The present invention relates to a modified viscose fiber, a process for the preparation of the viscose fiber according to the invention and their use.

In particular, the invention relates to a modified viscose with incorporated material from seaweed, with improved performance characteristics for textile applications, particularly in knitwear range, the consumers expectation of by

satisfy full washability and also requirements of industrial laundering, their use for the preparation of yarns and fabrics and to a process for the production of these fibers.

EP 1259564 describes the production of fibers and moldings according to the NMMO process of a polymer solution containing a biodegradable polymer - comprises and a material from Meerespfianzen and / or shells of marine animals, and optionally further additives - usually cellulose. Molded articles thus produced exhibit loud

EP 1259564 on a comparison with the corresponding molded articles according to the NMMO process without additives lower fibrillation tendency. This conclusion has been reduced, based on the in SEM images recognizable altered fiber structure more accurately a

Longitudinal orientation drawn.

EP 1,259,564 also discloses the preparation of the addition of a material of marine plants and / or shells of marine animals modified fibers and moldings for a viscose process. By way of example 15% (Example 7) and 1.7% (Example 8) of material from brown algae are added to cellulose. Fibers or moldings produced in this manner have, in comparison to a similar or viscose fiber without additives

slightly deteriorated physical fiber properties (Comparative Example 3).

Furthermore, EP 1259564 describes in Examples 9 and 10, the production of fibers and moldings, with the addition of a material of marine plants and / or shells of marine animals according to the carbamate. According to this method a very low tenacity dry tensile force is achieved, the further back by the addition of algal material depending on the amount of incorporation.

It is known that the addition of material from Meerespfianzen, particularly seaweed, fibers and cellulosic forms as well as textiles made from it gives a particularly soft feel and an enrichment with vitamins, micronutrients and

has trace elements causes and containing that in seaweed alginate moisture-retaining properties. It was also proved that algae and derived fibers have antioxidant properties [http://www.smartfiber.de/index.php/seacell-de/zertifizierungen, accessed on April 17, 2016]. For these reasons, a material of marine plants, especially algae-containing products are considered very skin-friendly.

All in EP 1259564 disclosed fibers, ie both the types of fibers produced by the NMMO process, the viscose and the carbamate, as well as the commercially available under the Trade Mark SeaCell ™ Lyocell type, satisfy various reasons, the requirements of modern textile industry inadequately :

The lyocellbasierten types tend without high processing or additional cross-linking despite the somewhat lower fiber longitudinal orientation to fibrillation and subsequently, after repeated washings for the formation of unsightly, weißgescheuerter textile surfaces. By the viscose fiber types produced on the other hand have a somewhat poorer resistance in the wet state (wet strength and wet modulus BISFA) than conventional viscose fibers. The types produced by the carbamate have too low dry tensile strength for commercial yarn. Moreover, this method has no economic significance, there are still no industrial

Fiber production after the carbamate.

Compared to this prior art, the object was to produce a cellulosic fiber into which a noticeable to the consumer is incorporated amount of material from algae to provide the desired properties of a natural softness,

Moisture storage capacity and achieve sufficient but in addition increased textile mechanical requirements both to the form stability and resistance to washing and low fibrillation of a skin-friendliness.

This object is achieved by a modified viscose fiber according to claim. 1

Preferred embodiments are given in the subclaims. The term "fiber" is intended (for example, so-called "staple fibers") as defined include for the purposes of the present invention, both fibers of relatively short length, fibers of very great length, referred to in the parlance as "filament".

BRIEF DESCRIPTION OF FIGURES:

Figure 1 illustrates the determined according to an adapted Canadian Standard Freeness tests Fibrillationsdynamik of cellulosic fibers.

Figure 2 shows the microscopic evaluation of the Fibrillationsverhaltens a fiber according to Example 3. FIG.

Figure 3 shows the fibrillation of a fiber according to Example 4. FIG.

Figure 4 shows the fibrillation of a SeaCell ™ fiber.

