DE2739856A1 - AZINE PIGMENTS - Google Patents

Description

Dr. F. Zu'irjKtein i en. - Dr. E. As.r.snn Cr. R. Koenig.oberger DipL-Phyo. tv. f-! o! r: bcuer - Dipl.-lnp. F K'ii.fjtc i ^ en-D- ". F. Zumr.tein jun.

TELtLf-ON: SAMMLlL NIi 22b ~, 41

TELEEX Ü29J79

TELECiRAM no. ZUMPAT

CHECK ACCOUNT:

MÜr <ICHUN 9113S-J109. I.ILZ 70O10O00

BANK ACCOUNT: BANK HOUSE H. AUFI! AUGER

KIONH. 397097. ULZ 7OO 306OO

8 MUNICH

BRÄUHAI ISSTRASSE

Case 3-10688 / MA 1671 / +

CIBA-GEIGY AG, CH-4-00? Basel / Schvreiz

Azine pigments

The present invention relates to azine pigments. The present invention relates to azine pigments

Formula:

809810/0985

-ε-

wherein X is an oxygen atom or an NRi radical, in which R * is hydrogen, alkyl having 1 to 4 carbon atoms, aryl having 6 to 10 carbon atoms or aralkyl having 7 to 12 carbon atoms, and Y is a hydrogen or halogen atom , R ₁ for hydrogen or a methyl group, Rp for hydrogen, alkyl with 1 to 4 carbon atoms, aryl with 6 to 10 carbon atoms or aralkyl with 7 to 12 carbon atoms and R, for alkyl with 1 to 4 carbon atoms, aryl with 6 to 10 carbon atoms , Aralkyl with 7 to 12 carbon atoms or an acyl radical with a carbocyclic aromatic ring, or Rp and R-, together with the carbon atom to which they are attached, form a 5- or 6-membered carbocyclic or heterocyclic ring, each of which is condensed Can carry rings and is optionally substituted in each case by one or more non-water-solubilizing groups, and R, - has the same meaning as R ·, where Rp and R, g are optionally substituted by non-water-solubilizing groups.

If X is an NR ^ radical, R ^ can be hydrogen, methyl, Ethyl, n-propyl, η-butyl, phenyl or naphthyl, but preferably

- 2 809810/0965

be hydrogen, methyl or phenyl. However, X is particularly preferably an oxygen atom.

If Y is a halogen atom, this can be a chlorine, iodine or, preferably, a bromine atom. Hydrogen will however preferred as substituent Y.

Methyl groups are preferred as substituents R, and R, -.

If R ₂ and / or R are alkyl groups, these are, for example, methyl, ethyl, n-propyl and n-butyl groups. Phenyl and naphthyl groups are examples of aryl groups R ₂ and / or R ^. If R ₂ and / or R 1 are aralkyl groups, these are, for example, benzyl, α-methylbenzyl, α, oc-dimethylbenzyl and naphthylmethyl groups. If R is an acyl radical with an aromatic ring, then anilido, o-chloroanilido and p-toluidido groups are examples of such radicals.

Preferably, R ₂ and R, together with the carbon atom to which they are attached, form a 5- or 6-membered carbocyclic or heterocyclic ring. Examples of pigments according to the invention _{which contain such preferred groups R 2} and R are those of the formula:

IA

809810/0965

and particularly

IB IC

wherein R,, R ₁ -, X and Y have their previous meanings and Rg stands for hydrogen or a group which does not make water soluble, such as a halogen atom, an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms or a nitro group.

Pigments of the formula I of particular interest are those of the formula:

II

where X, Y and R-, have their previous meaning, and of particular Interest is the pigment of the formula:

809810/0965

III

that differs from dehydracetic acid (3-acetyl-A-h: hydroxy-6-methylpyran-2-one) ,. a cheap and easily accessible substance. The present invention also relates to a method for the production of azine pigments of the formula I, which is characterized in that a hydrazone of the formula:

OH fl

C = N-NH,

IV

wherein X, Y, R, and R ₁ - have their previous meaning with an aldehyde or ketone of the formula:

where Rp and R, have their previous meaning, converts.

