DE1814519C3 - Process for the production of azo pigments - Google Patents

Description

H ₁ N

where Z - = H or

SO ₁ - N

CH ₁ -CH ₁ CN

and X = H. - CTI., CH., CN.AIkvl mil I bis 5 carbon atoms.

CH, ■ - CH ₁

or

is, with the acid chloride of 2,3-oxynaphthoic acid. of 2,3-oxycarbazole carboxylic acid. of coumarin-3-carbonic acid. a Phenylpyrazoloncarbonsiture or with acetoacetic ester or diketene is condensed and the condensation product thus obtained with a diazonium compound from aniline or naphthylamine. also with a maximum of three identical or different ones the following substituents

Cl. Br. (

OCfI ₁ .

N. SCN.
CONH ,.

(O

NO ,. C "! I Nf IC (KH ₁ .

C!

Cl

CII. (N

SO.CIU

SO, N

SO ₁ II. COOII. COOCH ₁ .

if there are still existing solubilizing groups _with salt solutions, which contain as cations ** ♦ Ca ⁺ / Cu ++ Ni ^{+ +} Mn ⁺⁺ or Al ^{++ +,} are loaded at temperatures between 40 and 95 ° C, possibly with the use of anionic or nonionic surfactants.

The invention relates to a process for the production of azo pigments, which are excellent for paints and plastics as well as for dyeing viscose pulp and for printing inks

[It is known to have alkyl-substituted sulfonamide groups to be incorporated into dyes (see Swiss Palentschrift 395 387 and Austrian patent specification ■ MO 488) In the German Auslegeschrift 1 242 774 and in Swiss patent specification 413 168 the possibility is mentioned, among other things Groups of Art

SO ₂ NlCH ₂ CH ₂ CN) ₂

Use / u. According to Swiss Patent 394 438, similar ones which are unsubstituted on the alkyl are known Groups in the diazo component. According to the German Auslegeschrift I 153 476, diazo components from a combination of the f-formula

SO ₂ CJU NNC ₆ H ₄ NH,

NU,

which can also be substituted, but the Alkylizruppen are not substituted, obtained.

Finally, the French are from the most recent times Patent documents 1 505 707 and I 505 70S to he mention the dyes show similar structure.

All of these patents deal with disperse dyes.

The aim and task of the hearing was now to Az.opiizmcnte to create on a similar basis that have better defects than those previously known.

It has now been found that valuable Azopimnenr.e obtained when compounds of the general formula

CII, CH, CN

may be substituted, where Y - H. Cl. CII ,. (XlI, or NO ₂ i:> l and X has the meaning given. Is coupled and any solubilizing groups present in the molecule of the dye are laked with salts of polyvalent Mc-UdIe.

2. The method according to claim I. characterized in that that the coupling in a very wakeful alkaline to weakly acidic medium at temperatures of 0 to 70 C and in the presence of anionic or 6s non-ionic surfactants is carried out.

3. The method according to claim! characterized, that in the Farbsloffmokkül

i nler

SO, N-

SO, N

NH,

SO, N

CW ₁ CW ₁ CN

X X

(H, (H, CN

where X = H, -CH ₂ -CH ₂ -CN, alkyl with I to 5 carbon atoms,

-CH ₂ - CH ₂

is condensed with acid chlorides of 2,3-oxynaphthoic acid, 2,3-OxycaΓbazoIcarbonsäure, coumarin-3-caΓbonsäure, a Phenylpyrazoloncarbonsäure or with acetoacetic ester or diketene and the condensation products thus obtained with diazonium starting from aniline or naphthyl amine, which also with a maximum three identical or different of the following substituents

Cl, Br, -CN, -SCN, -NO ₁ , -CH ₁ . OCH ₃ . -CONH ₂ . - NHCOCH ,.

- CO —f .. · O - ^{y /} ';. ·

CfI, CH ₁ CN

SO ₂ C ₂ H ₅

SO, N

SO ₁ H. - COOH. COOCH ₁ . OH.

substituted \ jin, where Y ^: II. Cl. CII ₁ .

