cellulosic regenerated fibers with improved functional properties for textile

Applications that also meet, for example, the requirements of an industrial laundry, their use for the production of yarns and fabrics, and a method for producing these fibers. 10 State of the art:

Cellulosic fibers basically have good moisture management and a pleasant touch feel since they are relatively reversible in their ability to absorb relatively high levels of moisture and are soft. Among other things, this leads to a high level of wearing comfort and also to many other good functional properties of the textiles produced therefrom.

Fibers by the viscose process are mainly known today as cellulosic regenerated fibers and are produced worldwide for standard applications in textile and nonwovens berelets having a nominal fiber titer of between 0.8 and 16 20 dtex; standard fleece fibers are today used extensively for light fashionable textiles. However, the low strength, especially in the wet state, the high elongation and the high Flδchenschrumpfüng put the use of viscose fibers but limits. For example, these textile properties do not permit use in segments which require frequent washing (especially industrial washes) of the fabrics. A measure of the washability is the area shrinkage. In order to be able to grasp the area shrinkage easily quantitatively, its relationship with the wet modulus, measured according to the regulations of the BlSFA and therefore hereinafter referred to as BISFA wet modulus, is exploited 30 (BlSFA, Testing methods viscose, modal, lyocell and acetate staple fibers and tows , 2004 Edition). 1 17/09/2012 15:30

Nr,: R798 P.005 / 035 i r-btr-döid 1 * 1: 11 Yon: u-ua mibNiwtbbN'wibi + 4J fbrd tm Hn: + 4b i bJib b.b'Jto ** ♦ · ·· « »! · Φ« ··· • · · · · · · · «« · * * ♦ ··· * +

Lanzing AG, PL0529

The connection between avenging shrinkage (after washing) and the BISFA wet modulus has been known for viscose fibers since the seventies of the last century (Szegö, L, Faserforsch, Text. Techn., 21 (10), 1970), see also FIG With a BISFA wet modulus of 2, 5 can be followed by a 15-20% wash shrinkage, with a BISFA wet modulus of 5 the shrinkage is already reduced to 4 * 7% (see FIG. 1),

Spun-dyed viscose fibers have been known for decades and are also commercially available from a wide range of manufacturers. Spin dyeing by spinning in color pigments into the dope solution is much more environmentally friendly and also cheaper than the conventional d. H. with substantive or reactive dyes working dyeing process for viscose fibers. 15 Spun-dyed viscose fibers are very elastic. This feature is advantageous for the fashion sector, as it can produce lightweight and flexible fabrics. On the other hand, because of the content of solids in the fibrous structure, splnn-dyed viscose fibers have only a low strength, especially in the wet state. For example, the textile-mechanical properties of these 20 fibers are always well below the values required for modal fibers by the BISFA definition.

The 25 values for dry strength and wet modulus required for modal fibers of the BISFA definition (BISFA, test methods viscose, modal, lyocell and acetate staple fibers and tows, 2004 Edition) are defined as follows and thus dependent on the individual fiber T (dtex) of the respective fibers ;

Strength (Bc) (in (cN)) in the conditioned state:

Be &amp; 1,3VT + 2T. 30

Wet modulus (Bm) (in (cN)) at an elongation of 5% in the wet state; 2 17/09/2012 15:30

No .: R798 P.006 / 035 1 f-btr-düld From: LHta KHItNIWLbtN'WiBl (b (cL (Ul bbHB ΗΠ: f I DJMdH bJb b. R'Jb

···· M

Lenzing AG, PL0529 Bm S 0.5 * VT.

State of the art for technical textiles;

Because of their weaker textile-mechanical properties, high-grade technical textiles can not be produced from the spun-dyed fibers known in the prior art, in particular not those textiles which can easily be destroyed under heavy mechanical stress. Spun-dyed viscose fibers, for example, can not be used in the automotive textiles, upholstery fabrics, carpets and textiles sectors for public transport (trains, buses, etc.).

State of the art for textile applications;

In the field of textile applications, especially for clothing, but also z. For example, for bedding, the modified modal fibers produced by a modified viscose process have long been known and popular for their softness and washability, and their textile-mechanical properties are characterized by the above values required by the BISFA definition reach or exceed. In order to produce colored textiles from modal fibers, preferably the finished fabrics 20 (knitwear or fabric) are subsequently dyed. A particularly popular, but also associated with particular difficulties color is red.

Lenzing AG has been selling spun-felted black modal fibers for about 20 years. However, in the context of the present invention, it must be clearly distinguished between tails and colorful spun-dyed fibers.

Although colorful spun-dyed modal fibers are variously mentioned in the literature (eg, Lenzing AG, R. Rauchenzauner, Lenzinger Berichte, 53, 14-17, 1982), these fibers could never be used in a commercial scale 3 17 / 09/2012 15:30

No .: R798 P. 007/035 I r-bbK-eMIc; I4i: ic! Yon! LI-Ha + 4J Cb Cd rül dy ^ lo Hn: + 4J I DJ4c4 SÄ b.a'js I r-bbK-eMIc; I4i: ic! Yon! LI-Ha + 4J Cb Cd rül dy ^ lö Hn: + 4J I DJ4c4 SÄ b.a'js • · • t ftt # · »* *« · «·

* ♦ * · I * · · · · · · · · · · · · · ·

Lenzing AG, PL0529. Lenzing also had to reorganize the production because it was not possible to produce fibers with a) uniform color depth and b) uniform color S during a production run. The biggest problem, however, was the reproducibility of slip fits. It was virtually impossible to re-create exactly the same color in terms of color depth and color tone. The description of the color is done here, as is common in the textile industry, by the so-called color space, a system with the 10 color coordinates L, a and b. However, these problems only occur in those spun-dyed fibers which are characterized in that either the coordinate a or b or both are different from zero, since only these shade shifts occur. If, however, only the L value is not equal to zero, the problems described above are not observed 15

The spun-dyed fibers described in the prior art or commercially available are all prepared by standard viscose methods. In summary, the state of the art thus discloses only spun-dyed viscose fibers, ie fibers which do not have sufficient strength, insufficient BISFA wet modulus and no adequate textile performance properties. Strictly speaking, some publications reveal nothing more than the intention of the authors to (also) produce spin-dyed 25 modal fibers or HWM fibers.

