DE2042858A1 - Pohamide fibers dyed with cationic dyes and the corresponding dyeing process - Google Patents

Description

Polyamide fibers dyed with cationic dyes and the corresponding dyeing process.

The invention relates to a method for dyeing polyamide fibers with cationic dyes. These dyes are because of their bright hues, especially in red and pink parben, and because of the fluorescence that some of the Cationic dyes are of particular interest for use in polyamides.

109811/2066

JL 20A2858

HT-201 / YP-29

Polyamide fibers are the subject of extensive research been in the field of dyeing and numerous dyes are available, particularly in the categories of Disperse dyes and acidic dyes. The cationis see However, dyes on polyamide fibers were characterized by low affinity and poor washfastness. Polyamide fibers that contain aromatic or cyclohexane components are particularly resistant to cationic ones Dyes.

The invention provides cationically dyed polyamide fibers with improved color yield, washfastness and physical properties Properties that do not differ significantly from those of the non-colored fibers. The invention also provides a method of making the improved cationically dyed polyamide fibers by dyeing with cationic dyes in the presence of zinc thiocyanate. ·.

'The invention provides cationically dyed polyamide fibers which are characterized in that they have a zinc thio-. Contain cyanate complex of the cationic dye, the ratio of zinc to thiocyanate in the fibers is 1: 4. The invention also relates to a process for preparing colored polyamide fibers using kationiecher dyes in an aqueous dyeing bath at a temperature of at least 90 ⁰ C, which is characterized in that the dye bath is 1 to 60 wt .- # zinc thiocyanate, based on the weight of the fibers , and less than 1.5 1 ° of zinc thiocyanate, based on the weight of the water, contains; The dyed fibers preferably consist of poly (meta-phenylene-isophthalamide) or poly (methylene-di-1,4-oyolohexylendodeoandiamide). Furthermore, it is preferred that the dyebath also contains a dye "carrier" and that

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the temperature of the dyebath is 90 to 132 ^° C. Even more preferably, the temperature of the Pärbebades is above 100 ⁰ C.

The polyamide fibers which can be dyed according to the process according to the invention include all customary known polyamides, such as poly (hexamethylene adipamide), the polymers obtained from ε-caprolactam and their copolymers. ' The process is particularly useful for the application of cationic dyes to fibers made from polyamides containing aromatic components, as described in U.S. Patent 3,063,966, and from polyamides containing cyclohexane components, as described in U.S. Patent 3,393 210 are described. The preferred polyamides are poly (meta-phenylene-iBophthalamide) and the polymer derived from bis (4-aminocyclohexyl) methane and dodecanedicarboxylic acid, ie. Poly (methylene-di-1,4-cyelohexylene- " _t dodecandiamide).

The cationic dyes (sometimes known as basic dyes) are generally chemical mixtures which contain compounds having one or more onium groups, such as the quaternary ammonium group. The onium groups carry a positive ^ charge; hence the name "cationic". The main component can also contain anidic water-solubilizing groups, such as sulfonic acid or carboxylic acid groups, provided that there are more cationic group equivalents than anionic group equivalents. A large number of suitable cationic dyes are described in Canadian Patent 794x953. Other suitable cationic dyes are disclosed in the United States patent 3,338,660 disclosed.

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The aqueous dyebath used in the present invention contain zinc thiocyanate, which promotes high color yield and high wash fastness without significantly impairing the physical properties of the fibers. The color yield for cationic dyes applied to polyamide fibers in the presence of zinc thiocyanate is usually at least 2.5 times as big as. the color yield without zinc thiocyanate The color yield of the dyed thread polyamides is assessed according to the K / S value (Kubelka-Munk absorption scatter factor), which is calculated using the following equation:

K / S «(1-R) ² / 2R

where R is that part of the light which is reflected by the dyed yarn or fabric at the wavelength of the absorption aximam. In order to obtain a relative color yield, the K / S value for the coloration in the presence of zinc thiocyanate is divided by the K / S value obtained in the absence of zinc thiocyanate and multiplied by 100. In the process according to the invention, the dyebath can contain zinc thiocyanate or its corresponding ionic components. It is clear that the zinc cations, thiocyanate anions or thiocyanate complex ions from separate chemicals can be used. It is only essential that the zinc cation and the thiocyanate anion are available in sufficient quantities so that 1 to 60 % of the equivalent zinc thiocyanate, based on the weight of the fibers, and less than 1.5% by weight, based on the weight of the water in the bathroom.

