DE1619376C - Process for level coloring of acrylonitrile polymers - Google Patents

Description

I 619

The dyebath is added according to the usual procedure for dyeing acrylonitrile polymers with an acid, a salt and dye and, if necessary, with a retarding aid and brings it quickly to the temperature that corresponds to the glass transition point of the fiber and that of the im generally lies between 70 and 85 "C. The temperature is then increased slowly and evenly up to 100 C and keep the bath at the boiling temperature until it is exhausted and you get a good one Achieved through dyeing of the fiber.

In this method, it is disadvantageous that a long heating time is required and that the temperature increase must be carried out with great care to prevent the dyes from being uneven. < wind up.

The so-called rapid dyeing process avoids the difficulties that dyeing during the Brings heating phase with it, by adding acid and salt to the bath, it quickly to boiling temperature bngt and only then add dye and, if necessary, retarder. The whole staining process takes place at the boiling temperature. This process is only suitable, however, in door dyeing machines which have a particularly rapid liquor circulation, because only in this way those added at boiling temperature Dyes are distributed homogeneously in the dyebath in a short time.

Another method for dyeing fibers made from acrylonitrile polymers is the so-called method jo for dyeing at constant temperature. There is no need for a retarder. The bath is mixed with acid and salt and brought to a temperature T which, depending on the depth of color to be colored, is between 80 and 100 ¹¹ C. As soon as this temperature has been set constant, the dyes are added and allowed to absorb.

The disadvantage of this method is that the experimental method for determining Γ is so imprecise that no temperatures can be given, only wide temperature intervals. The inaccuracy of the Door T determination method also results from the fact that a differentiation between dyes with different coloring behavior is not possible and that the test results simulate a linear dependence of the dyeing temperature on the depth of color to be colored.

The absorption rate of cationic dyes is so temperature dependent that they are in the As a rule, a change in temperature of only 4 ° C doubles or halves it. It follows from this that the specification of a temperature range which is customary in the process of dyeing at constant temperature is too imprecise and does not represent a basis for a safe working method.

It has now been found that textile material containing acrylonitrile polymers or consisting of them can be colored with kaiionic dyes regardless of whether the liquor is heated to the dyeing temperature T and dyed at this temperature with a defined bath depletion rate, the temperature T being derived from the equation

T ■ = K) O -

, '' (log tg "(100 C) - log h log (?) + l)

results in the

45

ι / the temperature change, the tg a (KX) C)

halved or doubled,
b the depth of color to be colored in milligrams of commercial dye per gram of Fasix material,

χ the bathroom exhaustion in percent,
f _r belonging to Badcrschöpfung / V

Coloring time in seconds.

* ^ the speed of creation at '. 'ι the' fempcratur T

and tg <i (100 C) = '' means.

[/ so

where (' _{r represents} the concentration of I landclass dye in the laser in milligrams per gram, which is present according to the / eit / with a dye set of 100 ° C. ss

For dyeing with a defined bath creation rate there are several variants. One can /. B. that with acid and optionally with salt offset dyebath, which already contains the textile material to be dyed, to the to calculated according to equation (1) Heat the dyeing temperature and then add the dissolved dyes.

In order to avoid disturbances caused by the differences in concentration temporarily occurring during the addition of the dyes To avoid this, it can be useful to fts the textile material before adding the dye quickly to remove from the Holle, add the dye and, as soon as it is homogeneously distributed. the textile material reintroduce. To the possibly occurring through heat radiation of the textile material To compensate for a drop in temperature, you can do that before removing the textile material Set the bath to a correspondingly higher temperature.

For single-bath bulking and dyeing of high-pile yarns using the new process the bath, which has been mixed with acid and possibly salt, is quickly heated to the boil and soaked for a long time Keep simmering until the twine is puffed up. Then cool down to the calculated temperature /, adds the dye and colors.

Finally, as with the conventional method, acid, salt and dye can also be added add low temperature, heat the bath to the temperature calculated according to equation (1) and add color at this temperature.

When the dyeing process has essentially ended at the temperature calculated according to equation (I), you can either cool the bath immediately or to a higher temperature, for example KK) C, heat to exhaustion and coloration the fiber can still be improved.

(Legalities of dyes come about from the fact that the absorption speed of dyes at various points on the fibrous material is different in size. For this different winding speed can be considered as influenceable Variables in the dye bath made temperature and concentration differences of the dye responsible will.