Task:

Compared to this prior art, the object was to provide a colored cellulosic fiber available, which meets the current requirements for an economically and ecologically sustainable manufacturing process and the increased textile-mechanical requirements, as for example at 17/09/2012 15:31

No .: R798 P.008 / 035 4 j. r-bth * &dll; U VOn * UH (a h'HltNIWtÄtN / Wlöl + Ηύ fbfd ful dy4b Hn: + ^ i dä &gt; ... * ··· * * # * »··· ♦ *** ♦ · · · * · # ·· »·» * · * ·· * + ····················

Lenzing AG, PL0529 an industrial cleaning of garments made therefrom or when used in technical textiles occur.

A further object was to produce a finished cellulosic fiber 5, which does not bleed in the household washing at elevated temperature up to Θ0 ° C, so that mixtures with bright colors in the textiles are possible.

In addition, the object was to provide a suitable production process for these 10 fibers,

Surprisingly, this object could be achieved by a modified modal process and a spun-dyed modal fiber made therewith, 15

The present invention is therefore first a spin-dyed Regeneratceiiulosefeser containing as coloring substance a eingeponnenes, particulate color pigment, characterized in that the fiber corresponds to the Modaldofinition. In a preferred embodiment, the colorant has a particle size distribution with xw less than 2.0 pm. Usual cutting lengths for staple fibers for the textile sector are between approx. 20 and 150 mm. Only such a uniform length of all fibers allows easy processing on the usual today in the textile chain machines 25 with high productivity.

The spun-dyed mod fibers according to the invention fulfill all the technical requirements which are required for the fields of application of tectmic textiles, in particular automotive, upholstery fabrics, carpets and transport textiles. These technical requirements include high strength, especially when wet, good elongation, high rub fastness especially in wet 5 17/09/2012 15:31

No .: R798 P.009 / 035

ii *: u of: i_Hip RHitN (WbbtN''wibi + * u ftifd rui "" tö Hn: + ^. ί I i-SHc »bJb b.IH'JS · ♦ · * * Μ · 4» * ···········································································.

Lenzing AG, PL0529

Condition (for all applications »correct) and high heat-fastness, especially for use in car seats, a. The spun-dyed modal fibers according to the invention also meet the requirements for the BISFA wet module. 5

The invention therefore also relates to the use of the spun-dyed modal fibers according to the invention for the production of technical textiles, in particular automotive, upholstery fabrics, carpets and transport textiles, such as seat covers and other textile surfaces in 10 cars, trains, buses, ships and all other means of public transport private traffic.

The spun-dyed modal fibers can be produced in the titer range 0.8 to 15 dtex. For applications In car seats special fibers with Z is up to 4 dtex suitable. For upholstery fabrics fibers between 1 and 4 dtex are suitable. For carpets, 1.5 and 15 dtex felts are used. Depending on the specific application, fibers are used in every detail for transport textiles. The pigments are strongly bound in the fiber structure and do not split off at elevated temperature, for example in a wash liquor. They therefore generally have a high HT over-dyeing resistance. The spun-dyed modal fibers according to the invention are also suitable for industrial laundering (hospitals and hotels) because the color remains brilliant even after many wash cycles.

The invention therefore also relates to the use of the spun-dyed modal fibers according to the invention for the production of sports textiles, outerwear (ladies & gentlemen), underwear and 30 baby clothing, souvenirs, blended fabrics with polyester and / or 17/09/2012 15:31

No .: R798 P. 010/035 6 K-btr-dWid w. ib vontLHta f-'HibNiwtbfcN'wj.bi ibftf for cry ^ ö HnS «M | j 1 t> s5b b.ii'Ä · * * ·« · · «· · ·« · ···· ♦♦ Φ · • * · ft »· | *

Lenzing AG, PL0S2S other synthetic fibers, industrial linen, bed linen, towels, fitted sheets, quilts, mattress covers and other home textiles,

In the area of sports textiles, outerwear (ladies' and men's), underwear and 5 baby clothing, epin-dyed modal fibers provide higher strengths than viscose spinning fibers, especially when wet. The dimensional stability in use is also much better. After several washing cycles, the textiles with spun-dyed modal fibers are better preserved in the form, or the textiles can be worn with spinngafärbten Modalfasem öftere 10 than textiles on spun-dyed viscose fibers.

