EP0746648B1 - Process for dyeing polytrimethylene terephthalate fibres and use of thus dyed fibres - Google Patents

Abstract

PCT No. PCT/EP95/00455 Sec. 371 Date Dec. 12, 1996 Sec. 102(e) Date Dec. 12, 1996 PCT Filed Feb. 9, 1995 PCT Pub. No. WO95/22650 PCT Pub. Date Aug. 24, 1995The present invention relates to a process for coloring polytrimethylene terephthalate fibers by treating the fibers with an aqueous liquor containing at least one dispersing colorant, in the absence of a carrier and the application of pressure. The temperature of the treatment is carried out at or below the boiling point of the liquid, within 20 DEG C. of the boiling point of the liquor. The coloring process begins at a liquor temperature between 20 DEG and 50 DEG C., and the temperature is raised over a period of 20 to 90 minutes. The liquor is then cooled to a temperature between 20 DEG and 50 DEG C., preferably at a rate of cooling of 1 DEG C. per minute, so that at least 95% wt. % of the colorant is absorbed by the fibers, and the dispersing colorant penetrates the fibers to a relative depth of at least 5% with respect to the diameter of the fibers.

Description

The invention relates to a method for staining Fibers of polytrimethylene terephthalate with Disperse dyes in an aqueous liquor at or below the cooking temperature of the fleet as well as the Use of the fibers dyed according to the invention.

Polytrimethylene terephthalate (PTMT) is a polyester that as the diol component 1,3-propanediol and terephthalic acid as Has dicarboxylic acid component. Large-scale Polyester synthesis can basically be done in two ways various procedures can be carried out (H.-D. Schumann in man-made fibers / textile 40/92 (1990), p. 1058ff).

Firstly, the older process, which lasted until around 1960 was used exclusively about the transesterification of Dimethyl terephthalate with a diol for Bishydroxyalkyl terephthalate and the subsequent Polycondensation of the same. Secondly, today predominantly applied processes of direct esterification of the Terephthalic acid with a diol and the subsequent Polycondensation.

In the transesterification, dimethyl terephthalate is transesterified with 1,3-propanediol with the addition of catalysts at temperatures of 160-210 ° C. and the methanol released is distilled off from the reaction mixture at normal pressure. The reaction mixture, which mainly consists of bis (3-hydroxypropyl) terephthalate, is further heated to 250-280 ° C. under reduced pressure and the 1,3-propanediol released is removed. The formation of the polytrimethylene terephthalate from bis (3-hydroxypropyl) terephthalate can be catalyzed by the same catalyst as in the transesterification or a different polycondensation catalyst is added after the same has been deactivated.

Already in GB 578079 the representation of Polytrimethylene terephthalate described. The transesterification of Dimethyl terephthalate with 1,3-propanediol is mixed with sodium and catalyzed magnesium. The alcohols released are distilled off at normal pressure and the The reaction mixture is further heated in a vacuum until polymeric Polytrimethylene terephthalate is obtained.

A composite fiber made of polyethylene terephthalate and GB 1075689 describes polytrimethylene terephthalate the representation of the polytrimethylene terephthalate is from Dimethyl terephthalate and 1,3-propanediol and Titanium tetrabutylate as transesterification and Polycondensation catalyst used.

From FR 2038039 two catalyst systems for the preparation of polytrimethylene terephthalate are known. Both are based on dimethyl terephthalate and 1,3-propanediol. On the one hand, NaH [Ti (OBu) ₆ ] is used as the transesterification and polycondensation catalyst and in the other process "Tyzor TBT" from Du Pont and MgCO _{3 are used} as transesterification catalysts and an antimony compound as the polycondensation catalyst.

In German Offenlegungsschrift 19 54 527 about Catalysts for the production of polyesters become one another way of catalysis in the manufacture of Polytrimethylene terephthalate described. Here too from dimethyl terephthalate and 1,3-propanediol.

Manganese (II) acetate tetrahydrate is used as the transesterification catalyst used and as a polycondensation catalyst finds hexagonal crystalline germanium dioxide with a Particle size less than 2 µm use. This Catalysts can also be used to make dipolymers from terephthalic acid, 1,2-ethanediol and 1,3-propanediol be used.

Another non-titanium based catalyst mixture is described in U.S. Patent 4,167,541. Be here Cobalt acetate and zinc acetate as catalysts for the Transesterification of dimethyl terephthalate with 1,3-propanediol described and for polycondensation is antimony oxide Catalyst used.

In U.S. Patent 4,611,049 and German Publication DE 34 22 733 is a new one Catalytic system described. Again starting from Dimethyl terephthalate and 1,3-propanediol Titanium tetrabutylate added as a catalyst. In addition p-toluenesulfonic acid is added as a promoter so that a higher molecular weight is reached.

In 1988 C. C. González, J. M. Pereña and A. Bello (J. Polym. Sci., Part B: Polymer Physics 26 (1988), 1397) linear polyesters based on dimethyl terephthalate, 1,3-propanediol and ditrimethylene glycol. As Transesterification and polycondensation catalyst Tetraisopropyl titanate used. With the same catalyst copolymers of terephthalic acid, Represent 1,3-propanediol and ditrimethylene glycol.

Only recently have various other catalyst systems been described in EP 547 553. Starting from dimethyl terephthalate and 1,3-propanediol, titanium tetrabutylate, sodium and titanium tetrabutylate, zinc acetate, cobalt acetate and titanium tetrabutylate as well as butylhydroxytin oxide are described as transesterification catalysts. Titanium tetrabutylate, antimony trioxide, butylhydroxytin oxide and the combination of antimony trioxide and butylhydroxytin oxide are used as polycondensation catalysts.
For the first time, a synthetic route for direct esterification is also given here. Starting from terephthalic acid and 1,3-propanediol, the esterification is carried out thermally under pressure and the subsequent polycondensation is catalyzed by antimony trioxide.

