DE2311073C2 - Sulphonic acid group-containing stilbene azo and / or stilbene azo oxy dyes - Google Patents

Description

O ₂ N

CH ₃

SOfN (R) ₄

10

15th

wherein R is an optionally substituted alkyl radical means and the aromatic ring A with the exception of the listed substituents no further Bears substituents, with an optionally substituted tetraalkylammonium hydroxide, wherein if desired, a terminal nitro group in the condensation products obtained a primary amino group can be reduced and / or the condensation products obtained with an alkali metal and / or ammo nium salt can be implemented.

2. A process for preparing sulfonic acid Stilbenazo- and / or Stilbenazoxyfarbstoffen, in which at least one sulfonic acid group is in the form of an optionally substi- tuted so Tetraalkylammoniumsälzes, characterized in that a compound of the formula I defined in claim 1 with a tetraalkylammonium hydroxide substituted gegeöenenfalls converts, if desired, a terminal nitro group in the condensation products obtained is reduced to a primary amino group and / or the condensation products obtained are reacted with an alkali metal and / or ammonium salt.

3. The method according to claim 2, characterized in that tetramethylammonium hydroxide is used for the condensation begins.

4. Process for dyeing paper, characterized in that one dyes according to claim 1 begins.

50

The invention relates to sulfonic acid groups Stilbenazo and / or stilbenazoxy dyes in which at least one sulfonic acid group is in the form an optionally substituted tetraalkylammonium salt is present, obtainable by reacting a Compound of formula I.

O ₃ N- <AV-CH ₃
SOfN (R) ₄

(D

hO

wherein R represents an optionally substituted alkyl group (.5 and the aromatic ring A bears, with the exception of the listed substituent no further substituents, with an optionally substituted tetraalkylammonium hydroxide, wherein a terminal nitro group can be reduced to a primary amino group, if desired in the resulting condensation products and / or the condensation products obtained can be reacted with an alkali metal and / or ammonium salt.

The invention also relates to a process for the preparation of sulfonic acid group-containing stilbene azo and / or stilbenazoxy dyes in which at least one sulfonic acid group in the form of an optionally substituted tetraalkylammonium salt is present, characterized in that a compound of the formula I, which is as defined above, with an optionally substituted tetraalkylammonium hydroxide converts, if desired, a terminal nitro group in the condensation products obtained reduced to a primary amino group and / or the condensation products obtained nit a Reacts alkali metal and / or ammonium salt.

Tetramethylammonium hydroxide is advantageously used to convert a compound of the formula I.

The alkyl radical R preferably stands for a low molecular weight alkyl radical; it can be 1 to 6 and preferably 1 or contain 2 carbon atoms.

If the alkyl radical is substituted, it is preferred a hydroxyl or cyano group, a halogen atom or an aryl radical, advantageously a phenyl radical.

The reaction of the compound of formula I with an optionally substituted tetraalkylammonium hydroxide usually takes place for 15 minutes to 2 hours, advantageously in water and at elevated temperatures, e.g. B. between 30 ⁰ C and boiling temperature, but mostly at 45-7O ⁰ C and at pH 7.5-14, preferably at pH 11-13. The reaction generally gives mixtures of salts, but at least one SOjH group is present in the form of a tetraalkylammonium salt.

The reduction of the nitro compounds to corresponding primary amino compounds can after known methods are carried out, e.g. B. in aqueous solution and in the presence of dextrose hydrate, Alkali sulfite or sulfide, glycerine, hydroxyalkylamine or an aldehyde; z. B. sodium sulfite or sulfide, hydroxymethylamine or acetaldehyde.

The conversion of the optionally substituted tetraalkylammonium salts obtained in the condensation reaction into the corresponding Li, Na, K or ΝΗ ,, - salts can be carried out by methods known per se, eg. B. with a tialogenide, sulfate, acetate or phosphate of ammonium, lithium, Natiiums or potassium, for example in water and at elevated temperatures, for. B. at 50-100 ⁰ C, but mostly at 70-85 ⁰ C. Suitable halides are the fluorides, chlorides, bromides or iodides, particularly preferred are the chlorides.

It is known e.g. B. from H. R. Schweizer, Artificial Organic Dyes and their Intermediate Products, 1964, page 406 ff., Or from K. Venkataraman, The Chemistry of Synthetic Dyes, Vol. 1.1952, Chapter XX Stilbene dyes, page 628 IT. That in the alkaline Self-condensation of p-nitrotoluene-o-sulfonic acid for the production of nouns dyes usually a mixture of several dyestuff bodies is obtained, the separation of which is not necessary for the use of cellulose, for example. As a result, they also fall dye salts according to the invention according to the condensation method used as mixtures,

in which the dye structures listed below are preferably represented. Compounds of the formula II are included

NO ₂

R, Ri, Ri

wherein R _{1 is} independently SO ₃ H in the form of the alkali metal, ammonium or tetramethylammonium salt and at least one SO ₃ H group is in the form of the tetramethylammonium salt; Preferred among these are compounds of the formula ΙΠ

