DE2415550C3 - Mixtures of water-insoluble disazomethine and monoazomethine dyes, process for their preparation and their use - Google Patents

Description

CHO

OH

and water-insoluble monoazomethine dyes' ^{5 of} the formula

R,

OH

in which R _{1 can also stand for R 3} and has the meaning given in claim 1.

4. The method according to claim 3, characterized in that the diamines in the form of their Salts used and condensation in the presence of ammonia, ammonium salts or Amines.

5. Use of the dye mixtures according to Claim 1 or 2 for pigmenting printing pastes, high molecular weight plastic masses or lacquers.

6. Use of the dye mixtures according to Claim 1 and 2 for the production of printing inks.

OH

wherein R ₁ , R ₂ and R _{3 are} hydrogen or nonionic substituents and the radicals R ₁ , R ₂ and R _{3 can be} identical or different.

2. Mixtures according to claim 1, characterized in that that they have the disazomethine dye to the monoazomethine dye in a molar ratio from 2: 1 to 1: 3, in particular in a ratio of 1: 2.

3. Process for the preparation of dye mixtures according to Claim 1 and 2, characterized characterized in that the condensation reactions named below are either using from 1.2 to 2.5 times the molar amount of a diamine of the formula The main subject of patent 2305 071 is water-soluble Disazomethine dyes of the general formula (la)

H, N

CH = N

N = CH

wherein R _{2 has} the meaning given in claim I, and twice the molar amount of one or more compounds of the formula

CHO

45

in which R ₁ , R ₂ and R _{3 are} hydrogen or nonionic substituents, where R and R _{3 can be the} same or different, furthermore a process for the preparation of these dyes in which either I moles of one or more diamines of the formula (II)

wherein R has the meaning given in claim I, or using the 1 molar Amount of a monoazomethine dye of the formula

55 R ₂

VX

H ₂ N- ^ y -NH ₂

(Π)

wherein Fl _{2 has} the meaning given above, with 2 mol of one or more compounds of the formula

CHO

NH ₂

R ₁ -f i.

OH

wherein R, and R _{2 are} those given in claim I wherein R _{1 has} the meaning given above,

condensed or 1 mole of a monoazomethine dye »Toffs the formula

These dye mixtures are produced according to the invention in such a way that advantageously 1.2 to 1.6 mol, preferably 1.5 mol of one or several diamines of the formula (II)

CH = N

NH,

H, N

OH

10

NH ₂

(H)

wherein R _{2 has} the meaning given above, with

wherein R ₁ and R _{2 have} the meaning given above be 2 moles or more compounds of the Foninel III, with ι moles of a compound of the formula

CHO

15th

condensed, where the radicals R ₁ and R _{3 can be} identical or different.

In a further embodiment of this inventive concept it has now been found that dye mixtures of water-insoluble disazomethine dyes Formula (Ia)

CH = N

N = CH

(la)

35

and water-insoluble monoazomethine dyes of the formula I b

(Ib)

40

45

in which the radicals R ₁ , R ₂ and Fl _{5 can be} identical or different and each denotes a hydrogen atom or a nonionic substituent, advantageously those with a molar ratio of the disazomethine dye (s) to the monoazomethine dye (s) of 2: 1 to 1: 3, preferably 1: 2, have significantly improved properties, in particular a higher color strength than the individual components and mechanical mixtures of the individual dyes.

Nichlionogenic substituents R ₁ , R ₂ and R ₃ are halogen atoms such as chlorine or bromine atoms, alkyl groups such as methyl, ethyl or propyl groups, alkoxy groups such as methoxy, ethoxy or propoxy groups. Cyano groups, nitro groups, alkyl or aryl sulfone groups, carboxylic acid ester or optionally substituted sulfonic acid amide or carboxylic acid amide groups are suitable.

The new dye mixtures are presumably in the form of mixed crystals.

CHO

OH

(HD

in which R ₁ also represents R ₃ and has the meaning given above.

