EP1761605A1

EP1761605A1 - Bridged bisanthraquinone dye derivatives

Info

Publication number: EP1761605A1
Application number: EP05756709A
Authority: EP
Inventors: Susana Basolas Tena; Pedro Jesús GONZALEZ MARTINEZ; Joan Jesús TUGUES ROURE
Original assignee: Clariant International Ltd
Current assignee: Clariant Finance BVI Ltd
Priority date: 2004-06-25
Filing date: 2005-06-24
Publication date: 2007-03-14
Also published as: TW200613452A; CN1997710A; WO2006003120A1

Abstract

The present invention relates to a compound of the formula (I) wherein the substituents have the meaning as given in claim 1, its production and its use in mass coloration which provides dyed polymers with excellent overall fastness properties.

Description

Bridged Bisanthraquinone Dye Derivatives

The present invention relates to novel colorants based on a bridged bisanthraquinone and its production. The present invention further relates the use of novel colorants based on a bridged bisanthraquinone dye derivative and to a method for mass coloring of polymers.

The presently used colorants lack in heat stability, color fastness and thermostability. Furthermore the presently used colorants are not stable under the conditions the dyed polymers are subjected to.

The object of the present invention therefore is to provide method for mass coloration of polymers with very high fastness levels and very good thermostability properties.

The present invention relates to a compound of the formula (T)

wherein R¹ signifies H, C₁ to Cio alkyl, Ci to do alkenyl, Ci to Qo alkoxy, cyclic C₅ to Cio alkyl, -CH₂-aryl, - CH₂CH₂-aryl, substituted Ci to Ci₀ alkyl, substituted Ci to Cio alkenyl, substituted Ci to Ci₀ alkoxy, substituted cyclic C₅ to Cio alkyl, substituted -CH₂-aryl, substituted -CH₂CH₂-aryl, -S(O)₂-aryl, -S(O)₂-aryl wherein the aryl moiety is substituted, R³-C(O)-halogene, R³-halogene, R³-(CH₂)₁.₂-halogene, wherein R³ signifies Ci to Ci₀ alkyl, Ci to Ci₀ alkenyl, cyclic C₅ to Ci₀ alkyl, -CH₂-aryl, - CH₂CH₂-aryl, substituted Ci to Cio alkyl, substituted Ci to Qo alkenyl, substituted cyclic C₅ to Cio alkyl, substituted -CH₂-aryl, substituted , -CH₂CH₂-aryl₃

R² signifies H, Ci to Ci₀ alkyl, Ci to Ci₀ alkenyl, Ci to Ci₀ alkoxy, cyclic C₅ to Ci₀ alkyl, -CH₂-aryl, substituted Ci to Ci₀ alkyl, substituted Ci to Ci₀ alkenyl, substituted Ci to Cio alkoxy, substituted cyclic C₅ to Ci₀ alkyl, substituted -CH₂-aryl, -S-aryl, -S-aryl wherein the aryl moiety is substituted, -O-aryl, -O-aryl wherein the aryl moiety is substituted; -S- aryl, -S-aryl wherein the aryl moiety is substituted, -0-(CH₂)o -₂-aryL, substituted -O-(CH₂)₀.₂-aryl, with the proviso that not both, R¹ and R² have the meaning of H at the same time.

The alkyl groups, alkenyl groups, cyclic alkyl groups, and/or the alkoxy groups may be substituted by Ci to C₄ alkyl, Ci to C₄ alkenyl, Ci to C₄ alkoxy, CN, NO₂, OH, Cl, Br, or F. By preference the subtituents at the alkyl groups, alkenyl groups, cyclic alkyl groups and/or the alkoxy groups are C₁ to C₂ alkyl, Ci to C₂ alkenyl, Ci to C₂ alkoxy, CN, OH or Cl and the most preferred subtituents at the alkyl groups, alkenyl groups, cyclic alkyl groups and/or the alkoxy groups are CN, OH or Cl.

The alkyl groups, alkenyl groups, cyclic alkyl groups, and/or the alkoxy groups may be substituted by aryl-moieties.