Is OCH, or NO, and X is the specified

Has meaning. clutch. If there are no solubilizing groups in the molecule, the resulting product is precipitated with dilute acid in the presence of anionic or nonionic surfactants. It represents the desired azo pigment. If there are still solubilizing groups in the molecule, the product must be separated off by salting it off and then coated with a salt solution of polyvalent metals to give pigments . The following cations are suitable for laking: Ba ⁺ \ Ca ⁺ \ Cu ^{+ +} , Ni ^{+ +} , Mn ^{+ +} , Al ^{+ + +} and others, which can be present as nitrates, chlorides, acetates, etc. The laking Performs to be temperatures between 40 and 95 ° C, especially at 70 ⁰ C, in a weakly basic, neutral Odei from the weakly acidic range. This should anionic or nonionic surfactants are used concomitantly One can, for. B. for the diazo component of a compound of the formula

NH, -

> - NH,

go out, where Y has the meaning given Diazotization produces cine bisdiazotization Compound that is best obtained with condensation products of acetoacetic ester or phenylpyrazolonecarboxylic acid clutch.

The coupling of the diazonium salt with the condensation product mentioned is weak alkaline to weakly acidic medium at temperatures. 0 to 70 ° C, advantageously 30 to 50 ° C and in the presence of anionic or non-

^ s ionogenic surfactants carried out.

A whole range of pigments can be produced in this way. simplestWIs a pigment foilscr formula

HO CO NII ^{y /}

NN ■ '"

SO, N

CH, CU, CN

CU, CH, CN

for which unsubstituted aniline and 2,3-oxy-haphthoic acid chloride form the starting materials.

The diazo component used is, for example:

Aniline. 2-anisidine. Cresidin, 4-chlorocresidin. Anthramic acid methyl ester. 2,4-dichloroaniline. 2.5-dichloroaniliii. 2-chloroaniline. 3- (chloroaniline. 4-chlorine ml in. 4-Ciilor-2-anisitlin. 4 - ('hlor-.l-ammoiohiol.

3-chloro-2-aminololuene. 4 - chloro-2-aminotoluene. 5 - chlorine - 2 - aminotoluene. 6 - chlorine - 2 - aminotoluene.

4 - chlorine - 2.5 - dimethoxyaniline. 5 - i'rifluormeihyl-2 - ehloraiiilin. 3.5 Bistrillluoromethane laniline. 5 - trifluoromethyl - 2 - ethersulfonvlaniline. 4 - aminobin / ophenone, 4 - aeelaminoaniliii. 2.6 - dichloro - 4 - nitroaniline. 4-rlioilaniline, 4-khodan -3-chloroaniline. 3-amini> bc ^l n / onitrile. 3-ainobene / amide. 4-Aininoben / ol-NN-his-2-cyanoethyl-sulfonamiil. 3-Aminoben / ol-NN -bis-2-cyanoithyl-stilfonamiil. 2-amini> benzene-NN-bis-2-cyanoethyl-sulfonamide. 4-aminobenzene-N-2-cyanoethyl-sulfonamide. 3-aminobenzene-N-2-cyanoethyl-sulfonamide. 2-Aminohynzol-N-2-cyanoethyl-sulfonamide. 3 - aminobenzene - NN - iithyl- (2-cyaiiäthylM'ilfonamid. 1-naphthylamine, 2-naphthylamine, 2-naphthylamine-1-silfonic acid, 2-chloro-5-aminotoluene-4-sulfonic acid.

Naphthalenesulfonic acids added in small amounts to stabilize labile diazonium salts do not interfere with the coupling.

Those which can be produced according to the crCindungsgcn process Azo pigments are ideal for incorporating into paints and plastics, especially into Polyvinyl chloride. They can also be used for dyeing

6 <i of viscose spinning mass and use for printing inks. They color very well oil, solvent and lightfast, pure yellow, orange, red, purple and brown Nuances of high color strength and brilliance. Against-

i 814519

The azo pigments according to the invention are distinguished, for example, as a zinc white blend in linseed oil or in Wetch PVC or as a heavy spar blend in the glue / water system, due to their noticeably greater colorability the end. The good oil and plasticizer properties of the dyes according to the invention should also be particularly emphasized. So shows z. B. the dye according to the invention 2,5-dimethoxy-4-chloraailin- ♦ 4-acetoacetylaminobenzene-N, N-bis - (/} - cyanoethyl) sulfonamide compared to the dye 4-ethoxy-3- known from the German patent 908 050 aminobenzene-N, N-bis- (n-propyte) -sulfonamide -> acetoacetylamino - 2,5 - dimethoxy-4-chlorobenzene a 2V ₂ step better oil resistance and a IV2 step better plasticizer fastness. The following examples should serve as an explanation:

example 1

20th

155.3 parts of 2,3 - oxynaphthoic acid - 4 - N ₁ N - bis (2-cyanoethyl) sulfanilide are made into a paste with 26 parts of sodium hydroxide solution (D = 1.32) and, after heating, diluted with 1200 parts of water. It is filtered and 73 parts of hydrochloric acid (D = 1.09) are added dropwise at 45 ° C. with stirring. A solution of 63 parts of diazotized! 2,5-dimethoxy-4-chloroaniline too. The mixture is stirred for a further 15 minutes, heated to 85 ° C. and filtered off with suction. After drying, a blue-black powder is obtained which, incorporated in polyvinyl chloride films, gives a migration-fast, deep blue-tinged violet coloration.

35

Example 2

501 vile of chlorobenzene, 2.5 parts of thionyl chloride and 0.5 part of dimethylformamide are heated to 70.degree. . Now it is 6.3 parts 2,3-Oxynaphthoesäurc added and heated 20 minutes at 100 "C in a vacuum Man drives off the excess thionyl chloride are 2 parts to dry pyridine and immediately gives a solution of 9.2 parts - Aminobcnzol -N ^ -bis- (2-cyanäthyi) -su! Famid in 25 parts of chlorobenzene and 1 part of dimethylformamide. The mixture is heated for 1 hour and suctioned off at 30 to 40 "C. It is washed with chlorobenzene, then with a little dioxane and finally with water, and 2,3-oxynaphthocic acid-4-N, N-bis (2-cy-ethyl) sulfanilide is obtained as a yellowish powder.

Example 3

34 parts of 4-chlorocresidine are mixed with 38 parts of glacial acetic acid. This solution dropwise with stirring «0 parts of hydrochloric acid (O = 1.16) and 500 parts of water to 400 parts of ice are now xu _t diazotized with 56 parts of 4-n nitrite solution. The mixture is stirred for 30 minutes and filtered. 63 parts of 4-acetoacetyl-N, N-bis (2-cyanoethyl) sulfamidanilide are dissolved in 2000 parts of water and 100 parts of 2-sodium hydroxide solution by heating. 100 parts of 2N acetic acid are added dropwise at 50 ^{° C. with stirring.} To the resulting suspension above diazo solution runs within 15 minutes at 50 C. ^D, giving a yellow powder, the polyvinyl chloride inking bright grünstichiggelb. These colorations are very fast to light and migration.

Example 4

92.5 parts of 4-aminobenzene-N, N-bis (2-cyanoethyl) sulfamide are suspended in 250 parts of water and 91 parts of hydrochloric acid (D = 1.16). After 30 minutes it is cooled with ice to -I-5 to 7 ° C and diazotized within 40 minutes with 167 parts of 2 n-N'atr.umnitrite solution, which you run under the surface leaves. The mixture is then stirred for 30 minutes. The coupling can now be carried out as indicated in Example 1.

Example 5

6.1 parts of o-dianisidine are dissolved in 160 parts of water and 62.5 parts of 2N hydrochloric acid diazotized as usual. The solution of the resulting bisdiazotic product runs under the surface of the following coupling solution at + 10''C within an hour. 18.0 parts 4-Acetoaec! Yl-N.N-bis- (2-cyanoethyl) -sulfurnidariilid are in 200 parts of water and 30 parts of 2 N sodium hydroxide solution solved by heating. After cooling to IOC, 33 parts of 2N acetic acid are added dropwise with stirring to. the coupling component precipitating as a white suspension. After coupling, the mixture is heated for 10 minutes to 90 ° C, sucks off and washes neutral. Finally you dry off. Yield: 22.8 parts. Colors Rubber migration-proof, red-tinged.

Example 6

4.35 parts of diazotic 2-nitranin-4-sulfonic acid are coupled to the coupling suspension Example 3. After the coupling has ended, 10 parts are added Salt and sucks. The filter cake is boiled in 330 parts of water with 3 parts of emulsifier and coated with 36 parts of 0% barium chloride solution at 70 "C within 20 minutes. After 30 minutes vacuum, rewash, dry. 10 parts of a loose yellow powder are obtained. It stains polyvinyl chloride pure yellow.