Analysis of polyamide yarns after dyeing shows that

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Zinc and sulfur atoms are present in a 1: 4 ratio are. This relationship appears to indicate that a complex is being formed between the zinc thiocyanate and the dye molecule that may make the composition

[Dye * J ₉ [Zn (SCN) ⁴ * "]

owns. The zinc ion and the thiocyanate ion are therefore no longer in the 1; 2 ratio of Zn (SCN) ₂ . The 1: 4 ratio is maintained regardless of the dye concentration { . I) the dye complex may possibly act via a disperse staining mechanism. The weight ratio of zinc thiocyanate to dye weight is not critical and the optimum thiocyanate concentration in the bath can in fact be considerably greater than would be required to provide one equivalent of zinc for one equivalent of "" dye . It is believed that the additional zinc thiocyanate as a swelling agent for. the fiber and acts for the dye complex, which promotes diffusion.

It is surprising to find that other thiocyanates have the λ

Promote coloring of polyamides with cationic dyes relatively less well. The superiority of zinc thiocyanate is not completely clear, but zinc thiocyanate is far superior to the other thiooyanates.

Although no additional dye ^M carrier said aqueous dye bath "need not contain" it is often desirable to such "carrier" su use, when processed sohwierig to be dyed polyamide fibers. In particular, Farbetoff- ^M oarrier "metaphenylene in the dyeing of poly ( -ieophthalamide) fibers and poly (methyltn-di-1,4-

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CyclohexylenedodecaridiamideJ fibers are useful. Suitable dye · ¹ carriers required "are for these two types of fibers benzoate, pelargonic, mixtures of benzanilide and dimethyl terephthalate, o-phenylphenol, chlorinated benzene» biphenyl and Salicylsäuremethyiester.

In the present practice of the invention, the temperature of the aqueous dyeing bath is at least 9O ⁰ C, Ge • residential but less than about 132 ⁰ C. Of course, must be in the dyeing in aqueous baths at temperatures above 1Oi.

half 100 ⁰ C corresponding pressure devices are available

In the present invention, the aqueous dye bath is preferably acidic. If desired, customary dye bath additives can also be used, such as surface-active agents and leveling aids. Citric acid is a particularly desirable leveling aid. ·

_r The following examples serve to further illustrate preferred embodiments of the present invention. In these examples, poly (metaphenylene isophthalamide) is abbreviated as "MPD-I" and poly (methylene-di-1,4-cyclohexylenedodecanediamide) is abbreviated as "PACM-12". In these examples, all percentages are weight percentages. ■

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example 1

Effect of zinc thiocyanate concentration on the color value 14PD-I-Pr ob en

10 samples of an aps MPD-I fiber woven fabric, each weighing 10 g, are introduced into 10 separate aqueous baths at 58 ° C. Each bath contains 0.1 g of "Merpol" HCS (a non-ionic surfactant), 1.5 g of "Latyl" Carrier A (a mixture of benzanilide and dimethyl terephthalate), 4 g of glacial acetic acid, 0.3 g of "Calcozine ¹¹ Acrylic Blue HP (a, cationic dye, Color Index 'Basic Blue 54). Each bath contains a different amount of zinc thiocyanate, as indicated in Table I. The baths containing the tissue samples are heated to ^{121 ° C. and} Maintained at this temperature for 2 hours · The samples are then removed from the baths and rinsed. Then the colored samples are immersed in 400 ml of an aqueous bath containing 0.1 g of "Merpol" HCS (non-ionic surfactant) for 30 minutes. and 0.1 g of tetrasodium pyrophosphate, ^{cleaned at a temperature of 93 °} C. The dyed and cleaned material is then rinsed and dried in Table I. j. specified.