The aryl-moiety which may be substituted or unsubsituted in the -CH₂-aryl-group are phenyl or naphtyl or a bicyclic or monocyclic ringsystem which may comprise heteroatoms consisting of up to 12 atoms, preferrably from 5 to 12 atoms, more preferred from 5 to 10 atoms. Prefferred heteroatoms are S and/or N and/or O. The preferred aryl moties are phenyl or naphtyl. The more preferred aryl moiety is phenyl.

When the aryl-moiety is substituted the preferred substituents are Ci to C₄ alkyl, Ci to C₄ alkenyl, Ci to C₄ alkoxy, CN, NO₂, OH, Cl, Br, or F, more preferred C₁ to C₂ alkyl, Ci to C₂ alkenyl, C₁ to C₂ alkoxy, NO₂, CN, OH or Cl and the most preferred subtituents of the aryl-moieties are ethoxy andmethoxy.

Halogene signifies Br or Cl.

In preferred compounds of the formula (I)

R¹ signifies H, Ci to Ci₀ alkyl, Ci to Qo alkenyl, cyclic C₅ to do alkyl, -CH₂-aryl, - CH₂CH₂-OTyI₅ substituted Ci to Ci₀ alkyl, substituted Ci to Ci₀ alkenyl, substituted cyclic C₅ to Qo alkyl, substituted -CH₂-aryl, substituted -CH₂CH₂-aryl, -S(O)₂-aryl, -S(O)₂-aryl wherein the aryl moiety is substituted, R³-C(O)-halogene, R³-halogene, R³-(CH₂)i_₂- halogene, wherein R³ signifies Ci to Cio alkyl, Ci to Ci₀ alkenyl, cyclic C₅ to

Cio alkyl, -CH₂-aryl, - CH₂CH₂-aryl, substituted Ci to Cio alkyl, substituted Ci to

Cio alkenyl, substituted cyclic C₅ to Ci₀ alkyl, substituted -CH₂-aryl, substituted , -CH₂CH₂- aryl, R² signifies H, Ci to Ci₀ alkoxy, substituted C₁ to Ci₀ alkoxy, -S-aryl, — S-aryl wherein the aryl moiety is substituted, -O-aryL, -O-aryl wherein the aryl moiety is substituted; -0-(CH₂)o -₂-aryl, -O-(CH₂)₀ -₂-aryl wherein the aryl moiety is substituted,

In more preferred compounds of the formula (I) R¹ signifies H, Ci to Ci₀ alkyl, Ci to Ci₀ alkenyl, cyclic C₅ to Ci₀ alkyl, -CH₂-aryl, substituted C₁ to Cio alkyl, substituted Ci to Cio alkenyl, substituted cyclic C₅ to Cio alkyl, substituted -CH₂-aryl, R² signifies H, Ci to Ci₀ alkoxy, substituted Ci to Ci₀ alkoxy, -O-(CH₂)₀.₂-aryl, substituted -O-(CH₂)₀.₂-aryl, with the proviso that not both, R¹ and R² have the meaning of H at the same time.

In even more preferred compounds of the formula (I) R¹ signifies H, C₄ to C₁₀ alkyl, -CH₂-aryl, substituted C₄ to C₁₀ alkyl, substituted -(CH₂)₀ -2-aryl, R² signifies H, C₁ to C₄ alkoxy, substituted C₁ to C₄ alkoxy, -0-(CH₂)o -2-aryl, substituted -O-(CH₂)₀ - 2-aryl, with the proviso that not both, R¹ and R² have the meaning of H at the same time.

In the most preferred compounds of the formula (T)

R¹ signifies H, C₄ to Ci₀ alkyl, -CH₂-phenyl, -CH₂-phenyl substituted by OH, CN, methoxy or ethoxy,

R² signifies H, C₃ to C_1O alkyl, methoxy or ethoxy, with the proviso that not both, R¹ and R² have the meaning of H at the same time.

By preference R² signifies H or Ci to C₄ alkoxy or substituted Ci to C₄ alkoxy, wherein the preferred alkoxy group is methoxy or ethoxy. In further preferred compound R¹ does not have the meaning of H.

The invention further relates to a process for the preparation of compounds of the formula (I).