In the protective clothing sector, spun-dyed viscose fibers can not be used at all in blends with high-performance fibers (meta-aramid, para-aramid, polyester, polypropylene, etc.), since for this application mechanically stronger fibers are necessary. For plaid fabrics (eg, shirts and bedding) blended with polyester, the spun-dyed viscose will break due to its low fiber strength. For the check effects (for example in the mixture Modal l polyester), however, the spin-dyed modal fibers according to the invention can be used very well. In the home textiles sector, the use of spun-dyed viscose fibers is not possible, since good dimensional stability is required for bed linen, towels and fitted sheets. Spun-dyed modal fibers, on the other hand, can be used both for filling materials for quilts and for mattress covers. The spun-dyed modal fibers are in the upper, d, h. outer part of the mattress cover preferred. For mattress covers, spun-dyed modal fibers can be blended with polyester, polyamide and / or polypropylene. The proportion of spun-dyed modal fibers according to the invention in mattress cover fabrics is 10 to 60%, 30 are preferred mixtures with 20 to 40%. 17/09/2012 15:32

Nr .: R798 P. 011/035 7 1 f-btK-dfeJId m: m Uon: LHb ^ IfcNIWbbbN'WltU + * U rbrb 001 ö ^ ö Hn: + HJi I OOHdH 030 b. lei'30 · «·· 4« ·· »·« 4 «· ··· * ♦« φ m ·· # · «· 4 4 • 4 4 4 4 4 4 · ··» e • 4 444

Lenzing AG, PL0529

Since the modal fibers according to the invention absorb much more moisture than cotton, they allow both a better wearing comfort in the clothing and more comfort in home textile applications such as bedding, towels etc.

S

The present invention also relates to the use of the fibers according to the invention for the production of a game. Such a yarn is distinguished from yarns made of fibers which have hitherto been available by a significantly higher strength and at the same time has all the advantages of the 10-layer-dyed fibers.

Likewise provided by the present invention is the use of the fibers according to the invention for producing a textile surface blend. In addition to the fibers according to the invention, this fabric may contain 15 additional fibers,

The fabric is preferably a woven, knitted or knitted fabric, but in principle may also be a nonwoven, also known today as Non * Woven, in particular in English-speaking countries. Even for high-quality nonwovens, the use of fibers with a high BISFA wet modulus and high strength is of crucial importance. In the case of a woven or knitted fabric, it is possible to mix the fibers according to the invention with other fibers either by mixing prior to the yarn production, the so-called intimate mixing, or by using in each case pure game of the various fiber types 25 during weaving, knitting or knitting.

The fiber according to the invention can be produced by a modified modal process according to the invention, which is likewise the subject of the present invention. Viscose processes for modal / HWM staple fibers and 30 continuous filaments have been known in principle for many years and, for example, in detail by K. Götze, man-made fibers by the viscose process, 1Θ67, and 8 17/09/2012 15:32

No: R798 P.012 / 035 ir-btr-Mici ihiih ofLHb KHifcNiwfcbfcN'wiöi + * o rbfd rm d ^ ö Hn: + Hj i wö b. ij'ä ♦ · 4 4 4 · 4 4 4 4 4 4 • 4 # 4 4 44 «

Lenzing AG, PL0529 described in AT 2879Q5. However, the textile properties of the fibers and filaments obtained therefrom are considerably influenced by many parameters. In addition, for many influencing factors, limits are set by the design of the existing production plants, which can not be exceeded for technical or economic reasons, so that any variations of the parameters are often are not possible at all and therefore the specialist would not be prompted to do so. 10 15 20 25

It has been found that, for the production of the fibers according to the invention, a cellulose concentration of 4-7% (pulp with an R-18 content of 93-98%) and an alkali ratio ("celluiose concentration / sodium hydroxide concentration, in g / l in each case) of 0, 7 to 1.5 represent the ideal conditions. However, the spinning parameters must be adjusted accordingly due to the addition of the color pigments.

The invention therefore also provides a process for producing a regenerated cellulose fiber dyed by means of colored pigments for textile applications by spinning a viscose with a content of 4 to 7% cellulose, 9 to 10% NaOH, 38 to 42% (based on cellulose) carbon disulfide and 1 to 5% (based on cellulose) of a modifier In a spin bath, stripping the coagulated filaments using a viscose whose spinnegamma value is 50 to 68, and whose spin viscosity is 50 to 120 falling seconds; where a. the temperature of the spinning bath is 34 to 48 ° C, b. the alkali ratio (= cellulose concentration / alkali content) of ready-to-spray viscose is 0.7 to 1.5, c. the following spin bath concentrations are used; • H2S04 68 - 90 g / l • NazSO4 90-160 g / l • ZnSO «30 -85 g / l, 9 17/09/2012 15:33

No .: R798 P. 013/035 30

If-Btt -'- Btub Won: Li-ta iJHltMiwtbbN''WitJl + ^ fbrd rül BB ^ B Hni-t-O i bbb * · · * 9 9 '«ft ** · | • ♦ ··· · | 9 · 9 · ♦ ···· i φ 9 • 9 * 9 «··· # • 9 * ·· 9 · 9 · # ·· ···· 9 * · 999

Lenzing AG, PLG529 b. the final discharge takes place from the spinning bath at a speed of between 15 and 60 m / min and where d. after the addition of the pigments to the spinning solution, the mixture passes through both static mixers and dynamic mixers, e. after step d. the mixture is ultrasonicated by means of an ultrasound unit, and f. the sulfuric acid concentration in the spinning bath is kept at a value equal to or less than + /. 0.3 g / l deviation from the set mean nominal value,

It is expedient to use a viscose which is added to the modifier only shortly before spinning the viscose. The inventively proposed measures of compliance with a certain spinning maturity, for which the Spinngammawert is characteristic, compliance with a certain viscosity, for which the falling ball values are characteristic, and compliance with certain conditions in the spinning bath, help to achieve the desired fiber properties, under Spinngammawert 20 is understood to mean the proportion of carbon disulfide molecules bound to 100 cellulose molecules. The spin gamma value is determined according to the 2elleheming leaflet draft by R, Stahn [1Θ58] and leaflet III / F 2. The term "spherical precipitate" refers to the viscosity determined by the falling ball method; it is expressed in terms of bullet seconds. The determination is given in K. Götze, 25 Chemiefasern [1951J, S, 175.