In this condensation reaction, it is best to use the diamines of the formula (II) in an amount of 1.2 to 2.5 mol, preferably 1.5-2.0 mol, based on 2 mol of the compounds of the formula (III), into the reaction mixture. The condensation reaction of (II) with (III) can be carried out either in a neutral or in an acidic aqueous, aqueous-organic or organic medium. However, particularly preferred is a method in which the condensation of diamines of the formula (II) with the aldehydes of the formula (UI) at 20-70 ⁰ C in a neutral aqueous medium with mechanical mixing, and at least temporarily acting grinding conditions, preferably under inert gas, undertakes.

The process is advantageously carried out in such a way that the reactants are in aqueous suspension or emulsion at e-.wa 10-30 ⁰ C, preferably starting at 20 ⁰ C, in the exactly or nearly stoichiometric ratio in several hours even at temperatures of about 50-8O ⁰ C preferably about 60-70 ° C heated.

To achieve the most uniform possible suspension or emulsion of the reaction mixture it is advantageous, a temporary or permanent shear by finely distributing grinding units, for example To produce wet mills, dissolvers, bead or sand mills, dispersers or the like, these apparatuses can serve both as reaction vessels and, particularly advantageously, in a circulating or shunted connection a normal boiler set can be used. An additional addition of a commercially available Dispersants or emulsifiers can also be advantageous.

This way of working results in permanent Exposing new surfaces results in a quantitative conversion and a very even grain the pigment formed.

According to the preferred procedure, these fall in excellent purity and yield and in for their further use particularly favorable Feinverieiiung, so that an additional finish often unnecessary.

The mother liquors are due to the water insolubility of the end products and the possibility of noticeable excesses of one or the other

tion partner, practically free of organic and inorganic compounds. They can therefore be discharged safely into the wastewater, but are also suitable for reuse in the following approaches, whereby the process according to the invention is practically free of wastewater is working.

As a result of the general reusability of the mother liquors for the next batch, a reaction partner, if it is water-soluble, it can also be used in excess, for example from 10-200% since it can be traced back to the process and only to the original one for implementation Molar ratio must be supplemented. This work variant enables shorter response times or achieve lower reaction temperatures, resulting in an even more favorable space / time yield or a lower energy consumption is achieved.

When using organic solvents as the reaction medium, for example, alcohols, such as ethanol, isopropanol or butanol, aliphatic carboxylic acids, for example formic acid or Acetic acid, dimethylformamide, xylene, chlorobenzene, o-dichlorobenzene or nitrobenzene are advantageous. the The reaction rate is generally rapid and, based on the aldehyde, a quantitative yield at a temperature of 50 to 100 C. If necessary, however, it can also be useful in one Solvent or in a mixture of solvents at a higher temperature, for example at 150 or up to 180 C, to work and a simultaneous to carry out azeotropic distillation of the water released by the condensation.

The new dye mixtures can also be prepared in accordance with the invention by one or more monoazomethine dyes of the above and defined formula are advantageously used (I b) with one or more hydroxynaphthaldehydes of the above formula (III). At this The hydroxynaphthaldehydes of the formula (HI) are best used in the condensation reaction an amount of 0.1 to 0.8 mol, preferably 0.3 to 0.6 mol, based on 1 mol of the monoazomethine dye of formula (I b), into the reaction mixture. In order to carry out the procedure the same reaction conditions as for the first-mentioned process are used, with the Condensation reaction in neutral aqueous medium at 20-70 ° C with mechanical mixing and at least partially acting milling conditions, preferably under inert gas, is preferred.

The monoazomethine dyes of the formula (Ib) required as starting materials for this procedure can be prepared, for example, by condensing the diamine of the formula (II) with the aldehyde of the formula (III) in an alcoholic medium at 0-20 ^J C and in the absence of Acid performs.

When condensing m-phenylenediamine which is very sensitive to oxidation, it can be advantageous to to use these in the form of their mineral acid salts and the reaction by adding at least one equivalent amount of ammonia, an ammonium salt :; or an aliphatic, aromatic or heterocyclic amine, for example triethylamine, N.N-dimethylaniline or pyridine.