CH = CH

CH = CH

NO ₂

SO ₃ M

SO ₃ M

SO ₃ M

SO ₃ M

in which M, independently of one another, denotes the cation Li, Na, K, NH ₄ or N (CH ₃ ) ₄ and the compound of the formula ΠΙ bears at least one tetramethylammonium cation.
Furthermore, compounds of the formula IV

R ₁ R, O Ri R,

NO ₂

NO ₂

R,

wherein Rj is independently SO ₃ H in the form of the alkali metal, ammonium or tetramethylammonium salt and at least one SO ₃ H group is in the form of the tetramethylammonium salt; Preferred among these are compounds of the formula V

SO ₃ M

SO ₃ M

SO ₃ M

C H = C H

SO ₃ M

SO ₃ M

SO ₃ M

NO ₂

NO ₂

SO ₃ M

in which M, independently of one another, _{denotes the cation Li, Na, K, NH 4} or N (CHj) ₄ and the compound of the formula V bears at least one tetramethylammonium cation.
Furthermore, compounds of the formula VI

Ri N- <X) V- CH = CH

CH = CH

Ri

N = N

N = N

CH = CH

NH ₂

NH ₂

R.

R.

wherein R _{1 is} independently SO ₃ H in the form of the alkali metal, ammonium or tetramethylammonium salt and at least one SOjH group is in the form of the tetramethylammonium salt; Preferred among these are compounds of the formula VII

SO ₃ M

SO ₃ M

SO ₃ M

ch = ch- / OVn = n

SO ₃ M

SO ₃ M

SO ₁ M

in which M, independently of one another, denotes the cation Li, Na, K, NH ₄ or N (CH ₃ ) ₄ and the compound of the formula VII bears at least one tetramethylammonium cation

Dyes of the formulas II to VTI in the form of the free Sulphonic acid or in the form of the lithium salts are known from British patent specification 11 14 944; you will be used for coloring paper.

It was surprising that the tetraalkyl ammonium salts of these compounds compared to the conventional powder brands of those commercially available Stilbenazo dyes from the aforementioned British patent have better cold water solubility. In addition, the new dyestuff salts are significantly stronger in coloring paper than the dyestuff salts of the aforementioned British patent.

The new dye salts are preferably suitable for the production of colored and sized ones in the mass and unsized paper; however, they can also be used for dyeing paper by the dipping process be used. The new dye salts have excellent solubility properties, in particular they are characterized by good cold water solubility. They continue to color the wastewater at the Papermaking only a little, which is particularly beneficial for keeping water bodies clean. You don't mottled do not color paper on both sides and are largely pH-insensitive. The colorations are brilliant and stand out are characterized by excellent lightfastness properties. The shade changes after prolonged exposure Tone in tone. The dyed papers are also wet-fast, not only against water, but also against milk, Fruit juices and sweetened mineral waters; because of their excellent alcohol resistance, they are also against alcoholic beverages resistant.

20 The dyes of the pulp can be directly, that is without previously dissolving, can be added as a dry powder or granulate, without a reduction occurs in the brilliance or reduction in color yield. Post-treatment with cation-active (post-) fixing agents achieves practically perfect wet and alcohol fastness properties. The colored papers can be bleached both oxidatively and reductively, which is important for the reuse of scrap and waste paper.

The new dye salts can be converted into concentrated liquid preparations, which over are stable for a longer period of time and are preferably used because of their shelf life. The production such concentrated liquid preparations is z. B. in the Belgian patent 7 18 007 described.

The use of solid dye preparations in granulate or powder form is also possible. Such Preparations can be prepared according to methods known in the Prir ^ ip, 7. B. as in the French patent 15 81 900 described.

In the following examples, parts are parts by weight, percentages are percentages by weight; the Temperatures are given in degrees Celsius.

For clarification it is also pointed out that in accordance with the above given Explanation with regard to the course of the condensation of the dyes listed in the examples in terms of formulas represent the main component of a dye mixture and are not separated.

In the examples, 100 parts of the press cake used contain 4-nitrotoluene-2-sulfonic acid 80.4 parts each of 100% 4-nitrotoluene-2-sulfonic acid and 2.55 parts of sulfuric acid.

example 1

The dye of the formula

(a)

sopx

so ', -> x

where X is a radical N (CH ₃ J ₄₎ can be prepared as follows:

11.9 parts of 4-nitrotoluene-2-sulfonic acid are in the Submitted in the form of a moist presscake and 40 parts of a 25% strength aqueous tetramethylammonium hydroxide solution added dropwise. A t> i blue-red solution results; the temperature rises to around 45 ° C. The solution is heated to 55 ° C. with stirring and kept at this temperature for 1 hour.

The red-brown suspension obtained is then cooled and neutralized with about 4.7 parts of 30% strength hydrochloric acid. The suspension is dried in a drying cabinet and 17 parts of a reddish-tinged yellow dye are obtained Formula (a).

To neutralize the condensation products can instead of 30% hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid or a Ammonium salt can be used.