In one aspect of the invention the process for the preparation of compounds of the formula (I) includes the reaction of a compound of the formula (A)

with two equivalents of a compound of the formula R¹ -X, wherein X signifies a leaving group as for example a halogene atom, preferably chlorine or bromine, wherein a compound of formula (T)

is formed

In a further aspect of the invention the process for the preparation of compounds of the formula (I) includes the reaction of a compound of the formula (B) (CI. Acid Blue 127:1)

with a strong alkaline solution as for example with NaOH or KOH in methanol followed by the addition of a compound of the formula R²-H, wherein X signifies R² signifies Ci to C₄ alkoxy or substituted Ci to C₄ alkoxy, wherein the preferred alkoxy group is methoxy or ethoxy, followed by the addition of two equivalents of a compound of the formula R^X, wherein X signifies a leaving group as for example a halogene atom, preferably chlorine or bromine, wherein a compound of formula (I)

is formed.

In a further aspect of the invention the process for the preparation of compounds of the formula (T) includes the reaction of a compound of the formula (B)

with a strong alkaline solution as for example with NaOH or KOH in methanol followed by the addition of a compound of the formula R²-X, wherein X signifies a halogene atom, preferably chlorine or bromine, or an other leaving group as for example a toluenesulfonyl group, by preference X signifies chlorine or bromine, followed by the addition of two equivalents of a compound of the formula R¹ -X, wherein X signifies a leaving group as for example a halogene, preferably chlorine or bromine, wherein a compound of formula (I)

is formed.

The invention further relates to the use of a compound of the formula (I) in mass coloration of polymers provides dyed polymers with the required properties.

Therefore the invention relates to a method for mass-dyeing a polymer using a as dyestuff, a compound of formula (I). The invention further relates to a mass-dyed polymer comprising, as dyestuff, a compound of formula (T).

The colorant used in the method of the present invention provides excellent compatibility with the polymer substrate, excellent heat stability and light fastness as required for mass coloring of polar and non-polar polymers. Polar polymers are for example polyamides, polyesters, polycarbonates and ABS; non-polar polymers are olefϊnic polymers such as polyethylene and polypropylene.

The present invention further relates to a method for dyeing polymers which comprises the steps of mixing polymer granules or polymer melts or polymer powders with the colorant by conventional methods and then forming objects with the mixture of the polymer and the dye according to the formula (I).

The mass-dyeing is carried out in conventional manner. The compounds of formula (I) and, if desired, in admixture with one or more other dyes indicated for the mass-dyeing of polyester, may be purified and ground in conventional manner prior to their incorporation.

The incorporation of the polymer into the polymer is made in a conventional manner like, e.g. by means of an extruder device.

When mixing the polymer with the dyestuff of formula (I), the dystuff may be used in solid form or in a liquid form which means that the dyestuff is dispersed or dissolved in appropriate solvent as for example a low melting polymer.

The mixing of the dyestuff(s) with low-melting polymer is suitably effected at low temperature, e.g. employing dry ice as coolant, and grinding them together to form a fine powder and, optionally, processing the powder through an extruder and forming chippings or a granulate from the extrudate.

Thereafter shaped objects and/or shaped articles are formed e.g. fibres, films, profiles, pipes, granules or powders are formed - for example, in melt spinning, injection or blow molding, extrusion, film blowing, stretch blow molding in a appropriate injection moulding or spinning maschine.

In one embodiment only the dyed polymer granules or polymer melts or polymer powders are used to form the desired objects.

In a second embodiment only a part of the polymer granules or polymer melts or polymer powders are dyed and are mixed with colorless (undyed) polymer granules or polymer melts or polymer powders before forming the objects. In this second embodiment the concentration of the dye in the dyed polymer granules or polymer melts or polymer powders is higher as the concentration in the final shaped objects and/or shaped articles. The dyed polymer granules or polymer melts or polymer powders of the second embodiment are so-called "master-batches". These so-called "master-batches" comprise generally 10 to 80% by weight of dyestuff, preferably 30 to 60% by weight of dyestuff. The color concentrates of the second embodiment, either in liquid form or in the pellet form (masterbatch) have to be mixed with the uncolored resin in a particular let-down ratio in order to achieve the desired color. The mixing can be done either by manual mixing, or, more commonly, by a batch-blend process using automated dosing equipment.

