CZ296786B6 - Concentrates of dyeing preparations for dyeing polyester textile fibers - Google Patents

Abstract

In the present invention, there are disclosed concentrates of dyeing preparations for dyeing polyester textile fibers containing 15 to 30 percent by weight of dyeing compositions and 85 to 70 percent by weight of a mixture of a polymeric carrier, wherein the dyeing compositions are comprised of carbon black being soluble in polyester in the ratio ranging from 3:1 to 5:1 and said polymeric carrier mixture is comprised of polyalkylene terephthalate, admixtures used to regulate the concentrate melt viscosity, sliding agents and stabilizers. The invented concentrates make it possible to increase considerably coloring power and achievement of a required color shade of so-called deep black type.

Description

Dye concentrates for dyeing polyester textile fibers

Technical field

The invention relates to colorant concentrates for dyeing polyester fibers in a mass. It falls into the processing of polymeric substances and is intended for the production of dyed polyester fibers.

BACKGROUND OF THE INVENTION

The dyeing of synthetic fibers today can essentially be carried out in two essentially different ways, namely dyeing in the preparation process, during spinning (mass dyeing) and dyeing the already finished fiber in the bath-soluble dye / dye (surface dyeing). Both methods are distinguished by the nature of the dyeing agents required by the manufacturing equipment and the final coloristic properties of the dyed fibers.

The dyeing of the polyester fibers in the mass is carried out either by admixing the dyes / pigments to the monomers prior to their polymerization, or by dosing the concentrate coloring the polymer to be polymerized and subsequently spinning the mixture.

spinning agents The coloring of polyester fibers to black shades was previously performed during the polycondensation of monomers with carbon black pastes in ethylene glycol. At present, dyeing concentrates of 25 carbon black, which are prepared by dispersion in a suitable polyester carrier together with the necessary other additives on special single- or multi-screw kneaders, are increasingly expanding.

The preparation of color concentrates is solved by U.S. Pat. No. 3,905,937, according to which deflocculants are added to the colorant and the polymeric carrier in order to improve the quality of the color concentrate for a given application area. The process for the preparation of pigment concentrates (optionally polyester films) is protected by British patent GB 1 490 320, according to which a copolyester with a melting point in the range of 150 to 240 ° C is used as the polymeric carrier. Dyeing of synthetic polymers using concentrates is disclosed in European Patent EP 194 382, which describes a process for preparing concentrates of dye compositions based on a mixture of two polymers. The preparation of a universal carrier concentrate is dealt with in European patent EP 705 875 (PCT / 96/68822) which solves the fluidity problem of highly concentrated pigment mixtures by the addition of various viscosity modifiers, plasticizers and other processing aids.

for dyeing fibers

The carbon black concentrates for coloring the polyester fibers in the mass to a black shade contain 15 to 30% 40 wt. soot of one type, respectively. mixtures of various types, various additives mainly to control the flow properties of the concentrate and polymer carrier, respectively. blend of different polymers. These concentrates are then metered either in the form of granules to the polyester into the hopper of the melter or in the form of a tar melt into the melt to be processed (injection dyeing) during its processing into fibers or films. It goes without saying that both materials must be thoroughly homogenized in the processing process.

In the field of synthetic fibers, there is now a strong trend in fiber production with increasing unit fineness. Especially for textile applications, it is inevitable to produce these fibers in the desired color shade. It is necessary to increase the content of pigments and / or dyes in the fiber, while guaranteeing the same color intensity of the polyester fiber 50 while reducing the unit fineness of the fiber.

Carbon black concentrates with increasingly smaller primary particle sizes are nowadays used to dye polyester fibers to a suitable black shade in order to achieve the required color saturation while guaranteeing 55 optimal fiber incorporation conditions. These fibers are then directed mainly

- 1 'I

- - · with natural fibers and in order to achieve the necessary saturation in color, it must be further dyed in a bathing process. They are then used as yarns in the textile industry.

The enhancement of the dyeing density (or dyeing force) of polyester fibers is today limited by the necessity of using special fine carbon black in the form of a concentrate with modified flow properties, used by the fiber preparation equipment and also by the resulting physico-mechanical properties of the dyed fibers. Only the use of concentrates with a substantially increased dyeing force will guarantee the color properties of the polyester fibers currently desired in the textile industry, even without subsequent dyeing in the bath process in a mixture with natural fibers, which also has considerable economic benefits.

