CH393252A - Process for improving the dyeability of textile fibers, such as are obtained by spinning mixtures of polyolefins with basic nitrogen compounds which are effective as color modifiers - Google Patents

Description

  

  



  Process for improving the dyeability of textile fibers, such as those obtained by spinning mixtures of polyolefins with basic color modifiers
Nitrogen compounds are obtained
The present invention relates to a process for improving the dyeability of textile fibers, such as those obtained by spinning mixtures of polyolefins with basic nitrogen compounds which are effective as color modifiers, and is characterized in that N-mono- and / or-diglycidyl derivatives of aliphatic, aromatic or heterocyclic amines or mono- or dichlorohydroxypropyl derivatives of these amines are allowed to act.



  Such fibers can also contain other additives such as stabilizers, solid dispersants, optical fillers, colors and the like.



   A particular embodiment of the present invention relates to the treatment of the fibers with monofunctional and bifunctional derivatives, as can be obtained by reacting epichlorohydrin with long-chain aliphatic, aromatic or heterocyclic amines, whereby the fibers treated in this way have a particular capacity for absorption Dyes in general, good color fastness and better handle obtained.



   Textile fibers made from mixtures based on synthetic polymers and color modifiers of a basic nature have a good ability to absorb dyes, but they have the disadvantage that the basic compounds mixed with the olefin polymer dissolve in water; in addition, the color modifiers easily escape from the fibers and thereby make the fibers greasy.



  To reduce these disadvantages it was proposed in the applicant's French patent no. 1,263,856 to use diepoxy compounds, e.g. B. Diglyzi dyläther of ethylene glycol to use as an aid, whereby the water solubility and the escape of the basic nitrogen compound from the fiber could be reduced. The glycidyl derivatives of amines used in the process according to the invention have the advantage that they are better compatible with the nitrogen color modifiers than the diepoxy compounds known from the French patent, and they also have a stronger effect on reducing the water solubility of the color modifiers.



   Since the glycidyl derivatives of amines used according to the invention also contain further nitrogen or. bring on the fiber, which in turn contributes to increasing the dyeability of the fibers with acidic dyes, smaller amounts of nitrogen-containing dye modifiers can be used when spinning the fibers than in the process of the French patent mentioned.



   The advantage of the method claimed here over that of French patent specification No. 1263 856 is thus two-part, namely:
1. The color modifier is made water-insoluble by means that are more compatible with it, where the water-insolubilizing effect is strengthened, and 2. the glycidyl derivatives used according to the invention add a further part of the increase in the fibers. of the. Colorability required
Spent nitrogen ...



   Particularly suitable compounds which can be used according to the invention are N-mono- and diglycidyl derivatives of n-dodecylamine: and of n-octadecylamine, the N-mono- and di-chlorohydroxypropyl derivatives of n-dodecylamine and of n-octadecylamine , N-glycidylpiperazine,
N, N # -Diglycidylprperazine, N-chloro-hydroxy-propylpiperazine and N, N # -dichloro-hydroxypropylpiperazine.



   The N-mono- and diglycidyl derivatives of primary C12-Ct8 aliphatic amines and of piperazine as well as the mono- and dichlorohydroxypropyl derivatives are made from solutions or dispersions in water or in an organic one. Solvent or used in an anhydrous state.



   After the fibers have been drawn, the treatment is usually carried out for a period of a few seconds up to 3 hours and at temperatures between room temperature and about 10 ° C. below the softening point of the base polymer.



   The textile fibers which can be treated according to the invention preferably contain at least 75% of a polyolefin, in particular polypropylene with predominantly isotactic macrosolecules, as is obtained from propylene using stereospecific catalysts, as well. 1 to 25% of the stain modifier.



   As dye modifiers for the production of dyeable textile fibers, wet nurse or. Imines of the polyalkylenimine type or nitrogen polycondensates of epichlorohydrin with a specific viscosity of 0.1 to 0.7 (determined in 1% isopropanol solution at 25 ° C.) can be used.



      The mixtures are spun in a melt-spinning device K after granulation or simple sintering; Its spinning diameter has a length to diameter ratio of over 1. have.



   The granulation and spinning are carried out in the absence of oxygen and preferably under iteration gas (nitrogen),
The spinning of the mixtures can expediently be carried out in the "presence" of a small amount of a solid dispersant, which facilitates the homogeneous dispersion of the "basic" nitrogen polycondensate in the molten polymer mass. The following are preferred.

   Compounds in question: cetyl and stearyl alcohols, stearic acid, benzoin, -, furoin, vinyl stearate, mono-, di- and tristearic acid esters of glycerine, monoethanolamine stearate, stearamide, N-di #ethanol-lauramide, C @ -C @@ aliphatic amines, condensation products of ethylene oxide with amines or phenols, polystearamide, polyacrylic acid, polystyrene and styrene copolymers, terpene polymers, etc.



   In addition to the nitrogen polycondensates, stabilizers, optical fillers and organic or inorganic pigments can also be added to the polyolefin during mixing.