Detailed description of the invention:

The present invention solves the above problem by providing non-fibrillating cellulosic regenerated with incorporated algal material available, which are prepared by an over EP 1259564 modified viscose process. The fibers of the invention are characterized by the known per se special softness of cellulose fibers with incorporated material from algae, but have opposite to the NMMO process based solvent-spun fibers have a significantly reduced tendency to Nassfibrillation on.

Surprisingly resulted in the minor procedural changes over that described in EP 1 259 564 Bl production method means that the inventive fibers compared to the fibers of the viscose rayon type with incorporated brown algae according to EP 1 259 564 Example 7 (with 15% brown algae) and Example 8: (with 1.67% brown algae on cellulose), and even as compared to Comparative example 3 of EP 1259564 (without

comprise admixing algae) significantly improved physical fiber properties, particularly a higher tensile strength and tenacity a higher wet modulus.

The fibers of the invention have a wet modulus at an elongation of 5% in the wet state, which satisfies the following formula:

Nassmodul (cN) > 0,5 *VT,

where T is the titre of the fiber in dtex.

This wet modulus corresponds to the wet modulus of a Modal fiber as defined by BISFA (The International Bureau for the Standardization of Man-Made Fibers) and is referred to hereinafter as "BISFA wet module" or "BISFA module". The wet modulus

and the other referred to in the subject application textile physical properties are measured according to BISFA defined by the measurement methods.

In a preferred embodiment, the fiber of the invention a

Fiber strength in the conditioned state, which satisfies the following formula:

Faserfestigkeit (cN/tex) > 27,38 -1,4*T.

This strength is signifcantly higher than that of viscose fibers modified described in EP 1,259,564.

The fibers of the invention may by weight, based on cellulose 0.5.% To 6 wt.%, Preferably 2 wt.%> To 6 wt.%>, More preferably 3 wt.% By weight> to 4.%> To

Algal material included.

The algae may originate from salt and freshwater. It is both the use of microalgae and macroalgae, especially kelp, possible.

Preferably the algae used generally comprise a Alginsäureanteil of 15 wt.%> To 50 wt.% On. In a preferred embodiment, fibers of the invention include algae Ascophyllum nodosum material of the type.

Moreover, fibers of the invention without supplementary addition of metal ions to an increased as compared with lyocell fibers and / or viscose fibers with the same dosing of algae zinc content.

The content of zinc ions is preferably at least 200 ppm, more preferably 200 ppm to 700 ppm.

The zinc content is also significantly increased compared to modal fibers and is located in the

Fiber of the invention at least partly present as Zn alginate. Zinc is an essential trace element with skin caring properties and is therefore used in skin care products. Zinc alginates are used, inter alia, in wound dressings. It is believed that the combined action of the alginate (as a humidity memory and natural softener) with releasable from the alginate zinc ions have improved skin conditioning properties achieved.

a method%% used for the production of viscose fiber according to the invention by spinning a viscose with a content of 4 wt. to 7 wt.% of cellulose, 5 wt.%> to 10%> Gew.NaOH, 34 wt.%> to 42 wt. .> (based on the cellulose) carbon disulfide, and 1 wt%) to 5 wt%> (based on cellulose) of a modifying agent in a spinning bath, peeling off of the coagulated filaments. wherein a viscose is used, the

Spin gamma value 50 to 68, and their spinning viscosity is 50 falling ball seconds to 150 falling ball seconds; wherein the alkali ratio (=

Cellulose concentration / alkali metal content) of the spin ready viscose is 0.7 to 1.5, and the temperature of the spinning bath 34 ° C to 48 ° C, the following

Spinnbadkonzentrationen be used:

H2S04 68 g/1 - 90 g/1

Na2S04 90 g/1 - 160 g/1

ZnS0 4 30 g / 1-65 g / 1,

wherein the final image from the spinning bath at a speed between 15 m / min and 60 m / min is performed and wherein an algal material is spun in the form of an aqueous dispersion.

The indicated numerical values ​​for the composition of the viscose reflect their state before addition of the dispersion of the seaweed material.