The I-Naphthaldchydc of the formula (Ul) used as starting compounds can according to known methods can be obtained, for example by reacting the corresponding 2-hydroxynaphthalenes with chloroform in an aqueous or aqueous-alcoholic medium in the presence of sodium hydroxide solution or by reacting the 2-hydroxynaphthalenes with hexamethylenetetramine and formaldehyde in the presence of acetic acid and / or its anhydride and also a mineral acid (cf. on this DT-PS 9 52 629).

The new mixtures are valuable yellow pigments that are particularly useful for printing inks suitable. But they can also be used for pigmenting high molecular weight organic material be e.g. B. of cellulose ethers and esters, polyamides, polyurethanes or polyesters, acetyl cellulose, Nitrocellulose, natural resins or synthetic resins, e.g. B. aminoplasts, especially urea and melamine - formaldehyde resins, aikyd resins. Phenoplasts, polycarbonates, polyolefins, such as Polyethylene or polypropylene, polyvinyl chloride, polyacrylonitrile, polyacrylic acid ester ^ rubber, casein, Silicone and silicone resins, individually or in a mixture. It does not matter whether the mentioned high molecular weight Connections as plastic masses. Melts or in the form of spinning solutions, lacquers or printing pastes are available. Depending on the intended use, it turns out to be advantageous to use the new pigments to be used as a toner or in the form of preparations.

The new pigments are notable for the compounds mentioned in the main patent higher color strengths, clear nuances, high transparency as well as excellent storage stability and rheological Properties in print varnishes.

The increase in color strength in the new products is particularly surprising. He only goes after the Achieve manufacturing alternatives according to the invention. Mechanically generated mixtures of separately synthesized Individual pigments of the formulas (Ia) and (Ib) do not show this phenomenon.

In the pigments according to the invention, the effect of increasing the color strength is so great that with technically very simple means products of equal or higher than commercial products in individual cases even higher color strength can be produced extremely economically.

It is noteworthy that with a given ratio of the starting components and constant Condensation process Azomethine mixtures of constant composition reproducible can be produced.

As a result of the conjugation interrupted by the meta linkage, they represent products with the desired neutral yellow nuance because of the normalization of color tones for multicolor printing are increasingly sought and needed. They are therefore excellent as a yellow component can be used for multi-color paper printing and are compared to those previously used for this purpose Due to their far more favorable storage and flow properties, dyes have a considerable technical effect Progress.

Compared to the next comparable orange to red compounds from the US Palentschrift 24 05 886, the pigments according to the invention have a significantly higher color strength and better flowability and printability of the printing inks produced with them.

The following examples serve to illustrate the invention; the parts are parts by weight.

specified analyzes has the following composition:

example 1

A mixture of 334 parts of 2-hydroxy-l-naphthaldehyde, 216 parts of m-phenylenediamine (molar ratio of aldehyde to diamine equal to 1: 1), 3 parts Resin soaps and 300 parts of water are made in the absence of air by means of a corundum disk mill for 4 hours long pumped at 30-40 ° C. This creates a yellow suspension which is then heated to 70 ° C for 15 minutes; it is then filtered and the filter material dried.

471 parts of a yellow pigment are obtained, which is good primarily for the production of very strong colors flowable and storage-stable gravure printing inks based on toluene is suitable.

On the basis of analyzes of the dye mixture obtained (quantitative thin-layer chromatography) and the condensation mother liquor (residual m-phenylenediamine content due to diazotization) is his to give the following formulaic composition:

OH

35

40 OH

After neutral washing of the filter material and drying, 48 parts of a strong yellow color are obtained Pigment, which is excellent for making printing inks; these show a strong storage stability on. Both its individual components and those made from these individual components by mechanical means Mixtures of pigment mixtures produced significantly outperforms the product produced in this example in color strength. - The implementation is in terms of the composition of the reaction product, as stated above, the yield and quality are reproducible.

In the above reaction mixture, the 2-methyl-m-phenylenediamine is replaced by the same Amount of 4-methyl-im-phenylenediamine replaced and proceeded in the same way as indicated above, a dye mixture of the following composition is obtained:

The yield is quantitative and reproducible, the mother liquor can after replenishing the reaction components the next approach can be reinstated on the above ratio door, so that no diamine loss occurs.

