DE2611826A1 - PIGMENT COMPLEXES AND PROCESS FOR THEIR PRODUCTION - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. E. Assmann Dr. R. Koenigs ^ s'cier - Dipl. - Phys. H. <- 'Olzbauer Dipl. -Ing. F. Klingseisen - Cr. f. to. «Stone jun.

Patent Attorneys 8 Manchen 2, Bräuhausstrasse

Case 3-9836 / MA 1608
GERMANY

Pigment complexes and processes for their preparation

The present invention relates to: new pigments and in particular, new metal complex azo pigments and processes for making the same.

According to the invention, a metal complex pigment of the formula

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2611828

includes where

A is an optionally substituted aryl or heterocyclic radical,

R is an optionally substituted aryl radical,

X an oxygen or sulfur atom or a carboxy group,

ρ the numbers 1 or 2,

when p = l, C is a hydrogen atom bonded to the radical A and if ρ = 2, C either a direct bond or a one Alkylene, arylene or aralkylene radical, the two radicals A connect with each other and

M is a metal from the first row of transition elements mean.

A preferred group of metal complexes according to the formula I. has the formula

609840/1027

X has the above meaning

M _{1 represents} Cu or Ni,

Y, Y- ,, Yj ^unc * ^Y 3 each have a hydrogen or halogen atom, a nitro or trifluoromethyl, an alkyl or alkoxy group with 1 to 4 carbon atoms, one optionally with a chlorine atom, an alkyl or alkoxy group with 1 to 4 carbon atoms substituted phenyl or phenoxy group a carbamoyl or an alkylcarbamoyl group with 2-5 carbon atoms,

Mean V, Vj, V "Vo, Z, Z ,, Z2 and _Z3 is a hydrogen or halogen atom, an alkyl or alkoxy group having 1-4 carbon atoms.

Metal complexes of the formula are particularly preferred

γ _ο _A Vnh- / Vn = N

III

609840 / 1Q27

wherein

X, M ,, Y, Y ,, X2 ^unc * ^ 3 ^ ^{e vorste} h ^en de meaning and

^Y 1 ^JY 2 ' ^Y 3 § ^{leicl1 are}

If A and / or R represent an aryl radical, the latter preferably contains 6 to 14 carbon atoms and can be selected from one aromatic ring or two or more condensed aromatic rings. The aryl radical can be unsubstituted be or with one or more groups which do not give the complex compound of the formula I any water solubility, be substituted, for example with alkyl, alkoxy, carboxyalkyl or alkylcarbamoyl, arylamide or alkylamide, nitro groups or halogen atoms. Preferred examples of the aryl groups A and / or R are naphthyl and especially phenyl radicals.

If A represents a heterocyclic radical, this can either unsubstituted or by one or more of the aforementioned non-water-solubilizing groups be substituted. Preferred heterocyclic radicals A are 4-methylcoumarin, coumarin, benzimidazolone and in particular 4-methyl-2-quinolone.

Preferably, p ^e l and C is a hydrogen atom bonded to the A radical.

2611828

However, when p <= 2, C can either be a direct bond, the two radicals A, e.g. phenylene or biphenylene radicals, with one another be connects, or an alkylene, arylene or aralkylene radical which connects two radicals A to one another.

M is a metal of the first row of transition elements, namely Ti, V, Cr, Mn, Fe, Co, Ni or Cu, but preferably Ni or Cu.

The present invention also provides a method for Preparation of a compound of the formula I, which is characterized in that a compound of the formula

NH

IV

metallized, in which

R, A, X, C and ρ are as defined above and R is a

Hydrogen atom or an alkyl group with 1-4 carbon atoms means.

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The metallization of the compound IV can be carried out directly in the reaction medium, used to prepare compound IV. Alternatively, the connection of the formula IV separated from their crude reaction mixture, washed free of impurities and prior to metallization suspended in a solvent identical to any solvent used to prepare Compound IV can be identical or different.

