EP2478138A1 - Fluorescent fiber, use thereof, and method for the production thereof - Google Patents

Abstract

The present invention relates to a cellulosic regenerated fiber, which contains a pigment that is spun in and a fluorescent dye that is applied by overdying, the use thereof to produce yarns and sheet materials, and a method for producing said fibers. Said fiber fulfills the requirements of EN 471 with regard to luminance, color space, and rubbing fastness and has a light fastness (ISO 105-B02, method 2) of more than 5.

Description

 Fluorescent fiber, its use and method for its

 manufacturing

The present invention relates to regenerated cellulosic regenerated fibers for use in high-visibility clothing such as described in standard EN 471, their use for

Production of yarns and fabrics, and a process for producing these fibers. State of the art:

 EN 471 deals exclusively with the warning effect of personal protective equipment, in particular warning clothing.

Warning clothing usually consists of a fluorescent

Background material and a retroreflective material. When

fluorescent material is, for the purposes of the present invention as defined in EN 471, a material that emits rather than absorbs radiation at longer wavelengths; in the text below, the term high-vis material is also used. The present invention relates to the fluorescent background material but not to

retroreflective materials.

So far, high-vis textiles are made only on the basis of synthetic fibers and in particular polyester, but the disadvantages in terms

Provide comfort and safety. The disadvantages of such textiles are especially in an unpleasant skin climate and in the

 Odor development after prolonged wear due to insufficient moisture-regulating material properties, and in the for

Synthetic fibers typical danger electrostatic charge.

An alternative represent complex textile structures whose

Outside contains the high-vis component and the inside

mainly consists of cellulosic fibers to improve the comfort, as described for example in WO 2006/017709. Fibers by the viscose process and lyocell process are known today as cellulosic regenerated fibers. They are used worldwide for standard applications produced in the textile and nonwovens sector with a single fiber titer between 0.8 and 16 dtex.

Although cellulose regenerated fibers can be dyed by the conventional bath method with fluorescent dyes. But the fibers dyed in this way do not meet the requirements of light fastness (ISO 105-B02, method 2> 5). After the xenon irradiation they are significantly bleached and show a strong change in hue and a greatly reduced color depth, which can be represented as a shift of the coordinates of the color space, for example.

For decades, it has been known to viscose fibers by spinning

Coloring pigments permanently. Corresponding fibers are available on the market. So far, however, there are no spun-dyed regenerated fibers that meet the requirements of EN 471.

Task:

 Compared to this prior art, the task was to provide a fiber available, on the one hand the requirements for protection and

Warning clothing, as described for example in EN 471 fulfilled, and on the other hand, wearing comfort and safety aspects of these clothes increased at a reasonable cost. It should therefore be possible to make the protective and warning clothing from such a fiber without admixture of other fiber types. It is particularly important that the textiles produced from these fibers meet the following requirements for background materials in accordance with EN 471:

 • Minimum luminance factor (CIE Publication No. 152 standard) and color space

 • Color after xenon irradiation: the exposure of the sample is carried out according to ISO 105-B02, method 3

 • Dry and wet rubbing fastness (ISO 105-A02)

In addition, the light fastness of the fibers was determined according to ISO 105-B02 method. Furthermore, the object was to provide a suitable manufacturing method for these fibers. Surprisingly, this task could be solved by cellulosic

 Regeneratfasern containing a spun color pigment and a dye applied by over-dyeing fluorescent dye are dissolved. These fibers of the invention have, in addition to the improved comfort and increased safety due to the cellulosic

Basic structure surprisingly a lightfastness - measured according to ISO 105-B02, method 2 - of more than 5 on. This was not achievable with previously known cellulosic fibers.

The fibers also comply with the other values required in EN 471 with regard to rub fastness, perspiration fastness, wash fastness,

 Dry cleaning fastness, hypochlorite bleaching fastness and ironing fastness.

The spun-dyed regenerated cellulosic fiber can after a

Viscose process, a modified viscose process (e.g.

Modalverfahren, zinc-free viscose process with Al sulfate, ...), but also after a solvent process that works with organic solvents such as molten aqueous amine oxides or so-called ionic liquids produced. The fibers can

accordingly be referred to as viscose, modal or lyocell.