According to the invention, the colorant is added to the viscose spinning solution in the form of a pigment dispersion. The selection of dispersions of suitable composition is in principle known to the person skilled in the art. to 17/09/2012 15:33

No .: R798 P.014 / 035 li-bth'-tfaid 1Η: ΐ5 VOη: LHto KHItNIWtbtN ^ Wlbl ftord dbHÖ Hns-NW i ajttd *! Mb b. lb ', DC &gt; ·· * · · ♦ IM «···· ······« «·» · * · * · » ♦ · ♦ · ** · * ·· ♦ ♦ ** «··

Lenzing AG, PL0S2Ö

Devices for the addition of the pigment dispersion to the spinning solution are known to the person skilled in the art. Essential for the invention, however, is that the mixture is performed after this addition by a combination ναι static and dynamic mixers that allow only a sufficiently homogeneous S mixing. Both types of mixers are also known in principle to the person skilled in the art. Examples of suitable static mixers are the mixers from Sulzer / Scchwelz, also known as "ulcer mixer H". Among the various types, one skilled in the art can select a suitable type without inventive activity. The same applies to suitable dynamic mixers, i. i Q h. Mixer with its own drive for a moving mixing unit.

Such mixer types are commercially available, for example, from the German companies IKA / Staufen and Lipp Mischtechnik / Mannhelm.

An essential feature of the process according to the invention is that the sulfuric acid concentration in the spinning bath is less than or equal to +/- 0.3 g / f

Deviation from the set average setpoint is kept constant. Only then can the coagulation process proceed so uniformly that the desired color pigment distribution in the fibers according to the invention is sufficiently homogeneous. All devices and equipment that influence the spin bath concentration should therefore be selected and adjusted accordingly. The known in the prior art devices are usually not suitable, The set average value itself depends on many boundary conditions that are different from production plant to production plant and can be set by Betriebspersonei a production plant without 25 other inventive step. It is therefore neither reasonable nor necessary to specify such in the present description of the invention.

The pigments used: 30 Various organic (for example azo and polycyclic) and inorganic pigments can be spun in according to the invention. The 11 17/09/2012 15:33

No .: R798 P.015 / 035 ir-bti -'- cMld 1H5ID FromSLHb MHIfcN1 »* fcbthKHJ.Öi + m fbfd OtJi di ** ö HrtJ + ^ UX SÄ b.Ib'Ä ·· ·· ··· · # ** "· · · · · · · · · ♦♦ ······ ·» · · · · · · ♦ · * * · # · | φ φ »·· ♦♦ ♦ * · ·« M »

Lenzing AG, PL0529

Shades of azo pigments range from yellow to orange, red and purple to brown. Of the group of polycyclic pigments, those of the present invention are by far the most important ones having a copper phthalocyanine structure. All blue and green shades of organic 5 pigments are based on this basic chemical structure. Other important polycyclic pigments that are commercially available are the chlacrofdone and perylene pigments, which cover the hues of orange and red; besides there are numerous other structures. Inorganic pigments used are various complex compounds based on iron, copper and 10 chromium.

The most important selection criterion is that the coloring groups of the pigments used are not destroyed in strongly acidic and strongly alkaline media. 15

The maximum permissible particle size depends on the desired titre of the finished fiber. It may not amount to more than 2 pm according to the invention for textile fibers with 1.5 dtex. Ansoneten there is a risk that the fine spinnerets clog. In the final product, the In Form 20 would have a nonhomogeneous color shade and the color intensity could also vary by changing the pigment concentration. Also, with uneven pigment distribution, the mechanical properties of the fibers could be degraded. However, the spun-dyed Mcdalfasem prepared by the process according to the invention retain high strength and good elongation.

In particular, the quality of the pigment dispersion has a significant influence on the fiber properties. This is determined by the average and maximum particle size of the pigments, the concentration of the dispersion during use, ie. H. 2 to the viscose, as well as type and quantity of the 17/09/2012 15:34

Nr .: R798 P.016 / 035 12 I r-bh ^ -düld 14: 1b Uon: LHb ΜΗ I LN I WbbtN'Wlöl + 4b rbrd 001 dtHti Hn: -H4b 1 bb'Hd ^ bbb b. i ♦ * ··· * «· ···« · * ♦ · · ·

Lenzing AG, PL0529

Dispersing aids. The particle size distribution of a still suitable dispersion is shown by way of example in FIG.

Preferably, the pigment dispersion should contain between 10 and 50% of the color pigment. In most prior art documents, the influence of the dispersant is not described in sufficient detail as would be appropriate. However, many chemicals that provide a superbly stabilized color dispersion have a negative effect on the spinning process, as they also have a modifying effect on the viscose, but do not positively affect the fiber strength, unlike the modifiers used. The ideal dispersants for the color dispersion for producing the fibers according to the invention which do not negatively affect the fiber strength have been found in particular those selected from the group consisting of modified polycarboxylates, water-soluble polyesters, alkyl ether phosphates, end-capped nonylphenol ethoxylates, castor oil alkoxyl esters and carboxymethylated alcohol polyglycol ethers , Preferably, the pigment dispersion should contain between 1.5 and 25% of the dispersing aid.

