WO2006003125A1

WO2006003125A1 - Process for the production of high visibility markers or high visibility clothing

Info

Publication number: WO2006003125A1
Application number: PCT/EP2005/052978
Authority: WO
Inventors: Urs Lauk; Hanspeter Meyer
Original assignee: Ciba Spezialitaetenchemie Holding AG; Huntsman Advanced Materials Switzerland GmbH; Ciba SC Holding AG
Current assignee: Huntsman Advanced Materials Switzerland GmbH; BASF Schweiz AG
Priority date: 2004-07-07
Filing date: 2005-06-27
Publication date: 2006-01-12
Anticipated expiration: 2007-01-07
Also published as: TW200615336A

Abstract

The invention relates to a process for dyeing textile fabrics of hydrophobic or hydrophilic fibre material intended for use as high visibility markers or high visibility clothing according to standard DIN EN 471, by introducing a fluorescent dye preparation into the fibres or applying such a preparation thereto, wherein the dye preparation comprises at least 80 % by weight, based on the total amount of dye, of a compound of formula (1), wherein R1 is hydrogen, methyl or chlorine.

Description

Process for the production of high visibility markers or high visibility clothing

The present invention relates to a process for dyeing hydrophobic and hydrophilic fibre material in order to produce high visibility markers or high visibility clothing.

Fluorescent dyes can in principle be used in the production of warning clothing, such as warning vests, jackets and trousers, as well as warning markers, for example armbands, belts and hat covers. However, this requires a high luminous intensity and adequate in-use fastness properties; in addition, the dyes should exhibit a precisely defined orange-red colour.

Standard DIN EN 471 lays down the criteria for high visibility or warning clothing, which are to ensure their conspicuous appearance and hence their warning action.

The requirements of that standard have hitherto been met predominantly by mixtures of fluorescent red and yellow dyes; however, such mixtures frequently undergo a reduction in or loss of fluorescence, so that the required high luminous intensity is not achieved.

It has now been found that, in the case of hydrophobic and hydrophilic fibre material, the coloristic specifications of standard DIN EN 471 are met by dyeing using a single fluorescent dye or using dye mixtures comprising a high proportion of that dye.

The present invention relates to a process for dyeing textile fabrics of hydrophobic or hydrophilic fibre material intended for use as high visibility markers or high visibility clothing according to standard DIN EN 471, by introducing a fluorescent dye preparation into the fibres or applying such a preparation thereto, wherein the dye preparation comprises at least 80 % by weight, based on the total amount of dye, of a compound of formula (1)

wherein Ri is hydrogen, methyl or chlorine.

The compounds of formula (1) are known and are described, for example, in DE 2844299. In the process according to the invention there is preferably used a dye preparation compri¬ sing a compound of formula (1a)

The dye preparations according to the invention preferably comprise at least 90 % by weight, especially at least 95 % by weight and more especially at least 99 % by weight, based on the total amount of dye, of a compound of formula (1 ).

Very special preference is given to dye preparations that comprise the compound of formula (1) as the only dye, that is to say dye preparations comprising 100 % by weight, based on the total amount of dye, of a compound of formula (1).

Preferably, the dye preparation according to the invention additionally comprises a UV absorber.

Preferred UV absorbers are 2-(2-hydroxyphenyl)-2H-benzotriazoles.

The amount of UV absorber is advantageously from 0.001 to 10.0 % by weight, preferably from 0.01 to 5.0 % by weight and especially from 0.1 to 1.0 % by weight, based on the amount of fibre material to be dyed.

The dye preparations according to the invention are advantageously prepared by grinding the dyes so that their particle size is on average from 0.1 to 10 microns. The grinding can be carried out in the presence of dispersants. For example, the dried dye is ground with a dispersant or is kneaded into paste form with a dispersant and then dried in vacuo or by atomisation.

The preparations so obtained can be used, after the addition of water, to prepare printing pastes and dyebaths. The dye preparations according to the invention can be used in the dyeing and printing of semi-synthetic and, especially, synthetic hydrophobic fibre materials, more especially textile materials. Textile materials composed of blends that contain such semi-synthetic or synthetic hydrophobic textile materials can likewise be dyed or printed using the dye preparations according to the invention.