The metallization can be carried out using a solution or suspension of any suitable salt or complex Metal M take place. For example, if metallization is a copper plating process, a suspension of a copper salt in an organic solvent or an aqueous solution of a copper salt such as copper acetate, cuprammonium sulfate or Sodium cuprotartrate, can be used. When the metallization is carried out using nickel, it is expedient to use a solution of nickel acetate tetrahydrate in Use methylcellosolve.

Many of the compounds of the formula IV are new compounds per se, however, they can be obtained by methods known per se.

The compounds of the formula IV can be prepared, for example, by using the diazo compound of an amine of the formula

609840/1027

with a compound of the formula

mh-r '

VI

couples, in which A, X and R have the preceding meaning.

The reaction becomes advantageous by dissolving the coupling component in a suitable solvent, for example dimethylformamide or in a mixture of solvents such as dimethylformamide / glacial acetic acid, followed by addition the diazonium solution of the amine of the formula V carried out.

The starting materials of the formula V are known per se.

Suitable coupling components of the formula VI can, for example by reacting 2,4,6-trichloropyriraidine with the following Amines are obtained:

609840/1017

aniline

2-, 3- or 4-chloroaniline '3,4-dichloroaniline 2,3-dichloroaniline 2, 4 ~ dichloroaniline * 2,5-dichloroaniline 2,6-dichloroaniline 2,4,5-trichloroaniline 2,4,6-trichloroaniline 2-, 3- or 4-bromoaniline 2,4-dibromaniline 2,5-dibromaniline 2-, 3- or 4-methylaniline 3,4-dimethylaniline 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 2,4,6-trimethylaniline 2-methyl-5-chloroaniline, 2-methyl-4-chloroaniline, 2-methyl-, 3-chloro aniline 2,4-dimethyl-5-chloroaniline 2,6-dimethyl-4-chloroaniline 2-chloro-5-trifluoroethylaniline 2-, 3- or 4-nitroaniline

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4-chloro-2-nitroaniline 2-chloro-4-nitroaniline 4-methyl-3-nitroaniline 2-methyl-5-nitroaniline 2-methyl-4-nitroaniline 2- or 4-methoxyaniline 2- or 4-ethoxyaniline 3-chloro-4-methoxyaniline, 2-methoxy-5-nitroaniline, 2-methoxy-5-chloroaniline 2-methoxy-5-trifluoromethylaniline, 2-nitro-4-ethoxyaniline 2-methoxy-4-chloro-5-methylaniline 3-amino-4-methoxy-benzoic acid amide 3-Amino-4-methoxy-benzoic acid ethylamide 2-amino-4-phenylaniline, 5-chloro-2-phenyoxyaniline, 5-chloro-2- (4'-chloro) -phenoxyaniline 5-chloro-2- (4'-methyl) phenoxyaniline.

Preferred coupling components of the formula VI are:

2,4,6-trianiline pyrimidine 2,4,6-tris (4-methylaniline) pyrimidine 2,4,6-tris (4-chloroaniline) pyrimidine 2,4,6-tris (4-methoxyaniline) pyrijnidine

609840/1021

2,4,6-tris (4-nitroaniline) pyrimidine 2,4,6-tris- (o-anisidine) -pyrimidine 2,4,6-tris- (4-carboxyamidaniline) -pyrimidine.

Examples of suitable amines which can be used according to the invention of Formula V include:

Anthracite in ilsic acid o-aminophenol

o-anisidine

5-methylanthranic acid Dianisidine

2-methoxy-4-nitroaniline, 2-methoxy-5-acetamidaniline 2,5-diaethoxy-4-phenylamidaniline 2-hydroxy-5-chloroaniline, 2-methoxy-4-nitro-5-methylaniline 5-acetamido-anthranilic acid, 4-methyl-6-methoxy-7-amino-2-quinolone.

When the amines are substituted with an alkoxy group in the 2-position the presence of an organic solvent is essential during the metallization phase.

Because of their insolubility in the reaction medium, the compounds of the formula I can easily be removed from the reaction mixture can be isolated by filtration.