However, compliance with the parameters described so far does not guarantee even dyeing of the fiber. Surprisingly, it was found that it was only by adjusting the sulfuric acid concentration to a maximum of +/- 0.3 g / l 25 deviation from the setpoint value that color variations could be eliminated. However, the color depth fluctuations described continued to occur. The use of static or dynamic mixing to distribute the color pigments in the spinning solution is not sufficient to solve this problem. Surprisingly, it was only through the use of an additional ultrasonic unit that it was possible to produce the fiber according to the invention, which had both a constant color shade and a uniform shade

No .: R798 P.017 / 035

Ιί-Btk öäIc; 14! Lb llllbbn-llllvlvtbtr'vtffl + 4j fbfd ffcJl dy4e Hn: + 4J 1 bJ4d4 bob b. 'S · · · · · · · · · · · · · · · · · · · · * * * * * IB IB IB IB IB IB IB IB IB IB ·· ·· t ··

Lenzing AG, PL0529 has consistent color depth. In this case, the ultrasonic unit is arranged so that the vibrations generated act as effectively as possible on the spinning solution after the color pigments had been added. For example, an ultrasonic tip which protrudes into the pipe through which the spinning solution after addition of the

Color pigments is transported. Corresponding ultrasonic devices for inline use are available commercially from Hielscher / Deutchland. Technical solutions for applying ultrasound, which act in a similar manner, are also of the inventive concept with umfasel io

Textile chain

Spun-dyed fibers can be well processed on all three spinning systems (ring, rotor, air jet). To improve yarn properties (lower hairiness, less thin and thick spots, less dust), the card settings and spinning machine settings are changed (e.g., different number of turns).

The present invention also relates to the use of the fibers according to the invention for the production of blends with other types of fibers. The mixture can be done before the yarn spinning by mixing the different types of fibers - the so-called intimate mixing - as well as in blended fabrics, in which several, each consisting of only one Fa & erart game are processed together.

The spun-dyed modal fibers according to the invention can be processed with other textile fibers (in very different proportions). Mixtures with natural fibers such as cotton, linen, hemp, flax, wool, cashmere, silk and angora and synthetic fibers such as polyester, polyamide, polypropylene, polyacrylate and lactic acid ester fibers, as well as with inorganic fibers such as glass or carbon fibers and also with cellulosic synthetic fibers are possible. 14 17/09/2012 15:34

No .: R798 P.018 / 035

Xf-btH-düid 14: lb VoniLHIa ΠΗ1 fcN I WtbtM &quot; Wibi + 4J rbf d. ful dy4ö HO I + HJ 1 DJ4d4 t> JJD b. ly-'e ee * e * ftft '··· ···· • e • ft ft • ft • ft ftft # ft • ft • ft ft ··································································

Lenzing AG, PL0529

In the mixture with synthetic fibers, spin-dyed modal fibers with z. As spun-dyed polyester, polyamide or Polypropyienfasem be processed in a Intimgammischung. Similarly, a white yarn PES i PA can be processed with yarn from spun-dyed modal fibers according to the invention and subsequently stained.

In the mixtures with keratin fibers, for example wool or silk, epine-dyed modal fibers may also be advantageous in comparison with spun-dyed viscose fibers. Due to the fine and soft fiber structure, 5 to 30% of spun-dyed modal fibers can be processed together with keratin fibers in 10 of the wool mill,

Cellulosic synthetic fibers are, in particular, lyocell fibers and in particular crosslinked lyocell fibers whose fibrillation tendency is particularly low. With such lyocell fibers, melange effects and peeling performance can be achieved. To produce finer Game 15, the spun-dyed modal fibers of the present invention may be blended with, for example, finer, white microfibers (with a titer of 0.8 to 1.0 dtex).

Spun-dyed modal fibers can be used for various textile chemical processes (refining steps), eg. B. Mercerization, Haiz Treatment 20 (to improve wrinkling, treatment by DMDHEU), refining with flame retardant (phosphorus, sulfur, halogenated FSM), finishing against oil, fats, water (e.g., silicones). During the various finishing steps, all properties of the modal fibers according to the invention (good strength and fastness properties) are preserved. 25 Spun-dyed modal fibers can be processed in textile processes such as knitting, knitting and weaving. Among others, the following fabric constructions are possible: plain weave (plain weave,

Cloth weave, panama weave), twill weave (broken twill, broken twill, abseiling twill, staggered twill, composite twill, shaded 30 twill, multi-burr twiner, multi-tier twill, reinforced twill and pointed twill) and atias weave (irregular atlas, translated atlas, combined atlas, 15 17/09 / 2012 15:35

No .: R798 P.019 / 035 I r-bth '^ dülc: 14: ir From: LHLa KHItNI Wfc ±> tN'WlBl fb rd FBI Hni + HJ 1 O & idH ^ • ♦ · * ·· ♦ » ♦ ♦ · · · · · · · · · · · ···

Lenzing AG, PL0529 shaded atlas, reinforced atlas and the Adriabindung). The game from the spin-dyed fibers of the invention can be on single-surface machines (jersey jersey, plated) and two-bladed machines (rib, interlok) are produced. In addition to the positive textile properties, spun-dyed modal fibers offer ecological benefits, as illustrated in the following examples.

The invention will now be explained by way of examples. These are to be understood as possible embodiments of the invention. By no means is the invention limited to the scope of these examples.