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TABLE I. i » Zinc thiocyanate 'related to K / S value Relative based on the fiber Color yield bath water 0 0 5 0.88 0.125 10 2.24 100 • 1 0.250 15th 2.45 254 2 0.375 20th 2.20 279 3 0.500 25th 2.20 250 4th 0.625 30 .. 1.22 • 250 5 0.750 35 . 1.71. 138 6th 0.875 40 1.55 195 7th 1,000 45 1.67 176 θ 1.125 1.59 189 9 181 '; 10
\
0

example

Effect of zinc thiocyanate concentration on the cationic coloration of PACM-12

21 samples of a fabric woven from PACM-12 threads, each weighing 5 g, are introduced into 21 separate 38 ⁰ C warn 200 ιοί baths. Seven of the baths contain 0.1 g of "Astrazon" -Yello * w 7GLL (a cationic dye, Color Index Basic Yellow 21). Seven others contain 0.1 g of ¹¹ S evr on "

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Brilliant Red D (a cationic dye, Color Index Basic Red 19). Another seven contain 0.1 g "Sevron" -Blue EG (a cationic dye »Color Index Basic Blue). Each of the baths also contains 4 g citric acid, 0.05 g "Herpol" HCS, 0.75 g "Cindye" DAC 888 (butyl benzoate), and zinc thiocyanate as indicated in Tobelle II. The baths were heated to 100 ⁰ C and 90 Hinuten maintained at this temperature. The dyed samples are then removed from the dye bath and rinsed. They are then purified for 30 minutes at 82 ⁰ C in a 200 ml aqueous bath containing tetrasodium pyrophosphate 0.05 "Merpol" HCS g and 0.05 g. The swatches are then rinsed and dried. I a series of yellow, red and blue dyes are obtained which have good wash fastness.

The effect of the zinc thiocyanate concentration on the color yield, as assessed by the K / S value, is shown in Table II specified. ,

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TABLE II 96 zinc thiocyanate based on Yellow K / S values Basic blue bath based on the paser 21 Red, 19 water 0 0.35 2.55 0 Ί0 2.65 2.07 5.16 1 0.25 20th 4.15 3.55 6.65 • 2. 0.50 30th 4.87 4.98 6.92 '3 0.75 40 5.06 . 5.60 7.25 4th 1.00 50 5.08 6.13 7.65 5 1.25 60 5.12 6.60 7.65 6th 1.50 5.92 7th

example

Effect of different dye carriers on the cationic staining of MPD-I

10 samples (10 g) of MPD-I woven fabric are placed in 10 separate aqueous baths at 38 ⁰ G, each 0.1 g of "Merpol" -HCS, 4 g of glacial acetic acid, 4.0 g of zinc thiooyanate (1 96 based on water, 25 i 'based on the fiber), 0.3 β "Calcozine" Acrylic Blue HP (Color Index Basio Blue 54) and 1.5 g of a Farbetoff-carrier contains. Different separate colorations are carried out, each with a different

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ren dye carriers. The effects of the various dye carriers on the dye yield, assessed according to the K / S-Yfert, are compiled in Table III. The parriers are added in such an amount that 15% by weight, based on the fiber, are present. The 10 baths, each containing a different carrier or no carrier, are ^{heated to 121 °} C. and kept at this temperature for 2 hours. The dyed materials are then removed from 'each' of the dye baths and rinsed. Purification is subsequently carried the colored materials at a temperature of 93 ⁰ C in 400 ml of another aqueous bath containing 0.1 g of "Merpol" HCS, and 0.1 g Tetranatriumjfyrophosphat contains 3oMn.lan £. The dyed and cleaned materials are then rinsed and dried. A number of blue dyeings are obtained which have good washfastness

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TABLE III

Dye £ - "Carrier"

None

"Phenetol" D

(Mixture of emulsified organic solvents)

"Cindye" DAC-888 (butyl benzoate)

Pelargonic acid

"Latyl" Carrier A '■

(Mixture of benzanilide and dimethyl terephthalate)

"Carolid" 50

(o-phenylphenol)

• "Chemo" carrier KD5W (Dimethyl phthalate)

"Tanavol" (chlorinated benzene)

¹¹ Char lab "M-1 ·

(Biphenyl) salicylic acid methyl ester color yield C / S

1.154 1.600

"1.713 1.542

1.883 2.010 1.179 1.646

1.613 1.624

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Example 4

Effect of different dye carrers on the cationic staining of tissues made from PACI-I-12

Sexton (5 g) of PACM-12 to bring tissue in 51 separate aqueous baths of 38 ⁰ C. Each of the -Bäder contains 200 ml of water, 4 g of citric acid, 0.05 g of "Merpol" HCS, 2 g of zinc thiocyanate (1 i » Based on water, 40 "/> based on the Paser) and 0.75 g of one of the .Parbctoff-Carriers indicated in Table IV. In addition, one of the three dyes indicated in Table IV is added. In each case, the amount of dye is 0. 1 g. it is then heated to 100 ⁰ C the bath and keeps it 90 Hinuten long b.ei this Teaperatur. then the stained tissue samples from the dyebath and rinsed away. Subsequently, cleans the stained samples for 30 minutes at 82 ⁰ C in 200 ml of another aqueous bath containing 0.05 g of "Merpol" HCS > and 0.05 g of tetrasol pyrophosphate The colored and cleaned materials are then rinsed and dried to give a range of orange, red and blue colorations with good wash fastness