Example 2

The dye of the formula
SO ¹ , 'X

SO ¹ , 'X

SOi "'X

SO ',' X

NH,

SO ',' X

SOi ¹ X

where X stands for a radical of the formula N (CH ₁ I ₄ ) can be prepared as follows:

17? T ^ iIt * 4 - \ 'ϊΐΓηΙοΙιΐίΐΙ-7- ^ π! Γηη «; ίιΐΓι" · u / i * riJ.M, in dpr

Presented in the form of a moist PreLikuchen. 40 parts of a 20% strength tetramethylammonium hydroxide solution are added dropwise to this. The resulting blue-red solution is heated to 40 ° with stirring. This is stirred for 2 hours at this temperature. 3.3 parts of dextrose hydrate are then added and the solution is stirred at 40 ° for 2 hours. The color

SO ₅ Ύ S

so ;, 'x

stotTliegl in a reduced form and has fallen out of solution. The mixture is cooled and neutralized ι ¹ ? with 1 0 Tpilpn 1Π%) ολγ.
..... - ..... _, ._ . . ^ j ..

I): tn: irh vt »r-

the mixture is thinned with water up to 150 parts and thus a clear, con / entrantle solution is obtained, which the contains orange dye of formula (b).

Example 3

The dye of the formula
SO ', ¹ Y

SO ¹ , ¹ Y

I = CH

SO, Ύ

NO,

SOi ¹ Y

wherein Y is a group of the formula

(CH,),

CH ₂ -CH ₂ OH

means, can be prepared with the help of (2-hydroxyethyl) trimethylammonium hydroxide as follows: 27.6 parts of 4-nitrotoluene-2-sulfonic acid are in the form of the moist presscake with 50 parts of water SOi " ¹ Y

presented and stirred. 60 parts of the 50% strengths mentioned above are then added dropwise over the course of 15 minutes aqueous choline solution too. The mixture is then heated to 75 ° and held for one hour Temperature. 20 parts of ice are now added. The cooled solution is neutralized with 11.7 parts of a 30% hydrochloric acid. This gives a clear, concentrated solution which contains the reddish-tinged yellow dye Formula (c) contains.

Example 4
The dye of the formula

Ο —Ν

SO ₃ M SO ₃ MQ

O> - ^ch = ^ch - <O> - ⁿ = n

SO ₃ M

SO ₃ M

can be made as follows:

5 parts of the dye powder obtained in Example 1 are introduced into 35 parts of water with stirring. This creates a dark red, clear solution. OK parts of sodium chloride are now added. The falls Dye quantitatively. The mixture is allowed to stir for a further 30 minutes and heated to 70 °. Then you suck the suspension from under vacuum. A moist press cake containing the reddish-tinged yellow dye is obtained of formula (d), where M as sodium and tetramethylammonium cation in a ratio of 2.8: 1 is present

ίο

Example 5

If in Example 4 instead of 10 parts of sodium chloride, 10 parts of ammonium chloride or 10 Parts of lithium or potassium chloride used, you get a moist press cake, the dye the Formula (d) contains, where M is the ammonium, lithium or potassium and tetramethylammonium cation Ratio of 0.75: 1 is present.

To convert the tetraalkylammonium salt of the dyes (a), (b) and (c) into the corresponding Alkalibzw. Ammonium salts according to the method in Examples 4 and 5 can be used in place of those used there Chloride also the corresponding sulfates, acetates, phosphates, etc. of the corresponding alkali or Ammonuintions are used. In addition, instead of the dextrose hydrate mentioned in Example 2 as a reducing agent also an equivalent amount of alkali metal or sulfide, (glycerine, hydroxyaikyiamine or an aldehyde can be used.

To determine the cation ratio, the dye is removed from excess salt with the help of dialysis freed, dried and using known analytical methods (titrimetry, gravimetry, flame spectrometry etc.) the percentage of cations is determined.

Dyeing instruction A

Milled 2000 parts of water. 0.2 part of the dye described in Example 1 is sprinkled over this mass. After a mixing time of 20 minutes, paper is made from this mass. The obtained in this way, sauglahigc paper is yellowish in color. The wastewater is practically colorless.

Dyeing instruction B

0.5 parts of the dye from Example 1 are in 100 Parts of hot water dissolved and cooled to room temperature. 100 parts of this solution are chemically added bleached sulphite cellulose that has been ground in a dutchman with 2000 parts of water. After 15 The glue is mixed for minutes. Paper made from this material is reddish-yellow in color Medium intensity shade with good wet fastness properties.

Dyeing instruction C

Fine absorbent paper web made of unsized paper is made at 40-50 ° by a dye solution of the following Composition drawn:

0.5 part of the dye from Example 1
0.5 parts starch and
99.0 parts of water.

Ip a Dutchman will be 70 parts chemically 30 The excess dye solution is by two bleached sulphite cellulose (from coniferous wood) and 30 parts pressed from rollers. The dried paper web is red-chemically bleached sulphite cellulose (made from birch wood) in a pungent yellow color.

Claims (1)

Patent claims: 1. Stilbenazo and / or sulphonic acid groups or stilbenazoxy dyes in which at least one sulfonic acid group in the form of an optionally substituted. Tetraalkylammonium salt is present, obtainable by reacting a compound of formula I.