Patent Application
20190127888
The present invention relates to a modified viscose fiber, a process for the production of the viscose fiber according to the present invention, and to its use.
In particular, the invention relates to a modified viscose fiber with an incorporated material from algae, with improved use properties for textile applications, particularly in the knitwear sector, which meet the consumer's expectations for unrestricted washability and, respectively, also the requirements of industrial washing, to its use in the manufacture of yarns and planar assemblies, and to a process for the production of those fibers.
EP 1 259 564 describes the production of fibers and molded bodies according to the NMMO process from a polymer solution which comprises a biodegradable polymer—usually cellulose—and a material from marine plants and/or shells of marine animals and, optionally, further additives. According to EP 1 259 564, molded bodies produced in this way have a lower tendency towards fibrillation as compared to corresponding molded bodies according to the NMMO process without additives. This conclusion was drawn on the basis of the changed fiber structure, which is visible in SEM images, more precisely on the basis of a reduced longitudinal orientation.
Moreover, EP 1 259 564 discloses the production of fibers and molded bodies modified by the addition of a material from marine plants and/or shells of marine animals according to a viscose process. By way of example, 15% (Example 7) and 1.7% (Example 8) of a material from brown algae are added on cellulose. Fibers and, respectively, molded bodies produced in this manner have similar or, respectively, slightly deteriorated physical fiber properties in comparison to a viscose fiber without additives (Comparative Example 3).
In addition, EP 1 259 564 describes in Examples 9 and 10 the production of fibers and molded bodies with the addition of a material from marine plants and/or shells of marine animals according to the carbamate process. According to said process, a very low fineness-related dry tear strength is achieved, which is reduced even further by the addition of algal material, depending on the incorporated amount.
It is known that the addition of material from marine plants, in particular seaweed, imparts a particularly soft feel to fibers and cellulosic molded bodies as well as textiles produced therefrom and causes enrichment with vitamins, micronutrients and trace elements and that alginate contained in algae has moisturizing properties. It has also been demonstrated that algae and fibers produced therefrom have antioxidant properties [http://www.smartfiber.de/index.php/seacell-de/zertifizierungen, queried on Apr. 17th, 2016]. For those reasons, products containing a material from marine plants, especially seaweed, are considered to be particularly skin-friendly.
All of the fibers disclosed in EP 1 259 564, i.e., the fiber types produced according to the NMMO process, the viscose process and the carbamate process, but also the Lyocell type commercially available under the trademark SeaCellTM meet the requirements of the modern textile industry only insufficiently due to various reasons:
Without high-grade finish or additional crosslinking, the Lyocell-based types tend to fibrillate and, subsequently, after repeated washings, to form unsightly textile surfaces that have been scrubbed white, despite the somewhat lower longitudinal fiber orientation. On the other hand, fiber types produced according to the viscose process exhibit an even slightly poorer stability in the wet state (wet strength and BISFA wet modulus) than conventional viscose fibers. The types produced according to the carbamate process have a dry tensile strength which is too low for commercial yarn production. In addition, said process has no economic significance, to this day, there has been no industrial fiber production according to the carbamate process.
In comparison to this prior art, it has been the object to produce a cellulosic fiber in which an amount of material from algae noticeable to the consumer is incorporated in order to achieve the desired properties of a natural soft handle, moisture retention capacity and skin-friendliness, but which, in addition, meets the increased textile mechanical requirements both for dimensional stability and wash resistance and for minor fibrillation behavior.
Said object is achieved by a modified viscose fiber according to claim 1. Preferred embodiments are indicated in the subclaims. For the purposes of the present invention, the term “fiber” is intended to encompass fibers of a defined, relatively short length (for example, so-called “staple fibers”) as well as fibers of a very large length, which, in linguistic usage, are also referred to as “filaments”.
The present invention solves the above-indicated problem by providing non-fibrillating regenerated cellulosic fibers with incorporated algal material, which are produced according to a viscose process modified in comparison to EP 1 259 564. The fibers according to the invention are characterized by the particular softness of cellulose fibers with an incorporated material from algae, which per se is known, but exhibit a significantly reduced tendency towards wet fibrillation as compared to solvent-spun fibers based on the NMMO process.