I Illegalities are therefore all the better prevented, the faster the liquor circulates in the dyeing plants. Here is the probability under given coloring conditions a level dyeing / u obtained is therefore dependent on the construction of the dyeing system; z. U. can in Kreuzspulfärheapparaien, called the Iotten / circulation is good, easy to be colored, on the other hand, for Siianggainfäparate with slower ! '! ottencirculalion for a good result of the staining often special precautionary measures are necessary agile.

Compared to the processes already known, the new process has the advantage that the bath scooping rate can be reduced for all dyeings with cationic dyes to one of the specified apparatus-related conditions can set optimal value. This value mainly depends on the Circulation of the liquor in the dyeing system and can be adjusted to that the dye bath, for example Is exhausted in 30, 60, 90 or 120 minutes.

Another advantage of this procedure ;; it follows from this that the probability of obtaining a level dyeing is the same for all dyeing machines if dyeing is always carried out at the same rate of depletion of the bath. If one has convinced oneself on the basis of a dyeing -i that under the given apparatus conditions a bath depletion time of, for example, 60 minutes leads to level dyeings, a level failure can be expected for all dyeings at this bath depletion time ίο

The equation (1) required for the new method to determine the door temperature T results from the following considerations:

When dyeing polyacrylonitrile fibers one must between winding speed and Baderschöpflug speed differentiate. The winding speed is given by the equation (2)

const.

I)

tg -ι = const.

If one specifies the drawn up color line length in files of b by the expression (A ': 100) ■ /> and the color / part associated with this 1 amount of raw material with l _f , then according to Fig. I equation Π)

const. · 1 /) . {.

= Concentration of the dye in the fiber in milligrams I landels dye per
Grams of fiber material,

- fiber constant.

■ - diffusion coefficient.

- ■ Time in seconds

40

given.

If the concentration C _f . against ■ r, one obtains a straight line whose slope

is a clear measure of the speed at which the dye in question is absorbed. As from the equation it can be seen that tg π is the concentration of the dye in the dyebath and thus of the one to be dyed Color depth independent.

In FIG. I, the drawing-up process for a coloration, the depth of which is intended to be variable and is denoted by b , is represented by such a straight line. (See Fig. I).

Since the supply of colors cannot exceed the value b , C _{h increases} . linear with [ t and ends

finally in the t: re straight line, which runs parallel to the abscissa with the distance b.

Ig 1 / -

(D,

b
100

Λ '- Uaderschöpfiing in "/».

I _x ■ = line for bath exhaustion -V.

b = depth of color to be dyed in milligrams of commercial dyes per gram of fiber.

('J - Bath exhaustion rate in the 1 '«/ ■' Temperature 7 ', which tells how much" » the bath wound up after a certain period of time is.

Equation (3) represents a., N quantitative relationship between the winding speed tg <i and

the bath depletion rate f J.

Taking into account the fact that tg η is a quantity-independent dye constant, equation (3) shows that the bath depletion rate must decrease with increasing depth h. which is consistent with practical experience.

The rate of absorption of cationic dyes on polyacrylonitrile fibers is very temperature-dependent above the Ci iasumwandungspunkt. With some fiber types, a reduction in temperature of just 3 ^° C is sufficient to halve the tg Vt value. If the temperature is lowered by 6 C, tg η is divided into four, and if the temperature is lowered by 9 C, the result is one eighth of the original tg 11 value.

In order to find a quantitative expression for the temperature dependence of the tg -1 value to be determined at 100 C, one can ask the question how often one has to halve tg n in order to get the smaller value tg <i (Γ), and this Formulate F'ra ^ e through an equation. Fs follows from this equation (4)

tg η (100 C)

tg <i (7:

π - = number of halves of tg «with a;: r temperature decrease from KX) 'to T (.

Since tg «is halved once by lowering the temperature by I · 3 C", halved twice by lowering the temperature by 2 · 3 C, and halved by η · 3 C "i times, gill

'7 -

55 One can therefore use (i in equation (4))
replace and obtain equation (6).

fiO tg K (IOO)
_Ί ^ KX) 'Γ

"3

= ig «(T).

Taking into account equation (3), equation (7) results

KK)

ilic one can still generalize if one considers the Number 3 by </ ersel / t: one obtains equation | K |

tg.il HW)) / V \.
_Λ KH) 7 V μ, ) y

H
KK)

ι / temperature reduction, the dun Ig .i-Werl halved.

By solving for 7 we get from (HeichnnglS) the equation (I):

7 KM), "- flew ig .. (im) l". "'''" P (,',) ' ² )

log 2 \ ^x; '''

With the help of this equation one can find a temperature 7 for every given color depth Λ.

at which the bath rate ()

corresponds to the optimal value under the given apparatus conditions. For the used Dyes only have to be 1g «(KX) C) experimentally be determined.