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The compounds of the formula I can be used as pigments directly after preparation; i.e., after they are from the crude reaction liquids were filtered off and dried. Alternatively, they can first be prepared using known wet or dry conditioning techniques such as grinding, either alone or in the presence of a water-soluble salt or another medium, which then can be easily removed, for example by washing, processed.

Accordingly, the present invention further provides a method for coloring organic materials, which consists in incorporating a compound der.Formel I into the organic material. The present invention also includes the organic material so colored.

The proportion of compound I used according to the invention to color the organic material can vary within broad limits, but is normally in the range from 0.1 to 10 percent by weight, based on the total weight of the organic material to be colored.

Organic materials that can be colored according to the present invention include high molecular weight organic material, for example Cellulose ethers and cellulose esters, such as ethyl cellulose, acetyl cellulose and nitrocellulose, polyamides, Polyurethanes and polyesters, natural and synthetic

609840 / 1Q27

Resins, such as aminoplasts, especially urea-formaldehyde and melamine-formaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefins, such as polyethylene and polypropylene, Polystyrene, polyvinyl chloride, polyacrylonitrile, polyacrylic acid ester, rubber, casein, silicones and silicone resins, individually or in a mixture, it does not matter whether these high molecular compounds are in the form of plastic masses or Melts or in the form of spinning solutions. However, the compounds of formula I are of particular interest for coloring lacquers, paints and printing inks.

Depending on the end use, it may be advantageous to use the compounds of formula I as a toner or in the form of a Pigment preparation to end.

As a rule, the compounds of the formula I are excellent Fastness properties, in particular light, varnish, weather and migration fastness, good heat resistance and characterized by very high color strength.

In the following examples, parts and parts are based on weight.

609840/1027

Preparation of ligands Examples 1-22

1. 3.7 parts of o-anisidine suspended in 7.75 parts of concentrated hydrochloric acid and 10 parts of water are ^{cooled to 0 °} C. and a solution of 2.1 parts of sodium nitrite in 10 parts of water is then added all at once. Stirring is continued for 3 minutes and a clear yellowish brown solution is obtained. This diazonium solution is added over the course of 2 minutes to a solution of 10.6 parts of 2,4,6-trisaniline pyrimidine in 250 parts of dimethylformamide. 20% strength aqueous sodium hydroxide solution is added to the suspension obtained in this way in order to adjust the pH of the mixture to 4. The suspension is stirred for 2 hours. Thereafter, the orange solid is filtered, washed with water and dried at 50-6O ⁰ C. In this way, 11.3 parts (77.5% of theory) of a brilliant orange solid of the formula are obtained

Analogous azo compounds can be prepared in the same manner by using those listed in Table I below Amines and coupling components are obtained.

809840/1027

TABLE I.

example

OCH,

Mr

OCH, coupling component

Yield "I.

la

CH,

NH

/ V-NH
N

NH

OCH,

- CH,

OCH,

78.1

82.0

€ 09840/1027

TABLE I.

example

Amine coupling component

Yield 7

NH,

OCH,

NH,

OCIL

(J

NH

NH

Cl

NO,

NH

nh

NH

NO,

91.4

81.2

9840/1021

- 16 TABLE I.

example

Amine

Coupling component

Exploitation

NH ₀

I £

OCH,

NO ₀

NH ₂

OCH,

NO

NH

NH

CH,

NH

NH

H,

82.7

84.8

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- 17 TABLE I.

example

Amin

Clutch component e

Looters

OCH,

NO,

CH.

NO _n

OCH,

.NH

N-NH

^0CH

NH

OCH,

Cl

NH NH

NH Hx / V-Cl

Cl 90.0

81.8

609840/1027

TABLE I.

example

Coupling component e

Off j yield \

CH,

NH,

O ₂ N

NH

NH

Cl

NH

NH

Cl

Cl

99.0

75.1

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- 19 TABLE I

example

Amine

Clutch component e

yield

OClL

CONH ₂

H,

OC

CONH ₂

NH

NH

NH

NH

CH,

CH,

89.3

85.1

609840/1021

TABLE I.

example

Amine

Clutch component

Yield 7

la

H ₂ NOC

CH.

