JPS58162666A - Manufacture of reactive dye composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for preparing compositions of reactive dyes having complex group-reactive components. These reactive dyes have the following formula: , A = group of dye chromophore, and = integer from 1 to 5].

The novel method is characterized in that it contains sulfo groups, is free of reactive groups and has the formula [wherein M"=H, NH4, Li, K over Na, and R", n and A are as defined above. ] and preferably contains at most 8% by weight (based on the amount of dye) of salt,
In the presence of an acid binder in an aqueous medium which may optionally contain concentration-increasing additions, the formula % formula % (16) [wherein R is as defined above and X represents fluorine or chlorine] ), the liquid composition thus obtained is optionally buffered or the liquid composition is dried and then, if desired, ground to a powder.

Customary standardizing agents and/or buffers which stabilize the pH value to aS~8 can be mixed in before and/or after drying. Drying can be carried out, for example, in a circulating air oven or using a nozzle lid dryer or a drum dryer, but is preferably carried out by spray drying using 1 or 20 nozzles or a rotating disk atomizer. In the case of some dyes, it is suitable to spray dry a hot solution of the ingredients.

In spray drying, the concentration of dye in water is usually 10-45% by weight.

In formula (11), Ml preferably represents Li, and R
1 preferably represents hydrogen or methyl.

It is already known that concentrated solutions of reactive dyes can be produced in the following way.

1. Dissolve the salt-containing presscake or dried salt-containing process material in water by adding a suitable solubilizer. However, this process is highly unsuitable for preparing concentrated solutions of reactive dyes (1) containing sulfonic acid groups due to the high salt content.

2 DE 2.94&292 Al describes a further method for producing concentrated reactive dye solutions.

A dilute salt-containing reaction solution or a dilute aqueous solution of a dye is subjected to pressure filtration to remove salts and concentrated. This method is expensive and pressure permeation filtration often partially hydrolyzes the reactive groups.

German Published Patent No. λ94 & 29f1 A1 also describes a method in which a dilute salt-containing reaction solution or a dilute aqueous solution of a dye is subjected to pressure permeation V filtration to remove the salt, concentrated, and then dried in a conventional manner. are doing. This method is very expensive.

An unsuitable method for producing concentrated solutions as well as solid compositions of the present reactive dyes (1) containing sulfo/acid groups is salting out of the reactive dyes using volatile ammonium salts followed by elevated temperature. It is to dry it. Most reactive dyes are hydrolyzed in this type of process.

The process according to the invention for producing concentrated liquid compositions of reactive dyes (1), in comparison to the above-mentioned O process, provides that the intended liquid composition is obtained directly as the final product during the synthesis of the dye and thus It has the surprising advantage that many costly steps can be omitted and the powder compositions that can be prepared therefrom are soluble in cold and hot water.

The concentrated liquid silk composition of the reactive dye may be a concentrated liquid crystal composition as well as a concentrated solution. This depends on the nature of the reactive dye used, ie its behavior under the reaction conditions used.

Reactive dye with excellent solubility in cold and hot water (1)
The method of the present invention for producing a solid composition containing a small amount of hydrolyzable reactive groups, without a refining step, than the above-mentioned production method, provides a very easily soluble composition containing a small amount of hydrolyzable reactive groups. It has the surprising advantage that powders or granules can be obtained.

The hetero-reactive group R in formula (1) is capable of reacting with the hydroxyl groups of the cellulose when the dye is applied to the cellulosic material in the presence of an acid binder and, if appropriate, under the action of heat, or with a high molecular weight 4-lyamide fibers, such as those having one or more X-ray reactive groups or leaving substituents that can react with the MB groups of these fibers to form covalent bonds when applied to wool. means.

Suitable me reactive groups containing at least one leaving group clamped to a hetero group group include, among others, a 5- or 6-membered hetero group group 1
For example, cynazine, cyazine, triazine, such as pyridine, biryzine, pyridazine, thiazine, oxazine or asymmetric or symmetrical triazine 11, or such ring systems fused with one or more 0@, such as quinoline, acridine, Those containing at least one reactive substituent attached to the quinnoline, quinoline, quinoxaline, acridine, 7enazone, and zenathridine ring systems. 2- or 6-membered compound having at least 1 reactive substituent; S *Those that can contain @ are suitable.