A similar regarding the parameters of the viscose used, the spinning bath and the spinning process described in WO 2011/026159 Al, so that reference may be made for further details to the spinning process to this document.

The modifying agent employed effected in a manner known per se

Shell structure of the inventive fiber. The modifier may be, for example, an ethoxylated amine.

The material used from algae is preferably pulverized and dried, a residual water content of <15%>, more preferably <10%>, in a particle size of x 99 μιη of <20, preferably <15 μιη before. In order to achieve the desired fiber properties, the algal material should preferably have a Alginsäuregehalt of at least 15%. The material is preferably immediately before use, optionally with addition of a

, Dispersing agent dispersed in water to prepare a dispersion with a weight solids content of preferably 2.%> To 15 wt.%> Yield. The aqueous dispersion may vented as required in a vacuum and, optionally after prior filtration to

Removal of undissolved particles in the desired ratio of the viscose are added, taking care to ensure an intimate mixing with conventional mixers, homogenizers, or the like. When incorporated into the viscose filtration can be done by candle filters before spinning.

The spinning can μιη through spinnerets having a hole diameter of 50 to 100 μιη carried out depending on the desired denier of the fibers.

The present invention also relates to the use of the invention

Viscose fiber for manufacturing yarns and textile fabrics.

The invention will now be explained using examples. These are to be understood as possible embodiments of the invention. By no means are not limited to the scope of these examples.

A detailed list of process parameters of all examples is given in Table 9 at the end of the Examples section.

Example 1: Production of an inventive modified algeninkorporierten

viscose

Of dried, powdered plant material from Ascophyllum nodosum a 10% dispersion in demineralized water was prepared, which was deaerated for 6 hours. Through spinnerets with 50 μιη hole diameter was prepared in cellulose with a net of 30 m / min, a viscose fiber without and with 2.5% and 5% algal material. The dosage of the algae dispersion was immediately prior to the homogenizer, with a residence time of <1 min prior to the spinneret.

Table 1: Fiber properties of a modified viscose, Example 1

Alge Titer FFk FDk FFn FDn Nassmodul

[%] To [dtex] [cN / tex] [%] [cN / tex] [%] (Bisfamodul)

Cell. [cN/tex]

0 (no) 1.72 39.0 11.8 23.2 13.5 6.4

2,5 1,71 31,3 10,6 18,6 12,1 5,6

5 1,79 31,3 11,4 17,2 12,1 5,3

Legend (also applies to the following tables):

Titer [dtex]: fineness (conditioned)

FFk [cN / tex]: tenacity tensile force dry or conditioned

FDk [%]: ultimate tensile elongation conditioned dry or

FFn [cN / tex]: tenacity tear strength wet

FDn [%]: Höchstzugkraft-NASS Dehnung

Wet modulus (Bisfamodul) [cN / tex]: fineness-related wet modulus at 5% elongation

Example 2: Production of an inventive modified algeninkorporierten

Viscose fiber using different concentrations powder dispersions

10% were nodosum of dried, powdered plant material from Ascophyllum strength, a 5% and produced a 2.5% dispersion in demineralized water, the dispersions were not primed. Through spinnerets with 50 μιη hole diameter and with a net of 30 m / min, a viscose fiber was without or with 5%

Algal material prepared in cellulose.

Table 2: Faserei characteris tics of a modified viscose, Bei iel 2

Legend (also applies to the following tables):

WRV [%]: water retention.

The algae dispersion with the highest concentration contained many air bubbles that often led to thread breakages during spinning due to high viscosity. Therefore, no good stretching and no higher strengths in this case could be achieved. When metering thinner algae dispersions this problem did not occur - the resulting fineness-related strengths are at a significantly higher level than at a

Viscose fiber according to EP 1,259,564.

The Alginsäuregehalt of the algal material used and the as-spun fiber was, after total hydrolysis of the fiber via HPLC on the basis of mannuronic and

Guluronsäuregehalts against a standard alginic acid (Fluka) analyzed. The

Alginsäuregehalt of the employed algae powder was 25%, the Alginsäuregehalt of the fibers was between 0.95% and 1.2%, corresponding to an algae content of 3.8% to 4.8%.