Examples:

Applied measuring methods: 15

Ermittluno of Sorotlonslsothermen:

By means of device BELSORP-max (manufacturer: BEL, Japan)

Water retention capacity (WRV1: 20 According to DIN 53614

Eeüttisiisn, (Wflgph - .. ^^ Bi, R: l.Wagslg (l Reib-, HT-Qiwrförlre Efrtheitt;

According to DIN EN IS0105 25 particle size distributionuno:

Using device HELOS / BF Particle Size Analyzer with laser diffraction electron microscope;

By means of device S-4000 REM (manufacturer: HITACHI, Japan) 16 17/09/2012 15:35

No .: R798 P.020 / 035 i r-btr-caaic: m: if From: LHki KHlbNINbbbN-'WiBI +4.3 fbfd fKJl db4ö b.bl ', »i r-btr-caaic: m: if From: LHki KHlbNINbbbN-'WiBI +4.3 fbfd fKJl db4ö b.bl ', »

· «·

Lenzing AG, PL0529

Example 1;

Eucalyptus prehydrolysis kraft pulp (R18 * 97%) was alkalized with mash liquor containing 240 g / l NaOH at 35T with stirring and pressed to an alkali cellulose nonwoven. The alkali cellulose nonwoven fabric was fiberized, aged 5 and ephedrided. The xanthate became a viscose with 5.6% cellulose, 6.8% NaOH and 39% CS2 with dilute sodium hydroxide solution. based on cellulose, dissolved.

The viscose was filtered 4 times and vented. The viscous 1% before spinning, 3%, based on cellulose, metered ethoxylated amine - a modifier that causes the formation of a shell structure. The viscose was ripened to a gamma value of 57. The viscosity during spinning was 80 falling seconds.

The color dispersion is added to this ready-to-use viscose and stirred into the viscose stream with series-connected static and dynamic mixers. The following compositions were used to achieve a fiber dyed in an inventive manner;

Example 1a: red; 0.504% Viscoflt Red A ~ R, 0.086% Vlscofil Violet BLNL, 0.373% Viscofil Yellow RR 31. 20

Example 1b: Beige; 0.11% Viscofil Yellow RR31,0,0441% Vlscofil Black VBC, 0,0593% Viscofil Red F5RK30.

Example 1c; Blue; 3.0184% Aquamarine blue EF / B, 1.5938% Violet B, 0.9899% 25 Black 300.

In addition to the classical mixing systems, an Ultrasehall tip, a special embodiment of an ultrasonic Inline for the treatment of the spinning solution after the pigment addition was used to dissolve pigment agglomerates, 30 caused by the pH shock when mixing the pigments in the strongly alkaline spinning solution. 17 17/09/2012 15:36

No .: R798 P.021 / 035 1 r-btr-citflc: 1 ^: ΐΓ UonILHb rHI tNI Wt ^ tN ^ WItfi + HJ Cb (ie CÜI Hn: -HH4 1 ΟύΜέ * bJb ii.dd 'Jb

* · · · E · »

Lenzing AG, PL0529

The nozzles used have a nozzle hole diameter of 60 mm. The spinning bath contains 72 g / l sulfuric acid, 120 g / l sodium sulfate and 60 g / l zinc sulfate, the sulfuric acid concentration was maintained at +/- 0.2 g / l of this set point throughout the spinning, 5 The spinning bath temperature was 38eC. The coagulated and partially regenerated plastic thread strand was passed over a galette (G 1) into a second bath whose temperature was 95 ° C. and stretched there between 120% by G1 and a second godet (G 2). The final discharge was 22 m / min. The tow was cut into stacks of 40 mm in length, which were completely regenerated in dilute 10% sulfuric acid, then washed free of acid with hot water, desulfurized with dilute sodium hydroxide solution, washed, rinsed, pressed and dried again. Fig. 3 shows an inventive preparation of Example 1a Fiber under the light microscope, recorded in transmitted light, The color pigments are clearly visible as dark spots. 15

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Eucalyptus prehydrolysis kraft pulp (R16 = 67%) was alkalized with mash liquor containing 240 g / l NaOH at 35 ° C. with stirring and pressed to an alkali cellulose nonwoven. The Alkalicellulosevlies was fiberized, matured 20 and suifidiert. The xanthate was dissolved with a dilute sodium hydroxide to a viscose with 5.6% cellulose, 6.6% NaOH and 39% CSa, based on cellulose.

The viscose was filtered 4 times and vented. The viscose was dosed with ethoxylated amine 1% prior to spinning 3%, based on cellulose - a modifier which causes the formation of a shell structure. The viscose was rinsed to a splinter ammonia value of 55. The viscosity was 65 spherical seconds during spinning.

The color dispersions in the same composition as in Example 1 are added to this ready-to-spin viscose: 30 2a) red 2b) beige 18 17/09/2012 15:36

Nr .: R798 P.022 / 035 i r-btt -'- düIc: Ι * Κΐθ νοη: ι_Ηθ bHifcNlwtbbN'Widi + Ηύ rbfd γβι dy ^ tö Hn: + HJ 1 z> x &gt; b.dj ''

Lenzing AG, PLQ529 2c) bleu and mH are stirred into the viscous flow in a dynamic mixer. An additional ultrasonic mixer was not used.

The nozzles used have a nozzle hole diameter of 60 .mu.m, 5 The spinning bath contains 72 g / l sulfuric acid, 120 g / l sodium sulfate and 60 g / l zinc sulfate. The sulfuric acid concentration was only maintained at + / · 2.6 g / l of this set point during the entire spinning.

The spinnbath temperature was 42.degree. C. The coagulated and partially regenerated plastic thread strand was led via a godet roll (G1) into a second bath whose temperature was 95.degree. C. and there by 120% between G1 and a second godet (G 2). stretched, The final discharge was 22 m / min. The tow was cut into stacks 40 mm in length, which was completely regenerated in dilute sulfuric acid, then acid washed with hot water, desulfurized with dilute sodium hydroxide solution, rinsed again, washed, pressed and dried. Flg. FIG. 4 shows the fiber produced according to Example 2a under the microscope, recorded in transmitted light. The color pigments are again clearly recognizable as dark spots, but it is equally evident that the pigments in the reader of example 2a are distributed much more unevenly and, in contrast to the fiber of example 1a, tend to agglomerate.