Liquid colors are normally pumped directly into the feed throat of the processing machine (e.g. an injection molding machine, a blow molding machine, a melt spinning system or the like) by using a small peristaltic pump.

By preference the use of masterbatches is the preferred method for coloring of plastics. Ease of handling and low costs compared to pre-colored resins are the main advantages for these products. Unlike liquid colors, the compatibility of masterbatches with the resin is excellent, since the carrier material of the masterbatch is in the most preferred cases identical with the resin.

An example of such automated dosing equipment for masterbatches is the volumetric feeding unit as represented by Figure 1 in WO2004/022633. The feeding unit comprises a resin feeder next to a masterbatch feeder, a mixer in a mixing area, a flap between the mixing unit and the hopper and a hopper mounted on an extruder or injection molder. The resin feeder, the masterbatch feeder, the mixer and the flap are controlled by a control unit, comprising a detector at the passage way from the hopper to the extruder or injection molder.

Masterbatches are commonly supplied in pellet or in micro-pellet form. There are few ways to produce a masterbatch. The first and most common way used by the masterbatch manufacturers is a so called one step process. During this process, pigments (or dyes), functional additives and the polymer carrier are mixed, the mixture is then processed through a dispersion unit, e.g. a co-rotating twin screw extruder.

The color concentrates (masterbatches) comprising the compound of formula (L) can also be obtained in a so called two step process, wherein in a first step, the masterbatch manufacturers produce a Single Pigment Concentrate (SPC) comprising the compound of formula (I). SPC is a masterbatch preparation containing only one pigment or dye (generally in very high concentration) fully dispersed in a resin carrier optionally comprising further additives. This first process step is very similar to the one step process.

In a second step, different SPCs are mixed together in order to achieve the required color specifications of the customer and to get the tailor made masterbatch. To reduce the pigment concentration, the SPCs are mixed together with some carrier resin. Since SPCs are already fully dispersed, only a mixing process is necessary. This can be performed for example with a single screw or twin screw extruder.

After addition of the master-batch, whether in powder, chippings or granulate form, to the undyed polymer, the resulting mix can be formed into shaped articles, such as films, foils, fibres or filaments, in conventional manner, e.g. by extrusion or spinning techniques, and such articles further processed, e.g. into yarn, cord, rope, woven, non- woven and knitted goods, or the mix can be formed into granules or chippings for subsequent melting and formation into such shaped articles.

The compound of formula (I) as well as being employable for the mass-dyeing of polymer by the method described above, can also be incorporated in the polymer by co- condensation with the polymer precursors. Such co-condensation may be carried out in conventional manner employing varying amounts of the compounds depending on the depth of shade desired.

The mass-dyed polymers according to the invention have good alhround fastness properties, e.g. to light, migration, gas-fumes, ozone and sublimation, as well as good wet fastness. Furthermore the mass-dyed polymers according to the invention have a good fastness under dry cleaning conditions e.g. against warm perchhloroethylene and the dyed polymers have good fastness against aqueous hypochlorite solutions and good fastness against rubbing when wet . Of particular interest, however, is the fact that the compound of formula (I) shows very good resistance to the extreme conditions employed in extrusion and especially spinning operations performed to produce shaped articles.

It is always possible to add more or different additional dyestuffs or to add additives before forming the desired objects in order to adjust the color shade or to impart additional desired properties. Besides further colorants at least one active ingredient selected from the group consisting of anti-blockhig, anti-fogging, anti-microbial, antioxidant, anti-slipping, anti-static or cleaning agents, compatibilizers, conductive agents, corrosion inhibitors, de-nesting agents, drying agents, fillers, flame retardants, foaming agents, infrared agents, laser marker agents, lubricants, matting agents, nucleating agents, opacifiers, optical brightener, phosphorescent agents, photodegradable agents, processing aids and/or UV stabilisers may be added before the object forming stage. Alternatively the at least on active ingredients may also be admixed already in the stage of mixing the polymer granules or polymer melts or polymer powders with Ihe dyestuff of formula (T).

The novel method according to the invention using the dyestuff according to the formula (I) give blue coloration in synthetic non polar or polar polymers, such as for example polyethylene, polypropylene, ABS, polyester, polycarbonate or polyamides.

