EP1825052B1 - Coloured polyolefin fibres application and method for production thereof - Google Patents

Description

The invention relates to vat dyes dyed polyolefin fibers, their use for forming a textile and a process for producing such colored polyolefin dyed or dyed fabrics based on polyolefin fibers or of textiles based on colored polyolefin fibers.

Due to their broad property profile, polypropylene fiber materials are becoming increasingly popular in various textile sectors (H.-J. Koslowski in Chemical Fibers Intern. 54 (2004), 272 ). The biggest disadvantage of PP fiber, and thus the biggest obstacle to a widespread introduction in the home textiles and clothing sector, is its very poor dyeability. This is due in part to the low affinity of most dyes for the completely nonpolar PP fiber surface, and to diffuse dyes, primarily disperse dyes incorporated into the fiber by the well-known Nemst release mechanism At very low temperatures, the high mobility of the macromolecule chains of the polypropylene prevails very easily again out of the fiber. This has bad wet fastness result. Although corresponding improvements could be achieved by modification of the disperse dyes (see, for example, W. Oppermann et al., Melliand Textilberichte 77 (1996), 588), these dyeings have the further disadvantage of exceptionally poor light fastness, which prevents the use of such dyed polypropylene fibers. Practically excludes materials.

There are a variety of approaches to retrospectively dye polypropylene, but the methods described have not yet found their way into production. The addition of dye acceptors in the spinning mass, the copolymerization and graft copolymerization and the chemical modification of the polymer chain are so far unsuccessful, as it comes to the introduction of polar groups in these ways to a greatly increased soiling behavior of the PP fiber and also other benefits that the Make the PP fiber's charm, get lost.

Apart from the pigmentation, polypropylene is now almost exclusively spun-dyed. As a result, although satisfactory washing and especially Light fastness achieved, but this method has the major disadvantage that a rapid adaptation fashion-related hues is not feasible. In order to achieve good fastnesses on PP, several attempts have already been made to dye PP with vat dyes, as in US 3,052,510 or US 3,104,150 and JP 24957/65 described. In order for the relatively large molecules of vat dyes to penetrate into the fiber interior, it has been preferred to dye under high temperature conditions. The dyeings carried out according to these instructions show good fastnesses, but the dyeings appear cloudy and they have a poor color yield.

The object of the invention is therefore to produce advantageous dyed with vat dyes polyolefin fibers, which are characterized by excellent wash, rub and especially light-fastness values. The dyeings are said to be comparable to vat dyeings on cellulose fibers in terms of hue and brilliance with the corresponding values of cellulosic fibers provided with vat dyeings. In addition, a particularly suitable method for producing such dyed with vat dyes polyolefin fibers are proposed, the disadvantages of the previously established methods should be excluded, such as the lack of flexibility of spin dyeing, the negative effect on the fabric handle of a pigment dyeing and their poor rubbing fastness and also the poor washing and lightfastnesses of other colors on optionally modified polypropylene.

According to the invention this object is achieved with polyolefin fibers dyed with vat dyes, which are characterized by a light fastness according to DIN EN ISO 105-B02 (at 50 ° C and 144 h exposure) of at least 5, a wash fastness to DIN EN ISO 105-C08C of at least 4 and a rubbing fastness according to DIN EN ISO 105-X12 dry of at least 4.

It is particularly advantageous if the light fastness of the polyalefin fibers according to the invention is at least about 6, whose wash fastness is at least 4 to 5 and / or whose rubbing fastness is at least about 4.