Surprisingly, the minor procedural modifications in comparison to the manufacturing process described in EP 1 259 564 B1 have had the result that the fibers according to the invention show significantly improved physical fiber properties, in particular a higher fineness-related tear strength and a higher wet modulus, as compared to the fibers of the viscose type having brown algae incorporated according to EP 1 259 564, Example 7 (comprising 15% brown algae) and Example 8: (comprising 1.67% brown algae on cellulose) and even in comparison to Comparative Example 3 of EP 1 259 564 (without admixture of algae).
The fibers according to the invention have a wet modulus at an elongation of 5% in the wet state which complies with the following formula:
wet modulus (cN)≥0.5*√T,
wherein T is the titer of the fiber in dtex.
This wet modulus corresponds to the wet modulus of a modal fiber as per the definition by BISFA (The International Bureau for the Standardization of Man-Made Fibers) and is hereinafter also referred to as “BISFA wet modulus” or “BISFA modulus”. The wet modulus and the other textile physical properties mentioned in the present application are measured according to the measuring methods as defined by BISFA.
In a preferred embodiment, the fiber according to the invention has a fiber strength in the conditioned state which complies with the following formula:
fiber strength (cN/tex)≥27.38−1.4*T.
This strength is significantly higher than that of the modified viscose fibers described in EP 1 259 564.
The fibers according to the invention may contain 0.5% by weight to 6% by weight, preferably 2% by weight to 6% by weight, particularly preferably 3% by weight to 4% by weight, of algal material, based on cellulose.
The algae can come from both salt and fresh water. The use of microalgae as well as of macroalgae, especially also kelp, is possible.
Preferably, the algae used have an alginic acid content of 15% by weight to 50% by weight. In a preferred embodiment, the fibers according to the invention contain algal material of the type Ascophyllum nodosum.
Moreover, the fibers according to the invention have, even without complementary additions of metal ions, an increased content of zinc in comparison to Lyocell fibers and/or viscose fibers with the same addition of algae.
The content of zinc ions preferably amounts to at least 200 ppm, particularly preferably 200 ppm to 700 ppm.
The zinc content is significantly increased also in comparison to modal fibers and is present in the fiber according to the invention at least partially as a Zn alginate. Zinc is an essential trace element with skin-caring qualities and is therefore used in skin care products. Zinc alginates are used, among other things, in wound dressings. It is believed that the combined effect of alginate (as a moisturizer and a natural softener) and of zinc ions releasable from the alginate achieves even better skin care properties.
A process serves for the production of the viscose fiber according to the invention which consists in spinning a viscose having a content of 4% by weight to 7% by weight of cellulose, 5% by weight to 10% by weight of NaOH, 34% by weight to 42% by weight (based on cellulose) of carbon disulphide as well as 1% by weight to 5% by weight (based on cellulose) of a modifier into a spinning bath, drawing off the coagulated filaments; wherein a viscose is used whose spinning gamma value ranges from 50 to 68 and whose spinning viscosity ranges from 50 falling-ball seconds to 150 falling-ball seconds; wherein the alkali ratio (=cellulose concentration/alkali content) of the viscose ready for spinning ranges from 0.7 to 1.5, and the temperature of the spinning bath ranges from 34° C. to 48° C., wherein the following spinning bath concentrations are used:
wherein the final draw-off from the spinning bath occurs at a rate of between 15 m/min and 60 m/min, and wherein an algal material in the form of an aqueous dispersion is spun in.
The numerical values indicated for the composition of the viscose refer to its state prior to the addition of the dispersion of the algal material.
A process similar in terms of the parameters of the viscose used, the spinning bath and the spinning has been described in WO 2011/026159 A1 so that reference can be made to this document for further details regarding the spinning process.
The modifier which is used produces a sheath structure of the fiber according to the invention in a manner known per se. For example, the modifier can be an ethoxylated amine.
The material from algae which is used is preferably provided in a powdered and dried state, with a residual water content of <15%, better <10%, at a particle size of x99≤20 μm, better ≤15 μm. So as to achieve the desired fiber properties, the algal material should preferably have an alginic acid content of at least 15%. Directly before use, the material is preferably dispersed in water, optionally with a dispersing aid being added, in order to yield a dispersion with a solids content preferably ranging from 2% by weight to 15% by weight. The aqueous dispersion can be deaerated in vacuo as needed and, optionally, can be added to the viscose at the desired ratio upon a preceding filtration for removing undissolved particles, while, in doing so, intimate mixing should be ensured by means of conventional mixing units, homogenizers or the like. Upon admixture to the viscose, a filtration by cartridge filters may occur prior to spinning.