The reaction can be carried out in aqueous media or in a polar organic solvent such as acetic acid, ethanol, Methoxyethanol, dimethylformamide or mixtures thereof take place.

The preparation of the starting material is preferably used

of the formula IV and the reaction with the compound of the formula V in the same reaction vessel without isolating the hydrazone, saving time and equipment.

With the exception of the hydrazone derived from dehydroacetic acid, the hydrazones of the formula IV are new compounds and as such constitute part of the present invention. The compounds of the formula IV can be prepared by reacting a Aldehydes or ketones of the formula:

VI

wherein X, Y, R-, and R ₁ - have their previous meaning, produce with hydrazine hydrate, hydrazine hydrochloride or hydrazine hydrosulfate.

The reaction can be carried out in an aqueous or a polar organic solvent as described above with regard to the method for the preparation of the pigments of the formula I described.

Pigments of the formula I can also be obtained by reacting a hydrazone of the formula:

^H 2 ^N " ^{N =} ° \

R ₃

where Rp and R have their previous meaning with an aldehyde or produce ketone of formula VI defined above. As the reaction media, such as with reference to the former are suitable

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Process for the adjustment of pigments of the formula I indicated.

This latter process is in turn preferably carried out in such a way that the starting material of the formula VII is carried out by Reaction of hydrazine or one of its salts with a compound of the formula V and then the compound of the Allowing formula VII to react further with a compound of formula VI without isolating the hydrazone.

The pigments of the formula I can be used in finely divided form for pigmenting high molecular weight organic material will.

The present invention accordingly also relates to compositions which have a high molecular weight organic Contain material and a pigmenting portion of an azine pigment of the formula I, as well as a process for pigmenting high molecular weight organic material, which is characterized in that one has a pigmenting portion of an azine pigment of formula I incorporated therein.

Such organic materials are, for example, cellulose ethers and esters such as ethyl cellulose, acetyl cellulose or nitrocellulose; Polyamides; Polyurethanes; Polyester; natural or synthetic resins, such as polymerization or condensation resins, e.g. aminoplasts, especially urea / formaldehyde and Melamine / formaldehyde resins; Alkyd resins; Phenoplasts; Polycarbonates; Polyolefins such as polystyrene; Polyvinyl chloride; Polyethylene; Polypropylene; Polyacrylonitrile; Polyacrylic acid ester; thermoplastic or curable acrylic resins; Rubber; Casein; Silicone and Silicone resins; on its own or in mixtures.

809 8 1 070 9 ~ 6 5

The compositions according to the invention preferably contain 0.1 to 5% by weight of the azine pigment of the formula I.

It doesn't matter if the organic material is in In the form of a plastic, a melt, a spinning solution, a varnish, a paint or a printing ink, but paints and varnishes are preferred.

Depending on the end use, it may be advantageous to use the azine pigment as a toner or in the form of a preparation. The azine pigments can be used immediately after production or they can be ground with salt before use.

The azine pigments are characterized by their insolubility in water and organic solvents, good fastness properties and high brilliance.

The following examples serve to explain the present invention in more detail. Parts and percentages are parts and percentages by weight. example 1

9.1 parts. Dehydracetsäurehydrazone are suspended in 100 parts of glacial acetic acid and added with stirring to the solution of 8.6 parts of 2-hydroxynaphthaldehyde in 50 parts of glacial acetic acid. After thirty minutes of stirring at room temperature, the reaction mixture is filtered off with suction at room temperature and the residue is washed with 100 parts of glacial acetic acid and 500 parts of water and, at 50-6O ⁰ Cgetrocknet. This gives 12 parts, 71%, of a solid which, in an ink medium, shows a bright greenish-yellow color and has a melting point of 254 ° C.

809810/0965

Microanalysis % C. H N Calculated 67.85 4.80 8.33 Found 67.77 4.92 8.19

Similar results are made using the series of hydrazones and aldehydes given in Table I below Azines in the same way.

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TABLE I.

CB O (O OO

«Ο CJl

example

Hydrazone

OH CH

^H 3 ^C H

OH CH

OH CH

OH ^CH 3 I.