Equation (I) shows that if you have a defined rate of urination you get a parallel running (ic-

load with the slope. ' _il must echo. if

the I ärbetemperatur T against the l-'arbticfc h in logarithmic Maßslab brushing. The temperature T for a combination of substances can also be determined with the aid of this straight line.

In Fig. 2 for this purpose on the basis of a combination out

0.5 "ι, of the dye 2
0.7% of the dye 3
0.9% of the dye 4

an example can be given (see Fig. 2).

The dyes have the following structural formulas, and the straight lines in I i g. 2 apply to a fiber with ii = 4 and the indicated Ig .i (KX) C) values.

CII ₁ O

ΠΙ C C. H H, C \ [
/ N Cl Dye:
tii.i (HM) C) = I '
CH., 0.81

CH.,

N-CH,

\ CH ₃ SO ₄

Dye 3
Iu, ι (100 C) = 0.93 _io

N ■ N

N (CH ₁ I,

(H ₁ CII ₁ SO ₁

Dye 4
lg "IHH) C) ■ --- 1.48

You first look for the temperature value for a () .5% coloring with the dye 2 up and over carries this value on the straight line that belongs to dye 3. Then the abscissa is 0.7 "ο Weiler, überv - '. mms the received temperature value on the straight line for dye 4 and add 0.9% on the abscissa. The received ordinate value corresponds to the dyeing temperature for the combination. This procedure assumes that in the Haderschöpfungsgeschwindigkcil 0.5% of dye 2 with 0.56% of dye 3 and 1.26% of the Dye 3 corresponds to 1.97% of Dye 4, so that a substitution of one dye

is justified by the other dye.

Similar to dyes, one can also use canonical retarders, which are called colorless dyes can be attached (see Fig. 1). on the Determine tg "value at 100 C straight lines that represent the at

defined bath exhaustion speed required Illustrate temperature 7 "depending on the amount used.

Fs follows from the fact that one also has to choose the temperature for a combination of color

substances and retarders can determine where a

defined bath depletion rate is present.

With the help of this straight line one can ai'ch

determine the amount of retarder for a specific

Dye combination must be used. around

to obtain a defined bath depletion rate at a given dyeing temperature. This The possibility is of great importance when dyeing units with automatic temperature control used as this increases the number of

necessary temperature time programs can be reduced to a low number.

If you z. B. has convinced that a bath depletion rate of equation (9)

= ^Iü0 = 1.67. _T 60

in which the bath would be exhausted after 60 minutes, sufficient for level dyeing, applies to all dyes and all color depths equation (10).

7 = KH) -

(I.

log 2 (log lg-1 (KX) C) - log J? - log 1.67 + 2)

7 8

For the general case. c'-iU one does not depend on a fixed bath scooping speed of
uisgchl. is applicable:

TK) O _U) " ₂ (log tg, HI (X) C) log /» - logf -M + 2V (II)

If one equation) 111 from equation (12)

7 "K) O," f log tg, ι (ΚΧ) Cl lon /> louf ') I 2) (I2 |

from / iehl. results in equation (13)

Equation (12) shows the dependence of the calculated temperature of 92 ° C.

..,.,. /. VX. The value 1.36 corresponds to a Hadcrschönf

exhaustion rate ^ 1 of a will- _{) ü ()}

..... .... ....;. 'Ίι speed of ^. .. ·. . . ie a Färhezcit

kurhch selected temperature /, on. ^e | W ■ (■> ()

Equation (13) is also of considerably more practical use of 90 minutes.

Importance. It can be used to determine that around 25 Has bath is heated to 92 C, and then how many degrees an arbitrarily selected dye temperature is added. After 90 minutes, the temperature T _n is heated below or above the optimal temperature 7 to 100 ° C. within 10 minutes and this ran if the BuI kept boiling for a further 20 minutes at a speed.

/.V \ ... . ,. . . r · ■ An excellently level dyeing is obtained.

. which can be determined is exhausted.

Equation (13) can therefore be used for this. e 1 s ρ 1 e

by means of a preliminary test by measuring the bath-loo parts of an acrylonitrile polymer gcwcbcsdi = 4)

ei speed of creation at temperature T ₁₁ . are in an aqueous bath. that
to find the temperature at which the optimal q 5 j _e j | _c i _ar h _s to (T 2

Wheel exhaustion speed is present. 35 "with a tg« (100 C) value of 0.81.