In a corresponding manner, azo pigments can be made from the components of the following list be won:

Azo pigments can be obtained in a corresponding manner from the components in the following list

will:

Dia / oticrur ^ skompoiienlc

2-anisidine

Anthranilic acid moilylcler
2.5 dichloroaniline

Coupling component condenses

2,3-oxynaphthoic acid

the same
the same

and:

4-aminobenzene-N, N-bis-2-cyanoethylsulfamide
the same

the same

Nuiincc

Blue red

Red
Bluestithigrnl

I Ii.i / mMci u

4 - ('chloroaniline

> (hlor-2-anisidine
4- (chloro-2-anisidine
Krcsidin
I-naphthylamine
.VC'hlor-2-toluidine
4-chloro-2-touidine
5 - ('chloro-2-toluidine
6 - ('chloro-2-toluidine
2.6-f) chloroaniline
2,4-dichloroaniline
4-chloro-kresidin
5-trifluoromethyl-2- ⁱ .hloi.milm
4-aminodiphenyl ether
1,8-chloronaphthylamine
4 - ('chloro-2.5-dimethoxyaniline
4-amino phenone
3.5-bis-trifluoromethane! Aniline
5 -Trifluormct h yl-2-äl hy lsulioinl-

a nil in
2-chloroaniline

VC'hloraniline

4-Aminohcn / <il-N.N-his-2-cyaniilliylsulfaniid

2.4 - [) inraniline

4-C'hl (ir-2-lociidin

ft - ('hlor-2-toluidine

2.5-I) ichloraniiin

2.fi - [) ichlor-4-Ni tran ilin

2 - ('van-4-nitraniiin

1 local / app

KlippllintskiMllpcllKMllC kMIHk ¹ IlMlTt

IMHl

2.3 - () \\ iiiiphthi'csiiiire

the same

the same

dcsgl

the same

the same

the same

the same

dcsgl.

the same

the same

dcsgl

dcsgl

dcsgl.

the same

the same

the same

the same

the same.

the same. 2.3-O χ year ba / oka r hon-

acid

likewise. C'umann-Vcarboiisäiire

dcsgl.

likewise 2.3-oxynaphlhocic acid

dcsgl.

the same

4-chloro-2,5-dimethoxyaniline dcsgl. 4-chloro-2-toluidine the same 2,4-dichloroaniline the same S-trifluoromethyl -2-chloroaniline the same 4-amine (iben / ophenon the same 2-anisidine the same 4-aminobenzene-N, N-bis-2-cyano- the same ethylsulfonamide 4-aminobenzoJ-N, N-bis-2-cyano- the same ethyl sulfonic acid 2,5-dichloroaniline the same 4-chloro-2,5-dimethoxyaniline the same 4-chloro-2-toluidine the same 14-dichloroaniline the same

4-Aminiibcn /. () L-N, N-his-2-cyanoethylsulfamide like. like. like. like. like. like. like. the same like. like. like. likewise. liesgl. the same. the same

the same.

dcsgl. dcsgl.

dcsgl. dcsgl. the same. the same. the same 4-Aminobcn / nl-N.N-bis-

2-eyanethylsulfamide

3-aminobenzene-N.N-bis-

2-eyanethylsulfamide

like. like. like. like.

3-aminobenzene-N.N-bis-2-cyanoethylsulfamide

the same.

2-aminobenzene-N, N-bis-2-cyanoethylsulfamide the same

like. like. like.

Red

Blue red

Bordii

ruby

violet

Ro ι

Blue red

Blue red

Red

Scarlet fever

Blue red

ruby

Scarlet fever

ruby

Bordo

Rolstichigblaii

Scarlet fever

orange

orange

RoI (ielbsiichigrot

Bluish red

Red-brown

Brown

Rotsüchiggelr

Rotstichiggell

Green cast

violet

violet

orange

Bordo

Scarlet fever

Scarlet fever

Yellowish orange red

Blue tinge, scarlet fever

orange

Reddish orange violet red

Scarlet fever

Dia / ot ienini »skomponenlc

5-Τι fluoromcth) l-2-chloroaniline

4-Amiriobcrizopheiion 2-anisidine

4-rhoclananiliin

4-Rh (iclan-2-toluidine 2,5-dichloroaniline

4-chloro-2,5-dimethoxyaniline 4-chloro-2-toluidine
2.4-l) chloroaniline
5-Trifluoromethyl-2-C'hU) rantitn