Examples that may be mentioned of reactive substituents on complex 11 are
f 7, (C1, By or F), 7'/I' (7V,
), thiocyanato, thio, thiol ester and hydroxy ether.

Reactive dyes suitable for the present invention are those having reactive groups based on the following systems: symmetrical mono- or dihalogenopyrimidinyl groups, mono-, di- or trihalogenopyrimidinyl groups or cyclohalon-substituted groups. Quinoxanylcarbonyl group.

Particularly suitable reactive groups are those having the following formulas (21, (31) and (2) and (2) and -, Xl, , F.

Xt = CJ J, NH,, NHR Tomi, oy.

cn, B Sagi or SX Tomi, X, = CL, F or CB,, X,=C1 or! as well as X,=C1,! Or CH.

however, R3-hydrogen, alkyl (especially optionally OH-).

80, H-also 1d C00H-”r: placetllkstL
fl:, Cs~C4 alkyl, aryl (especially occasionally S
Heh-.

C3 to C
I06M-, C1 to C47 are substituted with + Roux or C8 to C, alkoxy-)].

Dyes containing the abovementioned reactive group systems are known, for example, from the following publications: US Pat. No. 3,377.336, US Pat. No. 8 S27,
No. 760, British Patent No. L16 Tortoise No. 254, U.S. Patent No. 3
669.951, German Patent No. 1.644208, British Patent No. L1g to 606, German Published Patent No. & 817
．． No. 780 and Spanish Patent No. 47 Turtle 771.

The dyes produced according to the invention can be used in a wide range of dye systems, such as metal-free or metal-containing monoazo or polyazo dyes, metal-free or metal-containing azaporphine dyes, such as copper, cobalt or nickel phthalocyanine dyes, or anthraquinone, oxazine, dioxazine dyes. , triphenylmethane, nitro, azomethine or metal-free or metal-containing formazan dye systems.

The low temperatures used to produce concentrated reactive dye solutions or liquid crystalline compositions in the process of the invention (with a salt content of at most 8
% by weight, preferably FiS weight tqb) of the dye (kl"OsS卜-A-N-H Todoroki, where A, M" and the rest are as defined above) can be prepared as follows: A, dye (M”0.73%-A-N-Hwo, temperature 40~
1 Salting out the reaction solution by adding an ammonium salt that volatilizes at 250° C. and a pressure of 13 to 101 Of bar;
The presscake is then dried under these conditions.

Suitable ammonium salts are preferably ammonium carbamate and/or ammonium hydrogen salts, preferably ammonium hydrogen carbonate. Dye (M”0,5) n-A-
If H has already precipitated from the reaction solution in the adult cow, it is separated in a suction oven and the wet presscake is washed with a solution of volatile ammonium salts. In both cases, the dye 1 is obtained by drying and can be used in this state for further syntheses.

B. Dye (M"O,S)n-A-N-11 is precipitated with a small amount of non-volatile salt, such as NaCl, LiC1 or KC1, or by adding acid, and suction FJ is carried out as appropriate. If so, wash with a small amount of a solution of a precipitant or a solution of a volatile salt or with a dilute acid.If the dye has already been washed during the reaction, wash with a solution of a non-volatile or volatile salt or with a dilute acid. Washing with @?i or, if appropriate, with pure water is sufficient. If a saturated ammonium salt solution is used for washing the presscake, low salt dye (M"0.S) %-A-N Drying with A1 is required to obtain -H.

The reaction solution of C0 dye (M"O,S)s-A-N-H is subjected to pressure filtration and thus concentrated to remove salts. This low-salt concentrate is used for further synthesis. It can be used for.

Methods A and C are dyes (MS, S''P-A-N-H) It must be considered particularly suitable for construction.

Examples of concentration-enhancing additives that can be used in the new production process are lower aliphatic or cyclic amides, preferably m-caprolactam and N-methylpyrrolidone and/or lower aliphatic sulfoxides and/or sulfur-containing compounds such as dimethylsulfone. , soethylsulfone, sulfolane, sulhole and its α- and/or β-substituted derivatives and/or) hydrotropic compounds such as thiourea and urea and the corresponding derivatives, particularly preferably N,N'-tumethylurea.