Suitable semi-synthetic textile materials are especially cellulose 214 acetate and cellulose triacetate.

Synthetic hydrophobic textile materials consist especially of linear, aromatic polyesters, for example those of terephthalic acid and glycols, especially ethylene glycol, or condensation products of terephthalic acid and 1,4-bis(hydroxymethyl)cyclohexane; of polycarbonates, for example those from α,α-dimethyl-4,4-dihydroxy-diphenylmethane and phosgene, and of fibres based on polyvinyl chloride and on polyamide.

The process according to the invention is preferably used in the dyeing of polyesters and polyester blends.

The application of the dye preparations according to the invention to the textile materials is carried out in accordance with known dyeing procedures. For example, polyester fibre materials are dyed in the exhaust process from aqueous dispersion in the presence of customary anionic or non-ionic dispersants and optionally customary swelling agents (carriers) at temperatures of from 80 to 140⁰C. Cellulose 2^ΛA acetate is dyed preferably at approximately from 65 to 85⁰C and cellulose triacetate at temperatures up to 115⁰C. The dye preparations according to the invention can also be used successfully in the dyeing of polyester blends, for example polyester/cellulose fibre, polyester/polyamide or polyester/- polyurethane blends.

The dye preparations according to the invention are suitable for dyeing in accordance with the thermosol process, in the exhaust and continuous process and for printing processes. The exhaust process is preferred. The liquor ratio is dependent on the nature of the appara¬ tus, the substrate and the form of make-up. It may, however, be selected within a wide range, for example from 1 :4 to 1 : 100, but is preferably from 1 :6 to 1:25. - A -

The said textile material can be in a variety of processing forms, for example in the form of a fibre, yarn or nonwoven, or in the form of a woven fabric or knitted fabric.

For printing, the customary thickeners will be used, for example modified or unmodified natural products, for example alginates, British gum, gum arabic, crystal gum, locust bean flour, tragacanth, carboxymethylcellulose, hydroxyethylcellulose, starch, or synthetic products, for example polyacrylamides, polyacrylic acid or copolymers thereof, or polyvinyl alcohols.

The dyeings produced by the process according to the invention fulfil the conditions of standard DIN EN 471, even after irradiation with xenon light.

The dye preparations according to the invention impart to the mentioned materials, especially to polyester material, dyeings having good in-use fastness properties and, especially, high thermal stability.

The invention relates also to the use of a dye preparation comprising at least 80 % by weight, based on the total amount of dye, of a compound of formula (1) according to claim 1 in the production of high visibility markers or high visibility clothing.

The compounds of formula (1 ) are also suitable for the production of mass-coloured plastics or polymeric colour particles. The process for the production of coloured plastics or polymeric colour particles comprises mixing together a high molecular weight organic material and a tinctorially effective amount of a dye preparation according to the invention. The colouring of high molecular weight organic substances with the dye preparation is carried out, for example, by mixing the dye preparation into those substrates using mixing or grinding apparatus and homogenising the mixture, with the result that the dye preparation becomes finely distributed in the high molecular weight material. The high molecular weight organic material with the admixed dye preparation is then processed using processes known perse, for example calendering (especially in the colouring of PVC), compression moulding, extrusion, coating, spinning (wet and dry spinning processes, especially in the colouring of acetate, polyacrylonitrile and viscose, melt spinning processes), casting or injection moulding, whereby the coloured material acquires its final form. It is also possible for the admixing of the dye preparation to be carried out immediately prior to the actual processing step, for example by continuously feeding a pulverulent dye preparation and, at the same time, a granulated or pulverulent high molecular weight organic material, and optionally also additional ingredients, for example additives, directly into the intake zone of an extruder, where mixing takes place just before processing. In general, however, it is preferable for the dye preparation to be mixed into the high molecular weight organic material beforehand, because more evenly coloured substrates can be obtained.