In practicing the present invention, the particular nature of vat dyes is not critical. The person skilled in the art is free to select here, with suitable preliminary experiments, vat dyes which are particularly advantageous in the context of the invention. In the context of the invention, a dyeing is preferred with indanthrene dyes. These are dyes that consist of two or more bridged anthraquinone molecules. These dyes prove to be extremely light, washing and weathering in the practice of the present invention. A particularly suitable anthraquinone dye is indanthrene blue. Further particularly suitable dyes of this group of dyes can be indicated: Indanthren brilliant green FFB, Indanthren brilliant orange GK, Indanthren brilliant orange, Indanthren brilliant pink R ⁵ , Indanthren brilliant violet R, Indanthren-dark blue BOA, Indanthren blue BC and Indanthren blue RS ,

The inventively desired effects, as they are based on the above task, are achieved in that the polyolefin fibers have been subjected to a plasma treatment before coloring them with a vat dye. As a result, the color yield during dyeing or printing, compared with the non-plasma-treated polyolefin fiber increased by at least 55%, in the case of particularly suitable dyes by at least 120%. This means a significant economic advantage. The type of plasma treatment is not critical. It can take place in the atmospheric plasma (corona) or in the preferred case in the low-pressure plasma. In both cases, preferably oxygen or air plasmas are used. The plasma treatment of the polyolefin materials is carried out until the polyolefin has an oxygen incorporation of at least 10%, in particular at least 20%, in the surface layer to be detected by means of ESCA (electron spectroscopy for chemical analysis), the layer thickness being given as 6 nm.

The invention thus relates to colored with vat dyes polyolefin fibers. The idea according to the invention, which is reflected above in the advantageous parameters, is not critically dependent on the type of polyolefin used in each case. The vat dyeing can also be carried out in many ways, but the procedure is in particular the foulard HT process, which is described, for example, in H.-K. Rouette, "Lexikon fur Textilveredelung", Laumann-Verlag, Dülmen, 1995, is described. This means that a suitably concentrated dye liquor is applied to the material, for example by means of a padder, and the dye is subsequently taken up by the respective fiber under the action of, for example, high-temperature or saturated steam.

It has been shown that it is advantageous if the polyolefin is present in the form of a homo- or copolymer of ethylene, propylene and / or butylene, in particular in the form of a homopolymer of ethylene, propylene and / or butylene.

The vat dyed polyolefin fibers of the present invention can be used to particular advantage in forming a textile. The nature of the textile is not relevant to achieving the desirable effects. Thus, the polyolefin fibers according to the invention may be present in particular in a textile in the form of a woven, knitted fabric, fleece or fabric. It has proven to be expedient if such textiles contain not only the inventively colored polyolefin fibers integrated. Rather, in individual cases, it is of particular value to additionally include other fibers, i. into the fabrics, knitted fabrics, nonwovens or fabrics. These may be in particular cellulose, polyester and / or polyamide fibers. Here, the cellulose fibers are of particular value, especially if they are in the form of cotton or viscose fibers. Nevertheless, the method is also suitable for fibers based on cellulose esters, in particular cellulose acetates of very different degrees of acetylation.

The object of the present invention was also to propose a suitable preparation process for the polyolefin fibers according to the invention which are dyed with vat dyes. Thus, the invention also relates to an advantageous process for the production of colored polyolefin fibers or colored textiles based on the colored polyolefin fibers, as described extensively above, after which the polyolefin Polyolefin fiber-based fibers or textiles are subjected to a plasma treatment prior to dyeing with vat dyes. The coloring of the polyolefin fibers with vat dyes is carried out according to the pigment-pad method. The plasma treatment takes place in the form already treated above, ie an oxygen or air plasma treatment is carried out. In this case, the plasma treatment is carried out until the desired state has been established or the particular values of the light fastness, wash fastness and rub fastness which characterize the dyed polyolefin fibers according to the invention have been established.

The advantages of the process according to the invention can be seen in the fact that the polypropylene fiber materials subjected to prior activation of a vat dyeing have outstanding fastness properties after the dye fixation, with simultaneously deep and brilliant hues. Such values were not achievable by the previously known method. A further advantage of the invention lies in the possibility of dyeing fiber blends of polypropylene, in particular cellulose fiber materials, in one step in the context of the invention.

It has been found that in the case of the polyolefin fibers according to the invention, the color yield in the dyeing can be increased by at least 55%, in particular by at least 120%, compared with the non-plasma-treated polyolefin fiber.

The invention will be explained in more detail below with reference to various examples. In particular, the experimental parameters of the process as well as the color depths and fastnesses achieved in the final process product are described in more detail.