Possible acid binders are preferably alkaline 18 e.g. NaOH
, KOH, NaIC0@ , KICO,, Ca (O
H), .

LiOH, LitCO8, especially LiOH and LitCO
, is. Acid binders are preferably used to neutralize to pH 5-8.

The optionally added buffer substance is preferably p'Has~&
This buffers the value within 0. Examples of buffer systems that may be mentioned are l) mixtures of potassium dihydrogen phosphate/dipotassium hydrogen phosphate; 2) boric acid adjusted to pH'l ~8 with Na0B or LtOH and 3) adjusted to pH 8 with NaOH or LiOH potassium hydrogen phthalate,

The liquid reactive dye composition (concentrated solution or liquid crystalline composition) produced by the method of the invention has the following composition: Reaction in the concentrated solution or concentrated liquid crystalline composition produced by the invention The content of the color dye is 10 to 40% by weight (preferably 1
There is 3 to 30 weight t%i. Moreover, the liquid composition is pBll1
Up to 2% by weight of buffer substances for 1 to 8, preferably (L5 to 9% by weight, up to 30 qb by weight of concentration-enhancing additives if appropriate, and up to 4% by weight of alkali metal salts, preferably lithium salts) contains.

Furthermore, the invention relates to natural and synthetic materials, in particular cotton, wool,
It relates to the use of concentrated solutions or liquid crystalline compositions of reactive dyes (1) produced in this way for the production of dyeing baths and printing pastes for applications on regenerated cellulose, paper and leather. 2. - In the present invention, a concentrated liquid composition of a reactive dye having a complex reactive component is prepared by adding a low salt dye of the formula (ht"0,5ln-A-N-H) containing no reactive group to a suitable The dye is dissolved or dispersed in a small amount of water in the presence of concentration-enhancing additives, and the dye is reacted with a compound R-X (where X represents chlorine or fluorine) containing a reactive component to form the dye. HX
with an alkali (e.g. NaOH).

KOH, NatGO, KtCo, LiOH or Li
, jpOs) or alkaline earths (e.g. Cab, Ca(
OH) or a mixture thereof) to pH 5~
8 and, if appropriate, adding a buffer system (range 65-8).

When dyes containing amino groups but not reactive groups are reacted with reactive components that liberate HF, fluorination that liberates basic calcium salts is used for further neutralization near the end of the reaction. It is particularly advantageous to add stoichiometrically equivalent amounts to the hydrogen acid. After separating the precipitated calcium fluoride,
The liquid reactive dye compositions prepared according to the present invention contain free fluoride at less than αS%.

The following applies to the solid compositions produced by the method of the invention.

Possible customary standardizing agents are solid compounds which do not react with the reactive groups, such as inorganic salts, particularly preferably LiCL, Li,
S04 or 4-rephosphates, but preferably non-electrolytes such as polyvinylpyrrolidone, urea, salts of water-soluble aromatic sulfonic acids such as benzene sulfonate and anionic dispersants such as sulfated 1O to 18 carbon atoms.
primary or secondary alcohol, sulfated fatty acid amide,
Sulfated alkylenoxy adducts, sulfated partial ester polyhydric alcohols, and inter alia sulfonates such as long chain alkyl sulfonates such as lauryl sulfonate, cetyl sulfonate, stearyl sulfonate, mersolate, sialkyl sulfosuccinate) IJ bovine, such as dioctyl sulfosuccinate Sodium, e.g. tauride e.g. oleyl methyl tauride (
sodium salts), alkylarylsulfonates such as alkylbenzenesulfonates with straight-chain or branched alkyls having 7 to 20 carbon atoms, and monoalkylnataphrenosulfonates and dialkylnaphthalenesulfonates such as nonylbenzenesulfonate, dodecylbenzenesulfonate and hihexadecylbenzenesulfonate,
and 1-inzolobylnaphthalene-2-sulfonate,
Diisopropylnaphthalene sulfonate, non-butylnaphthalene sulfonate, diisobutylnaphthalene/sulfonate and especially condensation products of aromatic sulfonic acids and formaldehyde, such as naphthalene sulfonic acid, dutolyl ether sulfonic acid or terphenylsulfonic acid and formaldehyde and/or or a condensation product of cyclohexanone, formaldehyde and bisulfite and/or lidanine sulfonate. Customary dust inhibitors such as oils, oil/emulsifier mixtures or phthalates can also be added.