The pigment produced in this way significantly outperforms each of the separately produced individual pigments and _S o mechanically produced mixtures of these individual components in terms of color strength.

If 10 percent by weight of an alkanol is added to the water, heating can be dispensed with will.

Example 2

34.4 parts of 2-hydroxy-l-naphthp.ldehyd are dissolved in t, ₀ 150 parts of glacial acetic acid at 80 C. 19.5 parts of 2-methyl-m-phenylenediamine are added dropwise with stirring over the course of 10 minutes. dissolved in 100 parts of glacial acetic acid, to (the amounts of aldehyde and diamine used

OH

CH = N-r "^ pN = CH

CH ₃

CH = N- f ^V -NH ₂ CH ₃

in the same yield, which has a similar shade and properties.

Example 3

51.6 parts 2-llydro \\ - l-naphthaldchyd are at

are in the molar ratio of 2.0: 1.6). This (·> <, S5 ("" is dissolved in 500 parts of formic acid. Then The reaction mixture is stirred for 45 minutes with a solution of 29.9 parts of 4-chloro-m-phcn> lcn-

diamine in 2 (M) parts

80 C after, cools down to 20 C and isolates the precipitated Pigmenlgcmisch. that according to the formic acid in Example 1 within a Hour of dripping. The reaction components are

709 636/285

added in a molar ratio of 3: 2.1). This reaction mixture was stirred for 1 hour at boiling temperature. Thereafter, the hot solution in a mixture of 4000 parts of water and 12 parts of rosin soap at a mixing temperature was not higher than 70 should be ^u C, stirred. The product which precipitates out is filtered off with suction, washed neutral and dried. According to the analyzes given in Example I, it corresponds to an equimolar mixture of mono- and disazomethine compounds and has the following formulaic composition:

CH = N-ZV-N = CH
OH Cl

OH

CH = N

OH

NH ₂
Cl

75 parts of this yellow pigment are obtained, which is characterized by excellent dispersibility excels in printing inks and continues to excel for the production of very strong colors, the individual components In this regard, gravure inks clearly outperform and have perfect storage stability show suitable. The color of this pigment mixture corresponds to the standardized yellow of the DIN scale, so that there is no need to nuance it. - Its production is in terms of composition, Nuance and properties as well as yield reproducible.

If, instead of the above-mentioned diamine, a corresponding one in the above-mentioned molar is used Proportional amount of 4-bromo-m-phenylenediamine, 84 parts of a dye mixture of the following composition are obtained in this way:

CH = N

OH

-Λ

CH = N

N = CH-

Br

NH,

Br

OH

iJas has a slightly greenish shade of yellow and similarly good properties as the above

Product with regard to its dispersibility in printing inks and its storage stability in these printing inks and which has color strength.

Example 4

25.8 parts of 2-hydroxy-1-naphthaldehyde are ^{dissolved in 400 parts of ethanol at 60 °} C. and then 20.7 parts of 2,4-diaminoanisole are added with stirring (the amounts of aldehyde and diamine used are in a molar ratio of 1: 1 ). The reaction mixture is stirred for 3 hours. The deposited yellow precipitate is filtered off; washed with ethanol and water and dried.

Yield: 39 parts of a pigment mixture which, according to the analyzes given in Example 1, has the following composition:

CH = N-ZV-N = CH
V \

OH

OCH ₃

NH ₂
OCH ₃

OH

It is obtained in a purity that no longer requires a further finish of this pigment power. Excellent flowable properties are obtained by dispersing in common printing varnishes

Printing inks of high color strength and storage stability. ^6th

Is used in the abovementioned reaction mixture instead of ethanol as the solvent Methanol or isopropanol, the dye mixture is produced in the same yield and quality