^H 3 ^C

^C 6 ^H 5

aldehyde

yield

QiO.

CHO

HO

90 %

82%

74%

CHO

86%

Melting point

> 300 ° c

280 ° c

300 ° C

29O ⁰ C

Coloring in
Printing ink

Greenish yellow

Greenish yellow

Greenish yellow

Reddish yellow

CD 00 iS \ CD

TABLE I (CONTINUED) example

Hydrazone

OH CH.

aldehyde

yield

CHO.

OH CH.

OH CH,

H ₃ C

OH

H ₃ C

N-NH ₁

CHO

OH

/ ^C 2 ^H 5
C ₂ H ₅

; ho

Melting point

88%

84%

55 7.

CHO

Br

71%

245 ° C "

224 ⁰ C

159 ^Ü G

241 ⁰ C

Coloring in
Printing ink

Reddish yellow

yellow

Greenish yellow

yellow

TABLE I (CONTINUED) example

10

11

Hydrazone

aldehyde

GIO;

OH CH

H.

'N-NH,

CHO

OCH.

yield

76% -

Melting point

272 ⁰ C

248 ⁰ C

Coloring in printing ink

yellow

Greenish yellow

12th

13th

OH CH

rV

^H 3 ^C

₍ C = N-NH

A _d A ₀

OH

^C 6 ^H 5

CIIO

• 39%

292 ⁰ C

• \ v

CHO

93%

25O ⁰ G

CH

Greenish yellow

Greenish yellow

TABLE I (CONTINUED)

example Hydrazone 2x I. l
yS ^ sC «Ν-NH ₂ ^2x J ι · ^: 6 ^H 5 aldehyde the end
prey Melting point • > 300 ° C Coloring in
Printing ink OH CH ₃ H ₃ C 0 ^ 0 ³ ( OH CH ₃
^ Y '* "2
^ o ^ o CHO
j 14th OH CH, f
H ₃ C / 87 % > 30O ⁰ C 190 ⁰ C Greenish yellow CHO CHO 15th U 83 7. Greenish yellow CHO 16 CH ₃
Λ "■ 74 7, Greenish yellow CHO •

TABLE I (CONTINUED)

example

Hydrazone

aldehyde

yield

Melting point

Coloring in
Printing ink

CD O (O

17th

OH CH

^C 6 ^H 5

CII.j

8.1. X

278 ⁰ C

CHO-

Greenish yellow

18th

OH CH.

I i ■

Cr

H ₃ Cr OO

82%

> 300 ° C

Greenish yellow

Example 19

25 parts of isatin-ß-hydrazone are dissolved in 250 parts of dimethylformamide with heating, and a solution of 26.08 parts of dehydroacetic acid in 50 parts of warm dimethylformamide is added. The resulting mixture is refluxed for four hours with stirring, cooled to room temperature and suction filtered. The residue is washed with 100 parts of glacial acetic acid and then with 100 parts of ethyl alcohol and dried at 50-60 °, t where is 34 parts, 71%, of a solid of melting point obtained 304 ⁰ C, showing a reddish-yellow color in a Druckfarbenmediura.
Microanalysis % CHN

Calculated 61.74 4.18 13.50 Found 61.51 4.43 13.55 Using the information given in Table II below The hydrazones and ketones given above are used to prepare similar pigments in the same way.

- 15 809810/0965

TABLE II example

Hydrazone

20th

21

N-NH,

-NH,

Ketone

OH

Il

Aus <

booty ί melting point

%

%

246 ^OC

> 300 ° c

Coloring in
Printing ink

Brown

Red-brown

22nd

23

H-HH,

Oh? ^H 3

C = O

%

C.