All the listed publications showed different ways on how to get PTMT or fibers out of it manufactures. However, none of the publications gave one technical teaching regarding the dyeing of PTMT fibers.

With regard to other polyester fibers, e.g. B. There are quite a few polyethylene terephthalate fibers Series of investigations into the coloring Behavioral. So you know (Herlinger, Gutmann and Jiang in CTI, man-made fibers / textile industry 37/89, February 1987, Pp. 144 - 150) that the use of polyethylene terephthalate in textile technology with regard to dyeing was associated with certain problems.

Basically, polyester can only be used with carriers or under so-called HT conditions - d. H. with increased Temperature, e.g. B. 130 ° C in pressure vessels - optimal with Stain disperse dyes (Béla v. Falkai in "Synthesefaser", Verlag Chemie, Weinheim, 1981, p. 176). Carriers are special aids that the Dye liquors must be added to the To enable dye absorption practically only. Examples for carriers, also known as fiber swelling agents can be u. a. o-hydroxybiphenyl or Trichlorobenzene. It is believed that such auxiliaries Lower the freezing temperature, above which the larger one Molecular segments of the fibers in the non-crystalline Areas become agile, causing the staining process accelerates.

The need to remove carriers after staining the fiber to remove an unfavorable Influence on the usage properties of the fibers avoid environmental reasons (pollution of wastewater and air through carrier) and problems with dyeing Polyester wool blends (wool cannot be processed using the HT process stained) led to the development of carrier-free polyester fibers dyeable at cooking temperature.

To manufacture polyester without carrier Cooking temperature can be dyed without pressure, it is known that Modify polyester chemically or physically (Herlinger et al. In: Chemical fiber / textile industry CTI 37/89, pp. 144 - 150, in chemical fiber / textile industry CTI 37/89, pp. 806 - 814 and in chemical fiber / textile industry CTI 40/92, February 1990).

For chemical modification, for example ether-modified polyethylene terephthalate. So were during the manufacture of polyethylene terephthalate polymer (PETP) polyether blocks consisting of Polyethylene glycol (PEG) units in the PETP chains installed, which due to their Mobility makes it easier to draw up the dye. Attempts have also been made to replace the PEG units Polybutylene glycol units in polyethylene terephthalate polymerize. There is also one in these polyester types Decrease in glass transition temperature, and the coloring behavior is significantly improved.

It is also known to improve dyeing Properties copolyester made of polyethylene terephthalate and To produce polybutylene terephthalate, but none have sufficient thermal stability so that they as well as pure polybutylene terephthalate, the can also be dyed carrier-free, but one has such a low melting point that it does not allow the high levels necessary in the finishing steps Apply temperatures, as alternatives either come into question.

In contrast, physical stability is good modified types of polyethylene terephthalate by Coextrusion of mechanical mixtures from Polyethylene terephthalate and polybutylene terephthalate granules were manufactured.

From DE 36 43 752 Al it is known fibers of Polybutylene terephthalate carrier-free and pressureless To dye disperse dyes in an aqueous liquor.

From Ullmann, 4th edition, vol. 22, p. 678 (1983) it is known that that in PET you sometimes get very light tones of color can be achieved by dyeing without pressure without a carrier. Therefore disperse dyes are suitable that are already at Diffuse 100 ° C sufficiently quickly in PET fibers, e.g. B. C. I. Disperse Rot 60. With this procedure one obtains however, as mentioned above, at most weak Ring coloring of the fiber surface, i. d. R. only one extremely small part of what is offered in the fleet Dye is added. The result is in everyone Trap light shades with low color intensity. this applies generally for all disperse dyes, including those which have a high diffusion coefficient.

Finally, one knows from US 3,841,831 Dyeing process for polyester fibers, in which carrier-free and without printing with emulsion paints from an aqueous bath at 25 is colored up to 100 ° C. This general statement will however strong in the description of US 3,841,831 restricted, on the one hand to PET fibers, on the other others to only extremely small amounts of dye in the dye bath and besides, the specified dyeing process always includes an additional fixation step to a slightly deeper one To allow dye to penetrate the fiber. Alles this further supports the fact that the use of PET in the textile technology so far no carrier-free, unpressurized and allowed optimal staining.

Basically, it should be noted that most of the previously known carrier-free at cooking temperature Hardly dyeable polyester products hardly imaginable correspond to the consumer with the known Combines polyester fibers; partly the initial modulus of elasticity reduced (lobed handle), susceptibility to creasing increases, the wash resistance suffers, that Repeatability decreases or the susceptibility to pilling is increasing.

Given the state of the art, it was Object of the invention, a method for staining Specify fibers of polytrimethylene terephthalate, the one environmentally friendly permanent coloring of the Permits polytrimethylene terephthalate fibers and beyond leads to dyed polyester fibers that both over have excellent processing properties as well in thermal and mechanical terms Polyester fibers meet the demands made. In particular, the colored fibers are said to have an increased Color fastness when using fibers and always have textile products made from them there, where there is increased abrasion on the fiber surface can come.

These and other unspecified are solved Tasks through a process with the characteristics of characterizing part of claim 1. Advantageous Process modifications are defined in that of claim 1 dependent claims under protection.

Because polytrimethylene terephthalate fibers (PTMT fibers), with at least one disperse dye having aqueous liquor treated, the Temperature at or below the cooking temperature of the fleet no carrier is present, work is carried out without pressure, while staining at a liquor temperature temperature between 20 and 50 ° C is started within 20 - 90 min, preferably within 45 min, to the cooking temperature of the fleet or to a maximum 20 ° C below the cooking temperature of the fleet Dyeing temperature is brought, the dyeing at least 20 min at the dyeing or boiling temperature, preferred 30 - 90 min, is continued and then on a Temperature of 20 - 50 ° C, preferably with a cooling rate of 1 ° C per min, is cooled, so that at least 95% by weight of the dye on offer in the fleet PTMT fibers and the disperse dye at least at a relative depth of 5% based on the Diameter of the fiber to be dyed penetrates into it environmentally friendly dyeing of PTMT fibers possible and it are dyed PTMT fibers with excellent Color properties as well as with excellent mechanical and thermal properties available that are very advantageous for all kinds of woven, knitted or crocheted fabrics can be processed further.