The solid reactive dye composition produced by the method of the invention preferably has the following composition: The content of reactive dye of the composition produced according to the invention is from 20 to 90% by weight (preferably from 30 to SO % by weight) and the composition as desired #) pH value aS-&! ! To make the buffer material up to 5% II, and optionally the usual standardizing agent or
%, concentration increasing additives 10-70% and dust inhibitors 4
%. The invention furthermore provides for the preparation of compositions of reactive dyes (1) produced in this way for the production of dye baths and printing yeasts for application to natural and synthetic materials, in particular cotton, wool, regenerated cellulose, paper and leather. Concerning using.

In the present invention, readily soluble compositions of reactive dyes having heterocyclic reactive moieties are primarily composed of low 1 salts of the formula (It"0.S to A-NH) which do not contain reactive groups. Dissolving or dispersing the dye in a small amount of water, if appropriate in the presence of concentration-enhancing additives, and reacting the dye with a compound R-X containing a reactive component, where X represents chlorine or fluorine. The dense HX produced is advantageously produced by
Alkali (e.g. NaOH).

KOH, Na, CO, K, CO8, preferably Li0
B or Li, CO@) or alkaline earths, such as C
aO.

Neutralized to pH 5-9 by addition of CaCO@, Ca(OH), or a mixture thereof. A concentrated dye solution or liquid crystalline composition is obtained, to which, if appropriate, buffers and customary standardizing agents have also been added, which is then dried to give a solid composition.

The concentration of the dye in the dispersion or preferably in the solution or liquid crystal composition is between 10 and 40% by weight (preferably between 13 and 30%).
weight%).

Standardizers and buffers are preferably added before drying, but they can also be ground and mixed with the dye after drying or added to the ground dye.

If the reactive dye is dissolved or in the form of liquid crystals, the precipitated product can be separated out and, when dried, contains less than 1 wt. of free fluoroaline. A dye composition is produced.

The solid compositions prepared according to the invention are distinguished by excellent solubility in hot and cold water. The solubility is particularly good when the dye is in the preferred form, ie the lithium salt.

If the dye (M"0.8%-A-N-H) is reacted with the reactive group R-.X in a very small amount of water, the fume content of the hydrolyzed reactive dye is very low.

A further advantage of the process of the invention is that only a very small excess of the reactive component is required to produce the solid composition.

The following examples illustrate the method of the invention.

Example 1 3 moles of 2-amino-1-sulfo-5-aminomethylnaphthalene α was soazotized to v't-(benzoylamino)-
8-Hydroxy-36-naphthalenedisulfonic acid 0.3
combined into moles. The dyestuff, some of which has already precipitated, is salted out by adding 15% by weight of ammonium hydrogen carbonate, taken off in a suction oven and mixed with 3 ml of saturated ammonium hydrogen carbonate solution.
00- then 1010 mbar and 60°C
Dry to constant weight. The dried low salt dye (salt content: SS relative to the amount of dye) was dissolved in H,O'100w1 by addition of 25 mol of C-caglolactam &2,4
．． 6-) Rialol-5-chloropyrindiph-13 acid is neutralized by addition of 32 mol of solid lithium carbonate α, and just before the end of the reaction Ca0o. Further neutralization was achieved by adding 13 mol. When the reaction was completed, the solution was adjusted to pliT by adding phosphate buffer a@type weight and filtered.

This resulted in a concentrated dye solution having a long shelf life 5 and containing 19% by weight of the following anionic reactive dyes: This concentrated solution prepared according to the invention was stirred in water and By adding auxiliaries, a dye solution was obtained which dyes natural and regenerated cellulose fibers red.

Example 2 3 moles of 4-amino-1-acetylaminobenzene-3-sulfonic acid α were diazotized, and 1-(4-sulfophenyl)-5-pyrazolone-3-cal was bound to 0.3 moles of phosphoric acid. . After hydrolysis with sulfuric acid, the dye was separated in a suction oven and washed with sulfuric acid-containing water (pHs) 4o.