The cellulosic regenerate fiber may contain other additives. In a particular embodiment, the cellulosic regenerated fiber is additionally flame-retarded. A preferred embodiment of the flame-retarded fiber is made by incorporation of a pigmented flame retardant. As pigmented flame retardants come along with other types

in particular organophosphorus compounds in question, for viscose

For example, the well-suited and known 2,2'-oxybis [5,5-dimethyl- 1.S ^ -Dioxaphosphorinan ^ 'disulfide, available under the trade names Exolit and Sandoflam produced.

In a further preferred embodiment, the cellulosic

Regenerate fiber also antibacterial equipped. In this case, the substances known to the expert can be used.

Subsequent high-vis bath dyeing can be performed with dyes suitable for cellulosic materials (e.g., reactive dyes, direct dyes,

Vat dyes, ...).

The over-dyeing, d. H. the bath dyeing may be carried out either on the flake of the spun-dyed fiber, on a yarn containing the spun-dyed fiber or on a textile surface containing the spun-dyed fiber. In this case, it is possible to apply the continuous and discontinuous dyeing methods known in principle to those skilled in the art.

By suitable selection of the pigment for the spin dyeing and the high-vis dye for the bath dye also shades can be achieved, for

 c

There are no individual solutions so far.

The present invention also relates to the use of the fiber according to the invention for producing a yarn. In order to have suitable properties for the particular application, such a yarn according to the invention may, in addition to the fibers according to the invention, also contain fibers of other origin, for example

(flame-retardant) polyester, modacrylic, para and meta-aramid,

Polyamideimide (Kermel®), (flame-retardant) wool, polybenzimidazole (PBI), polyimide (P84®), polyamides, (flame retarded) polyamides, flame retarded acrylic fibers, melamine fibers, polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), glass fibers, cotton, silk, Carbon fibers, oxidized thermally stabilized polyacrylonitrile fibers (PANOX®) and electrically conductive fibers; and mixtures of these fibers. In a preferred embodiment, the mixing partners may also have high-vis equipment. Likewise provided by the present invention is the use of the fiber according to the invention for the production of a textile fabric. In addition to the fibers according to the invention, this fabric may also contain other fibers, for example (flame-retardant) polyester, modacrylic, para and meta-aramides, polyamide-imide (Kermel®),

(flame retarded) wool, polybenzimidazole (PBI), polyimide (P84®),

Polyamides, (flame retarded) polyamides, flame retarded acrylic fibers, melamine fibers, polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), glass fibers, cotton, silk, carbon fibers, oxidized thermally stabilized polyacrylonitrile fibers (PANOX®) and electrically conductive fibers, as well

Mixtures of these fibers. In a preferred embodiment, the further fibers may also have a high-vis finish. The textile fabric is preferably a woven, knitted or knitted fabric, but may in principle also be a nonwoven. In the case of a woven or knitted fabric, it is possible to mix the fibers according to the invention with the further fibers either by mixing before yarn production, the so-called intimate mixing, or by jointly using respectively pure yarns of the different fiber types during weaving, knitting or knitting.

In the same way, the subject of the present invention is also the

Use of the fibers according to the invention for the production of a

Garment or other warning article, wherein

Usually, the above-mentioned yarns or textile fabrics occur as intermediates within the textile warp. Other warning items to be understood for the purposes of this invention, for example, pennants, flags, flags and warning tapes or other items that are particularly well visible by a particularly eye-catching color or generate attention. The use according to the invention thus goes beyond the pure warning effect. If the fabric already mentioned above is used as the fabric - for example for use in

Pennants, flags, flags and warning tapes - of course that eliminates

Intermediate stage of the yarn. Different versions of such Garments and other warning articles are well known to those skilled in the art and therefore need not be further described here.

Likewise subject of the present invention is a process for the preparation of the above-described inventive fluorescent; cellulosic regenerated fibers in which a color pigment is spun into the fibers and these fibers are over-dyed in a later process step with a fluorescent dye. The spinning is usually carried out by adding the color pigments to the spinning solution. Such addition methods are generally known to the person skilled in the art for both the viscose and modal and solvent spinning processes. However, spun-dyed cellulosic fibers are usually not later over-dyed in a further step with another dye, as spin dyeing is generally considered to be a very effective method, with the high fastness properties, both rubbing and light, washing and perspiration fastness can be achieved! However, the present invention, which is in combination with a later over-dyeing step, satisfies the specific ones

Requirements for cellulose fibers for warning clothing.