Spinning may be effected through spinnerets with a hole diameter of 50 μm-100 μm, depending on the desired titer of the fibers.
The present invention also relates to the use of the viscose fiber according to the invention for the production of yarns and planar textile assemblies.
The invention shall 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 those examples.
A detailed listing of the process parameters of all examples can be found in Table 9 at the end of the example section.
A 10% dispersion was prepared in demineralized water from a dried, powdered plant material of Ascophyllum nodosum and was deaerated for 6 hours. A viscose fiber without or, respectively, with 2.5% or, respectively, 5% algal material on cellulose was produced through spinnerets with a hole diameter of 50 μm and with a draw-off of 30 m/min. The dosing of the algal dispersion took place directly before the homogenizer, with a residence time of <1 min in front of the spinneret.
Legend (Also Applies to the Following Tables): Titer [dtex]: fineness (conditioned)FFk [cN/tex]: fineness-related tear strength dry and, respectively, conditionedFDk [%]: maximum tensile force elongation dry and, respectively, conditionedFFn [cN/tex]: fineness-related tear strength wetFDn [%]: maximum tensile force elongation wet
Wet modulus (Bisfa modulus) [cN/tex]: fineness-related wet modulus at 5% elongation
A 10%, a 5% and a 2.5% dispersion was prepared in demineralized water from a dried, powdered plant material of Ascophyllum nodosum, and the dispersions were not deaerated. A viscose fiber without or, respectively, with, in each case, 5% algal material on cellulose was produced through spinnerets with a hole diameter of 50 μm and with a draw-off of 30 m/min.
Due to the high viscosity, the algal dispersion having the highest concentration still contained many air bubbles, which frequently resulted in thread breakages during spinning. Therefore, proper drawing and higher strengths could not be achieved in this case. When thinner algal dispersions were dosed in, this problem did not occur—the resulting fineness-related strengths are at a significantly higher level than that of a viscose fiber according to EP 1 259 564.
The alginic acid content of the algal material used and of the fibers thus spun was analyzed upon a total hydrolysis of the fiber via HPLC on the basis of the mannuronic acid and guluronic acid content against an alginic acid standard (Fluka). The alginic acid content of the algal powder used was 25%, the alginic acid content of the fibers was between 0.95% and 1.2%, corresponding to a content of algae of 3.8% to 4.8%.
As can be seen in Table 2, the fibers thus produced also have a significantly increased water retention capacity (WRV) compared with a modified viscose fiber without addition of algae. This shows the moisture retention capacity of the algal additive.
A viscose fiber without or, respectively, with 4% algal material on cellulose was produced through spinnerets with a hole diameter of 60 μm and with a draw-off of 20 m/min.
The alginic acid content of the fibers thus spun amounted to 0.77% to 0.83%, corresponding to a content of algae of 3.35%-3.60%, the algal powder used had an alginic acid content of 23%.
Viscose fibers modified according to the invention comprising 4% algal material on cellulose were produced through spinnerets with a hole diameter of 60 μm and with a draw-off of 19 m/min for approx. 40 hours.
The alginic acid content of the fibers thus spun was 0.80% - 1.0%, corresponding to a content of algae of 3.2% - 4.0%; the algal powder used had an alginic acid content of 25%.
Zinc contents of the modified viscose fibers algae-incorporated according to the invention:
The zinc content was determined after fiber pulping by means of ICP analysis on fiber samples from Example 3 and Example 4 in comparison to a standard viscose fiber (manufacturer: Lenzing AG), a modal fiber (manufacturer: Lenzing AG) as well as an algae-modified fiber produced according to the Lyocell process (SeaCell™, manufacturer: Smartfiber AG).
It was shown that the modified viscose fibers algae-incorporated according to the invention have a zinc content of 330 ppm to 530 ppm, whereas standard viscose fibers and modal fibers exhibit significantly lower zinc contents.
Comparison of the fibers produced according to the invention with the prior art from EP 1 259 564:
1) Comparison of the Tendency Towards Fibrillation with a Commercially Available SeaCell™ Fiber.
This fiber is a Lyocell type produced according to EP 1 259 564 with 3%-5% incorporated material of Ascophyllum nodosum.