A substantial increase in the coloring power cannot be achieved even by increasing the carbon black content of the fiber unless special coloring agents soluble in the polyester are used. Such coloring agents are to some extent described in the patent SK 283113, which are concerned with concentrates of pigments and additives based on polyalkylene terephthalate, which consist of a pigment and a polymeric carrier - a mixture of polyalkylene terephthalate and / or copolymers thereof and substituted organic alkyl and / or aryl- _x siloxanes. However, the incorporation of carbon black in the required concentration into such a mixture is not feasible in sufficient quality unless the flow and processing properties of the mixture are modified.

SUMMARY OF THE INVENTION

The present invention relates to concentrates of dye compositions for dyeing polyester textile fibers, which allow a substantial increase in color strength and achieve the desired shade of the so-called deep black type, which consists of 15 to 30 wt. % of coloring agents and 85 to 70 wt. polymeric carrier mixtures, wherein the colorant consists of a mixture of carbon black and polyester soluble dyes in a ratio of 3: 1 and 5: 1, and the polymeric carrier mixture consists of polyalkylene terephthalate, melt viscosity control agents concentrates, glidants and stabilizers. The polyalkylene terephthalate is preferably polyethylene terephthalate and / or polybutylene terephthalate and / or copolyesters having a melting point in the range of 80 to 250 ° C. The additives for controlling the melt viscosity of the concentrate preferably consist of fatty acid amides or polyester waxes or acid and alcohol esters having boiling points above the processing temperature of the polymer or montan waxes, the concentration of which is 0.5 to 3.0% by weight. The glidants are preferably organic polysiloxanes with a concentration of 0.5 to 3.0% by weight. and consists primarily of dimethylsiloxanes, methylphenylsiloxanes and diphenylsiloxanes. Up to 1.0 wt. The whole concentrate is preferably based on phosphites such as styrenized triphenyl phosphite, trisoctylphenol phosphite and others.

The use of such concentrates ensures that the color properties of the PES fibers needed and desired in the textile industry today are achieved even without subsequent dyeing in the bath process mixed with natural fibers, which of course also has considerable economic benefits.

In the manufacture of these concentrates, it is inevitable to use organic pigments (carbon black, color index: PIGMENT BLACK 7) of one type or a mixture thereof, with a primary particle size of up to 25 nm. The dyes must have sufficient thermal stability due to the long residence time of the concentrate melt in the fiber preparation plant. Most preferred are polyethylene terephthalate-soluble anthraquinone dyes.

AND

The total content of coloring agents may range from 15 to 30% by weight, preferably 25% by weight, of organic pigments and dyes in a ratio of 3: 1 to 5: 1, preferably 4: 1.

Fatty acid amides and / or polyester waxes and / or esters of acids and alcohols with high boiling points above the processing temperature of the polymer and / or montan wax in combination with organic siloxanes are used as the viscosity regulators of the concentrate melt.

especially dimethyl-,

-2r ·> «? _Sf . . > j: ..

C 299786 BÓ methylphenyl- or diphenylsiloxanes with increased thermostability, both components in amounts of 0,5 to

3.0 wt. (preferably 1.5% by weight)

When color concentrates are applied to more demanding fiber assortments, it is advantageous to add phosphite-based antihydrolytic stabilizers, such as styrenized triphenylphosphite, trisoctylphenolphosphite and the like, up to 1.0 wt. These not only have a positive effect on the flow properties of the concentrates, but also reduce the degree of degradation of the molecular weight of the polymeric carrier, and hence the sensitivity of the polymeric carrier to the presence of water, respectively. spinning polymer during its dyeing.

Polymers based on polyalkylene terephthalate, either polyethylene terephthalate, polybutylene terephthalate, copolyesters having a melting point in the range of 80 to 250 ° C, or mixtures thereof, can be used as polymeric carriers for the preparation of dyeing concentrates for dyeing PES fibers.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

3.2 kg of polydimethylsiloxane (viscosity 350 m ² , s ^-1 at 25 ° C) in liquid form and 1.6 kg of styrenized triphenylphosphite were added to 219.2 kg of polybutylene terephthalate powder while stirring. After stirring for 15 minutes, 96 kg of black pigment-black (PIGMENT BLACK 7) in powder form was added to this mixture. The mixture was stirred gently under constant heating at 160 ° C for 2.5 hours. The mixture was further melted on a WERNER-PFLEIDERER ZSK-53 operating twin-screw kneader and kneaded. The melt index of this concentrate was (at 280 ° C and a weight of 4.8 kg) at 148 g / 10 minutes.

After shaping, the feed of the thus prepared concentrate to the polyethylene terephthalate polymer in the process of preparing a fiber having a unit fineness of 1.7 dtex was 6.3% by weight. The fiber would have icy color properties (CIELab 10 ° / D 65):

L * = 16.4 a * = 0.1 b * = - 0.4.