The polyester, itself, is preferably linear, highmolecular weight, saturated, aromatic polyester and especially that produced by polycondensation of terephthalic acid and, optionally, isophthalic acid, with ethylene glycol and/or cyclohexanediol. Typically, it is the polyester employed in the textile industry.

The preferred polymer is a polyester wherein polyethyleneterephthalate is the most preferred polyester. The preferred poly(ethylene-terephthalate) is a linear (1,4)- ρoly(ethylene-terephthalate).

The preferred method of producing the preferred high molecular weight, mass-dyed polyester according to the invention is first to mix the dyestuff(s) with a relatively low- melting, linear, aromatic polyester, typically having a melting point in the range from 75°C to 230⁰C and a softening point in the range of 60⁰C to 80⁰C. to form a concentrate or so-called "master-batch" containing generally 30 to 60% by weight of dyestuff, and then adding this master-batch in molten form, in the desired amount, depending on the depth of colour required in the final polyester, to the molten high molecular weight polyester, and distributing the dyestuff throughout the melt. Alternatively after forming the a concentrate or so-called "master-batch" containing generally 30 to 60% by weight of dyestuff, this masterbatch may be cooled down and powdered or be brought into chippings and the mixed with undyed polyester and be mixed by mixing and kneating the polymers powders and/or chippings until a homogenous polymer mass results.

In the description, in the claims and in the examples below, all parts are parts by weight and % means weight-% unless it is otherwise defined.

EXAMPLE l

202 parts of C.I. Acid Blue 127:1 having the formula

were dispersed in 2000 parts of water. The mixture was heated to 8O⁰C. When the temperature of the mixture reached 8O⁰C, sodium hydrosulphite was added while at the same time a 25% sodium hydroxide solution was added in order to maintain the pH at 8,5. After the desulphonation the temperature was lowered to 65°C and 50 parts of a sodium hydroxide solution (25%) were added in order to adjust pH at 12. Additionally 140 parts of hydrogen peroxide were added. The product was filtered off and washed with water. 145 parts of the product of formula (A) were obtained.

This product of the formula (A) was dissolved in 1750 parts of hexylbromide and heated to 145°C during 8 hours. After cooling down the mixture to 85⁰C and adding 1500 parts of methanol the dye precipitated. The product was filtered off and was washed with methanol and water. The resulting dye had the following structure:

Lambda (max), measured in methylpyrrolidone, was measured at 612.9 nm.

EXAMPLE 2

57,4 parts of C.I. Acid Blue 127:1 were dissolved in 436 parts of methanol and heated to 50⁰C. 6 portions of 25 parts of solid sodium hydroxide were added while the temperature was maintained at 50-55⁰C. Then, the reaction mixture was heated and kept at 85⁰C for 4 hours. Thereafter the methanol was distilled off and the loss of volume was corrected by adding water. After the distillation of methanol was finished the precipitated product was filtered off and was then washed with water. The violet product had the following structure:

Lambda (max), measured in methylpyrrolidone, was measured at 593.1 nm.

EXAMPLES 3 to 9

Starting with C.I. Acid Blue 127:1 the following compounds were synthesized in a similar manner as in example2 leading to the following compounds

where the meaning of R is given in Table I. In Table I the star (*) shows where the R moiety is attached to the anthrachinone core,

Table I

EXAMPLE 10

The compound prepared according to EXAMPLE 2 was treated with hexylbromide analogously to example 1. This leads to the final product with a brown-red shade having the following formula:

Lambda (max), measured in methylpyrrolidone, was measured at 493.0 nm.

EXAMPLE 11 to 23 Starting with C.I. Acid Blue 127:1 the following compounds were synthesized in a similar manner as in example2 leading to the following compounds

where the meaning of Ri and R₂ is given in Table π.

Table π

EXAMPLE 24

The first part of the synthesis has been done analogousely to EXAMPLE 1 to produce the product A. 145 parts of A were mixed with 1800 parts of diethylene glycol dimethylether and heated to 140⁰C. After this temperature has been reached 84 parts of cyclohexane bromide and 13 parts of sodium carbonate were added slowly over 7 hours. The resulting condension product was allowed to cool down to 125°C and the dye was precipitated by adding 1500 parts of methanol. The product was filtered off at room temperature and was washed with methanol and water. The resulting blue product has the following structure:

Fibres which were mass dyed using this dyestuff had excellent sublimation and thermo- migration fastness properties. Lambda (max), measured in methylpyrrolidone, was measured at 615.0 nm.