Example 1:

A polypropylene fabric having a basis weight of 130 g / m ² each in the dimension of 30 cm (warp) x 15 cm (weft) is used. The fabric is prefixed at 130 ° C for 30 seconds in a suitable tenter. Subsequently, the fixed tissue is subjected to a plasma treatment using the following parameters: Plasma reactor "Domino" of the company Buck Plasma-Electronic (low pressure plasma), Power: 200 W / s Gas pressure: 80 Pa Base pressure: 40 Pa Process gas stream: 160 sccm of oxygen Electrode gap: 8 cm duration: 5 min Dye liquor: 43 g / l vat dye) Indanthren colloisol brands from BASF AG Ludwigshafen) 2 g / l dispersing agent Padding of the dye liquor onto the polypropylene fabric by means of a padder: 1.4 bar contact pressure with approx. 70% pinch effect, 20 ° C, Between Dry: 80 ° C / 30 seconds in a laboratory dryer type LTE from Mathis, Switzerland) Superheated steam fixation: 130 ° C / 1 min / 5% humidity in a steamer (type DHE from Mathis, Switzerland) To wash: 3 x at 70 ° C in a Thermostatisierbad with Zwischenschleudem. <u> Table 1: </ u> (color depths of the chopped polypropylene fabric without and with plasma pre-treatment) dye
CI = Color Index-No. K / S (color depth) without plasma pretreatment K / S (color depth) with plasma pre-treatment CI Vat Yellow 1 2.9 6.4 CI Vat Orange 9 2.7 7.0 CI Vat Red 32 4.9 9.3 CI Vat Blue 4 3.4 9.5 CI Vat Blue 14 2.9 9.7 CI Vat Blue 5 (Indigo) 1.3 3.4 CI Vat Blue 20 2.6 7.6 CI Vat Blue 16 3.1 9.4 CI Vat Brown 84 1.4 2.2 CI Vat Black 9 1.9 4.2

Measurement of color depth (K / S value) at the following wavelengths: Yellow: 470 nm Orange: 470 nm Red: 460 nm Blue: 580 nm Brown: 450 nm Black: 570 nm

• Prüfung A1M mit Mehrfaser-Begleitgewebe
• 40 °C / 150 ml / 45 min / 10 Stahlkugeln
• 4 g/l Skip-Waschmittel (ohne opt. Aufheller)

Tabelle 2: (Waschechtheitsnoten für die Färbungen auf Polypropylengewebe) Farbstoff Wolle Acryl PES PA 6.6 Bw 2,5 Acetat Änderung der Farbe C.I. Vat Yellow 1, Plasma 4 - 5 4 - 5 4 - 5 5 C.I. Vat Yellow 4 - 5 4 - 5 4 4 - 5 4 4 - 5 C.I. Vat Orange 9, Plasma 4 - 5 5 C.I. Vat Orange 9 3 C.I. Vat Red 32, Plasma 4 - 5 4 - 5 5 C.I. Vat Red 32 4 - 5 4 - 5 4 - 5 4 - 5 C.I. Vat Blue 4, Plasma 4 - 5 C.I. Vat Blue 4 4 C.I. Vat Blue 14, Plasma 4 - 5 4 - 5 5 C.I. Vat Blue 14 4 - 5 C.I. Vat Blue 5, Plasma 4 - 5 4 - 5 C.I. Vat Blue 5 4 - 5 4 - 5 C.I. Vat Blue 20, Plasma 4 - 5 C.I. Vat Blue 20 4 - 5 4 - 5 4 - 5 C.I. Vat Blue 16, Plasma 5 C.I. Vat Blue 16 4 C.I. Vat Brown 84, Plasma 4 - 5 5 C.I. Vat Brown 84 4 - 5 3 - 4 C.I. Vat Black 9, Plasma 4 - 5 5 C.I. Vat Black 9 4 - 5 3 - 4 Determination of wash fastness according to EN ISO 105-C08, 1997:

• Exam A1M with multi-fiber accompanying fabric
• 40 ° C / 150 ml / 45 min / 10 steel balls
• 4 g / l Skip detergent (without optical brightener)