Within the scope of the invention it has been found that basically all known per se Polytrimethylene terephthalate fibers with carrier free Disperse dyes can be colored. Especially this also includes those according to that in EP 0 547 553 disclosed method available fibers.

This was somewhat surprising since it started from the knowledge regarding the Polyethylene terephthalate were not readily available the favorable coloring behavior of the Polytrimethylene terephthalate was to be expected.

Even taking into account that from polyesters pure polybutylene glycol terephthalate was known to be that could be dyed carrier-free, this was for fibers from polytrimethylene terephthalate from the outset to assume. In addition to the coloring properties come namely u. a. also the thermal properties of the Polyester for wearability. So that one Polymer as a fiber raw material for textile purposes in question comes, the melting point of the underlying should Esters are well above 200 ° C. The Melting points of the esters from diols with odd numbers However, methylene groups in the diol are usually below the melting point of the ester with the next higher even number of methylene groups in the diol. This effect however, only shows up in the higher ones Methylene group numbers clearly. In case of Polytrimethylene and polybutylene terephthalate are the Melting points almost identical.

Also with regard to the glass transition temperature, which for good coloring properties at cooking temperature without Carrier addition should be as low as possible for that Prior art polytrimethylene terephthalate none clear indication of its suitability for a carrier-free Staining can be seen. So there are very different ones Information from various authors. G. Farrow et al. in Macromol. Chem. 38 (1960), p. 147 settle the Glass transition temperature at 95 ° C above that of Polybutylene terephthalate, while in U.S. Patent 3,681,188 for polytrimethylene terephthalate one Glass transition temperature of 45 ° C is specified. Also Jackson et al. in J. Appl. Polym. Sci. 14 (1970), p.685 published a glass transition temperature for Polytrimethylene terephthalate, which is above that of Polybutylene terephthalate was. So all things considered based on the existing physical data regarding the dyeing behavior from the outset not clearly related to the relationship Polybutylene terephthalate or polyethylene terephthalate getting closed.

Are particularly preferred in the invention Polytrimethylene terephthalate fibers dyed out Polytrimethylene terephthalate are available, which under Use of a single catalyst are preferred Titanium compounds, for the transesterification and the subsequent Polycondensation was made. Here it is from particular advantage that the transesterification catalyst is not converted to an ineffective form before polycondensation must become. Furthermore, the catalytically effective one Species in many cases only in the reaction mixture generated and it can at the end of the reaction in the polymer remain.

From the PTMT material obtained for the invention Fibers according to all methods familiar to the expert getting produced. This is preferred Polytrimethylene terephthalate for fiber production one Subjected to melt spinning, the Polymer material previously preferred at temperatures around 165 ° C dried to water contents of less than 0.02% by weight becomes. The polyester staple fibers obtained can be optional before staining with a person known to the person skilled in the art Stretching system at temperatures of 110 ° C (heating mandrel) and 90 ° C (block heater).

Those which can be used in the process according to the invention Disperse dyes are not on certain connections are limited but include all dyes of low water solubility, which in the Are capable of hydrophobic fibers from an aqueous dispersion stain. The disperse dyes in question are familiar to those skilled in the art as examples Dye classes of the azo series, amino or aminohydroxyanthraquinones or called nitro dyes. Add to that Monoazo dyes, which are several nitro or Possess cyano substituents, and heterocyclic azo and Polymethine dyes. Representatives of these dye classes can be used alone or in a mixture of several be, including representatives of different classes can be mixed together, for example to or to produce black tones. Also conceivable in senses according to the invention are dyes for dyeing processes, like they're basically for dyeing cotton can be applied, whereby a diaminoazo compound after colors the dispersion process, diazotizes on the fiber and with a suitable coupling component to the black Trisazo body implements. Furthermore belong to the invention also all so-called coloring variants for Disperse dyes.

The disperse dyes are in the beginning of the invention an aqueous liquor. They spread out when staining between aqueous liquor and the fiber treated with it as between two immiscible or limited miscible Liquids and finally pull at suitable Reaction management and substance selection on the fiber.

The treatment of the fibers takes place in the invention Process essentially by contacting fibers and Liquor (in aqueous the disperse dyes and if necessary. solution containing necessary auxiliaries), for example by immersing in and staying in the fibers Fleet instead. This process takes place essential to the invention without the addition of carriers and without pressure, d. H. without applying the atmospheric pressure presses at the boiling point of the fleet or at a temperature below the boiling point of the fleet in such a way that at least 95% by weight of that in the fleet offered dye on the PTMT fibers. This usually corresponds to a bathing coloring, d. H. the dye offered is part of the Detection limit completely from the treated fibers accepted.

In an expedient modification of the invention The procedure is used to stain the Polytrimethylene terephthalate fibers used a liquor between 3.0 and 7.0 g of disperse dye per kg PTMT fiber to be dyed. Especially advantageous process design contains fleet used between 4.5 and 5.5 g Disperse dye per kg of PTMT fiber. The above Amounts of disperse dye each relate to the im Commercial dye contained pure dye. Commercial dyes are known to contain large amounts of Auxiliaries (up to 80 wt .-%) contain.