To study the fibers' tendency towards fibrillation, the following procedures were used:
a) Wet abrasion value—method according to EP 0 943 027 B1 [0030]
b) Adapted CSF test based on the Canadian Standard Freeness T 227 om-99 standard
c) Shake test and microscopic assessment of the tendency towards fibrillation—method according to EP 0 943 027 B1 [0029]
20 single fibers are weighted down with a titer-dependent pretension weight and suspended from a metal roller with a diameter of 1 cm. The roller is covered with a viscose filament yarn stocking and is continuously moistened. During the measurement, the roller is rotated at a speed of 500 rpm. The roller simultaneously performs a pendulum movement transversely to the fiber axis with a deflection of about 1 cm. The number of rotations until the fibers are worn through is determined. The stronger the tendency towards fibrillation in the wet state, the lower is the number of achieved revolutions U, which indicate the value of the wet abrasion resistance based on the titer [dtex].
In the adapted ,Canadian Standard Freeness' test, a mixer serves as a measure of the tendency towards fibrillation, wherein fiber samples cut to a length of 5 mm are beaten in water in said mixer until they start to fibrillate. The CSF apparatus itself consists of a funnel with an overflow and a screen inserted therein. As the degree of fibrillation increases, the screen located in the CSF apparatus clogs, whereby more water gets into the overflow and less into the passage. In a standardized measuring cylinder, the water volume is determined in ml in the passage after various mixing times, whereby it is the higher, the less the fiber fibrillates.
The fiber types A to F examined according to
A standard Lyocell fiber 1.7 dtex
B viscose fiber without algae 1.7 dtex from Example 2
C algae-incorporated modified viscose fiber from Example 2
D algae-incorporated modified viscose fiber from Example 4
E normal viscose fiber 1.7 dtex
F 1.7 dtex SeaCellTM (Smartfiber AG), Lyocell-based algae-incorporated type
As shown in
The friction of the fibers among each other during washing and, respectively, finishing operations in the wet state is simulated by the following test: 8 fibers are placed in a 20 ml sample vial with 4 ml of water and shaken at level 12 for 3 hours in a laboratory shaker of type RO-10 from Gerhardt, Bonn (FRG). Thereupon, the fibrillation behavior of the fibers is evaluated under the microscope by counting the number of fibrils per 0.276 mm of fiber length and is indicated as a fibrillation value ranging from 0 (no fibrils) to 6 (strong fibrillation).
It is clearly evident that the fibers according to the invention do not or practically do not fibrillate.
2) Comparison of the Physical Fiber Properties of the Algae-Incorporated Modified Viscose Fibers Produced According to the Process According to the Invention with the Viscose Fibers Described in EP 1 259 564 B1.
As can be seen in Table 8, with the exception of a fiber sample from Example 2, where, as mentioned above, good strengths were not obtained because of thread breakages, the fineness-related tear strength in the dry state is higher than 25 cN/tex in all fibers produced according to the invention with incorporated algal material, i.e., significantly higher than that of the viscose fibers from EP 1 259 564, Ex. 7 and 8, and even higher than that of the reference viscose fiber EP 1 259 564, Comparative Example 3.
In particular, the wet modulus according to BISFA, i.e., the tensile strength at 5% elongation in the wet state, is higher than 4.0 cN/tex in all fibers produced according to the invention with incorporated algal material, whereas the wet modulus does not exceed a value of 3.0 in the viscose types from EP 1 259 564.
As far as the wet modulus is concerned, all algae-incorporated types produced according to the modified viscose process comply with the minimum values as defined by BISFA for a modal fiber.
With respect to the dry strength, only fibers of Examples 1 and 2 (except Example 2.1 with 100 g/l algal dispersion) achieve the values required in the modal definition according to BISFA.
Accordingly, the viscose fibers modified according to the invention having incorporated algae are not modal fibers in the true sense of the word, but it is still possible to infer significantly improved use values in comparison to EP 1 259 564, Examples 7 and 8, from the substantially improved physical fiber properties. The connection between the wet modulus of fibers and the surface shrinkage of fabrics produced therefrom has long been known (Szegö, L., Faserforsch., Text. Techn. 21.10 (1970). Puchegger has confirmed this connection for viscose and modal fibers (Puchegger, F Lenzinger Ber., 55, 32-36 (1983) and Puchegger, F., Lenzinger Ber. 58, 94-99 (1985)).
In the following table, the process parameters of Examples 1-4 are summarized:
| Number | Date | Country | Kind |
|---|---|---|---|
| A 50381/2016 | Apr 2016 | AT | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2017/059813 | 4/25/2017 | WO | 00 |