EXAMPLE 25 The synthesis was done analogousely to example 4 but benzyl chloride was used instead ofcyclohexane bromide. The resulting product is green and has the following structure:

Lambda (max), measured in methylpyrrolidone, was measured at 624.1 nm.

EXAMPLE 26

The first part of the synthesis has been done analogousely to example 1 to produce the product A. 36 parts of A were mixed with 200 parts of l-ethoxy-4-bromine-benzene and heated to 110⁰C for 1 hour. After 1 ,3 parts of 1 CuCl were added together with 16,8 parts of sodium carbonate and the reaction mass was heated to 160⁰C. The condensation was finished after 4 hours and the reaction mixture was allowed to cool down to 100⁰C and the dye was precipitated by adding 220 parts of methanol. The product was filtered off and was washed with methanol and water and a product of the following structure was obtained:

Lambda (max), measured in methylpyrrolidone, was measured at 645.0 nm.

EXAMPLE 27

The first part of the synthesis has been done analogousely to example 1 to produce the product A. 36 parts of A were mixed with 200 parts of diethylene glycol diethylether and heated to 12O⁰C. 32,5 parts of dimethylsulphate were added and the reaction mixture was heated to 16O⁰C. After 2 hours the reaction mixture was allowed to cool down to 100⁰C and 150 parts of methanol were added in order to precipitate the dye. The resulting product was filtered off and washed with methanol and water and to following product was obtained:

Fibres which were mass dyed using this dystuff had excellent sublimation fastness properties. Lambda (max), measured in methylpyrrolidone, was measured at 596.5 nm.

EXAMPLE 28

The first part of the synthesis has been done analogousely to example 1 to produce the product A. 36 parts of A were mixed with 200 parts of diethylene glycol dimethylether and heated to 114°C. Two portions of 105 parts of acetic anhydride were added and the reaction mixture was kept at the temperature of 114⁰C for 2 hours. Thereafter the reaction mixture was allowed to cool down to 100⁰C and 150 parts of methanol were added in order to precipitate the dye. The product was filtered off and washed with methanol and water. The resulting product has the following formula:

Lambda (max), measured in methylpyrrolidone, was measured at 576.5 ma

EXAMPLE 29

The first part of the synthesis has been done analogousely to example 1 to produce the product A. 36 parts of A were mixed with 200 parts of diethylene glycol dimethylether and heated to 95⁰C. During 4 hours 10,6 parts of epichloridrine were added and the temperature rose from 90⁰C to 100⁰C. The mixture was stirred for 12 hours. The dyes was precipitated with 150 parts of methanol. The resulting product was filtered off and washed with methanol and water. The dye with the following formula was obtained:

Lambda (max), measured in methylpyrrolidone, was measured at 623.0 nm.

EXAMPLE 24 to

Starting with the compound of formula A the following compounds were synthesized in a similar manner as in example 4 to 29 leading to the following compounds

where the meaning of Ri is given in Table m.

Table m

APPLICATION EXAMPLE A

(1% of the dye of EXAMPLE 1 in polypropylene fibres)

100 parts of polypropylene in the form of a powder are mixed with 0.1 and with 1.0 part respectively of the dye of EXAMPLE 1 in powder form in a drum mixer. After a short time, the powder is uniformly distributed. After about 10 minutes, the mixture is dried at 12O⁰C for 16 hours, transferred to a melt spinning machine and following a residence time of about 8 minutes is spun to fibers at 275-28O⁰C under a nitrogen atmosphere. The colored fibers are extremely lightfast. All other known synthetic polymers can be mass-colored in the same way, e.g. (HD/LD) polyethylene, polyamides, polyesters, ABS, polycarbonates.