> 300 ° c

Reddish yellow

Reddish yellow

Ca) CD OO

TABLE II (CONTINUED)

example Hydrazore 1 N-NH, Ketone OH f J H the end
prey Melting point Coloring in
Printing ink H cJs _o ^ O 24 O I.
H 51 7. > 300 ° C Reddish yellow ^ CN-NH ₂ O 25th ^C 6 ^H 5 66 7. > 300 ° C Reddish yellow OH

Example 26

5.5 parts of dehydracetic acid hydrazone are dissolved in 100 parts of glacial acetic acid, and 5.8 parts of 3-acetylcoumarin are added.
The mixture is stirred and refluxed for four hours, allowed to cool to room temperature and filtered off with suction. The residue is washed with 50 parts of glacial acetic acid and then with 500 parts of cold water and dried at 50-60 ° C., 7.0 parts, & 7%, of a pigment having a melting point of 228-230 ° C. which is obtained in a printing ink medium shows greenish-yellow color.
Microanalysis % CHN

Calculated 64.77 4.58 7.95

Found 64.24 4.76 7.93

Using the series of hydrazones and aldehydes or ketones given in Table III below
azine pigments are made in a similar manner.

809810/0965 ¹⁸

TABLE III

example Hydrazone Aldehyde / ketone the end
prey Melting point Coloring in
Printing ink 27 OH CH ₃ OH .0
I <! 68% 220 ⁰ C Greenish-yellow 28 N-NH ₂
-CO *
I.
H OH
H ₃ C Ij-
H 65 7. 295 ⁰ Cd Reddish yellow 29 Il OH
/ L · / COCH ₃
XX
HC Y ^ O
• 5 Au 28% 232 ° c, Reddish yellow

Example 30

8.4 parts of dehydroacetic acid are added to 100 parts of ethyl alcohol. 2.5 parts of hydrazine hydrate are added, and the resulting mixture is stirred and refluxed for two hours. The solution of 7.35 parts of isatin in 100 parts of glacial acetic acid is added and the mixture is stirred and refluxed for a further three hours. The mixture is cooled to room temperature and suction filtered.

The residue is washed with 50 parts of glacial acetic acid and then with 100 parts of ethyl alcohol. The resulting Solid is dried at 50-60OC which is 11 parts, 71% des pigment described in Example 19 results.

Similar results are made using two ketones and hydrazine as shown in Table IV below Azine Pigments.

- 20 809810/0965

TABEL example

O CO CO

31

32

33

34

First ketone

H ₃ C

OH CH

H ₃ C

₍ C-CH.

2. added
Ketone

yield

OH )

: 3

HCC-CH ₀ -C-

J It * · W

OO ^1-

Cl

HCC-CH-jC-NH-f ^
3 π 2 ,, X = /

O O

68%

"52%

61 7,

46.5%

Melting point

304 ° C

188 ° c

219 ⁰ C

220 ⁰ C

Coloring in
Printing ink

Reddish yellow

Greenish yellow

Greenish yellow

Brown

CO CD OO

TABLE IV (CONTINUED) example

35

36

37

First ketone

: -ch.

OH

z. added
Ketone

yield

OH

H ₃ C

AO ^ *

C = O O

Il

78%

65 7.

* 5 5t

Melting point

210 ⁰ C

293 ⁰ C

245 ⁰ C

Coloring in
Printing ink

Reddish yellow

Greenish yellow

Greenish yellow

CD CX)

Example 38

It is 7.35 parts of isatin in 200 parts V / ater, mixed with 2.5 parts of hydrazine hydrate and rests zv / ei hours at 90-98 ⁰ C. The solution is added of 8.4 parts of dehydroacetic acid in 100 parts of glacial acetic acid and then A further 100 parts of water / water are added and the mixture is heated and stirred for a further three hours at 90-98 ° C. The mixture is filtered off with suction while it is still hot and washed with 1000 parts of water. The resulting solid is dried at 50-60 ° C., which gives 11.5 parts, 75%, of the pigment described in Examples 19, 30 and 31.
Example 39

If the solution of 8.4 parts of dehydracetic acid in 100 parts of glacial acetic acid from Example 38 is replaced by a solution of

8.4 parts of dehydracetic acid in 210 parts of 1% sodium hydroxide solution, in this way, using the method described in Example 38, 5.2 parts of the same pigment are obtained.

Example 40

If the hydrazine hydrate in Example 38 is replaced

6.5 parts of hydrazine sulfate, 9.8 parts, 63% of the same are obtained Pigments.