As already stated, according to the invention there is no carrier without pressure at the boiling temperature of the aqueous liquor or at underlying temperatures stained. Depending on Composition of the aqueous liquor, in particular content of Dye or dyeing aids (no carriers) can the boiling point of the liquor is also above 100 ° C. However, it is clearly stated that at Cooking temperatures of over 100 ° C according to the invention without pressure, d. H. but without using a special pressure vessel for example in a closed staining cup, is stained. However, the cooking temperature becomes one Dyeing liquor in general through the addition of dye and / or tools changed only slightly. In advantageous embodiment of the invention PTMT fibers therefore at a dyeing temperature between approx. 80 and treated at about 110 ° C. The treatment temperatures are very particularly preferably between 90 and 100 ° C.

In the dyeing process according to the invention, a excellent uniform distribution of the dyes in the Fiber reached. The dyes are particularly penetrating quickly inside the fiber. Based on the Diameters of the fiber to be dyed penetrate the Disperse dyes according to the invention in at least one relative depth of 5% in this one. Particularly advantageous the fibers are among those according to the invention Coloring conditions are completely colored, in contrast to Polyethylene terephthalate fibers, which are compared under identical staining conditions only stained in a ring will.

Available according to the dyeing process according to the invention dyed PTMT fibers can be used in a variety of ways. Basically, they can be used in all sectors that also open to previously known dyed polyester fibers stood. Those in an invention are preferred Processed colored PTMT fibers for Manufacture of woven, knitted or crocheted fabrics used. Because of the excellent mechanical Properties of the colored PTMT fibers, especially the high ones Elasticity and recoverability is also a stake in heavily used textiles or as highly elastic Fabric preferred.

Figur 1:

einen exemplarischen Temperatur- und Druckverlauf bei der Synthese des Polytrimethylenterephthalats;

Figur 2:

für den Farbstoff C. I. Disperse Blue 139 die Farbstoffaufnahme in Abhängigkeit von der Färbetemperatur für Polytrimethylen- und Polyethylenterephthalatfasern;

Figur 3:

für den Farbstoff C. I. Disperse Red 60 die Farbstoffaufnahme in Abhängigkeit von der Färbetemperatur für Polytrimethylen- und Polyethylenterephthalatfasern;

Figur 4:

Färbemuster von PTMT und PET Faserpolymeren bei gleicher Färbedauer mit C. I. Disperse Blue 139 in Abhängigkeit von der Färbetemperatur, dargestellt durch Grautöne;

Figur 5:

Färbemuster von PTMT und PET Faserpolymeren bei gleicher Färbedauer mit C. I. Disperse Red 60 in Abhängigkeit von der Färbetemperatur, dargestellt durch Grautöne;

Figur 6:

Faserquerschnitte von Fasern, die bei 95 °C mit C. I. Disperse Blue 139 gefärbt sind; Polytrimethylenterephthalat (links) und Polyethylenterephthalat (rechts);

Figur 7:

Faserquerschnitte von Fasern, die bei 120 °C mit C. I. Disperse Blue 139 gefärbt sind; Polytrimethylenterephthalat (links) und Polyethylenterephthalat (rechts); und

Figur 8:

die Eindringtiefe des Farbstoffs C. I. Disperse Blue 139 in Abhängigkeit von der Färbetemperatur für Polytrimethylen- und Polyethylenterephthalat.

The invention is explained in more detail below with reference to the attached figures using examples. Show in the figures

Figure 1:

an exemplary temperature and pressure curve in the synthesis of the polytrimethylene terephthalate;

Figure 2:

for the CI Disperse Blue 139 dye, the dye absorption as a function of the dyeing temperature for polytrimethylene and polyethylene terephthalate fibers;

Figure 3:

for the CI Disperse Red 60 dye, the dye absorption as a function of the dyeing temperature for polytrimethylene and polyethylene terephthalate fibers;

Figure 4:

Coloring patterns of PTMT and PET fiber polymers with the same dyeing time with CI Disperse Blue 139 depending on the dyeing temperature, represented by shades of gray;

Figure 5:

Coloring patterns of PTMT and PET fiber polymers with the same dyeing time with CI Disperse Red 60 depending on the dyeing temperature, represented by shades of gray;

Figure 6:

Cross sections of fibers dyed at 95 ° C with CI Disperse Blue 139; Polytrimethylene terephthalate (left) and polyethylene terephthalate (right);

Figure 7:

Cross-sections of fibers dyed at 120 ° C with CI Disperse Blue 139; Polytrimethylene terephthalate (left) and polyethylene terephthalate (right); and

Figure 8:

the penetration depth of the dye CI Disperse Blue 139 as a function of the dyeing temperature for polytrimethylene and polyethylene terephthalate.

Production of the polymers

The production of the polytrimethylene terephthalate was carried out on polycondensation plants with a capacity of 2 or 20 dm ³ . Approach: Dimethyl terephthalate (fiber grade from Hüls) 45 moles 8739 g 1,3 propanediol (Degussa AG) 10.125 mol 7705 g Titanium tetrabutylate (Sdpkt: 155 ° C at 0.015 Tor) 27 mmol 9.19 g n-butanol (Spp .: 117 ° C, water content <0.01%) 83.7 g

The batch size is 45 moles based on the amount used Dimethyl terephthalate, the ratio 1,3-propanediol (Diol batch D with a 1,3-propanediol content of 99.96%, 0.011% 3-hydroxymethyltetrahydropyran content, 0.005% 2-hydroxyethyl-1,3-dioxane content, 0.02% carbonyls and 0.04% Water content) to dimethyl terephthalate becomes 1: 2.25 selected and titanium tetrabutylate comes as 10 wt .-% Catalyst solution in n-butanol in a concentration of 600 ppm with respect to dimethyl terephthalate.

Transesterification:

Dimethyl terephthalate, 1,3-propanediol and the Catalyst solution are in the polycondensation filled and under a constant light Nitrogen stream heated to 140 ° C. After that Dimethyl terephthalate has melted, the stirrer switched on and the temperature increased to 220 ° C. That at the transesterification released methanol is distilled off until the calculated amount has almost been reached.