The effect of different dye carriers on the color yield is determined by measuring K / S values for the dyed fabrics. Fabrics which had been dyed in the same way without using a carrier were also evaluated. The values obtained are summarized in Table IV. It will be understood that a wide variety of carriers can be used. The preference of any one of these carriers depends, besides the color value, on other properties, for example the washfastness, the physical properties of the fiber, the heat stability and the lightfastness.

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TABLE-IV

Parbetoff "carrier"

cationic dye

"Maxilon", "Sevron" "Sevron"

Brilliant Brilliant Blue 5G

Orange RA Red D (Color

(Color Index (Color In- Index

Basic Orange), dex Basic Basic

Red 19) Blue 4)

No t 10981 0.0819 0.536 • 0.385 "Cindye" DAC-888
(Butyl benzoate) 1.497 5.425 5.836 "Latyl" Carrier A
(Mixture of benzanilide
and dimethyl terephthalate) 1.423. 4.939 6.323 "Carolia ¹¹
(o-phenylphenol) 1,530, 6.845 7.070 "Tanavo1"
(chlorinated benzene) 1.576 5.433 6.869 "Phenetol" D
(Mixture of emulsified orga
niche solvent) 1,700 5.704 5.794 "Chemo ¹¹ Carrier KD5W
t-dimethyl phthalate) 0.376 1.118 2.150 "Tanalid" 004
(p-phenylphenol) 0.607 2,880 2.970 "Charlob" MS
(Biphenyl) 1.187 3.810 4,837 Pelargonic acid .1,838 4.830 6,931 Octyl alcohol 0.641 6.690 3.170 Benzyl alcohol 0.207 1.674 8.532 Dimethyl sulfone 0.361 2,500 2,450 Benzoic acid 0.410. 3.090 2,620 Dimethyl phthalate 1.519 1.325 1.486 Hexanol 1.019 2.830 7.447 Methyl alicylate 1.046 5.704 5.812 - H. - 1/2066

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example

Effect of temperature on the coloration of MPD-I

One brings samples of MPD-I woven fabric, each 10 g Weigh, in 12 aqueous 400 ml baths, each containing 0.3 g of one of the .In Table V specified dye.

Each of the baths also contains 0.1. g "Merpol" HCS, 1.0 g of zinc thiocyanate (0.25 i "based on the weight of water, 10 i 'based on the weight of the fiber), 3.5" Latyl "g. Carrier A and 4 »0 g ice sea fish. The dye baths are heated to the temperatures given in Table V and held at this temperature for 2 hours. Is carried out identical staining at 100 ⁰ C 110 ⁰ C 121 ⁰ C and 132 ⁰ C. Then the colored material is removed from the baths and rinsed. The dyed material is 30 minutes at 93 ⁰ C in 400 ml of another aqueous - purified bath containing tetrasodium pyrophosphate 0.1 "Merpol" HCS g and 0.1 g. The stained and cleaned

'Materials are then rinsed and dried. A number of fabrics dyed yellow, red and blue are obtained which each have good wet fastness.

The effect of temperature on the relative color yield, judged by the K / S value. goes from the following Table V.

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TABLE V

temperature

O S. co -J.
cn co I. '.K)

«Astrazon« ¹ Yellow "Basaci-yl" Red GL

"Calcozine"

Acrylic Blue IIP

100 ⁰ C 110 ⁰ C 121 ⁰ C 132 ⁰ C 30th 25th 100 * 90 35 * 30 100 * 105 28 30th • 100 * 100

* The ^{samples colored at 121 °} C. were arbitrarily assigned the value 100.

