DE2247009C3 - Iminoisoindolinone dyes and use for pigmenting high molecular weight organic material - Google Patents

Description

There were new valuable 1-minoisoindolinone dyes of the general formula

V, Z ₁

N = N-

Cl

Cl

O Cl

wherein V, and V _{2 are} hydrogen or halogen atoms, where at least one of the substituents V |

Alkyl or alkoxy groups containing I to 4 carbons and Z _{2 is} an alkyl or alkoxy group, found,

substance atoms, Z ₁ and Z ₂ hydrogen atoms, alkyl or 45 You get to them if you have an azo compound

Alkoxy groups containing 1 to 4 carbon atoms of the general formula

V ₁

H ₂ N

wherein V, and V _{2 are} hydrogen or halogen atoms, alkyl or alkoxy groups containing I to 4 carbon atoms, Z ₁ and Z _{2 are} hydrogen atoms, alkyl or alkoxy groups containing 1 to 4 carbon atoms, where at least one of the substituents V ₁ and Z _{2 is} an alkyl or alkoxy group, with a 4,5,6,7-tetrachloro-isoindolinone-1, which contains easily exchangeable substituents in the 3-position, which claim two bonds according to type or number and are more mobile than the one in! -Position oxygen, condensed in a molar ratio of 1: 2.

The 4,5,6,7-tetrachloroisoindolinones to be used as starting materials contain, for example, two easily exchangeable substituents in the 3-position

Halogen, especially chlorine atoms, two tertiary amino groups, for example piperidino or morpholino groups, an imino or a thioxo group or in particular two alkoxy groups, preferably those containing I to 4 carbon atoms, in particular

bo special methoxy groups. These raw materials are known.

The diaminoazo compounds used are well-known bodies that can be obtained, for example, by Coupling the diazo compound of a monoacylated diaminobenzene with an aminobenzene and deacylation of the azo dye obtained or by coupling the diazo compound of a nitroaniline with an aminobenzene and reduction of the nitro

group in the obtained azo dye. As examples the following diaminoazo compounds may be mentioned:

2-chloro-4,4'-diaminoazobenzene,

3-chloro-4,4'-diaminoazo benzene,

2-methyl-4,4'-diaminoazobenzene,

3-methyl-4,4'-diaminoa2o benzene,

2-meth <ixy-4,4'-diaminoazobenzene,

3-methoxy-4,4'-diaminoazobenzene,

2,5-dimethyl-4,4'-diaminoazo benzene,

2,3-dimethyl-4,4'-diaminoazobenzo !,

5,2 ', 5'-trimethyl-4,4'-diaminoazo benzene,

2,5-2'-dimethyl-4,4'-dianlinoazobenzene,

2,5,2 ', 5'-tetramethyl-4,4'-diaminoazo benzene,

3-methyl-2 ^/ methoxy-4,4'-diaminoazobenzene,

2-chloro-2'-meibyl-4,4'-diaminoazobenzoI,

3-chloro-2'-methyl-4,4'-diaminoazo benzene,

3-ChloΓ-5-2'-dimethyl-4,4'-diaminoazobenzene,

2-chloro-5-2'-dimethyl-4,4'-diaminoazobenzene,

3-chloro-5-2'-dimethoxy-4,4'-diaminoazobenzene,

3-chloro-2 ', 5'-diethoxy-4,4'-diaminoazobenzene,

2,5-dimethyl-2'-methoxy-4,4'-diaminoazobenzene, 2,5-dimethyl-2'-methyl-5'-methoxy-4,4'-diaminoazobenzene,

2,5-dimethyl-2 ', 5'-dimethoxy-4,4'-diaminoazo-

benzene,

2,5,2 ', 5'-tetramethoxy-4,4-diaminoazo benzene,

2,5,2 ', 5'-tetraethoxy-4,4'-diaminoazobenzene,

2,5-diethoxy-2'-methoxy-4,4'-diaminoazo benzene, 2,5,5'-trimethoxy-2'-methyI-4,4'-diaminoazo-

benzene.

Some of the condensation takes place in the cold, possibly with warming of the intimately mixed Components, particularly advantageous in the presence of inert, d. H. not participating in the reaction organic solvent.

If one goes from 3-imino-, 3-thioxo- or 3-3-bistert.amino- ^ oj-tetrrachlorisoindoline-1 -ones or of alkyl salts of 3,3-dialkoxy-4,5,6,7-tetrachloroisoindolin-1-ones off, it is advantageous to use water-miscible organic solvents such. B. lower aliphatic alcohols, such as lower alkanols, for example methanol, isopropanol or butanol, lower cyclic ethers, such as dioxane, ethylene glycol monomethyl ether, lower aliphatic ketones, such as acetone 1 The condensation takes place here already at relatively low temperatures. It is advantageous to work in the presence of base-binding agents; as such are, for example, lower fatty acids, which then simultaneously serve as solvents, in particular Acetic acid, to mention.