Polycondensation:

The pressure in the polycondensation apparatus is gradually reduced and the 1,3-propanediol used in excess and the 1,3-propanediol formed during the condensation are distilled off. The temperature is slowly increased to 270 ° C and the pressure is further reduced until finally oil pump vacuum (p ≤ 0.05 mbar) is reached. The end of polycondensation is reached when the dropping rate of the 1,3-propanediol has dropped below 0.5 drops per minute. This information applies to the 2 dm ³ polycondensation plant. The power consumption of the agitator motor was used in the 2 dm ³ system as an indirect measure of the progressive condensation. In the 20 dm ³ system, the torque is determined as a measure of the progress of the polycondensation. The vacuum in the polycondensation apparatus is released and the finished polytrimethylene terephthalate is discharged into a water bath with a gear pump under nitrogen pressure, drawn off with a take-off device and immediately granulated.

The reproducible temperature control during synthesis is controlled by a microprocessor-controlled temperature program guaranteed. The other conditions like pressure and The stirrer speed is always manually the same Time program changed.

The end of the polycondensation was determined in preliminary tests a torque absorption on the stirrer shaft determined; the Torque increases with increasing molecular weight and passes through a temperature-dependent maximum. After When the maximum value is passed, the torque drops again since the degradation reaction is now faster than that Chain construction. The optimal condensation time for the respective temperature is determined and in the Follow-up experiments kept constant.

In Figure 1, a drop in temperature is about 210 minutes of reaction time. The cause of this is the rapid distillation of large quantities 1,3-propanediols, the reaction mixture being more energy is withdrawn as fed from the outside through the heating can be.

It is also noteworthy that the specified final temperature the polycondensation apparatus is at 240 ° C. This Temperature is reached 75 minutes before the end of the polycondensation reached and then until the end of polycondensation kept constant. However, as can be seen from FIG. 1, the melting temperature rises to the end of the Polycondensation continues continuously up to 267 ° C. The heat required for this is not from the outside through the Heating supplied, but arises from the heat of stirring in of the apparatus itself. That this effect only occurs towards the end of the Polycondensation occurs with the steadily increasing Explain the viscosity of the polycondensation melt.

A number of polymers are produced in the manner described. The most important properties of the polymers used in the subsequent spinning tests are listed in Table 1. Polymer batch M _W (g / mol) COOH [meq / kg] L * a * b * A) PTMT 20/14 49700 34 69 -1.8 +6.7 PTMT 20/11 50400 35 69 -1.6 +7.4 PTMT 20/13 51000 27 70 -1.5 +5.8 B) PTMT 20/12 53100 29 70 -1.7 +6.2 PTMT 20/18 55200 24th 69 -1.7 +5.7 PTMT 20/19 55900 26 69 -1.6 +5.9 C) PTMT 20/15 57300 26 70 -1.8 +6.4 PTMT 20/16 59400 25th 70 -1.7 +5.6 PTMT 20/17 60100 25th 69 -1.7 +5.3 PET Rhodia standard:
M _n = 20500 34 matted granules

The analytical data of Table 1 were as follows receive:

Molecular weight (M _W (g / mol)):

The weight average molecular weight is determined using the static light scattering determined. To do this Polymer solutions with concentrations of 2, 4, 6, 8 and 10 g / l made in 1,1,1,3,3,3-hexafluoroisopropanol. The filtered solutions are at 20 ° C in the beam path a helium laser (λ = 633 nm) and the intensity of the scattered light depending on the observation angle certainly. As a standard for determining the optical Toluene becomes constant and for tempering the samples used. The scattered light intensities are in Dependence on the angle and the concentration in one Zimm diagram plotted.

A device from the Société française d'instruments de contrôle et d'analyses arrives; Photogonio / diffusoétre from Wippler & Scheibling.
The refractive index increment is determined using the Wyatt Opilab 903 Interferometric Refractometer from Wyatt Technology Corporation.

Carboxyl end groups (COOH [meq / kg]):

To determine the carboxyl end group content, 4 g Polymer at 80 ° C in 70 ml of a solvent mixture Phenol / chloroform = 1: 1 (g / g) dissolved. After cooling 5 ml of benzyl alcohol and 1 ml Water added and the solution with 0.02 normal Benzyl alcoholic potassium hydroxyl solution conductometric titrated. The potassium hydroxyl solution is added continuously with a Dosimat 665 from Methrom and the conductivity is checked with a DIGI 610 from the WTW a conductivity measuring cell (cell constant: 0.572) connected, tracked.

Color measurement (L *, a * and b *):

The color of the polymers is determined using the CIELAB color values specified. The polymer granules are with the Minolta CR 310, whose spectral sensitivity is close the CIE 2 ° normal observer function is adapted, measured. The measuring field diameter is 5 cm and the Calibration is carried out using a white standard.

Manufacture of the fibers Drying

Before the spinning tests, the polymers are dried in batches of about 25 kg each in a tumble dryer with a capacity of 100 dm ³ from Henkhaus Apparatebau. The polymer batches PTMT 20/14 + PTMT 20/11 + PTMT 20/13, PTMT 20/12 + PTMT 20/18 + PTMT 20/19 and PTMT 20/15 + PTMT 20/16 + PTMT 20/17 are received of mixed batches A), B) and C) mixed (see Table 1).

Table 2 shows the drying conditions. 1 hour 80 ° C [130 ° C] p <0.2 mbar 1 hour 100 ° C [130 ° C] p <0.2 mbar 10 hours 165 ° C [180 ° C] p <0.2 mbar

Obtain the temperatures given in square brackets the drying of polyethylene terephthalate, the under conditions similar to polytrimethylene terephthalate is processed into fibers.