H ₂ NOC

OCH,

OCH,

NH

-H
\
NH

OCH,

OCH,

Cl

NH

NH

- ^ Λ / h ^cl

Cl 87.1

86.3

609840/1027

TABLE I.

example

Amin coupling component e

yield

16

17th

COOH

COOH

NH: N

NH

CH,

NH

NH

CH,

77.2

85.6

609840/1017

TABLE I.

example

Coupling component

prey 7

19th

NH,

COOII

NH ₂

COOH OCH,

^X -N NH

> -NH

OCH ₃

87.6

OCH, Cl

NH

NH

NH

Cl

Cl

609840/1021

TABLE I.

example

Amine coupling component

Yield η

. 20th

21

COOH

NO,

NH,

COOH

NH

NH

NH

CH,

NH

NH

CH,

75.4

82.9

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- 24 TABLE I.

example

Amine

Clutch component

yield

NH ₀

Cl

OCH.

OCHo OCH,

OCH,

NH

NH } - ^NH :

OCH

NH

Γ V NH

/ TVnh

NH

85.9

90.9

89.1

609840/1027

TABLE I.

Coupling component

yield

/ ο

25th

26th

NEL

SH

nh

■ Ν

'-NH

/ V-NH

.N

/ VN

J-NH

y = N

80

80

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Preparation of Metal Complexes Examples 27-51

27. 2.44 parts of the product from Example 1 are dissolved in 25 parts of methyl cellosolve. A suspension of 1.0 part of copper (II) acetate monohydrate in 25.0 parts of dimethylformamide is added to this solution. The resulting suspension is heated for 8 hours under reflux, filtered, washed with methyl cellosolve and ethanol and dried at 50-6O ⁰ C. In this way, 0.7 parts (17.0% of theory) of a red-violet powder with a melting point of over 360 ^° C. are obtained.

Repeating this procedure using the various ligands listed in Table II below and metals, you get a number of pigments of formula I.

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σ> ο to

GAME

28

29

LIGAND

HeI

OCH,

METAL

copper

copper

YIELD
Ί

COLOR LIGHTNESS ONE! IN PAINT PAINT

37.4

51.6

Blue red

Bordeaux

Good

Good

METAL

. OFF- {COLOR IN BOOTY! ONE% LACK

LIGHTNESS

IN THE
PAINT

copper

copper

83

Bordeaux

Good

50.6

violet

Excellent

EXAMPLE

30 31

LIGAND

OCH,

N ₅₅ N- / V-NH- /

OCH,

OCH,

/ -N / V

• ° 2 ^N

CH ₃ HN

METAL

OFF-I COLOR IN ¹ LIGHT FASTNESS

IN LACIC

BAG ONE
PAINT

copper

copper

66.9

violet

40.2

violet

Excellent

Good

EXAMPLE

LIGAND

METAL

YIELD

COLOR IN A 'LACQUER

LIGHTNESS

IN PAINT

copper

63.7

violet

Excellent

copper

62.5

Bordeaux

Excellent

EXAMPLE

LIGAND

HN

OCH,

VNH- /

OCH

HN

OCH,

HN A V ^0CH 3

OCH.

EXAMPLE

36

H ₂ NOC

H ₂ NOC

LIGAND

Y N __ N- /

OCH ₃ HIT

N = Ν

OCH,

METAL

YIELD

COLOR IN

ONE

copper

copper

36.3

30.5

Brownish red

Red

LIGHTNESS

IN THE
LA CK.