When using 3,3-dihalo-4,5,6,7-tetrachloroisoindolin-1-ones preference is given to organic solvents free of hydroxyl groups, such as hydrocarbons, z. B. aromatic, such as benzene, toluene, xylene, tetrahydronaphthalene or diphenyl or cacloaliphatic, z. B. cyclohexane, then also halogenated hydrocarbons, such as aliphatic, z. B. Carbon tetrachloride or tetrachlorethylene, or aromatic ones such as chlorobenzene or di- and trichlorobenzene cyclic ethers, such as dioxane, also ketones, such as acetone or esters, namely esters of lower fatty acids with lower alkanols such as ethyl acetate in the presence of acid-binding agents.

The new pigment precipitates from the reaction medium immediately after its formation. It is for certain purposes can be used directly as a raw pigment; but it can also be done by methods known per se, for example by extracting with organic solvents or by grinding with again afterwards removable grinding aids, e.g. B. Salts, in their properties, especially with regard to purity, form, Opacity to be improved.

The new dyes are valuable pigments which, in finely divided form, are used for pigmentation

ίο used by high molecular weight organic material can be, e.g. B. cellulose ethers and esters, such as ethyl cellulose, acetyl cellulose or Nitrocellulose, polyamides, polyurethanes or polyesters, natural resins or synthetic resins, e.g. B.

is aminoplasts, especially thermoplastic and curable acrylic resins, urea and melamine-formaldehyde resins, also alkyd resins, phenoplasts, polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, Polyacrylic acid esters, rubber, casein, silicone and silicone resins, individually or in mixtures. It does not matter whether the high molecular weight compounds mentioned are used as plastic masses, Melts or in the form of spinning solutions, lacquers, paints or printing inks. Depending on Intended use proves to be beneficial to the new pigments as toners or in the form of preparations to be used. The new pigments are distinguished by high fastness properties, in particular excellent Light, migration and weather fastness off.

The Iminoisoindolinofarb- according to the invention

Fabrics are highly fast, strongly colored orange pigments that can be produced economically or ecologically.

Compared to the example 1 of GB-PS 8 33 548 from 4,4'-diaminoazobenzo! draw obtained pigment those according to the invention are distinguished by a significantly higher color strength.

example 1

For the solution of 17 g of 3,3,4,5,6,7-hexachloroisoindoline-1 -one in 100 ml of 1,2-dichlorobenzene becomes the hot solution of 5.65 g of 2-methyl-4,4'-diaminoazobenzene in 200 ml of 1,2-dichlorobenzene. It imagines itself immediately orange-yellow precipitate. The suspension is heated to 160 to 170 ° C. with stirring and held for 2 hours.

The insoluble pigment is filtered off at 130.degree and washed with methanol, acetone and water. After drying, 14 gan-orange-yellow are obtained Powder, which in this form is used directly for coloring plastics and for incorporation into paints can be. The dyeings achieved in this way are distinguished by excellent fastness properties.

Example 2

18.2 g 4,5,6,7-tetrachloro-3,3-dimethoxy-isoindoline 1-one with 55 ml of 1N sodium methylate solution dissolved in methanol. Now 6.8 g of 2,5-dimethoxy-4,4'-diaminoazobenzene and 100 ml of 1,2-dichlorobenzene are added admitted. The temperature is raised to 100 ° C. while the methanol is distilled off and the mixture is stirred thoroughly increased, whereby a clear solution is formed temporarily and then the sodium salt of the pigment separates. After adding more

100 ml of 1,2-dichlorobenzene and 20 ml of glacial acetic acid, the temperature is increased to 140 to 145 ⁰ C and stirred for 2 hours at this temperature. The precipitated Piement is filtered off at 120 ° C, with alcohol, acetone

washed clay and water and ^{dried at 70 0} C in a vacuum. 17 g of a red pigment are obtained which, incorporated into printing pastes, give prints of very good lightfastness

Example 3

16.5 g of 3,4,5,6-methyl tetrachlorocyanobenzoate are stirred with 55 ml of a 1N sodium methylate solution in methanol to form a clear solution. The sodium salt of 3,3-dimethoxy-4,5,6,7-tetrachloroisoindolin-1-one is formed. Under good 6.05 g of 2-methoxy-4,4'-diaminoazobenzene and 100 ml of o-dichlorobenzene are then added with stirring. the The temperature is now increased to 100 ° C. while methanol is distilling off. There is temporarily a homogeneous solution, then it separates

Tabel

Sodium salt of the pigment. It is diluted with a further 100 ml of o-dichlorobenzene, acidified with 20 ml of glacial acetic acid, the temperature is increased to 140 to 145 ° C. and kept stirring well for 2 hours. The insoluble pigment is ^{filtered off at 120 °} C. and washed with methanol, acetone and water. After drying, 17.6 g of a strongly colored, reddish-tinged orange pigment are obtained which, in this form, is used directly for coloring plastics and for production

ίο are used by printing pastes and color lacquers, can. The dyeings produced therewith are distinguished by excellent fastness properties.