The tumble dryer is then left for 12 hours Cool to room temperature and aerate with nitrogen.

The water contents of the dried polymers are below 0.0025%, making a significant Polymer degradation in the melt spinning process must be excluded.

Melting spinning:

In the spinning trials, a structure and properties of fibers made from polyethylene / polybutylene terephthalate blends is produced in a rapid spinning process at TC Barth, dissertation. 1989, Univ. Stuttgart, described spinning system used. Spinning plant: Extruder screw 30 mm; 25 D Spinnerets 32 x 0.20 mm (32 x 0.35 mm) Spinning pump 2.4 cm ³ / rev Spinning temperature 250 ° C [290 ° C] Winding speed 2000 to 5000 m / min

An aqueous emulsion of 10% limanol is used as the preparation PVK and 1.6% Ukanol R. The preparation pad is about 0.5%.

The density of the polymer melt must be known in order to produce defined spinning titers. The same applies to a defined preparation pad: Polytrimethylene terephthalate ρ 250 ° C = 1.09 g / cm ³ Polyethylene terephthalate ρ 290 ° C = 1.29 g / cm ³ Preparation solution ρ 20 ° C = 0.923 g / cm ³

During the spinning tests was next to Polytrimethylene terephthalate is also commercially available Spun polyethylene terephthalate. The Spinning speeds are at a spin titer of 16 tex with 32 single filaments in the range from 2000 to 5000 m / min varies. The spin titer is at one constant spinning speed of 3500 m / min in the area from 9.6 to 22.4 tex with 32 individual filaments each varies. This corresponds to a fineness of 0.3 to 0.7 tex per single filament.

In the case of polytrimethylene terephthalate, the Spinning temperature in the range between 240 and 270 ° C varies with the best results at 250 ° C will. In addition, polytrimethylene terephthalate different spinnerets with nozzle hole diameters of 200 to 350 µm used. The best results are with achieved with a 200 µm nozzle.

The staple fibers obtained are drawn on a drawing system The company Appensebau stretched. The stretch factors are chosen so that the drawn fiber is about 25% Has stretch.

The mechanical properties of the staple fibers and the stretched polytrimethylene and Polyethylene terephthalate are listed below:

Polytrimethylene terephthalate staple fibers:

Spinning speed [m / min] Spinning titer [tex] Maximum tensile force [CN / dtex] Starting module [CN / dtex] Strain [%] 2000 15.9 1.68 19.9 139 2500 16.1 1.97 20.8 107 3000 16.1 2.25 22.0 85 3500 16.1 2.48 23.2 68 4000 16.3 2.59 23.6 60 4500 16.3 2.53 23.3 59 5000 15.8 2.59 22.9 55 3500 9.6 2.54 23.2 68 3500 12.9 2.49 23.0 68 3500 16.1 2.48 23.2 68 3500 19.4 2.44 22.7 67 3500 22.7 2.34 22.4 64

Drawn polytrimethylene terephthalate fibers:

Spinning speed [m / min] Stretch factor Stretch titer [tex] Maximum tensile force [CN / dtex] Module [CN / dtex] Strain [%] 2000 1.78 9.0 2.76 24.1 42 2000 1.90 8.8 2.92 24.3 38 2000 2.00 8.4 2.97 24.8 32 2000 2.11 7.9 3.20 26.2 26 2000 2.20 7.9 3.34 24.6 24th 2000 2.32 7.2 3.75 26.8 22 2000 2.41 7.1 3.98 27.1 20th

Drawn polytrimethylene terephthalate fibers:

Spinning speed [m / min] Stretch factor Stretch titer [tex] Maximum tensile force [CN / dtex] Module [CN / dtex] Strain [%] 2000 2.16 7.9 3.26 24.7 26 2500 1.87 9.2 3.43 25.1 26 3000 1.66 10.4 3.52 25.3 24th 3500 1.44 12.1 3.29 25.5 25th 4000 1.37 12.8 3.38 25.4 26 4500 136 12.8 3.34 25.1 25th 5000 1.35 13.1 3.35 25.4 27 3500 1.44 7.1 3.49 25.8 24th 3500 1.44 9.6 3.41 25.8 25th 3500 1.44 12.1 3.29 25.5 25th 3500 1.44 14.5 3.29 26.0 24th 3500 1.44 16.8 3.24 24.4 22

Polyethylene terephthalate staple fiber:

Spinning speed [m / min] Spinning titer [tex] Maximum tensile force [CN / dtex] Starting module [CN / dtex] Strain [%] 2000 15.8 1.82 21.3 156 2500 15.8 2.07 23.5 131 3000 15.3 2.29 27.1 110 3500 15.9 2.55 33.3 93 4000 15.9 2.67 41.2 79 4500 15.6 2.86 51.4 68 5000 14.8 3.21 60.2 60 3500 9.6 2.63 40.6 89 3500 12.8 2.56 37.2 90 3500 15.9 2.55 33.3 93 3500 19.0 2.54 32.9 93 3500 22.2 2.46 31.4 93

Drawn polyethylene terephthalate fibers:

Spinning speed [m / min] Stretch factor Stretch titer [tex] Maximum tensile force [CN / dtex] Module [CN / dtex] Strain [%] 2000 1.79 8.9 3.45 68.1 43 2000 1.88 8.5 3.75 76.7 38 2000 1.98 8.1 3.93 82.8 31 2000 2.08 7.8 4.01 91.5 24th 2000 2.20 7.4 4.26 104.0 17th 2000 2.29 7.1 4.50 108.7 9 2000 2.42 6.8 5.25 117.2 6 2000 2.07 7.8 4.10 97.5 24th 2500 1.85 8.7 4.08 100.2 25th 3000 1.69 9.2 4.20 103.0 24th 3500 1.55 10.5 4.21 103.3 26 4000 1.46 11.1 4.19 106.8 26 4500 1.38 11.6 4.06 105.1 25th 5000 1.31 11.5 4.34 112.6 25th 3500 1.55 6.4 4.26 110.5 24th 3500 1.55 8.4 4.31 108.0 25th 3500 1.55 10.5 4.21 103.3 26 3500 1.55 12.6 4.17 102.3 25th 3500 1.55 14.6 4.15 101.8 25th