I washed it with go. The wet presscake is added to H,0450- and dissolved by addition of lithium hydroxide, 2.3
-133 mol of dichloroquinoxaline carbunyl chloride were added. The acid liberated during the reaction was neutralized by addition of 12 mol of solid lithium carbonate α. When the reaction is completed, the solid is separated in a suction oven, and the P solution is mixed with a phosphate buffer of 0.6
The pH was adjusted to 7 by weight I%. As a result, a liquid crystalline composition with a long shelf life and containing 23% by weight of the reactive dye of formula (5) was obtained.

By stirring this concentrated liquid crystalline composition prepared according to the invention in water and adding the usual auxiliaries for reactive dyeing, a dye solution is obtained which dyes natural and nasal cellulose fibers reddish-yellow. Nine.

Example 3 0.3 mol of acidic anthraquinone dye containing 5 wt. 0.33 mol of 2.3-N chloroquinoxaline chloride was slowly added at 30°C. The acid liberated during the reaction was neutralized by the addition of solid LiOH. When the reaction was completed, N,Nl -, add another 130II of trimethylurea and mix the mixture with buffer a, 6fold sr.
% to pH 13 and suction-filtered. This resulted in a solution having a long shelf life and containing 19% by weight of reactive dye (7).

Example 4 2-Amino-l-sulfo-5-aminomethylnafretane (L3 mole was diazotized to N1-(benzoylamino)-
3 to 8-hydroxy-4,6-naphthalenedisulfonic acid
combined into moles. The precipitated dye was separated in a suction furnace and washed with 30G of water containing sulfuric acid (pffL5). This presscake (solids content 319 G) was stirred with 2 $ mol of water sS- and C-carbloctam and! , 4.6-) Riproluor-5-chlorpyrimidif 13 The acid liberated during the reaction is neutralized by the addition of xztoH-a, s mol, and Ca00.1 is added before the end of the reaction.
Further neutralization was achieved by adding 2 mol. When the reaction was completed, the pH of the solution was adjusted to 7 by adding 0.6 weight j'qbt of phosphate buffer, and the precipitated C a S 04 and Ca^ were separated by F9. This resulted in a concentrated dye solution with a long shelf life and containing 23% by weight of reactive dye and 1% by weight of fluoride α. By stirring this concentrated solution prepared according to the invention in water and adding auxiliaries for reactive dyeing,
A dye solution was obtained for dyeing natural and long cellulose fibers red.

Example 5 1 mole of acidic anthraquinone dye containing up to 6 wt. of salt is mixed with 2.24 moles of N,Nl-dimethylurea and
By adding L-OH-80, H, O'! , 46°C at pH 7. 14 liters of zochloroquinoxaline carpoer chloride was added, and during the reaction the OpH value was adjusted to L(, C(
The solution was then maintained at 40 °C for 3 h and clarified. Borate buffer aos molar (pHy, o ), dust inhibitor α3% by weight and desalting condensation product of naphthalene sulfonic acid and formaldehyde 11
．． 5% by weight was added and the resulting solution was spray dried. The powder compositions of reactive dyes produced in this way have significantly lower solubility compared to the conventional powder compositions synthesized according to German patent publication no. Illustration 9: By stirring this reactive dye composition prepared according to the invention in water and adding the usual auxiliaries for reactive dyeing, a dye solution is obtained which dyes natural and regenerated cellulose fibers blue. Ta.

Example 6 Acid azo dye (3
) 1 mol of water L1 by addition of 16 mol of N,N'-zomethylurea α and 101 mol of C-caprolactam in water.
4j. This dye is reacted with 1 mol of 2,46-dryfluoro-5-chloropyridine, and the acid liberated during this reaction is reduced to about 15 mol of LiOH.H.
Neutralized with a o smol.

When the reaction was completed, the dye solution was clarified, adjusted to pH 7 v4 with borate buffer 0.2% by weight and normalized to the desired staining intensity with the condensation product of naphthalene sulfonic acid and formaldehyde.

Spray drying resulted in a solid reactive dye composition with excellent solubility. By stirring this reactive dye composition prepared according to the invention in water and adding the usual auxiliaries for reactive dyeing, a dye solution was obtained for dyeing natural and regenerated cellulose fibers in red.