Good

Good

te

H <

- <ι-5

pq H Pd W

4-1

4J O

ι W! co H

U Cl)

OO

V4

OJ

PM CO

00 en

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cn σ to oo

EXAMPLE

40

41

LIGAND

/> - NH

N ₈ -N- / \ _NH- / COOH NH

METAL

copper

Copper 32.8

YIELD

FAKbE IKi LIGHT FASTNESS

EIKEM
PAINT

68.4

yellow brown

Brown

IN THE
PAINT

Excellent

EXAMPLE

CD O CO DO

42

43

LIGAND

N = N- / VNH - // V Cl

METAL

copper

copper

YIELD

11.0

44.4

COLOR IN I LIGHTNESS

ONE
PAINT

Orange red

! egg brown

IN THE
PAINT

Excellent

Good

K) CD

OO

he.·

EXAMPLE

σ co οο

44

45

LIGAND

N-N- / *

0OH

NH

METAL

copper

copper

YIELD

12.5

40.4

COLOR IN 1 LIGHT FASTNESS

A PAINT

Yellow-brown

Brown

IN PAINT

Excellent

Good

ο
co
αο

EXAMPLE

LIGAND

OCH

^ 0CH

3 NH

OCH.

METAL

copper

nickel

THE END.
PREY

45.6

61.2

COLOR IN! LIGHTFASTNESS

ONE
PAINT

Bordeaux

Bluish
Red

IN THE
PAINT

Good

Good

ro Cn

oo cn

ίΧ>
□ Ο

EXAMPLE

48

49

LIGAND

NO,

NH

«Ν N-N -4 /) - ΝΗ

OCH

3 NH

NO.

N _s N -f V-NH

METAL

copper

copper

•YIELD

56.0

45.2

COLOR IN LIGHTNESS

A PAINT

Brown

Bordeaux

IN PAINT

Good

Good

ro cn

oo

CD

2! ^ H Ü

MH ₁ J

(U

+ Y • A

eq

4-y

ω ο

• rl

4-1

+ J O

fa

OO VO

t-1

co vo

Q)

ISI

a)

O M ■ J

H W

μ a. co

in in

609840/1027

Claims (9)

Claims 1. Metal complex of the formula ß'-NH— wor in A is an optionally substituted aryl or heterocyclic radical, R is an optionally substituted aryl radical, X is an oxygen or sulfur atom or a carboxy group, ρ the numbers 1 or 2, if p = 1, C is a hydrogen atom bonded to the radical A and if p = 2, C is either a direct bond or a Alkylene, arylene or aralkylene radicals which connect two radicals A to one another and M is a metal from the first row of transition elements mean. • 609840/1027 2. Metal complex according to claim 1 of the formula Z- II X has the above meaning Represents M-, Cu or Ni, Y, Yp Y ₂ and Υ «each represent a hydrogen or halogen atom, a nitro or trifluoromethyl, an alkyl or alkoxy group with 1 to 4 carbon atoms, one optionally with a chlorine atom, an alkyl or alkoxy group with 1 to 4 Carbon atoms substituted phenyl or phenoxy group a carbamoyl or an alkylcarbamoyl group with 2-5 carbon atoms, V, Vp, V ₂ , Vo, Z, Zp Z ^ and Z _{3 represent} a hydrogen or halogen atom, an alkyl or alkoxy group with 1-4 carbon atoms. 609840/1027 3. Metal complex according to claims 1 and 2 of the formula III wherein X, MpY, Yp Y ₁ ^ and Y ^ are as defined above and Yp Y ₂ , Y _{3 are the} same. 4. Process for the preparation of a metal complex of the formula I, characterized in that a compound is used the formula IV metallized, in which R, A, X, C and ρ have the meaning given in claim 1 and R is a hydrogen atom or a 1 to 4 carbon atom means containing alkyl group. 6098 40/102 7 5. The method according to claim 4, characterized in that that the metallization of the compound of formula IV is direct in the reaction medium used to prepare the compound of formula IV. 6. The method according to claim 5, characterized in that that the compound of formula IV is separated from its crude reaction mixture, washed free of impurities and suspended in a solvent prior to metallization that is identical or different to any solvent used to prepare the compound of formula IV can be. 7. A method for coloring high molecular weight organic material, characterized by the use of a metal complex according to claim 1. 8. The method according to claim 7, characterized in that the high molecular weight organic material is a lacquer Is a paint or a printing ink. 9. The colored high molecular weight organic material obtained according to claims 7 and 8. 609840/1027