DD208477A3 - PROCESS FOR THE PREPARATION OF DISPERSION TOZO FIBROUSES IN FAERBESTABILITY MODIFICATIONS - Google Patents

Abstract

The invention relates to the preparation of faerbestabiler modifications of dispersion azo dyes. They are obtained by using the azo coupling according to the invention in the presence of from 0.5 to 5% by weight, based on the dry dye yield, of polymerization products of ethylene oxide having molecular weights greater than 1500 and / or ethoxylated fatty alcohols or fatty acids in the preparation of the dispersion azo dyes in an otherwise conventional manner. which contain per mole of fatty alcohol or fatty acid 50 to 100 moles of ethylene oxide, takes place and after filtering off and washing neutral the dye paste on the filter press with hot water of 60 to 90 degrees C is treated.

Description

VEB CEEMZSKOIiIBETAa: BITOJERPELD 2248

Method 21: 2? Production of dispersion soda dyes in dye-stable modifications

The invention relates to the preparation of dye-stable modifications of dispersion-type dyes »

Disperse dyes are relatively small molecular weight colored compounds with very low water solubility. They are zujin as finely dispersed aqueous suspensions

amide, cellulose testes ". *" The dye suspensions must be thermally sufficiently stable to ensure an undisturbed dyeing process, ie, * Tinfcf rl Q "nr = al C" · f / io ^ i 'o.iViavi Pal ρ σ - -Ί-ρ σαη r; ο Q "ir ΐΐ -ν-1 Vi ^ i _

2 - O /. η £ -1 ^ S 2243

For the generation of this dispersion stability is the 'use of highly effective dispersants in Maßfeinstmahlung required, on the other hand, the milled grain of its internal thermodynamic structure must be sufficiently stable * In dispersion azo dyes arise at the moment of the meeting of diazo and coupling component, the virtually water-insoluble reaction products »First form Microcrystalline primary particles with dimensions usually far below 1 / μm, which then coagulate coarsely disperse secondary particles. "Agglomerate * In this gate, they are separated from the reaction medium and purified. The water retained by the dye gives an approximate measure of the specific 'surface energy'. The tendency to reduce the surface energy is due to the morphological changes that are collectively referred to as Ostwala ripening. * It leads to the coagulum ('tizw. . flocculates) in which the primary crystals are liable only by bridges of "structural · ™ turwasser" each connected to the 'fused at points and edges Agglomeratan and shallow way. Aggregates up to the regular macrocrystal * The coagulum - agglomerate ~ aggregal transitions are predominantly realized by dmla decay of primary crystals, while the path to the macrocrystalline state proceeds via the urine solution.

In the Piaßfeinstmahlung, attempts to convert the secondary particles in a particle size spectrum, the maximum of unter.2 / 4m is located and is das'praktisch free of particles larger than 5 / Wm. In this case, effective grinding aids have to be used, ~ / ie they z * 3. DD-PS 150 391 describes * The need to continually re-formed during the grinding active breaking points, the dye particles having a strongly adherent

_ / / t t j S

XX years O 'W JVJ U -L WXJ-W WO * J ' - Ksi-L J ^ i. WWJ, JJ U- ¹ C 1- w- ^. Ο -'.- 1. ^ - '_i._L · O _ ι. C-C2. ι = ί: =. -L "-'iiiC- _ C ^ ί> _- ^ Ij.

- ^ "Io ö - ^ -.'- τΐ η π λ V. λ Q ^ - γλ Vi *?" Ϊ́ -. 4- ρ. -τ-

{jTTi iPii / Z'a'Ds, 2T ~ tUcU-ILaJ- ¹ S -Psiife ^^^ rao. dsT ¹ Tsilcipe ⁷ ! Si ⁷ ^ s S "i" t ~ · distinctive role * If s, B, subjected to a dye paste in Flokkulat- or Agglomeratsustand grinding, then be at Einsata powerful DisOergieris.ittel high F'E already "after a relatively Icürser grinding invert In the case of Eaumt he is stable for a longer period of time. * If, however, such a dilute suspension is used, that it coalesces, then large numbers of coarsely dispersed particles form, which can lead to fecal complications. Dye ", which the light microcosm

T O.COn l ^ oi-i ^ OTlriPiar! CT ^ Vi-V -rr-; ^ l ^ λ ^ -ιτο ^ οΤ ¹ * nflh1 hP "" Ί 1 of

_{1 £} -j OO - - - "i

detectable

_Λ 7ρ1 ο τ ττ!

