DE2247009B2 - Iminoisoindolinone dyes and use for pigmenting high molecular weight organic material - Google Patents

Description

There were new valuable iminoisoindolinone dyes of the general formula

N = N

NH

Cl

Cl O

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

Alkyl or alkoxy groups containing 1 to 4 carbons and Z _{2 is} an alkyl or alkoxy group, found.

Substance atoms, Z ₁ and Z ₂ hydrogen atoms, alkyl or r> You get to them if you have an azo compound

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

H, N

wherein V ₁ and V _{2 are} hydrogen or halogen atoms, alkyl or alkoxy groups containing 1 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-tetrachloroisoindolinone-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 the! -Position oxygen present, condensed in a molar ratio of I: 2.

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

NH ₁

Z-,

Halogen, especially chlorine atoms, two tertiary Amino groups, for example piperidino or morpholino groups, one imino or one thioxo group or, in particular, two alkoxy groups, preferably those containing 1 to 4 carbon atoms, in particular melhoxy groups. These raw materials are known.

The diaminouzov connections used are provided known bodies, which can be monoacylated, for example, by coupling the diazo compound of a Diaminobenzols with an aminobenzene and EiU-acylicrung of the obtained azo dye or by coupling the diazo compound of a nitroaniline with an aminobei.zol and reduction of the nitro

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

2-chloro-4,4'-diaminoazobenzoI,

3-chloro-4,4'-diaminoazobenzene,

2-methyl-4,4'-diaminoazobenzene,

3-methyl-4,4'-diaminoazobenzene,

2-methoxy-4,4'-diaminoazobenzene,

3-methoxy-4,4'-diaminoazo benzene,

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

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

5,2 ', 5'-trimethyl-4,4'-diaminoazobenzene,

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

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

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

2-chloro-2'-methyl-4,4'-diaminoazobenzene,

3-Ch! Or-2'-methyl-4,4'-diaminoazc benzene,

3-chloro-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'-diaminoazo benzene,

2,5-dimethyl-2'-melhoxy-4,4'-dialninoazobenzene, 2,5-dimethyl-2'-methyl-5'-methoxy-4,4'-diaminoazo benzene,

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

benzene,

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

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

2,5-diethoxy-2'-methoxy-4,4'-diaminoazo benzene, 2,5,5'-Trimelhoxy-2'-melhyl-4,4'-diaminoa? .O-

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-linino-, 3-thioxo- or 3,3-bistert.amino ^^ oj-tetrrachlorisoir.dolin-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, ethyl glycol monomethyl ether, lower aliphatic ketones like acetone! 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-lctrachlorisoindoline-i-one 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, dan η 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 alcohols 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 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 can be used by high molecular weight organic material, 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.

Aminoplasts, in particular 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 ester, rubber, casein, silicone and silicone resins, singly or in mixtures. It does not matter whether the mentioned high molecular weight Compounds as plastic masses, melts or in the form of spinning solutions, lacquers,

2 ^r > paints or printing inks are available. Depending on the intended use, it proves to be advantageous to use the new pigments as toners or in the form of preparations. The new pigments are characterized by high fastness properties, in particular an excellent

JO expects light, migration and weather fastness.

The lminoisoindolino color according to the invention

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

Compared to example I of GB-PS 8 33 548

r, draw pigment obtained from 4,4'-diaminoazobenzene those according to the invention are distinguished by a significantly higher color strength.

Example I.

To dissolve 17 gS.

I -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 taking

«Stirring heated to 160 to 170" C and held for 2 hours.