As can be seen from Table 2, the fibers thus produced exhibit even against a modified viscose fiber without algal addition a significantly increased

Water retention capacity (WRC) on. This shows the moisture-holding capacity of the algal addition.

Example 3: Production of an inventive modified algeninkorporierten

Viscose - incorporation of 4% algal powder (Ascophyllum nodosum) on Celluose dosed than 6% dispersion in water.

Through spinnerets with 60 μιη hole diameter and with a net of 20 m / min, a viscose fiber was produced with or without 4% algal material cellulose.

Table 3: Faserei characteris tics of a modified viscose Example 3

The Alginsäuregehalt the as-spun fibers was 0.77% to 0.83%, corresponding to an algae content of 3.35% - 3.60%, the algae powder used had a

Alginsäuregehalt from 23% to.

Example 4: Production of an inventive modified algeninkorporierten

Viscose - incorporation of 4% algal powder (Ascophyllum nodosum) on Celluose dosed than 6% dispersion in water.

Through spinnerets with 60 μιη hole diameter and with a net of 19 m / min modified viscose fibers were produced with 4% algal material cellulose according to the invention for about 40 hours.

Table 4: fiber properties algeninkorporierter modified viscose fibers,

Beis iel 4

Legend (also applies to the following tables):

Titer Cv: [%]: Standardvariationskoeffizient

SFk [cN / tex]: tenacity loop strength conditioned

SDk [%]: conditioned sling strain

The Alginsäuregehalt the as-spun fibers was 0.80% - 1.0%, corresponding to an algae content of 3.2% - 4.0%; algal powder used had a Alginsäuregehalt of 25%.

Zinc contents of the present invention algeninkorporierten modified viscose:

The zinc content was performed on fiber samples from Example 3 and Example 4 in Vergeich to a standard viscose fiber (manufactured by Lenzing AG), a modal fiber (manufactured by Lenzing AG) (as well as a modified seaweed fiber, which was prepared by the lyocell process SeaCell ™, manufacturer: Smartfiber AG), as determined by ICP analysis after fiber opening.

It turned out that the inventively modified algeninkorporierten viscose fibers have a zinc content of 330 ppm to 530 ppm, while standard viscose and modal fibers have significantly lower zinc contents.

Table 5: Zn content of the inventively modified algeninkorporierten

Zn algae

[%] [mg/kg]

Fiber sample Example 3 4410

Example 4 Fiber Sample 1 4530

Example 4 Fiber Sample 2 4330

Example 4 Fiber Sample 3 4400

Example 4 Fiber Sample 4 4360

Example 4 Fiber Sample 5 4380

Standardviskosefaser (type of textile) 0 41

Zn algae

[%] [mg/kg]

Modalfaser A 0 73

Modalfaser B 0 165

Seacell ™ Phases 3 to 5 May

Comparison of the inventively produced fibers having the prior art of EP 1259564:

1) Comparison of the tendency to fibrillation of a commercially available SeaCell fiber.

In this fiber is produced according to a EP 1259564 Lyocell type with 3% - 5%-incorporated material from Ascophyllum nodosum.

In order to investigate the tendency to fibrillation of the fibers, the following methods were used:

a) wet abrasion value - The method according to EP 0943027 Bl [0030]

b) Adapted CSF-test in accordance with the standard Canadian Standard Freeness T 227 om-99

c) shaking test and microscopic evaluation of the tendency to fibrillation - method according to EP 0943027 Bl [0029]

a) Test of Nasscheuerwertes (and wet rub resistance or NSF '):

20 single fibers with a pretension weight titerabhängigen complained hung on a metal roll having 1 cm diameter. The roller is provided with a

Viskosefilamentgarnstrumpf plated and is continuously moistened. During the measurement, the roller is rotated at a speed of 500 rpm. The roller simultaneously performs an oscillating movement transverse to the fiber axis at approximately 1 cm by deflection. determining the number of rotations to the fraying of the fibers. The stronger the tendency to fibrillation when wet, the lower the number of reached

U revolutions which, based on the titer [dtex] the value of the wet abrasion resistance arise.