Information on parts and percentages in the following q η j _c ^ _e Jarstoff 3

Examples are based on weight. ' _{with a lg} " _{{m C)} . _{Value of a93}

Example I ^ .9 parts of dye 4

,,, "_ ,. , ■ _A ,,, ·. . with a tg .1 (100 C) value of 1.48

100 \ hasten a Acrylnitnlpolymerisatgewebes with 40th

a value of a = 4 in an aqueous bath, -, _T ·, peciocHnrp

the 4 parts of larbslofTs 3 with a tg, i (100 ^r C> ^p

Value of 0.93 and contains 3 parts of acetic acid, with contains, with a liquor ratio of 1:20 and

a liquor ratio of 1:12 and a temperature of 93.5 ° C colored. The temperature

temperature T of 98 "C. 45 is shown graphically on the basis of FIG. 2. as on page 11

The temperature T = 98 C results from the described, determined.

^ The bath is quickly heated to 95.5 ° C.

7-100 - (log 0.93 - log 40 - log 1.67 + 2). the yarn out of the liquor and sets the loosened

- - dyes too; as soon as the dyes are homogeneously distributed

The value 1.67 is the value of the quotient for which 50 are the yarn is reintroduced. Through this

". , .. _r , ■ .-, · / VN. Operation cools the liquor to 93.5 ° C from Man

Hand exhaustion speed, "( _? J under an ^ ^ _minutes ^ _{djeser Te} ^" ^ _kül ^

would assume that after 1 hour a 100% bath is then removed. The coloring obtained is extremely irrelevant.

exhaustion achieved. The bath is initially set to 98 C

heated, then the dye solution is added. 55 B e i s ρ i c 1 4

After a dyeing time of 60 minutes, the liquor is

pulled out and is cooled. The color is 100 parts of a high-volume acrylonitrile polymer

excellent does not matter. games (a = 4) are played in an aqueous bath. that

Example 2 ^ 0.5 part of dye 2

100 parts of an _{Acrylnitnipolymerisatnockenma.- "7 Tejle} ^ ™ '""OOO'O value of 0.81.

rials with a value a = 3 are written in an aqueous' _m :,.; "" _. " _Mnn ,,,, ...." ,,

Bad, the 2Te.le dye4 with a tgr, (100 "CV ™ d ^{h V0} "'"

Value of 1.66, 3 parts acetic acid and 10 parts, _{τ; ί} Pcciocäiire

(contains silver salt, with a hotten ratio of < >;

1: 15 and one according to contains, with a liquor ratio of 1:30 and

.j colored at a temperature of 9ΓΓ. The lemperatiii

7 K) O '- (log l.dd Ina 20 - log 1.36 + 2) is determined graphically as in Example 3
Inn 2

ing / Rj

9 10

The bath is quickly brought to 100 C and the dyes and the acid are brought to K '' (

Bulked yarn for 5 minutes at this temperature. adjusted dye bath added. After 60 Minu'.ei

After cooling and adjusting the temperature of the extracted liquor is cooled. The coloration

9IC, the dissolved dyes are added to the bathroom - it doesn't matter,

given. After a dyeing time of 60 minutes, 5

the exhausted bath cooled down. The dyeing is above Example 8 no matter quickly.

B e I 5 100 parts of an acrylonitrile polymer fabric / - 5

be with

100 parts of an acrynitrile polymerizatgev / 'ibesti / = 4) io - ... ... , .

, ■ ■ .. '"■ ' ,, Ii 2 (rapid dye4

are in an aqueous bath that.,. ,,., ..., ... ,,,,,

^& with a tg. <(KK) (l-value of 2.4 and

1.3 parts of the retarder I of the formula 3 parts of acetic acid

, -jl _{ - | with an air ratio of I: 40 upd with einci

■ '15 temperature of K7 C colored. The temperature ergihi

ii / ·· μ, - λ II ,, ι can be derived from the following specification

I falling speed of = 2.05:

/ - •! Ι '41) 6')

with a tg π (K) OC) -We-I of 0.70. ^{; o} 7 = KW) \ (log 2.4 log 20 log 2.05 * 2i

I part dye 4 * ~

with a tg <, (KX) C) value of 1.48 ,, ...,,, ·., ·, “,. . _r .

, ^B The dye bath is at 60 (with acetic acid and

3 parts of acetic acid dye are added and the mixture is heated to 87.degree. Color it

'25 40 minutes at this temperature and improved

contains, with a liquor ratio of 1:20 and then the color of the fiber through

a temperature of 95 "C, ;; colored. The temperature 10 minutes heating the hotte to KW) C. Ma"

if it is determined graphically analogously to Example 3, it has an extremely level coloration.