The fiber prepared in this way can be considered as a standard in terms of color strength and its color strength as 100% value.

Example 2

To a conical mixer with 216.7 kg of polybutylene terephthalate powder and 2.5 kg of montan wax in powder form was added 3.2 kg of polydimethylsiloxane and 1.6 kg of styrenized triphenyl phosphite while stirring. After stirring for 15 minutes, 96 kg of carbon black (PIGMENT BLACK 7) in powder form was added to this mixture. This mixture was then stirred under continuous conditions

160 ° C for 2.5 hours. The mixture was then processed to form a concentrate under the same conditions as in Example 1. The melt index of the concentrate was increased to 170 g / 10 minutes over Example 1. At the same concentrate dosing as in Example 1, it produced a polyester black fiber having the following coloristic parameters:

heating to b * = - 0.3.

The fiber thus prepared had a color strength of 100.83% compared to Example 1.

TUH * -

. if

In this example, the effect of the use of montan wax as a flow regulator of the color concentrate was positively reflected mainly in a decrease in the number of fiber breaks during fiberizing. Increasing the color strength is practically irrelevant. At the subsequent concentrate, ie increasing the carbon black content of the fiber, the color strength increased only by 1.4% (to 101.4% at 1.98% by weight of the carbon black in the PES fiber), respectively. began to fall.

increase dosage

The carbon black concentrates prepared in Examples 1 and 2 failed to substantially increase the color strength level of the polyester fibers even with increased concentrate dosing in the fiber preparation process.

Example 3

4.8 kg of a polymethylsiloxane / triphenylphosphite liquid mixture (2: 1 ratio) was added to the blender with 219.2 kg of polybutylene terephthalate polymer powder while stirring. After stirring for 15 minutes, the following coloring agents were added to this mixture: 24% by weight. carbon black (PIGMENT BLACK 7) having a primary particle size of 22 nm and 6% by weight of a soluble anthraquinone violet dye. The weight of the whole mixture was 320 kg. The concentrate was then prepared and incorporated into the polyester fiber in the manner as in the example the ester fiber after molding had the following coloristic properties:

1. Stained polyL * = 14.9 and * = 0.0

The color strength was 115.6%.

b * = - 0.68.

Example 4

4.5 kg of a liquid mixture of polymethylsiloxane and phenyl phosphite was added to a slow-running mixer to 235.5 kg of polyethylene terephthalate powder (2: mixing was added carbon black (PIGMENT BLACK 7) at 50 kg and 10 kg of anthraquinone soluble dye (D) VIOLET 57) The powder mixture thus prepared was after 2.5 hours stirring and drying in the form of a premix was processed on a kneaded twin screw extruder and subsequently used as a concentrate for dyeing polyester textile fibers in the mass (concentration of the concentrate: 9.5% by weight). The fibers having a unit fineness of 1.7 dtex after had the following coloristic properties:

with stirring

1). After 10 minutes by frictional shaping

L * = 15.03 a * = 0.0 b * = - 0.5.

The dyeing level of the dyed fiber according to CIELab (10 ° / D 65) was 113.1% using the fiber prepared in Example 1 as a standard.

Example 5

In a conical mixer, to a powder mixture of polymers (polyethylene terephthalate and polybutylene terephthalate 8: 1) in an amount of 236.4 kg, a liquid mixture of a glidant (polymethylsiloxane) and an antihydrolytic stabilizer (trisoctylphenol phosphite) in a ratio of 2: 1 in an amount of 3 was added. 6 kg. After stirring for 20 minutes, the following coloring agents were added to this mixture:

- 30 kg of carbon black (P. BLACK 7) with a primary particle size of 22 nm,

- 18 kg carbon black (P. BLACK 7) of primary size. 18 nm

- 12 kg of soluble anthraquinone dye of blue color of sufficient thermal stability.

This mixture was then stirred for 170 minutes with constant heating at 145 ° C. The premix was subsequently processed on suitable twin-screw kneading machines from WERNER-PFLEIDERER using suitable technological plates. The resulting color concentrate with a melt index of 39 g / 10 minutes (280 ° C, 2.16 kg) was dosed at 9.4 wt. used in dyeing polyester textile silk of a mass with a final unit fineness of 1.7 dtex. The following coloristic properties were obtained on the remission spectrophotometer according to the CIELab method:

L * = 14.40 a * = -0.1 b * = - 0.9.

Compared to the standard (polyester fiber of Example 1), the measured color strength level was 119.0%.