APPLICATION EXAMPLE B (0.1% of the dye of EXAMPLE 1 in polyamide fibres)

100 parts of polycaprolactam in the form of a powder are mixed in a drum mixer with 0.1 parts of the dye of EXAMPLE 1 in powder form. After a short time, the powder is uniformly distributed. After about 10 minutes, the mixture is dried at 120⁰C for 16 hours, transferred to a melt spinning machine and following a residence time of about 8 minutes is spun to fibres at 275-280⁰C under a nitrogen atmosphere. The blue colored polyamide fibres are extremely lightfast.

APPLICATION EXAMPLE C

(0.1% of the dye of EXAMPLE 1 in polyester fibres) Polyester fibres containing 0.1 parts of the dye of EXAMPLE 1 have been prepared according to the following method: the polyester mixed with the dye is fused and extruded through a drawing plate at constant rate by gear pump regulation. The spinning machine is heated during 2 hours at temperatures of 260-265⁰C under pressure of 80 bars. The drawing plate is heated in an oven at 350⁰C for at least 30 minutes. The obtained fibres are recovered on a bobbin. The obtained fibres provide a strong blue color with excellent light and weather fastness.

APPLICATION EXAMPLE D

1000 Parts of a commercial linear copolyester, formed by co-condensation of terephthalic acid, isophthalic acid, ethylene glycol and neopentyl glycol, and having a molecular weight of between 18,000 and 20,000, a melting range of between 90 ⁰C and 150 ⁰C, and softening point of 65 ⁰C, are ground to a powder together with 1000 parts of dry ice in a pin mill which has been cooled to about -30 ⁰C with dry ice, and the polyester particles then have a diameter of between 300 and 600 micro-meter. This polyester powder is mixed well at room temperature in a closed mixer with 500 parts of the finely ground dyestuff of EXAMPLE 1, and this is subsequently processed in an extruder at 130 ⁰C to form a cable which is then cut to a granulate. The dyestuff concentrate, produced as described above, is melted in the shunt current of a helical spinning machine and is added at 270-275 ⁰C by a metering device to commercial, linear, aromatic polyester (polyethylene terephthalate) in the primary current of the spinning machine. The metering device adds to the polyester current 1 part of dyestuff concentrate per 48 parts of polyethylene terephthalate. The mixture is then spun at 270 °C-275 °C at a winding off speed of 200 meters per minute, the spun fibres are stretched at 90 ⁰C in a drawing machine in the ratio of 1 :4, and are twisted in the usual manner in a ring twister. A blue mass-dyed yarn is thus obtained with good fastness properties.

APPLICATION EXAMPLE E

1360 Parts of ethylene glycol and 1700 parts dimethyl terephthalate were stirred with 0.55 parts of manganese acetate for 31/2 hours at 180 ⁰C and the methanol produced was distilled off.

The mass is then transferred to a vacuum container suitable for polycondensation and a mixture of 80 parts of ethylene glycol, 0.45 parts of antimony trioxide, 20 parts of tri- nonyl phenyl phosphite and 17 parts of the dyestuff of EXAMPLE 1 (in powder form) added thereto. The vacuum was successively increased to less than 1 Torr at 275 ⁰C, until the intrinsic viscosity of eta=0.70 is reached by distillation of ethylene glycol.

The dyed polyester obtained is then extruded and granulated. The granules are vacuum dried at 140 ⁰C for 16 hours and finally spun, stretched and twined as described in Example 5. A blue yarn is obtained.

APPLICATION EXAMPLE F

Using the method of example 6 a polyester flat yarn of 5,5 dtex was produced. Two batches were produced: one comprising 0.1% colorant of EXAMPLE 1 and one in mass dyed having a deeper shade and comprising 1 % of of EXAMPLE 1. These yarns were used to produce non-woven swatches. The dyestuffs of the EXAMPLES 2 to 36 may be used in a similar manner as described in the APPLICATION EXAMPLE A to F