Example 41

If the solution of dehydroacetic acid in glacial acetic acid from Example 38 is replaced by a slurry of 8.4 parts of dehydroacetic acid in 200 parts of water, 9.9 parts, 64%, of the same pigment are obtained.
Example 42

8.4 parts of dehydracetic acid are added to 100 parts of v / water

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and mixed with 2.5 parts of hydrazine hydrate. The solution of 7.35 parts of isatin in 300 parts of hot water is added and the resulting mixture is stirred and heated at a temperature of 90-98OC for five hours. It is suctioned off while still hot and the residue is washed with 6,000 parts of hot water. The resulting solid is dried at 50-60 ° C., which gives 11.7 parts, 78%, of the pigment described in Examples 19, 30, 31 and 38-41.
Example 43

7.35 parts of isatin are added to 200 parts of water, and 2.5 parts of hydrazine hydrate in 25 parts of glacial acetic acid are added. The mixture is stirred and heated to 95 ° C. with internal steam. A hot solution of 1.5 parts of rosinamine D (a commercially available aminated rosin based on abietic acid from Hercules Inc.) in 25 parts of glacial acetic acid and 50 parts of water is added, and stirring is continued for two hours at 95 ° C Suspension forms. 8.4 parts of dehydroacetic acid in 100 parts of glacial acetic acid and 100 parts of water are added and the mixture is heated and stirred at 95 ° C. for a further 3 hours. The mixture is filtered hot, washed with warm water until colorless and dried at 55-60 ° C., which gives 9.4 parts, 60.6%, of the pigment described in Examples 19, 30, 31 and 38-42.
Example 44

9.66 parts of isatin-ß-hydrazone are added to 200 parts of water and 25 parts of glacial acetic acid and stirred and heated to 95 ° C with steam. 1.8 parts of rosinamine D are heated in a steam

- 24 809810/0965

bath dissolved in 25 parts of glacial acetic acid and 50 parts of water, and the resulting solution is added to the above mixture with stirring. 10.8 parts of dehydroacetic acid in 100 parts of glacial acetic acid and 100 parts of water are added and the mixture is stirred for a further two hours while maintaining the temperature of 95 ° C. by means of internal steam. The bright orange precipitate obtained is filtered off and washed with 5000 parts v / poor water and the solid formed is dried at 55-60 ° C. This gives 12 parts, 64%, of the pigment described in Examples 19, 30, 31 and 38-43.
Examples 45 to 47

8.5 parts of 3-acetyl-4-hydroxy-6-methylpyrid-2-one are stirred in 250 parts of ethyl alcohol at room temperature, 2.75 parts of hydrazine hydrate are added and the mixture is stirred at room temperature for five minutes, filtered off with suction and air-dried , 9.1 parts, 100%, of a light yellow solid with a melting point of 300 ^° C. and the indicated chemical constitution are obtained.

OH k CH ₃
^ C = N H I ₂ N , 20 ^H 3 ^C ι
H C. 6, 23 , 97 Microanalysis % 53 6, 22nd Calculated 53 , 04 08 Found , 10 11

Using the ketones given in Table V below, one similarly builds up hydrazones in the same way

- 25 809810/0965

TABLE V

At £ piel Ketone Generated hydrazone N-NH ₀
OH I) 2
X ^ -CH ₃
^ N ^ iO
I.
^C 6 ^H 5 the end
prey Melting point 46 ^H 3 ^C ' OH NM ₂
H ₃ C ° 100% 220 ⁰ C 47 OH 0
(TV ^CH 3
koAo ^H 3 ^C 80 % > 30b ^ö c OH 0
H ₃ C ^^^>
^C 6 ^H 5

Example 48

30 parts of the product from Example 19 v / ground, which is brought into a finely divided state by grinding with salt, using an automatic paint grinder (4-100 revolutions at 10.5 kg / cm ^) in 70 parts of one made from Surkyd 131 (a commercially available long-oil alkyd resin ) and VT.V. 568 (a phenolic resin modified with rosin from Mander Kidd Ltd.) in a ratio of 3: 1. The printing ink obtained is used to produce a reddish-yellow print with very good lightfastness on paper. Example 49