To obtain the degree of maturity or degree of the dye paste which should give stable suspensions after Tennahlung _} Trerden in the patent literature various

^ 32j) .O ?, 1 _; ', -υ 5j2 ,. 1 /; j jji and 1; ₍ J j _((((((( As As As As As As - - - - - -

t v

pastes and, in other cases, heated to temperatures of from 80 to 100 g of lignin derivatives and ethoxylated fatty alcohols, with the result that there is a modification, reaction and release of the dyestuff which, according to Versiahlu-ng.

become in the DS-AS 2 721 18? and 2,835,544 and in DS-OSs 2,921,210, 2,943,016 and 2,950,583, the

i τ *

raised stabili

Additives. "Also the grinding at temperatures and a Tortrccknung the dye pastes

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should lead to the same result »These procedures are preceded by a series . 2Taealites Affected "Renewed amnesia of the dye paste results in the dye being virtually recrystallized. These procedures reduce productivity and can lead to the macrocrystalline state leading to uneconomically long times in hemodial precipitation. Since the milling aggregates have a very low energetic efficiency. is then wasted much valuable Jiut3energie to achieve the required fine distribution «

According to German Offenlegungsschrift 2 313 003, a method is proposed for achieving stable dye suspensions, in which anionic dispersant, such as llaphthalenesulfic acid condensation products, dispersants, are used during the coupling.

Lignosulfonic acids, combined with branched lonvl

and drying takes place ..

The ITachteile disss ^ ^"1 procedure are" 3s wsrder-FarbstoffsusTJensionen obtain the _f a no-hen. Water ™ bsw * salinity is 3s. It is known that with the dilution of the grinding suspension the intensity n_Q-f ? 'Jp' 3 "Ppi ti .yhrn.-o 'η 1 n ^ -i ~ and di ⁵ " ^^ td " ¹ · ^α R ^ rtn-7 .ci -rr - Ai.Q'oo-vj-.ci

Energy and material costs * by the extension

The high salt content of the dye suspension leads beyond 'su on the one deterioration of thermal dispersion stability,' The application of this procedure as part of customary batch Farbstofftechno- losrie ⁷ ^ ^"1" c "^ t Ch ^ T I thou ^ c ^ ¹ - ^ * ¹ '- -' said anionic dispersant such feinteilii dye precipitates arise that are permeable

can."

Similar disadvantages are found in the D3-0S 2 533 603 ^ '' UD ό 1 up & ir Ruhrweksku "elu2uhlen with the addition of anion.i ~

the resulting dye suspension neutralizes ^a

and at 30 to 90 ^ C weitergememahlen * Due to the

high dispersion of the suspension can be the dye

no longer by presses bsv? »centrifuges, but

J.2. υ

become,

DS-AS 2 455 332, DS-OS 2 509 5cO and 2 603 83o describe processes in which the stable modification by addition of organic solvents, such as

mixtures, is erseugt in dye coupling * After part of this is that the high solution Sittel shares forcing 3U elaborate procedural Konseauensen (safety technology, Lösungsinittelriickge "-winnung etc") *

The object of the invention is a method of stabilizing the color stable to disioercionic substance modifications

technoiogy, which does not require any additional "productivity-reducing" procedures

 ö

Loan - ^^ d * ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^

wnr-n ^ found ,, that the stated target

¹ T ⁷ £ 5 S ο ""! "V-) -Ω ~ f * ο *?" · --.- ^ Tu "] O ^ Ci"' ^T ~' ^ Ci ~ f; **>?

Positioning of the Disperse Aso Dyes in Otherwise Usual Way Di ^ -. SokuOwlur

j_ W _i_ Υ: Ί ";" O ¹ CS * -. ' ~ ^. ^ i-jO -J __ -J-. t. i ^lV - i _y 7 "'' -. C- O ^ J

"wet of 21m ^ it" ^ ens ì juu ocis

^: ί ι 3 s-J -e-fl O Ο! '· Q (scr 3 νώ'".-'CC-VO

Anlagerimgsprodukten of Sthylenoxids to fatty alcohols or fatty acids containing per mole of fatty alcohol bz ^ / _a fatty acid 50 ois 100 moles of ethylene oxide, or in the presence of Mischunylenoxid, y

conditions of the named polymerization and AnIa ^; In the further course, after filtration and neutral washing, the dyestuff paste on the filter press is treated with hot water of 60 to 90 g. Of the compounds, 0.5 to 5% by mass, based on the dye yield, calculated as dry matter. Of course, the Qxethylierungsprodukte of fatty alcohols or »fatty acids must not have a cloud point (Phaseninver s sion point) in the temperature range in which the He 13-water treatment, otherwise clumping occur, which leads to difficulties in the grinding or» transport of the Ground material to be ground through the pipelines. Preferably, therefore, the ethylation products of fatty alcohols or fatty acids are obtained from esters of C ,, to G

Fatty acids with esters of C ,,,. to G _x . ^ - used *

Execution on so I le

The following examples serve to confine a more detailed explanation de "^ ¹ ^ Sr ^ irdun without them.