Table 1: Fiber data:

Fiber titer [dtex] FFk teN / tex) FDk f%] BISFA wet modulus [cN / tex] Example 1a 1.5 35.6 14.4 5.4 Comparative Example 2a 1.5 34.6 14.3 5.4 19 17/09 / 2012 15:36

Nr .: R798 P.023 / 035 1 f-btr-öJld IHHÖ yomLHIa l-'HIfcNIWfcbbN'Wl.tU -HJ fbU ± roi dbHÖ Hn: + ^ J 1 bb '+ d ** bbb b.c ^' Jb

«* ···» ···· * «·· I * ·« «* * * * · · ····« * · · * 4 ··· * ·· * * «« · · I ·· t * a

Lenzing AG, PL0529

The results in Table 1 clearly show that the mechanical properties of the spin-dyed modal fibers are not impaired by the high energy input by the ultrasonic mixer in the production process of the invention. 5

FIG. 5 shows the sorption isotherms of commercially available modal fibers and cotton fibers. The samples were placed in the meter at defined relative humidities (RH) and mass gain was measured. After the unit had 90% RH, the relative humidity (RH) in the unit was reduced to 0%. Oabel is a Desorptlonsprozese. The sorption behavior of the spin-dyed modal fibers according to the invention corresponds to that of the commercial modal fibers shown in FIG. IS The behavior towards water is also shown in Tab. 2. Tab. 2 shows this

Water retention (WRV in%) of the spun-dyed modal fibers of Example 11m compared to standard modal fibers and the synthetic fiber polyester. It can be seen that the water retention capacity of the inventive, spun-dyed Modalfasem 20 corresponds to that of the commercial Modalfasem and - not surprisingly - considerably above that of synthetic fibers.

Tab. 2:

Color WRV [%] Modal Red (Ex. 1a) 57.1 Modal Beige (Ex. 1b) 54.8 Modal Blue (Ex. 1c) 55.3 ^ Modal Standard Uncoloured 54.2 Polyester 0.6 20 17/09 / 2012 15:37

No .: R798 P.024 / 035 i r-btr-dUic: i <4: ia uoniLHta r'HifcNiwfcbfcN'wiöi + * tJ fbfd rm cäwö Ηηί + Ηύ ι bbb b.dbOb ···· ·· * ·· ····························································································.

Lenzing AG, PL0529

Tab. 3 shows the results of various authenticity measurements of the spun-dyed modal fibers according to the invention which are significant for the performance properties. They all show very good scores according to the underlying scoring scales of 1 (bad) - 5 very good). 5

Tab. 3:

Modal Blue Waach 60 * C Tail eauer Tail alkali Waaer-authenticity Reamery HT Over-baskets Authenticity dry naaa Fbg 5 5 5 5 4-5 4 4-5 Anbl. CMD 5 6 5 5 6 app. BW 4-5 4-5 4-5 4-5 4 Modal Red Wasoh 60 * c Sweat Away Sweat Alkali Waaaarech theit Reliefhehe HT Upper Rest Drying fastness naaa Ft &gt; 0 5 5 6 5 4-5 4 4-5 Abl. CMD 4-S 4-5 4-5 $ 4-5 Anbl. BW 4-5 4-5 4-5 4-5 4 Modal Beige Waach WC Welding Sour Sweat Alkali Wfcaaer · genuine Reichenchtholt HT-Oberttrbe Authenticity dry naaa Fbg s 5 5 6 5 4-5 4-6 Alibi, CMD 6 5 5 5 4-5 app. BW 4-5 6 5 6 4 21 17/09/2012 15:37

No .: R798 P.025 / 035

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Lenzing AG, PL0529

In Tab. 3 mean: Fbg - color change, Anbi.CMD = bleeding towards Modalfasem, Anbl. BW = bleeding in relation to cotton.

Tab. 4 shows mechanical data of spun-dyed Fibers in contrast to spun-dyed viscose fibers according to the prior art.

Tab. 4:

Pattern Feetlökeli [cN / tex] Elongation (¾) Model Blue 3e 14.4 Model Red 3 $ 14.4 Viscose Blue 2 $ ίβ Vlekoee Red 28 16

The IMass module of the spun-dyed ones met the BISFA * definition. io

6 shows several images of fiber cross-sections by means of the transmittance electron microscope (TEM): a) spun-dyed modal fibers according to prior art, example 2a) with agglomerated particles. I5 b) spin-dyed modal fibers with a homogeneous distribution of pigments according to the invention, Ex. 1a).

FIG. 7 additionally shows surface photographs with a scanning electron microscope (SEM) of various spun-dyed modal fibers: a) spun-dyed modal fibers according to the prior art, example 2a). Agglomerates give an uneven surface. b) Spun-dyed modal fibers with a homogeneous distribution of pigments according to the invention, from left to right: Bap. 1a), 1b), 1c). They show a 25 evenly smooth surface. 17/09/2012 15:37

No .: R798 P.026 / 035 22

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· »· · · ·. ··· »···· I Φ &lt; ··« (· &lt;, * * * * * * * M * ··

Lenzing AG, PL0529 Processing Examples:

Two knit fabrics were made from Rlnggam Nm 50/1: The first sample (Example 3) was made from standard white modal fibers (textile grade 1.3 dtex fineness, 38 mm length). The second sample (Example 4) was prepared from 5 spun-dyed modal fibers of Example 2a) according to the invention.