6 parts of the product of Example 19 in the usual manner in 32 parts of Beetle Resin BA 99/5 (a low-oil alkyd resin \ 12 parts Epok V9192 (a etherified melamine / formaldehyde resin) and 50 parts of a 4: 1 mixture of "xylene" and The resulting stain is applied to a strip of aluminum card as a wet film 0.15 mm thick using a block applicator, the film is allowed to evaporate for ten minutes and baked for 15 minutes at 140 ° C., producing a bright, strong reddish-yellow film with good lightfastness results.
Example 50

Rutile titanium dioxide from. Pigment quality is in proportion of 10 parts of titanium dioxide to one part of the product from Example 19 are incorporated into a pigmented lacquer produced according to Example 49. A 0.15 mm thick film of the resulting lacquer is applied to an aluminum card and left for 10 minutes

- 27 -

809810/0965

evaporate and then burns a fifteen-minutes at 14O ⁰ C, resulting in a bright reddish-yellow paint film with good lightfastness.
Example 51

0.5 parts of the product of Example 19 are combined with 0.5 parts of titanium dioxide Rutü-incorporated pigment grade in the usual manner in 99 parts of PVC plastisol and removed as a film of about 1 mm thickness on release paper. The film is melted for 5 minutes at 165 ° C., resulting in a reddish-yellow PVC strip with good lightfastness.

/ ^ ORIGINAL INSPECTED

80981_0 ^ ₈ 0_96 5

Claims (1)

Patent claims: wherein X is an oxygen atom or an NR ^ radical in which R ^. for hydrogen, alkyl with 1 to 4 carbon atoms, aryl with 6 to 10 carbon atoms or aralkyl with 7 to 12 carbon atoms, and Y denotes a hydrogen or halogen atom, R- denotes hydrogen or a methyl group, Rp denotes hydrogen or alkyl with 1 up to 4 carbon atoms, aryl with 6 to 10 carbon atoms or aralkyl with 7 to 12 carbon atoms and R ₅ for alkyl with 1 to 4 carbon atoms, aryl with 6 to 10 carbon atoms, aralkyl with 7 to 12 carbon atoms or an acyl radical with a carbocyclic aromatic ring , or Rp and R ^ together with the carbon atom to which they are attached form a 5- or 5-membered carbocyclic or heterocyclic ring, each of which can carry condensed rings and is optionally substituted by one or more non-water-solubilizing groups, and Rn has the same meaning as R ^, where R ₂ and R are optionally substituted by non-water-solubilizing groups d. 2. Azine pigments according to claim 1, characterized in that X denotes an NR ^ radical and R ^ denotes hydrogen, methyl or phenyl. 3. Azine pigments according to claim 1, characterized in that 809810/5 ^ 5 original INSPECTED that X represents an oxygen atom. 4. azine pigments according to any one of the preceding claims, characterized in that Y stands for hydrogen. 5. azine pigments according to any one of the preceding claims, characterized in that R ₁ and R ^ are methyl groups. 6. azine pigments according to any one of the preceding claims, characterized in that R ₂ and R, together with the carbon atom to which they are bonded, form a 5- or 6-membered carbocyclic or heterocyclic ring. 7. azine pigments according to claim 6, of the formula Azine pigments according to claim 6, of the formula R, wherein R,, R, -, X and Y have the meaning given in spoke 1 to have. 9. azine pigments according to claim 6, of the formula OH R ₁ Y. XC = NN _V __ ^ _ic ^V 6 - 30 809810/0965 wherein R,, R, -, X and Y have the meaning given in claim 1 have and Rg for hydrogen, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a nitro group. 10. Azine pigments according to claim 9, of the formula OH * f "3 N- wherein X, Y and R have the meaning given in claim 1. 11. Azine pigment according to claim 9, of the formula OH CH. = N - N III 12. Compositions, characterized in that they contain a high molecular weight organic material and a pigmenting one Part of an azine pigment of the formula I contain. 13. Compositions according to claim 12, characterized in that the organic material is a printing or painting medium is present. 809810/0965 - 31 -