-ι st-) i αϊ Λ

-i ™>'<~ J -1- VJ J- ^. 1

After cooling the resulting nitrosyl sulfuric acid to 1; 363 kg of 2,6-dichloro-4-nitraniline are charged under charges. In parallel

1 ^ / ΐ

man lanssain 4-16 ks. N-G ~ aneth ~ l ~ ~ ~ ~ O3: 3thylaniline in 4-80 kp acetic anhydride enter «

To the presented diazo component are added 20 kg of Bthylenoxid polymer with a molecular weight of at least 1500 ^ nd then the iüipplungslösung at - 3 to O "C run, After completion of coupling and Nachrührzsit τ / ird the approach to a filter press, sedates * Here becomes the dye cake

- λ η ^ \ j> Λ. /, T-, -

/ <y> y ρ O

first washed neutral with cold water, then treated for about 60 minutes with hot water of 80 ⁰ C and lockable Bend awsi blow to three hours with PreBluft.

. One thus receives a Därbstoffpaste that in the in DD-PS 14-? described manner is very easy to grind and Därbstoffdisper ions with excellent thermal dispersion stability

The advantages of the process according to the invention are apparent from the following table, in which the following variants are compared

Color st off paste A: method of operation according to the invention

e; Coupling without additive, no hot water treatment

G * TTi τ ~ r \ τϊ "I τ; ~"! C ⁸ * n Ί "h ^ 7. Ϊ 1 ¹ ^! ^" ^ * ^ 0 ¹ ^ ^ ^.-Γ ρ ^ - ^ ή? z> Q ^ o -r> ~ r \ -ο Ή ο -'-. H ".

1 11T1O ¹

D; Its addition to piping, but hot-water treatment

Ais target variables are the surpassing of the appropriate fine distribution necessary 2iahldauer t-, _T under the conditions described in the embodiment of DD-PS 144 735 conditions, and the thermal dispersion stability DS of the spray-dried dye, also shown in the cited references,

Hsglersusatz hot treatment

Paste at Azo on Filter ^ DS coupler ^; press (min)

approximately 7 Ο ca » Ι OO 60 ca » ISO

A + + ca, 70 0_

0.75

0.62 D-- + 'ca, ISO O ₅ SI

8 _ & * "W V 3 '*** W 224-8

Example 2

; .., '! "*. '^ J.'vrf-U. , ¹ ^ - '_ ¹ I * ^ ι ν -.UJ ¹ - ^ -μ i ^ J ¹ ^ J ~ i-> - / ^ i- i A-Lw -; - -j-, ^ s OO vi / -1- - * - «J ^ <^ .J. JT - J -i. Vj ¹ w '-i * _, ¹ ^ i i_ ί-f \ "f __ V» / »L. js_> t *. · "<

will be at 15 C 28? kg 2-cyano-i-nit'raniline, registered, (Diaz ο sals

ο.

The coupling component is formed by dissolving 315 kg of N-cyanoethyl K-ethylaniline in dilute hydrochloric acid (2800 l of water and 210 l of HCl 32%) and adding 30 kg of an ethoxylated stearyl alcohol containing on average 70 mol of ethylene oxide per mole of jettalcohol. 2000 ml of water and 7000 kg of 3is are added to the clear amine salt solution. The azo coupling is carried out SO _{3 of} the coupling solution about 10 % of the diazosalt solution is added. »The mixture is allowed to stir for about 90 minutes and then the remaining diazosalt solution is added within minutes should not exceed 5 ° C

st iron, The batch is followed up for 10 to 20 hours

The filter press is pumped * ϊ after pressing the mother liquor is

• neutralize with cold water and add the press

treated ". The drainage cocks of the filter press remain closed during this time,

The dye obtained after completion of the thermal treatment with respect to grindability and dispersion stability under dyeing conditions largely the behavior of the described in DD-FS 122 257 B-modification *

Claims (1)

\ *) / Π ζΖ 1 "4 H _.o -_ ^ L * ^> 7WV 1 ~ V * J 2248 Process for the preparation of dye-stable disperse dye modifications of azo dyes of the general formula Δ τ * - T ¹ I - ο α he 4r - N = ^ T - Ar - N = N - 4r where Ar ^, Ar _? and Ar-substituted or unsubstituted mono- or acyclic aromatics äars'Gel.lenj by Diazotieruiig and coupling using non-ionic dispersants based on ethylene oxide, characterized gekennaichnet in that already Waiirend the Kuppiungsreaktion 0 _} 3 to 5 Massenprosent _} based on Därbst off dry yield _{} of} a Tyrolisa- product of 3thylthio: dd with a lalolinasse greater than ISOO and / or ethoxylated fatty alcohol or ethoxylated fatty acid containing 50 to 100 moles of ethylene oxide per mole of jettalcohol or ethylene salt for the reaction mixture Become your aftertreatment filter and wash the parestoff paste on the skin. "G ¹ ^ i 1 -J- ^. -V ^, ~~ i, - ^ - · - ^ -. T ~. -A J-" - ^ - O - -o .-- r ^ ' - i "^) - r \ - · a O ^ - ~> - ^ - OO, '" 1 ^ .-, V ^ -, - ^,, 4 -, T -ii - _τ -ϊ -ν -, - Ξ