   After spinning, the fibers are stretched, with stretching ratios between 1: 2 and 1:10 at temperatures of 80 to 150 ° C. and in stretching devices which are heated with hot air, steam or the like or are provided with a heating plate.



   The fibers obtained in this way are then subjected to a dimension stabilization treatment with free or restricted shrinkage at 80 to 160.degree.



   The fibers obtained by pressing out the mixtures according to the invention can be mono- or plurifiles and can be used to produce voluminous yarns or voluminous staple fibers acidic, metallized and disperse dyes. They also have a good affinity for basic and vat dyes; have a better grip and a special color fastness
In addition, the fibers obtained according to the invention show better lightfastness.



   The control stain & were 1% hours at boiling point. carried out in B # countries, the 21/2%, based on. the weight of the fiber contained in dye; with a fiber to wheel ratio of 1:40.



   The dyeing with acidic and metallized dyes was carried out in the presence of 3% ammonium acetate (based on the fiber weight) and. 1% of the condensation product from 6 to -20 moles. #thylenoxyd with one mole of alkylphenol, such as p-tert. Octylphenol, Nonylphenol and similar, as surface-active agents:
30 minutes after the start of boiling, 2% (based on the fiber weight) of a 20% vinegar solution was added in order to improve the utilization of the bath.



   After dyeing, the passes were rinsed with running water and after treatment with acidic, metallized and disperse dyes show intense discoloration.



   The color fastness to light, washing and rubbing is very good.



   Example l
A yarn is produced by compressing a mixture @ of @ a 9600 kg of polypropylene with a limiting viscosity [#] of 1.58 (determined in T # trahydronaphthalene- at 135 # -C), an ash content of 0.012% and a residue @ after the Heptanext @ action by
96.2% and b) 0.400 kg of a basic nitrogen polycondensate, obtained by reaction of 1.30 mol
Epichlorohydrin with 0.3 mol of octadecylamine and 1 mol of piperazine, which has a specific viscosity [11Sp] of 0.32 (determined in 1% isopropanol solution at 25 ° C.).



   The mixture is spun and then- with diglyzidyloctadecylamine under. the conditions given in Table 1; treated. With the dyes indicated in Table 2, good colorations are obtained throughout.



   Example 2
A yarn is produced by pressing a mixture of., A) 9600 kg of polypropylene with an intrinsic viscosity [a7] of 1.58 (determined in tetralin at 135 ° C.), an ash content of 0.012% and a residue after the heptane extraction of 97.2% and b) 0.400 kg of a basic nitrogen polycondensate obtained by. Reaction-by-0.65 moles
Epichlorohydrin with 0.3 moles of dodecylamine and 0.35 moles of piperazine, which has a specific viscosity [N9p] of 0.27 (determined in 1% isopropanol solution at 25 ° C.).



   The mixture is spun, and thin. treated with diglycidylpiperazine under the conditions given in Table 1, with the colorants given in Table 2. throughout. good coloring.



   Example.



   A yarn is produced by pressing a mixture of a) 9800 kg of polypropylene with an intrinsic viscosity # t [#] of 1.62 (determined in tetralin at −1359 ° C.), an ash content of 0.015% and a residue after the heptane extraction of 95.6% and b) 0.400 kg of a basic nitrogen polycondensate, obtained by reaction of 1-DiH glycidylpiperazine with 1 mol of piperazine, which has a specific viscosity of 0.29 (determined in l% 'Isopropanol solution at 25 C)'.



   The mixture is spun and then treated with Di chlörhydroxypropyldödecylämin under the conditions given in Table 1; The dyeings given in Table 2 give consistently good colorations.



   Example 4- "
A yarn is produced by pressing a mixture of a) 9600 kg polypropylene with an intrinsic viscosity of 1.62 (determined in tetralin at 135 ° C.), an ash content of 0.015% and a residue after heptane extraction of 95 , 6%, and b) 0.400 kg of a basic nitrogen ply condensate, obtained by reaction. of 1, 3, moles
Epichlorohydrin with 0.3 moles of octadecylamine and 1 mole of piperazine, which has a specific viscosity # t [X15p] of 0.32 (determined in 1% isopropanol solution at 25 ° C.).



   The mixture is spun and then treated with Di glyzidylpiperazine under the conditions given in Table 1; The dyeings given in Table 2 give consistently good colorations.



   Example 5
One-yarn is produced by pressing a mixture of 'a) 9600 kg of polypropylene with an) intrinsic viscosity M of 1.62 (determined in tetralin at. 135 ° C), an ash content of 0.015.% And a reverse viscosity after the heptane extraction of 95.6% and b) .0.400 kg of poly-2-vinylpyridine with a limiting viscosity # t [#] of 0.45 (determined in dimethylformamide at 30 ° C.), produced with. stereospecific catalysts.



   The mixture is spontered and then treated with diglycidylpiperazine under the conditions given in Table 1. With the dyes given in Table 2, good colorations are obtained throughout.