Example 7 One mole of 4-amino-1-acetylaminopense/-3-sulfone tR was diazotized and coupled to 1-(4-sulfophenyl)-5-pyrazolone-3-carboxylic acid. After hydrolysis with sulfuric acid, the dye is suctioned and separated, and water containing sulfuric acid (p
Washed with Ht)too-. This wet presscake was added to H,0140Gd, dissolved with the addition of lithium hydroxide and reacted with 1 mole of 2,4-difluoro-5-chloro-6-methylpyrimicine L. The acid liberated during the reaction was neutralized by adding lithium hydroxide and 0.3 mol of Ca. When the reaction was complete, the solution was clarified, adjusted to pH 7 with 11% by weight borate buffer, and standardized to the desired staining intensity with the condensation product of naphthalene sulfonic acid and formaldehyde. As a result of spray drying,
A solid reactive dye composition with excellent solubility was obtained.

When added with the usual auxiliaries for reactive dyeing, this dye composition is suitable for printing natural and regenerated cellulose fibers in reddish-yellow colors.

Example 8 next anion N.B.

1 mole of acidic azo dye (4) having a salt content of 5 fold fIAqb or less was added to 0.0 mole of N,N'-dimethylurea in water.
It was dissolved in 1.31 mol of water by addition of 18 mol and 0.01 mol of 6-caprolactam. This dye was reacted with 1 mole of 2,46-drifulby-5-chlorpyrimidine,
The wax liberated during this reaction is treated with LiOH.fl, about 0.1.
Neutralized with 5 mol and C600.03 mol.

When the reaction is finished, the dye solution is clarified and added to borate buffer 0.2 weight 11%.
．． , standardized to the desired stain strength by the condensation product of naphthalene sulfonic acid and formaldehyde.

Spray drying resulted in a solid reactive dye composition with excellent solubility. After stirring this reactive dye composition prepared according to the invention in water and adding the usual auxiliaries for reactive dyeing, a dye solution was obtained which dyes natural, natural and regenerated cellulose fibers red.

Patent originator Bayer Akchenr Sellschaft Continued from page 1 Priority claim 9 April 29, 1982 West Germany (DE
) CP3215933.1 0 Inventor Tart Falkenberg Federal Republic of Germany Day 5000 Cologne 410 Berthobloomstrasse 9 463-

Claims (1)

[Claims] 1. Formula [wherein M''=NH4, Li, Nα or 1R=heterocyclic reactive group, R1=hydrogen or alkyl (C+ to C4'>, A=dye chromophore and 9% c++ an integer from 1 to 5] containing sulfo groups, free of reactive groups and having the formula [wherein M"=H, NH4 , Li, NematadK, and R'
, s and A are as defined above] and containing at most 8% by weight (relative to the amount of dye) of salt in an aqueous medium which may optionally contain concentration-enhancing additives. 1 in the presence of an acid binder in
The liquid composition thus obtained is reacted with a reactive component of the heterocyclic group of formula % formula % (16) [wherein R has the same meaning as above and x represents fluorine or chlorine]. A process for preparing a composition of a reactive dye of formula (1), optionally buffering or drying the liquid composition and then optionally grinding it to a powder. 1 The reactive component of 2R-X used has the formula [wherein X=Ct or Fl X1=F. X, = C1, F, NHL, OH meaning
, CH, R or SR, X, = C1, F spanning C1i X, = Ct or Fl The method described in Scope 1. 1! I! 3. The method according to claim 1, wherein the strength increasing additive is a lower aliphatic or Fi cyclic compound and/or a sulfur-containing compound and/or a hydrotropic compound. Table Acid binder: NaOH, KOH, NaJ: 0. . K, CO, , Cab, Ca(OH), , LiOH and L
A method according to claim 1, wherein the series of compounds comprises i, Q)s. 2. The method according to claim 1, wherein the liquid composition is dried by a spray drying method in order to obtain a solid composition. One standardizing agent and/or pH to obtain the al1 body composition
2. A method according to claim 1, wherein a buffer is mixed before and/or into the drying of the liquid composition, which stabilizes the value at aS~8. 7. Use of the compositions prepared according to claim 1-M for making dye baths and printing pastes for natural and synthetic materials.