Preference is given to the colouring of thermoplastic plastics, especially in the form of fibres, granules or moulded articles, for example containers for solid or liquid substances, for example bottles. Preferred high molecular weight organic materials suitable for colouring according to the invention are very generally polymers having a dielectric constant of > 2.5, especially polyester, polycarbonate (PC), polystyrene (PS), polymethyl methacrylate (PMMA), polyamide, polyethylene, polypropylene, styrene/acrylonitrile (SAN) or acrylo- nitrile/butadiene/styrene (ABS). Special preference is given to polyester, polymethyl meth¬ acrylate and polycarbonate. Very special preference is given to linear aromatic polyesters, which can be obtained by polycondensation of terephthalic acid or naphthalene-2,6- dicarboxylic acid and glycols, especially ethylene glycol, or condensation products of terephthalic acid and 1,4-bis(hydroxymethyl)cyclohexane, for example polyethylene tereph- thalate (PET), polytrimethylene terephthalate (PTT), polyethylene naphthalene-2,6- dicarboxylate (PEN) or polybutylene terephthalate (PBTP); also polycarbonates, for example those from α,α-dimethyl-4,4-dihydroxy-diphenylmethane and phosgene.

The Examples which follow illustrate the invention.

Example 1 :

1200.00 g of polyester granules (PET Arnite D04-300, DSM) are predried at 13O⁰C for

4 hours and then mixed homogeneously with

0.25 g of the dye of formula (1a) in a "roller rack" mixing apparatus for 15 minutes at 60 revolutions per minute.

The homogeneous mixture is extruded in an extruder (twin screw 25 mm from CoIMn,

D-85560 Ebersberg) with 6 heating zones at a maximum temperature of 275⁰C, cooled with water, granulated in a granulator (Turb Etuve TE 25 from MAPAG AG, CH-3001 Bern) and then dried at 130⁰C for 4 hours. The resulting orange-red-col oured polyester granules exhibit good allround properties after processing, especially very good light fastness and high-temperature light fastness.

Example 2:

4 hours and then mixed homogeneously with

0.56 g of the dye of formula (1a) and

3.60 g of a UV absorber of the formula

in a "roller rack" mixing apparatus for 15 minutes at 60 revolutions per minute.

The homogeneous mixture is extruded in an extruder (twin screw 25 mm from Collin,

D-85560 Ebersberg) with 6 heating zones at a maximum temperature of 275⁰C, cooled with water, granulated in a granulator (Turb Etuve TE 25 from MAPAG AG, CH-3001 Bern) and then dried at 13O⁰C for 4 hours.

The resulting orange-red-coloured polyester granules exhibit good allround properties after processing, especially very good light fastness and high-temperature light fastness.

Claims

What is claimed is:

1. A process for dyeing textile fabrics of hydrophobic or hydrophilic fibre material, intended for use as high visibility markers or high visibility clothing according to standard DIN EN 471 , by introducing a fluorescent dye preparation into the fibres or applying such a preparation thereto, wherein the dye preparation comprises at least 80 % by weight, based on the total amount of dye, of a compound of formula (1 )

wherein Ri is hydrogen, methyl or chlorine.

2. A process according to claim 1 wherein the dye preparation comprises at least 80 %, based on the total amount of dye, of a compound of formula (1a)

3. A process according to claim 1 wherein the fluorescent dye preparation is applied by the exhaust process.

4. A process according to claim 1 wherein the hydrophobic fibre material is polyester or a polyester blend.

5. A process according to claim 1 wherein the dye preparation comprises at least 99 %, based on the total amount of dye, of a compound of formula (1 ).

6. A process according to claim 1 wherein the dye preparation comprises a UV absorber.

7. A process according to claim 6 wherein the UV absorber is a 2-(2-hydroxyphenyl)-2H- benzotriazole.

8. Use of a dye preparation comprising at least 80 % by weight, based on the total amount of dye, of a compound of formula (1) according to claim 1 in the production of high visibility markers or high visibility clothing.

9. A process for the production of mass-coloured plastics or polymeric colour particles, which comprises mixing together a high molecular weight organic material and a tinctorially effec¬ tive amount of a dye preparation comprising at least 80 % by weight, based on the total amount of dye, of a compound of formula (1).