Staining attempts

The glass transition temperature of the polymers in aqueous medium is of greater importance for the dyeing behavior of the synthetic fibers. DR Buchanan and JP Walters, text. Res. J., 47 (1977), 398, define a color transition temperature. For this purpose, the dye absorption of the synthetic fibers is determined as a function of the temperature. The temperature at which the dye absorption reaches 50% of the equilibrium value is defined as the color transition temperature. However, the color transition temperature depends on the dyeing time and the structure of the dye.

Substrates:

The use of fiber flake in dyeing tests has the Disadvantage that the fibers can knot and then can no longer be washed around evenly by the dye liquor can. The uneven dyeings obtained from this can be used for Determination of the dye content should not be used. The dyeing attempts are therefore made with knitted fabrics drawn fibers. To make the Knitted into a knitted tube (diameter 10 cm) served a circular knitting machine of the type Elba Machine factory Lucas.

Knitted fabrics made from the following fibers are used for the dyeing tests: polymer Spinning speed [m / min] Spinning titer [tex] Stretch factor Stretch titer [tex] PTMT 3500 16.1 1.44 12.1 PET 3500 19.0 1.55 126

So that the stretch titer and thus the fiber diameter of the coloring fibers are comparable, because of the different stretching factors in the Polyethylene terephthalate fiber a higher spider titer chosen.

The fibers are knitted on a Circular knitting machine washed around when spinning remove the applied preparation.

Pretreatment:

To remove the spin finish, the knitted fabric is washed as follows: Washing conditions: apparatus Mathis LAB Jumbo Jet with washing drum temperature 30 ° C Duration 120 min Wash liquor 1 g / l Kieralon® EDB from Bayer AG Fleet ratio 1:50

To avoid shrinkage during dyeing and to improve the dimensional stability of the knitted fabrics, they are heat-set at 180 ° C. for one minute. The tensions in the fiber that arise during stretching are relaxed. The thermofixed knitted fabrics show a greater surface shrinkage in the case of polytrimethylene terephthalate than in the case of polyethylene terephthalate. Fixing conditions: apparatus Mathis dryer temperature 180 ° C Duration 1 min

Dyes:

Two disperse dyes are selected that differ significantly in their diffusion coefficient: dye Diffusion coefficient [10 10th cm -2 · S] CI Disperse Blue 139 0.8 Mono-azo dye resolin navy blue GLS from Bayer AG CI Disperse Red 60 3.4 Antrachinone dye Resolin Red FB from Bayer AG

For the quantitative determination of the dye absorption the Extinction coefficient of the pure dye to be known. The cleaning of the above-mentioned disperse dyes will with E. M. Schnaith (dissertation 1979, Univ. Stuttgart) detailed.

The dyeing temperatures are in the range between 60 ° C and 140 ° C varies.

The coloring is always started at 40 ° C and the Heating rate selected so that after 45 minutes Dyeing temperature is reached. The cooling rate is always 1 K / min until the bath temperature reaches 40 ° C.

Staining conditions:

Dyeing machine Ahiba Polymat Staining time 60 min Fleet ratio 1:20 fleet 1 g / l dye 2 g / l Avolan® IS from Bayer AG 2 g / l sodium dihydrogen phosphate dihydrate

Reductive post-treatment:

To remove the dye that is on the Has deposited fiber surface, the dyeings reductively treated. The heating rate of the Reduction liquor is 2 K / min, the cooling rate is 1 K / min.

Reduction conditions:

apparatus Ahiba Polymat temperature 70 ° C Fleet ratio 1:20 fleet 3 g / l sodium dithionite 1.2 g / l sodium hydroxide 1 g / l Levegal® HTN from Bayer AG

Finally, the knitted fabric with 5% formic acid acidified.

Dye absorption:

To determine the dye absorption, the fibers dyed at different temperatures are extracted exhaustively with chlorobenzene. The extracts are diluted to a defined volume and the extinctions of the solution are determined using a Lambda 7 UV / VIS spectrophotometer from Perkin Elmer in Bodensee. From the extinction of the extraction solution at the characteristic wavelength CI Disperse Blue 139 604 nm and CI Disperse Red 60 516 nm the dye content can be determined using the corresponding calibration line.

The determination of the dye content FG in g / kg of goods is done with the numerical equations:

C.I. Disperse Blue 139:

FG [g / kg goods] = E + 3.2 x 10 -3 0.05948  x Volume of the extraction solution [ml] Mass of the extracted sample [mg]

C.I. Disperse Red 60:

FG [g / kg goods] = E + 4.67 x 10 -4 0.04115  x Volume of the extraction solution [ml] Mass of the extracted sample [mg]

Figures 2 and 3 show the dye uptake of Polytrimethylene terephthalate fibers depending on the Dyeing temperature compared to Polyethylene terephthalate fibers.

In Figures 2 and 3, the horizontal line marks that Dye supply in the dye liquor based on the amount of substrate used.

From Figure 2 it can be seen that the coloring of the Polytrimethylene terephthalate fiber already at around 70 ° C begins, while the polyethylene terephthalate fiber only at Temperatures from 90 ° C are markedly colored.

The maximum determinable dye absorption is around 95% of the maximum possible dye absorption because the Reductive treatment of fiber samples before extraction will. In doing so, the one adhering to the fiber surface Dye reductively destroyed and the maximum determinable This lowers the dye content.