The PES fiber thus obtained has a black shade at the level of the polyester fiber dyed on the mass of Example 1, which was subsequently dyed in blend with the natural fiber by a bath process.

The shade thus obtained is referred to as the "deep black" type.

Example 6

In a quick mixer (turbulent), 21.2 kg of ethylene bis stearamide was added to the previously dried polymer blend (polyethylene terephthalate and polybutylene terephthalate 6: 1) in an amount of 0.75 kg. To the mixture thus prepared (after 2 minutes of stirring) was added a liquid mixture of polymethylphenylsiloxane and phenylphosphite (2: 1 ratio) in an amount of 0.54 kg during stirring. After stirring for 5 minutes, organic carbon black pigments (PIGMENT BLACK 7) having a primary particle size of 22 nm and 17 nm (1: 1) in an amount of 5.625 kg and a blue dye of anthraquinone chemical composition of 1.875 kg were added to this mixture. it is soluble in polyester. The mixture was stirred at room temperature for 10 minutes. The premix thus prepared was processed on a twin-screw kneading machine. For the prepared color concentrate, the melt index at 280 ° C and 2.16 kg of weight was measured at 49 g / 10 minutes.

When dyeing 1.7 dtex PES fibers in the mass, the dye concentrate thus produced was fed into the hopper at 7.6% by weight. to a spun polyester polyester polymer granulate. The colored fiber after frictional shaping had the following coloristic properties:

L * = 14.52 a * = -0.15 b * = -1.02.

The color strength of the dyed fiber compared to the standard (Example 1) was 118.4%.

Example 7

In a quick mixer (turbulent), 21.38 kg of ethylene bis stearamide was added to a previously dried polymer blend (polyethylene terephthalate and polybutylene terephthalate in a ratio of 6: 1) in an amount of 0.75 kg. After stirring for 2 minutes, 0.36 kg of polymethylphenylsiloxane was added to the mixture. After stirring for 5 minutes, organic carbon black (PIGMENT BiJACK 7) having a primary particle size of 22 nm and 17 nm (1: 1) in an amount of 5.625 kg and a blue dye of anthraquinone chemical composition of 1.875 kg were added to this mixture. The mixture was subsequently stirred at room temperature for 10 minutes. The premix thus prepared was processed on a twin-screw kneading machine. The color concentrate had a melt index under conditions similar to Example 6 at a level of 62.1 g / 10 minutes.

-5GB 296786 B6

When dyeing the polyester fiber having a fineness of 1.7 dtex, the concentrate thus produced was dosed in an amount of 7.6% by weight. to a polyester polymer spinning. The dyed fiber after shaping had the following coloristic properties:

The color strength of the dyed fiber compared to the standard (Example 1) was 117.2%. Compared to the results obtained in Example 6, the absence of a stabilizer does not have a significant effect on the colorist properties, but can affect the stability of the spinning process due to the long exposure times of the concentrate under its processing conditions, i.e. fiber production.

Claims (7)

PATENT CLAIMS Dye concentrates for dyeing polyester textile fibers, characterized in that they are composed of 15 to 30 wt. % of coloring agents which consist of a mixture of carbon black and polyester-soluble dyes in a ratio of 3: 1 to 5: 1, and of 85 to 70 wt. a polymeric carrier mixture consisting of polyalkylene terephthalate, melt viscosity control concentrate, glidants and stabilizers. Concentrates of coloring agents for dyeing polyester textile fibers according to claim 1, characterized in that the polyalkylene terephthalate is polyethylene terephthalate and / or polybutylene terephthalate and / or copolyesters with a melting point in the range of 80 to 250 ° C. 3. Concentrates of coloring agents for dyeing polyester textile fibers according to claim 1, characterized in that the additives for controlling the viscosity of the concentrate melt consist of fatty acid amides or polyester waxes or acid esters and alcohols having boiling points above the processing temperature of the polymer or montan waxes, the concentration is 0.5 to 3.0 wt. 4. Concentrates of coloring agents for dyeing polyester textile fibers according to claim 1, characterized in that the glidant is organic polysiloxanes having a concentration of 0.5 to 3.0% by weight. Dye concentrates for dyeing polyester textile fibers according to claims 1 and 4, characterized in that the organic polysiloxanes are in particular dimethylsiloxanes, methylphenylsiloxanes and diphenylsiloxanes. 6. Dye concentrates according to claim 1, characterized in that they contain stabilizers in an amount of up to 1.0% by weight. for the whole concentrate. Dye concentrates for dyeing polyester textile fibers according to claims 1 and 6, characterized in that the stabilizers are phosphite-based, such as styrenized triphenylphosphite, trioctyphenolphosphite and others.