   Table 1 # transfer
Example 1. Example 2. Example 3 Example 4 Example 5 characters
A 250 C 250 C 250 C 250 C 250 C
B. 250 # G 250 # C 250 # C 250 # C 250 C
C 240 # C 240 # C 240 # C 240 C 240 C
D 60 / 0.8. 16mm 60 / 0.8.16 mm 60 / 0.8.16 mm 60 / 0.8.16 mm 60 / 0.8.

   16 mm
E 75,68,105 81 78
F 300 300 300 300 300 G 130 # C 130 # C 130 # C 130 # C 13.0 C
H Steam Steam Steam Steam Steam 1 1: 5.3 1 #: 5.3 1: 5.3 @ 1: 5.3- 1:

   5.3
Table 1 (continued) Transfer transfer example 1 Example 2 Example 3 Example 4 Example 5
K - 25 C-- L 25 C --- M-250 C-250 C 50 C
N 5.1 5.5 5.3 5.25 5.3
0 25 22 26 24.5 27
Legend to table I spinning conditions:
Screw temperature (A)
Head temperature (B)
Spinneret temperature (C) Spinneret type (D) Maximum pressure (kg / cm2) (E)
Winding speed (m / min) (F) stretching conditions:
Temperature (G)
Medium (H)
Stretch ratio (I) completion:

  
Treatment for 5 min with a 5% methanolic solution of dichlorohydroxypropyldodecylamine (K)
Treatment for 5 min with a 5% methanolic solution of diglycidyl octadecylamine (L)
Treatment for 5 min with a 5% methanolic solution of diglycidyl piperazine (M) Properties of the drawn fiber:
Tensile strength (g / den) (N)
Elongation (%) (O)
Table 2 Acid dyes: Alizarin yellow 2G (C. I. mordant yellow 1) Wool red B (C. I. acid red 115) Alizarin red S (C. I. mordant red 3)
Alizarin blue SE (C.

   I. acid blue 43)
Acid black JVS (C. I. acid black 1) Metallized dyes:
Lanasyn yellow GLN (C. I. acid yellow 112)
Lanasyn red 2 GL (C. I. acid red 216)
Lanasyn brown 3 RL (C. I. acid brown 30) disperse dyes:
Setacyl yellow 3 G (C. I. disperse yellow 20)
Cibacetscharlach BR (C. I. disperse red 18) Brillantsetacylblau BG (C. I. disperse blue) Color fastness with acidic dyes.



  Color fastness with metallized dyes.



  Color fastness with disperse dyes.

 

Claims (1)

PATENT CLAIM Process for improving the dyeability of textile fibers, as obtained by spinning mixtures of polyolefins with basic nitrogen compounds which are effective as dye modifiers, characterized in that N-mono- and / or-diglycidyl derivatives of aliphatic, aromatic or heterocyclic amines are applied to the fibers or mono- or dichlorohydroxypropyl derivatives of these amines are allowed to act. SUBCLAIMS 1. The method according to claim, characterized in that fibers are used which contain at least 75% of the base polymer. 2. The method according to claim or dependent claim 1, characterized in that fibers made of poly-α-olefins, which consist of macromolecules with a predominantly isotactic structure, are used. 3. The method according to dependent claim 2, characterized in that the poly-α-olefin used is polypropylene, which consists mainly of isotactic macromolecules. 4. The method according to dependent claim 1, characterized in that the fibers contain color modifiers in an amount of 1 to 25 wt.%. 5. The method according to dependent claim 1, characterized in that the fibers as color modifiers amines or imines, for. B. Polvalkylenimine contain. 6. The method according to claim and the subclaims 1 to 4, characterized in that the fibers contain basic nitrogen polycondensates of epichlorohydrin as color modifiers. 7. The method according to claim 6, characterized in that the fibers contain basic nitrogen polycondensates of 1 mole of epichlorohydrin with a total of 1 mole of n-octadecylamine and piperazine or with a total of 1 mole of n-dodecylamine and piperazine. 8. The method according to dependent claim 1, characterized in that the fibers of the action of N-mono- and / or diglycidyl derivatives of aliphatic, aromatic or heterocyclic amines or mono-dichlorohydroxypropyl derivatives of these amines for a period of a few seconds up to 3 Hours and at a temperature from room temperature to about 10 C below the softening point of the base polymer. 9. The method according to dependent claim 8, characterized in that the N-mono- and / or-diglycidyl-n-dodecylamine or mono- or dichlorohydroxypropyl-n-dodecylamine is used. 10. The method according to claim and dependent claims 1 to 8, characterized in that the N-mono- or diglycidyl-n-octadecylamine or mono- or dichlorohydroxypropyl-n-octadecylamine is used. 11. The method according to claim and the dependent claims 1 to 8, characterized in that the N-mono- and / or-diglycidylpiperazine or mono- and dichlorohydroxypropylpiperazine is used. Cited writings and images French patent specification No. 1263 856