<u> Table 2: </ u> (wash fastness grades for the dyeings on polypropylene fabric) dye Wool acrylic PES PA 6.6 bw 2.5% acetate Change of color CI Vat Yellow 1, plasma 4 - 5 4 - 5 4 - 5 5 CI Vat Yellow 4 - 5 4 - 5 4 4 - 5 4 4 - 5 CI Vat Orange 9, Plasma 4 - 5 5 CI Vat Orange 9 3 CI Vat Red 32, Plasma 4 - 5 4 - 5 5 CI Vat Red 32 4 - 5 4 - 5 4 - 5 4 - 5 CI Vat Blue 4, plasma 4 - 5 CI Vat Blue 4 4 CI Vat Blue 14, plasma 4 - 5 4 - 5 5 CI Vat Blue 14 4 - 5 CI Vat Blue 5, plasma 4 - 5 4 - 5 CI Vat Blue 5 4 - 5 4 - 5 CI Vat Blue 20, plasma 4 - 5 CI Vat Blue 20 4 - 5 4 - 5 4 - 5 CI Vat Blue 16, plasma 5 CI Vat Blue 16 4 CI Vat Brown 84, Plasma 4 - 5 5 CI Vat Brown 84 4 - 5 3 - 4 CI Vat Black 9, Plasma 4 - 5 5 CI Vat Black 9 4 - 5 3 - 4

• Gerät: Xenotest Beta LM der Fa. Alias
• Heißllchtechtheit bei 50 °C
• Prüfung auf Mindestanforderung des Lichtechtheitstyp 5
• Bewertung nach 144 Stunden Belichtung
• Alle Färbungen nach Plasmavorbehandlung

Tabelle 3: (Lichtechtheitsnoten der plasmabehandelten und küpengefärbten PP-Gewebe) Färbung auf PP-Gewebe Lichtechtheitsnote C.I. Vat Yellow 1 5 C.I. Vat Orange 9 5 C.I. Vat Red 32 6-7 C.I. Vat Blue 4 7 C.I. Vat Blue 14 6 C.I. Vat Blue 5 (Indigo) 4 C.I. Vat Blue 20 5 C.I. Vat Blue 16 6 C.I. Vat Brown 84 6 C.I. Vat Black 9 6 Determination of lightfastness according to DIN EN ISO 105-B02, July 2002:

• Device: Xenotest Beta LM from the company Alias
• Heat-fastness-fastness at 50 ° C
• Test for minimum lightfastness requirement 5
• Review after 144 hours exposure
• All stains after plasma pretreatment

<u> Table 3: </ u> (Light fastness grades of plasma-treated and vat-dyed PP fabrics) Staining on PP tissue Light fastness rating CI Vat Yellow 1 5 CI Vat Orange 9 5 CI Vat Red 32 6-7 CI Vat Blue 4 7 CI Vat Blue 14 6 CI Vat Blue 5 (Indigo) 4 CI Vat Blue 20 5 CI Vat Blue 16 6 CI Vat Brown 84 6 CI Vat Black 9 6

• Begleitgewebe Baumwolle, ISO 105 - F09

Tabelle 4: (Reibechtheitsnoten der plasmabehandelten und küpengefärbten PP-Gewebe) Färbung auf PP-Gewebe trocken
ohne Plasma trocken
mit Plasma nass
ohne Plasma nass
mit Plasma C.I. Vat Yellow 1 3 4 2-3 2 C.I. Vat Orange 9 3-4 4-5 2-3 2-3 C.I. Vat Red 32 3 4-5 3 3 C.I. Vat Blue 4 3 3-4 3 3 C.I. Vat Blue 14 3-4 4 3 3-4 C.I. Vat Blue 5 (Indigo) 4 3-4 4 4 C.I. Vat Blue 20 5 4-5 2-3 3-4 C.I. Vat Blue 16 5 3 1-2 1-2 C.I. Vat Brown 84 5 4-5 5 5 C.I. Vat Black 9 3-4 4-5 4-5 4-5 Determination of rubbing fastness according to EN ISO 105 - X12