The solution of dye and auxiliary is the

95 C hot dye bath added. After 50 minutes w

it is cooled down and an excellently level example 9 is obtained Coloring.

η _e j _{s D} j ,. ι 6 ^{When dyeing l0} ° 'rush Acrylonitrilpolymerisr

^f 'fibers (<i = 3) with

ICO parts of a mixture of 50 parts of an acrylic is “ _1T .,. ,,. . . .

!! ^! polymer ^fiber (a = 4) and 50 parts of tree- ° ² ieilen * -arbstoiTA only one

want to be known with, _{7 τ Ί} "" en tg., (lOOC) -Vert.

1.7 parts dye B with a

I part dye unknown tg .1 (100 (') value.

miici.-cm tg «i (.IO) C) value of 0.93 and 0.6 parts of dyes with a

3 parts of acetic acid unknown tg "(100 C) - value uiul

with a liquor ratio of v: m 1:50 and with 3 parts of acetic acid

accordingly one finds in a preliminary experiment that with you

4 arbitrarily selected temperature T = 90C

7 = 100 - - (log 0.93 - log 20 - log 1.36 + 2) 45 _n , .... _L " _I00

log 2 bath depletion rate of - ^ L-. = 1.0-

calculated temperature of 93C with a bath.

Depletion rate of 1.36 colored. For the desired bath exhaustion speed "

The bath is at 60 ° C with glacial acid and dye,. lon

and heated to 93C .. After l '/ ₂ hours, 50 ^{of Keit)} / ω "-Ίη ^=' · ⁶⁷ 8 ^{he lbt SLCH mj} t help of

Dyeing at 90 ⁰ C one increases the temperature rapidly equation (13) one of

on KX) C and hold her door there for 20 minutes. Man ^

thus receives an exquisitely level coloring. ^ = 90 + '--- (log 1.67 lot; 1.05) = 92 C

B e i s ρ i 0 i 7

100 parts of a fiber blend of 50 parts of an example 10

Acrylonitrile polymer (a = 4) and 50 parts of poly- To determine u of an acrylonitrile polymer

esters will be made with fiber of unknown origin KX) parts of this

0.2 parts of dye 2 ^ ^fiber ™ terials with

with a tg «(100'C) -Weri of 0.81. 3 parts of dye 3 with one on this fiber

0.2 parts of dye 3 unknown tg “ (100C) value and

with a tg «(10OC) value of 0.93 3 parts of acetic acid

3 parts acetic acid. ? ^ei J, ™ ⁾ , ^{and W} \ 8 ^elUrbt · From the measured Had-

⁵ fts exhaustion speeds with a liquor ratio of 1:40 and one

Colored temperature of 89 C. The temperature becomes (^ \ j _vw / V \

determined graphically analogously to Example 3. VI ', / ,, »,, \ j / _% /" ₍

Claims (3)

vim 2.4 b / w. 0J2 results with the help of Cilcichiinji (T11, - '/; ,,) Ιοί: 2 lon () lou (' V) (K) O - Wl · log 2 "~: log 2.4 log 0.12 =" ίο patent claims : 1. A process for the level colors of acrylonitrile polymers containing or consisting of textile material with cationic dyes, characterized in that the liquor is heated to the dyeing temperature T and dyes at this temperature at a defined rate of ragging, the temperature T being derived from the calibration 7 = 100 - 'J ₁ flew tg -ι (100 C) - log /. log ('\ rl \ in the C) α the change in temperature, the tg «(100
halved or doubled, / 'the depth of color to be colored in milligrams I landels dye per gram of fiber material, .V the rag exhaustion in percent, ? _r belonging to the rag creation X dyeing time, in seconds, the bath depletion rate at temperature T and tg <((100 C) = mean. T = 7 ". f- log 2 • rubs, whereby (rl), the rate of rage to be measured at temperature Γ means and Ivohei C _{F is} the concentration of commercial dye In the laser in milligrams per gram, (here according to the time. 'Is available at a dyeing temperature of 100 ° C. 2. The method according to claim I, characterized in that if the value of Ig η (100 C) of a dye on a fiber is unknown, at an arbitrarily selected temperature of 7 | ₍ . colors, Ivobei the dyeing temperature T according to claim I from the equation 30 and α have the meanings given for claims 1. 3. The method according to claim I, characterized in that if the value of <one fiber is unknown, two arbitrarily selected l'cmpe temperatures T ₁₁ . and /;, colors, where α is derived from the equation '' (/ ", 7,;,) log 2 results in the and the / u measuring bath speeds at the arbitrarily chosen temperatures 7 “. and 7 “. are 1 sheet of drawings