Example 5

ι ς I

^ } yy 1 - naphthaldehyde and -. ⁶ -. ^Meth0 * y-2-hydroxy-1-naphthaldehyde

Αί T ^{1: 1) Are in} 150 parts glacial acetic acid ^ '5 ^OC 8 ^e ! ^east -. 32.4 parts of a 50% strength aqueous m-phenylenediamine solution (molar ratio of total water to diamine of 1: 1) are added dropwise over the course of one hour with stirring; the reaction mixture is for 30 minutes at 80 to 90 ⁰ C "n ^ ^stirs · ^then 150OTeUe water from -OC slowly allowed to flow The precipitated pigment is filtered off with suction After washing and Trockerhalt one p 35 parts of a";.. _"m" n. ., <, _m ; ^ h «:

nen

which has the following composition based on the analytical methods given in Example 1:

reflux for two hours to a mixture of azomethine the following composition

and has excellent printing properties. In particular, this product, which is available in reproducibly obtained, an even higher color strength than that mentioned in Example 1 and pigment mixture produced.

Example6

20.7 parts of 6-chloro-2-hydroxy-1-naphthaldehyde are suspended in 400 parts of isopropanol at 0 ° C. with stirring. After that it will be 18.7 parts 4 - bromo - m - phenylenediamine added {molar ratio of the aldehyde used to the diamine such as 1: 1). The reaction mixture is subsequently stirred at 0 to 5 ° C. for 3 hours. The monoazomethine compound formed the formula

condensed. After cooling the reaction solution, this mixture is obtained in equimolar amounts filtered off, washed with isopropanol and water and dried. The 45 parts thus obtained Pigment with a neutral shade of yellow is suitable for coloring polyvinyl chloride in dei Mass and for the production of very strong, storage-stable printing inks.

If the 4-bromo-m-phenylene diamine used above is replaced by a corresponding one mentioned above th molar ratio existing amount of 2,4-diamino benzamide, the result is a pigment that has only one < Has slightly lower color strength, but has better fastness to bleeding and solvents It has the following formulaic composition

OH

CH = N

OH

N = CH

CONH ₂

NH,

CONH ₂

OH

Cl

OH

CH = N- ^

NH,

Br

Example 7 to 12

after the addition of 8.6 parts of 2-hydroxy-1-naphthaldehyde (Molar ratio of the diamine used to the aldehyde such as 2: 1) and one part of glacial acetic acid If you work as in Example 1 give angi and use 2-hydroxy-1-naphthaldehyde m m-phenylenediamine to angi using the ii molar ratio in the table below given quantities, one obtains in quantitative! Yield of yellow pigments according to the invention of the nacl following composition given in the table: Settlement:

13th

CHO + χ Wf iT ^NH

OH

CH = N- / |
V

p N = CH

NH,

OH

example

: 1.50

: l, 00
: 0.80
: 0.70
: O, 65
: 0.60

0.35
0.36
0.40
0.50
0.60
0.70

0.65 0.64 0.60 0.50 0.40 0.30

Example 13

25.0 parts of 6-bromo-2-hydroxy-1-naphthaldehyde are in 200 parts of dimethylformamide at 70 C.

anilide (molar ratio of aldehyde to Diamii as 1: 1), stir the mixture for 15 minutes and then add dropwise a solution of! 5.4 parts of ammonium acetate in 75 parts of glacial acetic acid. This reaction mixture is then stirred for 2 hours at 70 ° C. and this is how it is produced! Product precipitated by adding 1000 parts of water and isolated by filtration, washed and dried. 34 parts of a pigment, the analysis methods indicated in Example 1 according dei du has the following composition equimolar:

OH

-HC = N-

NH ₂

NH-CO-CH ₃

will get; it is ideally suited for the production of yellow standard printing inks, which are due to highlight very high color strength, excellent flowability and storage stability. The pigment is also advantageously a settable for coloring plastics, in particular in addition to the high coloring

solved. Then one adds 23.8 parts of 2,4-diamino-acet- ₄₀ starch, its migration fastness should be mentioned.

Claims (1)

Patent claims: 1. Mixtures of water-insoluble disazomethine dyes of the formula ^R l Have meaning, and 0.1 to 0.8 times the molar amount of a compound of the formula