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example

For bur. g of a mixed, endless yarn

Ln £ it goes out, endless yarn of 60 denier, which contains 18 endless? 11ΰοη from PACI-I-T2 and 18 endless threads from a copolymer, which of bis - ^ - aminocyclohexyl) -. . methane and a diacid mixture. consisting of 19 mol- ^ dodecanedicarboxylic acid and 10 mol-5 »isophthalic acid; is derived, is prepared for coloring in a pack dyeing device. 24 packages of 0.227 kg (1/2 lb.) {are made using 2 twist / cm, Z-twist yarns. Lie yarns are first wound on collapsible sleeves and then pre ^{-shrunk by treatment in a steam autoclave at 127 ° C. for 30 minutes.} The yarn is then wound * from the sleeve onto 24 perforated steel cylinders. The cylinders are then placed in a 182 liter (48 gallon) kettle with a 19 liter (5 gallon) expansion tank. All subsequent process steps, such as cleaning, dyeing, etc., are carried out at the maximum capacity of the boiler. The bath: fiber weight ratio is 35: 1 for a 12 lb yarn load. The direction of flow g liquor in the boiler is changed every 3 minutes.

The yarn is vorge3chrumpfte each with 54.5 g of "Merpol" -HCS and letranatriumpyrophosphat for 20 minutes at 82 ⁰ C to give finish materials or to remove oils that have been deposited during previous processing steps cinu. A fresh bath is then made at room temperature containing 54.5 grams of "Merpol" HCS and 1980 grams of citric acid. 24 »5 g» 1.09 g and 36.5 g of dyes (1), (2) and (3), the formulas of which are given below, are added to this bath:

" ¹⁷ " BAD ORIGINAL

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ΗΤ-201 / ΪΡ-29.

(1) (C ₂ H ₅ ) ₂ N

N (C ₂ H ₅ ) ₂ ClO (ZnCl ₂ )

O C-OC ₂ H ₅

CH

3

CH = CH-N '

Coll, CN

^C 2 ^H 5

H ₂ PO ₄

- 18 -

π / ■> η ν. c

After 10 minutes, 2180 g of a 50% aqueous solution of zinc thiocyanate are added [0.5 ^c ß> Zn (SCN) ₂ based on water, 20%. based on the Paser, 1760 ⁰ Jo based on the! dye]. After 10 minutes, the bath temperature is increased at a rate of 1.67 ° C./min. "increased to 116 ° C At 71.1 ⁰ C (160 ⁰ P) gives you 1,635 g benzoate (" Cindye "DAC-472) added. At 96 ⁰ C the kettle is closed by the expansion tank, so that pressure is ENTV / as developed. The dyeing is carried out under pressure at 116 ^° C. for 2 hours. The bath temperature is then ^{lowered to 88 °} C. and the bath is discarded. The dyed yarn is then each with 54.5 g of "Merpol" HCS and tetrasodium pyrophosphate {

Cleaned for 20 minutes at 60 ^° C. in order to remove surface dye. The dyed yarns are "finally removed from the JCessel and dried with hot compressed air." · ·

The formulation described above - provides an attractive <"- bright fluorescent pink tint on the yarn. The dye wash fastness tests are carried out with the * yarn samples as described in AAICC Technical Manual, 1968 , pages B95 and 96, test nos. 61-1968, -Table I, Method HA ', Evaluation Method 8.1, carried out. A rating of 4 to 5 is achieved, which indicates little or no change in Parb <-'

Example 7 '

Effect of various metal salts on the color value K / S

The superiority of zinc thiocyanate as a complexing agent against other metal salts and thiocyanates is determined by laboratory piece dyeing using a Vistamatic-

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20A285Ö

Parbo illustrated. The colorations are at a bath: fiber ratio of about 60: 1, where one uses a smooth fabric structure which has been cleaned by shaking and has 47 threads / cm in the warp and 27.5 wefts / cm in the weft (120 ends / inch and 70 picks / inch). The yarn is a mixed one in warp and weft continuous yarn of 60 denier of the same composition as in example 6.

8 baths of 120 ml are prepared at room temperature, each containing 0.02 g of "Merpol" -HCS, 2.4 g of citric acid, 0.03 S dye of the following formula:

and 0.2 g of butyl benzoate ("Cindye" DAC-472). A 2 g sample of fabric is placed in each bath. The effect of various thiocyanates and other salts on colorability is then determined by adding 0.8 g of one of the salts listed in Table VI to each. Add dye bath. After 10 Hinuten the Badtemperatur.mit a rate of 1.1 ° C / min, to 100 ⁰ C erhöht.'Die dyeing is continued for 2 hours at .Siedepunkt .. The dyed pattern is then for 30 minutes at 6O ⁰ C cleaned in a fresh bath containing 0.02 g each of "Merpoi" -HCS and tetrasodium pyrophosphate

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contains to remove surface dye. The Huster be treated finally 2 Hinuten at 163 ⁰ C in an oven, to remove residual Butylbenzoatcarrier to.