The over-dyeing, d. H. the bath dyeing can be carried out either on the flake of the spun-dyed fiber or on a yarn or a textile surface containing the spun-dyed fiber. In this case, it is also possible to use the continuous and discontinuous dyeing processes which are likewise known in principle to the person skilled in the art.

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.

Example 1 :

A spun-dyed flame-retarded viscose fiber contains 1.25% by weight of Pigment Yellow 3 (eg Aquarine Yellow 10 G) and 22% by weight of 2,2'-oxybis [5,5-dimethyl-1S-dioxaphosphorinane-3'-disulfide ( Exolit 5060, Fa. Clariant) in each case based on cellulose. This fiber is then over-dyed with Remazol Leuchtgelb FL (DyStar) according to the following recipe:

The flake is placed in a dyebath containing 2% Remazol Leuchtgelb FL (DyStar Co.) and 100 g / l sodium sulfate at a liquor ratio of 1:10 and an initial temperature of 25 ° C and a heating rate of 1 ° C min to 50 ° C heated. After 10 min at this temperature, 5 g / l of soda is added and after a further 30 min 1, 2 ml / l NaOH (50%). After a further 40 minutes, the dyebath is allowed to cool and includes an aftertreatment with the rinse - soaps - rinse - soaps known to the person skilled in the art.

The fiber was then dried and a fabric made therefrom. This showed the test results shown in Table 1. These results show that the fibers, yarns and textiles produced according to the invention are outstandingly suitable for use in high-visibility clothing and do not fade.

Table 1: Test results (for Example 1)

Example 2 (Comparative Example)

A commercially available viscose fiber (Lenzing FR), which was also flame-retarded with Exolit 5060 and contained no spun-in color pigment, was over-dyed by the same method as described in Example 1. Were however, 6% Remazol Leuchtgelb FL (DyStar Co.) instead of 2% as used in Example 1. The fiber showed the test results shown in Table 2.

Table 2: Test results (for Example 2)

Hue and color depth changed significantly by the exposure in the fiber according to the prior art in Example 2 than in the inventive fiber of Example 1, which can be clearly seen in the stronger shift of the coordinates of the color space. The luminance also deteriorates considerably more in the case of the non-inventive fiber as a result of the exposure than in the case of the fiber according to the invention. Particularly serious, however, is the significantly poorer lightfastness of the fiber in Example 2 over the fiber of Example 1 according to the invention.

Claims

claims: 1. Cellulosic regenerated fiber comprising a spun color pigment and a fluorescent dye applied by over-dyeing  Contains dye. 2. Cellulosic regenerated fiber according to claim 1, which is a  Light fastness, measured according to ISO 105-B02, method 2, of more than 5. 3. Cellulosic regenerated fiber according to claim 1, which according to a  Viscose, modal or lyocell method is produced. 4. Cellulosic regenerated fiber according to claim 1, in addition  equipped flame retardant. The regenerated cellulose fiber according to claim 4, wherein the  flame retardant equipment a braided  Organophosphorus compound (preferably 2,2'-oxybis [5,5-dimethyl-1, 3,2-dioxaphosphorinan] 2,2'disulfide). 6. Cellulosic regenerated fiber according to claim 1, in addition  is equipped antibacterial. 7. Use of the fibers according to claims 1 to 6 for  Production of a yarn. 8. Use of the fibers according to claims 1 to 6 for  Production of a textile fabric. 9. Use of the fibers according to claims 1 to 6 for Manufacture of a garment or other warning article. 10.A method for producing fluorescent cellulosic  Regenerate fibers according to claims 1 to 6, characterized  characterized in that a color pigment is spun into the fibers and these fibers are over-dyed in a later process step with a fluorescent dye. 11.A method according to claim 10, wherein the over-dyeing is carried out by a continuous or discontinuous process step. 12. A method according to claim 10 or 11, wherein the over-dyeing is carried out on a yarn or fabric made of the cellulosic regenerated fiber.