Claims

1. A compound of the formula (T)

wherein R¹ signifies H, Ci to Cio alkyl, Ci to Qo alkenyl, Ci to Ci₀ alkoxy, cyclic C₅ to Qo alkyl, -CH₂-aryl, - CH₂CH₂-aryl, substituted Q to Q₀ alkyl, substituted Q to Cio alkenyl, substituted Ci to Qo alkoxy, substituted cyclic Cs to Qo alkyl, substituted -CH₂-aryl, substituted -CH₂CH₂-aryl, -S(O)₂-aryl, -S(O)₂-aryl wherein the aryl moiety is substituted, R³-C(0)-halogene, R³-halogene, R³-(CH₂)i-₂-halogene, wherein R³ signifies Ci to Qo alkyl, Q to Ci₀ alkenyl, cyclic Q to Cio alkyl, -CH₂-aryl, - CH₂CH₂-aryl, substituted Q to Cio alkyl, substituted Q to Cio alkenyl, substituted cyclic C₅ to Cio alkyl, substituted -CH₂-aryl, substituted , -CH₂CH₂-aryl, R² signifies H, Q to Cio alkyl, Ci to Q₀ alkenyl, Q to Q₀ alkoxy, cyclic C₅ to Ci₀ alkyl, -CH₂-aryl, substituted Q to Cio alkyl, substituted Q to Qo alkenyl, substituted Q to Qo alkoxy, substituted cyclic C₅ to Cio alkyl, substituted -CH₂-aryl, -S-aryl, -S-aryl wherein the aryl moiety is substituted, -O-aryl, -O-aryl wherein the aryl moiety is substituted; -S- aryl, -S-aryl wherein the aiyl moiety is substituted, -O-(CH₂)₀.₂-aryl, substituted -O-(CH₂)₀.2-aryl, with the proviso that not both, R¹ and R² have the meaning of H at the same time.

2. A compound of formula (I) according to claim 1 characterized in that

R¹ signifies H, Cj to Ci₀ alkyl, Ci to Ci₀ alkenyl, cyclic C₅ to Ci₀ alkyl,

-CH₂-aryl, - CH₂CH₂-aryl, substituted Ci to Ci₀ alkyl, substituted Ci to Ci₀ alkenyl, substituted cyclic C₅ to Ci₀ alkyl, substituted -CH₂-aryl, substituted -CH₂CH₂-aryl, -

S(O)₂-aryl, -S(O)₂-aryl wherein the aryl moiety is substituted, R³-C(O)-ha!ogene, R³-halogene, halogene,

wherein R³ signifies Ci to Ci₀ alkyl, Ci to Ci₀ alkenyl, cyclic C₅ to Ci₀ alkyl, -

CH₂~aryl, - CH₂CH₂-aryl, substituted Ci to Ci₀ alkyl, substituted Ci to Qo alkenyl, substituted cyclic C₅ to Cio alkyl, substituted -CH₂-aryl, substituted , -CH₂CH₂-aryl,

R² signifies H, Ci to Ci₀ alkoxy, substituted Ci to Ci₀ alkoxy, -

S-aryl, -S-aryl wherein the aryl moiety is substituted, -O- aryl, -O-aryl wherein the aryl moiety is substituted; -O- (CH₂)o -₂-aryl, -0-(CH₂)o -₂-aryl wherein the aryl moiety is substituted,

3. A compound of formula Q) according to claim 2 characterized in that

R¹ signifies H, Ci to Ci₀ alkyl, Ci to Ci₀ alkenyl, cyclic C₅ to Ci₀ alkyl, -CH₂- aryl, substituted Ci to Cio alkyl, substituted Ci to Cio alkenyl, substituted cyclic C₅ to Ci₀ alkyl, substituted -CH₂-aryl, R² signifies H, Ci to Cio alkoxy, substituted Ci to C₁₀ alkoxy, -0-(CH₂)o .₂- aryl, substituted -0-(CH₂)o-₂-aryl.

4. A process of forming a mass colored polymer characterised in that a compound of formula (I) is mixed in a first step with a polymer homogenously and in a further step the polymer is shaped by a converted by a process selected from melt spinning, injection molding, blow molding, extrusion, film blowing and strech blow molding.

5. A process according to claim 4 characterised in that in a further step the dyed polymer of the first step is admixed with not dyed polymer and mixed homogenously and therewith forming a second dyed polymer and in a further step the second polymer is converted by a process selected from melt spinning, injection molding, blow molding, extrusion, film blowing and strech blow molding.

6. A mass-colored polymer comprising a compound according to formula (T) as defined in Claim 1.

7. A colored polymer dyed with a compound according to formula (I) as defined in Claim 1.