The color value is then determined for each tissue sample, the values obtained are summarized in Table VI. V. ^r ie one is üiüht thiocyanate wei.t better than the other salts, including other thiocyanates, in promoting Pärbbarkeit of polyamide fabric with a cationic Parbstoff. ■

TABLE VI

Complexing agent "color value K / S

Zinc thiocyanate 6.3

Calcium thiocyanate 1.1

Zinc chloride 0.3

liatrium thiocyanate ■ 1.5 ■

Amonium thiocyanate. 1.0

Calcium chloride 0.1

Lithium bromide "0.4

no 0.3

'; BATH ORIGINAL

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Example 8

Coloring with various cationic dyes

39 separate fabric samples, made from the mixed continuous yarns described in Example 6, are placed in 39 separate baths, each of which is 2 ^c /> _t based on the weight of the fibers, one of the cationic dyes listed below and zinc thiocyanate in one Amount 'of 40 ^c />, based on the weight of the fibers and 0.1' / 6, based on the weight of the water in the bath. The following standard commercially available cationic dyes were used individually in these baths:

"Bacacryl" Yellow 5 RL

"Baaacryl" Yellow 5 GL "·". "'

"Basacryl" Yellow 7 GL, "Kaxilon" Yellow 2 RL

"Haxilon" Br. Palvine 10 GPP '*. .

"Aatraaon" Yellow 7 GLL "Haxilon" Br. Yellow 7 GLA "Maxiion" Br. Yellow 5 GL "Sevron ¹¹ Yellow R.

"Astrason" Yellow 8 GL ·

"Aatrason'V Yellow GRL

"Aütrazon" Golden Yellow .GLD "Astrazon" Orange L-. "Sevron" Orange G "Haxilon" Br. Orange RA "Astrazon" Orange 3 RL

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"Astrazon" Pink BL "

"Astrazon" Pink EBB D / L. ■

"Maxilon" Red BL

"S evr on" Br. Red 4 G- '·

"Sevron" Br. Red D. ·

"Astrazon" Pink FG
: "Sevron" Br. Red B ·

* "Sevron" Br. Red BN ..: _ .., ·

"Sevron" Br. Red 2 B.

"Sevron" Br. Red 3 B. ' ''

"Astrazon" Red 6B ... λ

"Basacryl" Violet RL ". '

"Maxilon" Br. Green 3G

"Sandocryl" Green BG ■ ·

"Du Pont" Br. Green Crystals. '

"Sevron" Blue 2 G

"Maxilon" Blue 5 RL

"Sevron" Blue 5 G '

"Sandocryl" Blue 2 BGLE

"Maxilon" Blue 5 g '·

"Sandocryl" Blue B3G

"Sevron" · Blue EG. I.

"Sevron" Blue ER

Each bath is maintained at 9O ⁰ C. The resulting dyed fabric samples are subjected to Vaschech.th.test using the AATCC Washfastness. Test used in Example β. None of the 39 stained tissue samples showed any change in Kuance and all had a color value of 5

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Claims (6)

PATENT CLAIMS: 1. Cationically dyed polyamide fibers, characterized in that that they contain a zinc mocyanate complex of the cationic pigment, the ratio of .Zinc to thiocyanate in the lines is 1: 4. 2. Pipes according to claim 1, characterized in that the fibers consist of poly (meta-phenylene isophthalamide). J. Pasern according to claim 1, characterized in that the fibers made of poly- (methylene-di-1 ^ -cyclohexylenendodecanediamide) exist. 4. A method for producing the dyed polyamide fibers of claim 1 using cationic paring agents in an aqueous dye bath at a temperature of at least 9O ⁰ C, characterized in that the dye bath 1 to 60 wt .- # Zinkthiocyanat, based on the weight of the - • 24 • 1098 1 1/2066 COPY HT-2O1 / YP-29 ^ ^ Pasern and less than $ 1.5 zinc thiocyanate based on that Weight of water, - contains. 5. The method according to claim 4, characterized in that the-Pärbebad also includes a Parbatoff-en-carriers and the temperature of the dyebath 90 to 132 ⁰ C. 6. The method according to claim 4, characterized in that that the temperature of the dye bath is above 100 ° C. COPY