The insoluble pigment is filtered off at 130.degree and washed with methanol, acetone and water. After drying, 14 g of an orange-yellow color are obtained

w Powder, which in this form can be used directly for coloring plastics and for incorporation into paints. 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 sodium methylate solution dissolved in methanol. 6.8 g of 2,5-dimethyl-4,4'-diaminoazobenzene are then added and 100 ml 1,2-dichloro

bo benzene added. With removal of methanol by distillation and stirring well, the temperature is increased to 100 ° C, whereby a clear solution is temporarily obtained and then the sodium salt of the pigment is deposited. After adding more

_b r, 100 ml of 1,2-dichlorobenzene and 20 ml of glacial acetic acid, the temperature is increased to 140 to 145 "C and stirred for 2 hours at this temperature. The precipitated pigment is filtered off at 120" C, with alcohol, Acc-

washed clay and water and at 70 "C in a vacuum dried. 17 g of a red pigment are obtained, which are incorporated into printing pastes, prints of very good quality Provides 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 give a clear solution. The sodium salt of 3,3-dimethoxy-4,5,6,7-letrachloroisoindolin-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, with 20 ml of glacial acetic acid acidified, the temperature increased to 140 to 145 ° C and kept stirring well for 2 hours. The insoluble pigment is filtered off at 120.degree. C. and washed with methanol, acetone and water. After drying, 17.6 g of a strong color are obtained reddish-tinged orange pigment, which in this form is used directly for coloring plastics and for manufacturing

ι «are used by printing pastes and color varnishes, 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,

NH ₂

NH,

yellow-orange

yellowish orange

yellowish orange

CH ₁

CH ₃

NH

Red

orange

orange

CH

OCH ₃

NH ₂

NH

CH ₃

\ _ _{N = N} _y

N = N

NH ₂

NH, orange

orange

OCH ₁

CH ₁

continuation

Example no.

NH ₂

OCH, OCH.,

OCH,

N = N

-NH ₂

OCH ₃

CH,

NH, -

-N = N

OCH,

OCH,

NH ₂

OCH,

OCH ₃

-NH ₂ OCH ₃ OC ₂ H ₅

NH ₂ OC ₁ H ₅

OCH., C ti,

N =

-NH ₂

CH,

CH ₃ O

NH ₂ - / ~ S-N == N- / " ^N CH ₃ CH ₃

NH, - f \ - N = N - <f ^ 'y- NH,

Cl CH ₃

NH ₂ - <f ~ VN = N- ^< \ ^r ^ y-NH ₂

CI OCH ₃

CH ₃

NH ₂ - / "VN = N- /"

Cl CH,

orange

Brown

bordeaux

bluish red yellow-orange

brownish orange

yellow gclborangc orange

yellow

continuation

Example no.

NH,

NH-,

NH,

NH,

NH,

NH

NH orange

rolstichiaorangc

Brown

gclorange brown ichigorange reddish brown brownish red marron

violet t / murron

OCH,

continuation

Example no.

OC ₂ H ₅
NH, - <^ V- N = I

NH ₂

IOl

-NH ₂ bordeaux

H, N

OCH,

Brown

Example 34

2 g of the pigment prepared according to Example 2 will be with 36 g of alumina hydrate, 60 g of medium viscosity linseed oil varnish and 0.2 g of coball linolate in one Three-roller mill rubbed.

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

Example 35

0.6 g of the pigment prepared according to Example 3 are mixed with 67 g of polyvinyl chloride, 33 g of dioclyl phosphate, 2 g of dibutyltin dilaural and 2 g of titanium dioxide mixed together and on a roller mill during Processed into a thin folio at 160 "C for 15 minutes. The reddish-tinged Oiang coloration produced in this way is strongly colored, migration, heat and lightfast.

Example 36

10 g of Ti'andioxyd and 2 g of the prepared according to Example 3, Pigments 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% solids content), 8.8 g of 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 "C, then you get an orange varnish which, with good color intensity, has a very good varnish, Characterized by light and law.

Claims (2)

Claims: 1. Iminoisoindolinone dyes of the general formula Cl Cl O Cl wherein V and V _{2 are} hydrogen or halogen atoms, alkyl or alkoxy groups containing 1 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 V _{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 1.