If the 2-methoxy-4,4'-diaminoazobenzene is replaced by appropriate amounts of the diaminoazobenzenes listed below replaced, then pigments with similarly good properties are obtained:

Example no.

NH ₂

yellow-orange

yellowish orange

yellowish orange

Red

orange

orange

orange

orange

OCH ₃

CH ₃

^T place setting

Example no.

N ¹ H ₂

Vn ^ n / "" V

NH ₂

OCH ₃

NH,

OCH ₃ OCH ₃

NH ₂

OCH ₃

NH,

CH ₃ OCH ₃

NH

NH ₂ -

NH

OCH ₃ OCH ₃

OC ₂ H ₅

\ ~ / - N = N - * \\ - ^NH 2

OCH ₃ OC ₂ H ₅

^ f ^r ^^ N = N ^^ J> -NH ₂ OCH ₃ OCH ₃

A ³

// ^ _{N = N} ^ Q> -NH ₂ CH ₃ OCH ₃

CH ₃

NH,

NH,

NH ₂

CH ₃

CH ₃

I = N- ^ V-NH ₂

CI CH ₃

^ N = N-ZvNH ₁

CI OCH ₃

CH ₃

NH ₂

₌ VI ^ V

N = N

NH ₂

Cl

CH ₃

oransc brown bordeaux bluish tint

yellow-orange

brown tichieoranee yellow

yellow-orange

orange

yellow

continuation

Example no.

NH,

Cl

OCH,

orange

NH, -

-N = I

OC ₂ H ₅ reddish orange

NH,

= N- <f Vnh ₂

N Η

CH ₃

NH,

N = I

NH,

OCH ₃

= N-f 1 ^ NH ₂

OCH ₃

NH ₂

-N = I

brown yellow-orange brown-tinged orange red-tinged brown brown-tinged red

NH,

N = I

marron

NH-

N =

OCH ₃

N-f V-NH ₂

OCH ₃ violet / marron

continuation

Example no.

31

32

33

OC ₂ H ₅ NH ₂ Y? >> OC ₂ H ₅ OC ₂ H ₅ NH ₂ - OC ₂ H ₅ "V-N = N- Γ
H ₂ N i = N ^^> - NH ₂ OCH ₃ OC ₂ H ₅ I = N- ^ V-NH ₂ OC ₂ H ₅ OCH ₃ - / ^ NH ₂ j
OCH,

Red

bordeaux

Brown

Example 34

2 g of the pigment prepared according to Example 2 are mixed with 36 g of alumina hydrate and 60 g of medium-sized linseed oil Viscosity and 0.2 g cobalt linoleate rubbed on a three-roll mill.

The red prints produced with the corresponding color paste are strongly colored and extremely lightfast.

Example 35

0.6 g of the pigment prepared according to Example 3 are mixed together with 67 g of polyvinyl chloride, 33 g of dioctyl phthalate, 2 g of dibutyltin dilaurate and 2 g of titanium dioxide and processed on a roller mill at 160 ^° C. for 15 minutes to form a thin film. The reddish orange coloration produced in this way is strongly colored, migration, heat and lightfast.

_jo example 36

10 g of titanium dioxide and 2 g of the pigment prepared according to Example 3 and listed in the table under 6 are mixed with 88 g of a mixture of 26.4 g of coconut alkyd resin, 24.0 g of melamine-formaldehyde resin (50%

J5 solids content), 8.8 g ethylene glycol monomethyl ether and ground 28.8 g of xylene in a ball mill for 48 hours.

If this lacquer is sprayed onto an aluminum foil, predried for 30 minutes at room temperature and then baked for 30 minutes at 120.degree. C., then an orange coating is obtained, which at good color strength through a very good overcoat. It is characterized by light and weather fastness.

Claims (2)

Claims: 1. I minoisoindolinone dyes of the general formula V ₁ C. . V ₂ Vn = N-A-N HN Il Cl T CI
/ Cl r O 1 Cl / I NH Z _{2 c} / V / \ ^ C ⁷ / N T \ Ii Cl O Y Cl wherein V ₁ and V ₂ contain hydrogen or halogen atoms, alkyl or alkoxy groups! up to 4 carbon atoms, Z ₁ and Z _{2 are} hydrogen atoms, alkyl or alkoxy groups containing 1 to 4 carbon atoms, where at least one of the substituents V ₁ and Z _{2 is} an alkyl or alkoxy group. 2. Process for pigmenting high molecular weight organic material, characterized through the use of the dyes according to claim I.