Table 6: Results of the wet abrasion test dtex of fibers having incorporated alginate every 1.7

Legend:

CV [%]: coefficient of variation (standard deviation in% of the mean)

b) Adaptierte CSF-Prüfung ,Canadian Standard Freeness' (CSF):

When adapted, Canadian standard freeness' test serves as a measure of

Tendency to fibrillation, a blender, being beaten in the cut to 5 mm long fiber samples in water until they begin to fibrillate. The CSF apparatus itself consists of a hopper with overflow and a sieve placed therein. With

increasing fibrillation clogged the sieve located in the CSF apparatus, whereby more water passes into the overflow and less in the run. In a standardized graduated cylinder, the volume of water in ml in the run, after

different Mixzeiten determined, which is the higher, the less fibrillated fiber.

Figure 1 illustrates the Fibrillationsdynamik determined in accordance with these experiments. On the abscissa the mixing time is indicated in minutes on the ordinate the volume of water in the flow in ml.

The investigated according to Figure 1 fiber types A to F, there were the following fibers:

A Standard-Lyocellfaser 1,7 dtex

B viscose fiber without alga 1.7 dtex from Example 2

C algeninkorporierte modified viscose fiber from Example 2

D algeninkorporierte modified viscose fiber of Example 4

E Normalviskosefaser 1,7 dtex

1.7 dtex SeaCell ™ (SmartFiber AG), lyocellbasierte algeninkorporierte

F Type

As shown in Figure 1, both Lyocelltypen fibrillate, both the standard lyocell fiber and the SeaCell ™, already after 10 minutes mixing time. All types of fiber, which is a viscose based, including the algeninkorporierten fibers according to the modified method according to the invention show in the CSF test even after a mixing time of 45 minutes, no signs of fibrillation.

c) fibrillated by means of shaking test and microscopic evaluation

The friction of the fibers to each other in washing or Ausrüstevorgängen in the wet state is simulated by the following test: 8 fibers are placed with 4 ml of water in a 20 ml sample vial, and during 3 hours in a laboratory mechanical shaker of RO-10 from Gerhardt. Bonn (Germany), at stage 12th The fibrillation of the fibers is assessed under the microscope by counting the number of fibrils per 0.276 mm fiber length and is specified in a fibrillation value from 0 (no fibrils) to 6 (strong fibrillation).

Table 7: Spleißprüfung after the shaking test, of fibrils and touch after 3 hours

Figures 2 to 4 show the results of the microscopic examination of the fibers:

Figure 2 shows the fibrillation of the fiber of Example 3. FIG.

Figure 3 shows the fibrillation of the fiber of Example 4. FIG.

Figure 4 shows the fibrillation of SeaCell ™ fiber.

It is clearly evident that fibers of the invention does not fibrillate or practically do not.

2) Comparison of the physical properties of the fiber produced by the inventive method algeninkorporierten viscose fibers modified with the methods described in EP 1259564 Bl viscose fibers.

Table 8: Overview of the physical fiber data compared

Legend:

owc: on weight of cellulose - content by weight of cellulose n: Not available

As shown in Table 8 it can be seen is with the exception of a fiber pattern of Example 2, in which, as mentioned above, due to thread cracks no good strengths are achieved, the fineness-related breaking force in the dry state at all according to the invention fibers with incorporated algal material higher than 25 cN / tex, that is significantly higher than that of viscose fibers from EP 1259564 Ex. 7 and 8 and even higher than that of the reference viscose EP 1259564 COMPARATIVE eXAMPLE 3.

In particular, the wet modulus, the tear strength is to BISFA, that at 5% elongation in the wet state at all according to the invention fibers with incorporated algal material is higher than 4.0 cN / tex, during wet modulus at the Viskosetypen from EP 1259564 a value of 3 , does not exceed 0.

As for the wet modulus, all algeninkorporierten types produced by the modified viscose meet the minimum values ​​defined for Modal to BISFA.