4-aminobenzophenone i-anisidine

4-amine η benzene-N.N-bis-cyanathylsulfamide

I-aminoben / ol-N.N-bis-2-cyano- ■ 'thyl-stilfoiiiiiiiid

J-aminobenzene-N.N-his-2-evanalhvl-sulfonamide

3-Aminoben / ol-N.N-his-2-e \ anathylsulfonamid

J-Amiiioben / ol-N.N-bis-12-cvim -) - sulfonamide

2-Aniinobenzol-NN-his-l2-L-yiin-; it Ii \ I) -Mi Ha miil
desjjl.

l ^; ortsct7iing

Ic

Kiippliinj. "Ikn mpnncrilL · koiulcnsicri j the same Nu; uKC ims the same 2.3-Oxynaphlhocic acid c (ielborangi the same Seharlach the same Borclo the same the same Sacred the same uiul 4-ammobenzene-N.N-bis- Bordo the same 2-AiTiinobenzol-N.N-bis- 2-cy; in; illiy Isulftin- ruby 2-cyanoethylsulfamide amide the same .1-aminobenzene-N.N-his- the same the same Bordii the same the same RoI the same the same 2-cyiiiiiithylsulfoti- Seharlach the same .miiil (absolutely 2-Aminohyn / ol-N, N-bis- orange the same - ■ eviiniiihvlsiilfon- RoI the same aniiil ruby the same ; 4-aminobcii / ol- Seharlach the same N-2-e> aii.ilh \ Kii | foii- Reddish aniiil orange 4-aminobenzene . ^ - Aminoben / ol-N.N-bis- the same N-2-eyanälhylsuiron- 2-cyan; i I h y I sit I Ht m κ I Seharlach amide : 2-Amiiioben / ol-N.N-bis- the same 2-cvaii; ilh \ isulfamid the same the same Scarlet fever the same : 4-aminohene / oT- the same the same Red the same ι Rol the same , Seharlach ^{: the} same I bra

desul.

N-2-cyanoethyl suirotiamide

4-Amiiioben / ii | -N.N-his-2cvanath \ lsulfamiil

Red

2-Naphthylamine l-sulfonic acid

2-C'hloi "-4-siiiro-5-aniinoioliiol 4-chlorocresidine

2J-O \ ynaphihoesaure

desul.

4-aminobenzene-NN-bis- (2-c \ analh \ llsulfamiil
the same

4-Acetacetylaminohenzo | -N.N-bis-2-cyano;: th \ isulfamide

Ba
Mn

Ba
Mn

\ ll.llKC

Blue tint blue tint

Blue tint Blue tint Green tint!

Ί 4-chloro-2.5-duT) clhoxyaniline 1814519 ^. 12th Greenish yellow 11th J-chloro-4-nitroaniline continuation Vcrliickimu Greenish yellow 4-chloro-2-nitroaniline Coupling iMiiskiMiipnneniL Greenish yellow J-nitro-4-toluidine 4-acetacetylaminobenzene-N, N-bis- Greenish yellow } -Nitraniline-4-sulfonic acid 2-cyanoethylsulfamide yellow the same the same yellow the same the same Green yellow • -dianisidine the same Ba yellow 4-chlorocresidine the same Approx Greenish the same Cu yellow 4-chloro-2,5-dimethyloxyaniline the same Greenish
yellow 2-chloro-4-nilraniline the same Greenish
yellow 3-nitro-4-toluidine .VAcetoacetylaminoben / .ol-N.N-bis- yellow 4-chloro-2-nitroaniline 2-cyanoethylsulfamide yellow 2-nitroaniline-4-sulfosaurc the same yellow the same the same yellow the same the same Green yellow o-I) ianisidine the same Ba Grüiii.tichig-
yellow 4-chlorokiesidine the same Approx yellow the same Cu 4 - (. 'Hlor-2.5-di met liox> aniline the same yellow 2-chloro-4-nitroaniline the same yellow 4-chloro-2-nitroaniline 4-Aeetoacetylaminobcn / o! - yellow i-nitro-4-ioliiidin N- (2-cyanathy!) - sulfamide Reddish yellow 2-nitroaniline-4-sulfos; ii.i'c the same ', (o'.pinky yellow the same the same : Rolstichiggclb the same the same CJeIb o-l) ianisidine the same Ha Rotslichiggclb the same Approx j the same Cu ^; the same the same

Claims (1)

Palent claims: I. Process for the preparation of azo-pigmenia. characterized in that a Compound of the general formula CH ₁ - CH, - CN SO ₁ -N