The yarn construction of the spun-dyed modal fibers was also set to Nm 50/1. To make comparable samples, the construction of knitwear must necessarily be the same; in this case a single jersey was chosen. 10

Example 3:

The fabric of the white fibers was dyed in the Ties Soft TRD apparatus to achieve the same color as that of the spun-dyed fibers. The following dyeing conditions were used: liquor ratio 10: 1 (200 kg 15 fabric In 20001), The process of dyeing was carried out at 60 ° C according to the recommendations of the colorant manufacturer. The fabric was prewashed prior to staining to remove the remnants of the finish applied to the modal fibers during the manufacturing process. The waxes and lubricants applied at the gamher position must also be removed. Dyeing recipe: Remazol Ultra Yellow RGB 0.9%, Remazol Ultra Red RGB 4.5%, Na2S04 60 g / l, Na2COs 20 g / l. After dyeing, the fibers were washed in several stages with soap at 20.70 and 89 C; then at 70 and 40 * C with water. The entire dyeing process takes 405 minutes. 25

Example 4:

The fabric made from the spun-dyed fibers was only washed to remove the waxes and lubricants used in gambling. The process takes 83 minutes. 23 P. 027/035 17/09/2012 15:38 Nr .: R798 lr-btK-düXÄ iHiiy υοηη-Hb withNivbtstN ^ witJi + * rbftf reix c »4 *» Hn: -H4Ji α ^ sMci4 * wö b .dö 'Jö

* * * ##

Lenzing AG, PLQ529

The comparison of the necessary reeources is summarized in Table 5.

Tab 5:

Dyed Fabrics Example 6 Tissue made of Splnng-dyed Fibers (Example 4) Savings per Kg of Fibers Process Time [mini 405 83 322 min Production Rate tkg / hl 30 145 Water Consumption fm3i 14 3.5 10.5 m3 Water Consumption Fl / kf Tissue] 70 17 5 92.51 Energy consumption m______ 2467 4Θ2 • Energy consumption [MJ / kg Gawebel 12.3 2.5 9.8 MJ Dye consumption [g dye per kg tissue] 54 0 54g Saizvarbrauch [g Na * S04 per kg tissue] 80 0 80 g Salt consumption [ g NajCOa per kg of tissue 20 0 20 g

Surprisingly, it was invented that in the production of fabrics from the spun-dyed modal fibers of the present invention significant savings are achieved in the necessary resources compared to the conventional dyeing of fabrics from undyed modal fibers, especially at 10% water and energy: the cost savings for water are 66%, 60% for energy, 100% for dye chemicals and 60% for process time. 17/09/2012 15:38

No .: R798 P.028 / 035 24

Claims (9)

1 r-btr-düld 14: dB ^ oniLHb KH i tN 1 wtbtN'wibi + **. I rbfd vül db4ö Hnr + HJ 1 5Λ Lenzing AG, PL0529 Claims: 1. Spun-dyed regenerated cellulose fiber containing as spun substance a spun, particulate Color pigment contains, characterized 5 characterized in that the fiber corresponds to the mode definition. 2. Spin-dyed fiber according to claim 1, characterized in that the color pigment has a particle size distribution with Xoo less than 2.0 μm, 10 3. Use of the fibers according to claims 1 to 2 for the production of a game. 4. Use of the fibers according to claims 1 to 2 for the preparation 15 of a textile apex structure. 5. A process for the preparation of a regenerated cellulose fiber dyed by means of colored pigments for textile applications by spinning a viscose with a content of 4 to 7% cellulose, 5 to 10% NaOH, 36 20 to 42% (based on cellulose) carbon disulfide and 1 to 5% (based on cellulose) of a modifier In a spin bath, stripping off the coagulated filaments using a viscose whose spin gamma is SO to 68 and whose spin viscosity is 50 to 120 falling seconds, where 2 $ a. the temperature of the spin bath is 34 to 46 ac, b. the alkali ratio (= cellulose concentration / alkali content) of ready-to-use viscose is from 0.7 to 1.5, c. following Spinnbadkonzentrationen be used: • HaSO * 68 - Θ0 g / J 30 · Na4SO4 90-160g / l • ZnS04 30 - 65g / i, 25 17/09/2012 15:38 No .: R798 P.029 / 035 bfc. h'-tiìld ΙΉ-Ζΰ Ζΰ i i i K K H H IB IB IB IB + 4 4 b b b b b b b 01 01 01 01 01 01 01 01 01 01 01 + + + + + + + + + + + L L L L L L L L L 15 15 15 15 15 15 15 and characterized in that, after the addition of the pigments to the spinning solution, the mixture 5 passes both static mixers and dynamic mixers, e. after step d., the mixture is ultrasonicated by means of an ultrasonic generator, and f, the sulfuric acid concentration in the spin bath is less than or equal to +/- 0.3 g / l deviation from the set mean constant value) is kept 0, 6, use of the fibers according to claim 1 for the production of technical textiles, in particular upholstery fabrics, carpets and transport textiles, such as seat covers and other textile surfaces in cars, trains, 1S buses, ships and all other means of public and private transport 7. Use of the fibers according to claim 1 for the production of sports textiles, outerwear for men and women, underwear and 20 baby clothing, protective clothing, industrial linen, bed linen, towels, Spannleintücher, quilts, mattress covers and other home textiles, 8, using the fibers according to claim 1 for the production of 25 blended fabrics with polyester, polyamide, polypropylene and other synthetic fibers. 9. Use of the fibers according to claim 1 for the production of fabrics from a mixture with crosslinked Lyocellfasem. 26 17/09/2012 15:39 No .: R798 P.030 / 035