• Cotton accompanying fabric, ISO 105 - F09

<u> Table 4: </ u> (rubbing fastness marks of plasma-treated and vat-dyed PP fabrics) Staining on PP tissue dry
without plasma dry
with plasma wet
without plasma wet
with plasma CI Vat Yellow 1 3 4 2-3 2 CI Vat Orange 9 3-4 4-5 2-3 2-3 CI Vat Red 32 3 4-5 3 3 CI Vat Blue 4 3 3-4 3 3 CI Vat Blue 14 3-4 4 3 3-4 CI Vat Blue 5 (Indigo) 4 3-4 4 4 CI Vat Blue 20 5 4-5 2-3 3-4 CI Vat Blue 16 5 3 1-2 1-2 CI Vat Brown 84 5 4-5 5 5 CI Vat Black 9 3-4 4-5 4-5 4-5

Example 2:

A nonwoven fabric of the composition 70% viscose / 30% polypropylene with a basis weight of 60 g / m ² in the dimension of 40 cm x 30 cm is used. The plasma treatment was carried out analogously to example 1. The thermofusion was carried out in a laboratory dryer type LTE from Mathis, Switzerland at 175 ° C. for 2 min and a calibration gap of 2 mm. Dye fleets of CI Vat Yellow 1, CI Vat Red 32 and CI Vat Blue 14 are padded onto the nonwoven at room temperature using a padder (contact pressure 1.0 bar). The composition and concentration of the dye liquors is analogous to Example 1. It is pre-dried for 1 min at 80 ° C and then fixed in hot steam under the conditions described in Example 1. The dyeing is rinsed 3 times at 70 ° C. <u> Table 5: </ u> (color depths of the veiled nonwoven fabrics of viscose / polypropylene without and with plasma pre-treatment) dye
CI = Color Index-No. K / S (color depth)
without plasma pretreatment K / S (color depth)
with plasma pretreatment CI Vat Yellow 1 0.27 0.40 CI Vat Red 32 0.62 0.75 CI Vat Blue 14 0.40 0.55

Example 3:

A nonwoven fabric of composition 70% polypropylene / 30% polyethylene having a basis weight of 50 g / m ² in the dimension of 40 cm x 30 cm is used. The plasma treatment was carried out analogously to Example 1. The thermofusion was carried out analogously to Example 2, but with a 3 mm calibration gap. Using a padder, a dye liquor of CI Vat Yellow 1 (composition and concentration see Example 2) was padded onto the nonwoven at room temperature (contact pressure 1.0 bar). The further work steps were carried out analogously to Example 2. <u> Table 6: </ u> (color depths of the polypropylene / polyethylene polyethylene pulp dyed non-woven and with plasma pre-treatment) dye
CI = Color Index-No. K / S (color depth)
without plasma pretreatment K / S (color depth)
with plasma pretreatment CI Vat Yellow 1 0.85 1.13

Example 4:

It is used a prefixed polypropylene fabric analogous to the specification mentioned in Example 1. The material was plasma treated according to the parameters shown in Example 1. Plasma-treated tissue pieces were each treated with the vat C.I. Vat Red 32, C.I. Vat Blue 4 and C.I. Vat Yellow 1 printed in a planographic printing process and the obtained color depths and fastness compared with printing the same dyes on non-plasma-treated polypropylene fabric.