Fig. 2 also shows that at a dyeing temperature of 100 ° C the entire dye from the dye liquor on the Polytrimethylene terephthalate fiber absorbs. Against pulls at 100 ° C dyeing temperature only about 15% of the offered Dye on the polyethylene terephthalate fiber.

So that the dye offered completely on the Polyethylene terephthalate fiber pulls up the Dyeing temperature can be increased to 130 ° C. This has to Consequence that the bathing coloring of the Polyethylene terephthalate fiber in closed vessels under Printing (HT dyeing conditions) must be carried out.

The C.I. Disperse Red 60, a disperse dye with higher diffusion coefficient, is almost identical Course of the dye uptake with the dyeing temperature as observed at C.I. Disperse Blue 139.

However, the curve is in the case of the C.I. Disperse Red 60 by about 5 to 10 K to lower temperatures shifted as with C. I. Disperse Blue 139. This The fact is with the higher diffusion coefficient of C. I. Disperse Red 60 to explain because of the dye molecules can diffuse into the interior of the fiber more quickly.

Staining with C.I. Disperse Red 60 shows a maximum Dye absorption of the polytrimethylene terephthalate fiber a dyeing temperature of 95 ° C.

In the case of polyethylene terephthalate fiber, the maximum Dye absorption only reached at 120 ° C dyeing temperature, so that here too the bathing coloring closed apparatus can be carried out under pressure got to.

The color transition temperature of polytrimethylene and polyethylene terephthalate are thus: PTMT PET CI Disperse Blue 139 91 ° C 107 ° C CI Disperse Red 60 84 ° C 100 ° C

The dyeing transition temperature is in both dyeings Polymers with C.I. Disperse Red 60, due to its higher Diffusion coefficient, about 7 K lower than at Staining with C. I. Disperse Blue 139. The difference of 16 K of the color transition temperatures of both polymers remains constant, however.

4 and 5 show color patterns of both fiber polymers with the same staining time depending on the Dyeing temperature. Here is the difference in the Best to recognize dye absorption. The Differences in color intensity are caused by shades of gray shown.

Dye distribution:

The dye distribution in the fiber can be determined using Fiber cross sections are assessed. You can do it Differentiate between color and ring color. Fiber cross sections are obtained by using the fibers in Acrylic acid esters are embedded and using a Minot microtome from Jung to a thickness of 10 µm get cut. The cross-sectional images are with taken with a Zeiss Axioplan microscope. The reality a staining, when the stained Fabric, is higher than in the case of color change in the case of a ring coloration in which the dye is only in the outer layer of the fiber is embedded.

For the cross sections, stains were made with C.I. Disperse Blue 139 selected because this dye has a very has low diffusion coefficients. In the Use other dyes with higher Diffusion coefficient is already lower Coloring temperatures are expected to be colored completely.

6 and 7 show cross sections of polytrimethylene and polyethylene terephthalate fibers at 95 ° C and 120 ° C are colored with C.I. Disperse Blue 139.

In the case of polyethylene terephthalate fiber, these are To recognize titanium dioxide particles with which the used Polymer granulate is matted.

The cross sections of the fibers show that the dye faster inside the polytrimethylene terephthalate fiber can penetrate like this at the Polyethylene terephthalate fiber is the case.

Fig. 8 shows that related to the fiber diameter Depth of penetration of the dye depending on the Dyeing temperature.

Comparing Fig. 8 with Fig. 2, the following can be said determine:

The polytrimethylene terephthalate fiber can be Excellent cooking temperature with C. I. Disperse Blue 139 to dye. The fiber takes the whole in the Dyeing liquor offered dye. The Dye concentration is at the edges highest. In the case of HT staining, the dye diffusion accelerated so that a uniform color through the entire fiber cross section can be observed.

In contrast, the dye absorption is the Polyethylene terephthalate fiber clearly at cooking temperature less. The dye absorption of the fiber is only 10% of the dye offered in the dyeing liquor. Under HT conditions can also the polyethylene terephthalate fiber stain well. The entire dye offered penetrates the fiber is on, but the fiber is colored C. I. Disperse Blue 139 not observed.

Further advantages and embodiments of the invention result from the following patent claims.

Claims (6)

1. Process for colouring fibres of polytrimethylene terephthalate (PTMT fibres), in which the PTMT fibres are treated in at least one aqueous liquor containing a dispersion dye at or below the boiling point of the liquor, characterised in that
   the PTMT fibres are coloured without applying pressure and in the absence of a carrier, wherein the colouring process is started at a liquor temperature between 20 and 50°C, the temperature is brought up to the boiling point of the liquor or to a colouring temperature which is at most 20°C below the boiling point of the liquor, within 20 - 90 min, preferably within 45 min, colouring is continued for at least 20 min, preferably for 30 - 90 min, at the colouring temperature or boiling point and then is cooled to a temperature of 20 - 50°C, preferably at a rate of cooling of 1°C per min, so that at least 95 wt.% of the dye provided in the liquor is extracted onto the PTMT fibres, and the dispersion dye penetrates into these to a relative depth of at least 5 % with respect to the diameter of the fibres being coloured.
2. Process according to Claim 1,
   characterised in that
   a liquor is used which contains between 3.0 and 7.0 g of pure dispersion dye per kg of PTMT fibres to be coloured.
3. Process according to Claim 2,
   characterised in that
   a liquor with a concentration of dispersion dye of 4.5 to 5.5 g of pure dye per kg of PTMT fibre is used.
4. Process according to one of the preceding Claims,
   characterised in that
   treatment is performed at a colouring temperature between 80 and 110°C, preferably between 90 and 100°C.
5. Process according to one of the preceding Claims,
   characterised in that
   the fibres are completely dyed.
6. Use of coloured PTMT fibres obtained in accordance with one of the preceding Claims for producing woven or knitted fabrics.

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