With regard to the dry strength of only the fibers of Examples 1 and 2 achieve

(Except Example 2.1 100 g / 1 dispersion algae) required in the Modaldefinition by BISFA values.

Accordingly, it is in accordance with the invention modified viscose fibers with incorporated algae not to modal fibers in the strict sense, but 1,259,564 Examples 7 and 8 use significantly improved values ​​due to the significantly improved physical fiber properties are inferred with respect to the EP. The relationship between the wet modulus of fibers and the area shrinkage of produced therefrom tissues has long been known (Szegö, L., fiber Forsch., Text. Tech. 21:10 (1970). Puchegger has this relationship for viscose and modal fibers confirmed (Puchegger, F . Lenzinger Ber. 55, 32-36 (1983) and Puchegger, F., Lenzinger Ber. 58, 94-99 (1985)).

The following table lists the process parameters of Examples 1-4 are summarized:

Table 9:

Viscose composition: Ex 1 Ex 2 Ex 3 Ex. 4...

NaOH concentration in the

Viscous wt. [%] 6.2 6.1 6.5 6.7

alkali ratio

(Cellulose:NaOH, beide g/1) 0,9 1,0 0,9 0,8

CS 2 in the viscose [wt.% To

Cellulose] 37 39 36 38

Modifiers [wt.%>] 3 3 4 4

Ripeness (gamma value) 58 58 57 59

Spinnviskosität

[Falling ball seconds] 96 80 95 82

Dusenlochdurchmesser 50 microns 50 microns 60 microns 60 microns

Spinnbadzusammensetzung:

H2S04 [g/l]: 75 73 74 72

Na 2 S0 4 [g / l]: 128 123 125 120

ZnS04 [g/1]: 60 65 65 60

T Spinnbad [°C]: 38 38 37 37

T secondary bath [° C] 97 97 97 97

Final image from the spinning bath

[M / min] 30 30 20:19

Claims:

A modified viscose fiber containing incorporated an algal material,

characterized by a wet modulus at an elongation of 5% in the wet state, which satisfies the following formula:

Nassmodul (cN) > 0,5 *VT,

where T is the titre of the fiber in dtex.

2. viscose fiber according to claim 1, characterized by a fiber strength in

conditioned state, which satisfies the following formula:

Faserfestigkeit (cN/tex) > 27,38 -1,4*T.

3. viscose fiber according to claim 1 or 2, characterized by a content of zinc ions of at least 200 ppm, preferably 200 ppm to 700 ppm.

4. viscose weight according to one of the preceding claims, characterized by a content of algal material of at least 0.5.%, Preferably 2 wt.%> To 6 wt.%.

5. A process for producing a modified viscose fiber according to any of

previous claims by spinning a viscose having a content of 4.% to 7 wt.% of cellulose, 5 wt.% to 10 wt.% NaOH, 34 wt.% to 42 wt.% (based on the cellulose) carbon disulfide, and 1 wt .%> to 5% by weight> (based on cellulose) of a modifying agent in a spinning bath, peeling off of the coagulated filaments. wherein a viscose is used, the spinning gamma value 50 to 68, and their spinning viscosity is 50 falling ball seconds to 150 falling ball seconds; wherein the alkali ratio (= cellulose concentration / alkali metal content) of the spin ready viscose to 1.5 is 0.7, and the temperature of the spinning bath 34 ° C to 48 ° C, with the following Spinnbadkonzentrationen be used: H 2 S0 4 68 g / 1 - 90 g / 1

Na2S04 90 g/1 - 160 g/1

ZnS0 4 30 g / 1-65 g / 1,

wherein the final image from the spinning bath at a rate between

takes place 15 m / min and 60 m / min and wherein a Algenaterial is spun in the form of an aqueous dispersion.

6. The method according to claim 5, characterized in that the aqueous

Dispersion has a content of seaweed material of 2 wt.% To 15 wt.% By weight.

7. Use of a viscose fiber according to any one of claims 1 to 4 for

Production of yarns and textile fabrics.