The printing tests were based on the following parameters: Thickener: Meyprogum R-600, Kemmehlether, a (strain: 14%) Printing paste: 59 g strain 40 g demineralized water 1 g vat dye (powder) Lithographic printing: Squeegee pressure setting «3» Doctor blade diameter: 1 cm Squeegee speed: setting "100" 1 squeegee pull Dry: 40 ° C / 5 min / 1500 rpm Fix: Superheated steam 130 ° C / 10 min / fan setting "50" washing after printing: 3 times 90 ° C / 2-3 min with intermediate spin <u> Table 7: </ u> (color depths of polypropylene fabric printed with vat dyes without and with plasma pre-treatment) Vat Red 32 Vat Red 32 Plasma Vat Blue 4 Vat Blue 4 Plasma Vat Yellow 1 Vat Yellow 1 Plasma 0.87 2.03 0.27 1.23 0.4 1.33 Wash fastness 40 ° C Vat Red 32 Vat Red 32 Vat Blue 4 Vat Blue 4 Vat Yellow 1 Vat Yellow 1 plasma plasma plasma Wool 4-5 4-5 5 5 5 5 acrylic 4 4-5 3-4 4-5 4-5 4-5 PET 4 4-5 3-4 4-5 5 5 PA 6.6 2-3 3 4 4-5 3-4 4 bw 4 4 4 4-5 5 4-5 2.5% acetate 2-3 3 4 4-5 3 3-4 Change the color 4-5 4-5 4 4 4-5 4-5 Pressure on PP fabric Light fastness rating CI Vat Red 32 6-7 CI Vat Blue 4 7 CI Vat Yellow 1 5

Claims (14)

1. A method of producing coloured polyolefin fibres or coloured textiles based on coloured polyolefin fibres, whereupon the fibres or textiles are plasma-treated before colouring, characterised in that the polyolefin fibres or the textiles based on polyolefin fibres are treated with oxygen or air plasma until the polyolefins in the fibres or textile, in a surface layer of 6 nm on the fibres, contain at least 10% interstitial oxygen as measured by ESCA analysis (electron spectroscopy for chemical analysis), after which the polyolefin fibres or the textile based on polyolefin fibres is coloured with vat dyes by pigment padding, wherein the resulting coloured polyolefin fibres or coloured textiles based on coloured polyolefin fibres are characterised by the following features:

   - a light-fastness to DIN EN ISO 105-B02 (at 50°C and 144 h exposure) of at least 5,

   - a wash-resistance to DIN EN ISO 105-C08C of at least 4 and

   - a resistance to rubbing to DIN EN ISO 105-X12 of at least 3 when dry.
2. A method according to claim 1, characterised in that the fibres or textile is coloured by HT padding.
3. A method according to claim 1 or claim 2, characterised by use of a vat dyestuff in the form of anthraquinone.
4. A method according to claim 3, characterised in by use of indanthrene blue dye.
5. A method according to at least one of claims 1 to 4, characterised in that the polyolefin in the fibres is in the form of polyethylene, polypropylene and/or polybutylene.
6. A method according to at least one of claims 1 to 5, characterised in that the textile is in the form of a woven or knitted fabric, a non-woven or a cloth.
7. Polyolefin fibres dyed with vat dyestuffs or coloured textiles on the basis of coloured polyolefin dyes, obtainable by the method according to at least one of claims 1 to 6 and having the following features:

   - a light-fastness to DIN EN ISO 105-B02 (at 50°C and 144 h exposure) of at least 5,

   - a wash-resistance to DIN EN ISO 105-C08C of at least 4 and

   - a resistance to rubbing to DIN EN ISO 105-X12 of at least 3 when dry.
8. Fibres or textiles according to claim 7, characterised in that the light-fastness is at least about 6 and/or the resistance to washing is at least 4 to 5.
9. Fibres or textiles according to claim 7 or claim 8, characterised in that the fibres are coloured with a vat dye in the form of an anthraquinone dye, especially indanthrene blue.
10. Fibres or textiles according to at least one of claims 7 to 9, characterised in that the polyolefin is in the form of polyethylene, polypropylene and/or polybutylene.
11. Fibres or textiles according to at least one of claims 7 to 10, characterised in that the dyestuff yield, compared with polyolefin fibres not treated with plasma, is increased by at least 55%, especially by at least 120%.
12. Use of the fibres according to at least one of claims 7 to 11 for producing a textile, especially in the form of a woven or knitted fabric, a non-woven or a cloth.
13. Use according to claim 12, characterised in that cellulose, polyester and/or polyamide fibres are present in addition to the polyolefin fibres.
14. Use according to claim 13, characterised in that the cellulose is in the form of cotton or viscose fibres or a cellulose ester, especially cellulose acetate.