DE1808017C3 - Water-insoluble monoazo compounds, process for their preparation and their use as pigments - Google Patents

Description

Z CO-NH- < > - N

ι 'I

R ₁ R

wherein X is a hydrogen, chlorine or bromine atom or a methoxy group, Y and Z are hydrogen, chlorine or bromine atoms, nitro, methoxy, ethoxy, butoxy groups, phenoxy groups optionally substituted by chlorine atoms or methyl groups, methyl, trifluoromethyl, Cyano, lower alkyl carboxylates, carboxamides, lower carboxylic acid monoalkylamide groups, optionally in the phenyl radical by methyl, methoxy or trifluoromethyl groups or chlorine atoms substituted carboxylic acid phenylamide groups, acetamino, sulfonic acid amides, lower sulfonic acid or methoxy groups, or optionally in the phenyl radical by Chlorine atoms substituted sulfonic acid phenylamide groups, R is an alkyl group with 1 to 6 carbon atoms and R _{1 is} a hydrogen, chlorine or bromine atom or a methyl or methoxy group.

2. Compounds according to claim 1, wherein the group Y in the general formula is a group of the formula R ₃ HNO ₂ B-, in which R _{3 is} a hydrogen atom, a lower alkyl group or the optionally substituted phenyl radical as indicated in claim I.

3. Compounds according to claim 1, wherein the group Y in the general formula is a group of the formula R ₃ HNO ₂ S-, in which R _{3 is} a hydrogen atom, a lower alkyl group or the optionally substituted phenyl radical as indicated in claim 1.

4. Monoazo compounds according to claim 1, wherein the group Y in the general formula is a group of the formula R ₄ OOC- in which H _{4 is} a lower alkyl group.

5. Process for the preparation of the compounds according to claim 1, characterized in that one diazotized amines of the general formula The present invention relates to new, valuable, water-insoluble monoazo compounds of the general formula

χ COCH ₃ ^H

N CO

Η-ΝΗ- / Λ-

R ₁ R

N (1)

wherein X is a hydrogen, chlorine or bromine atom or a methoxy group, Y and Z hydrogen, chlorine or bromine atoms, nitro, methoxy, ethoxy. Bu oxy groups, optionally through chlorine atoms

, phenoxy groups substituted by o or methyl groups.

- methyl, trifluoromethyl, cyano, lower carboxylic acid alkyl esters, Carboxamia- lower carboxylic acids monoalkylamide groups, optionally in the phenyl radical by methyl, methoxy or fluoromethyl

"Groups or chlorine atoms substituted carboxylic acid

phenylmide groups, acetamino sulfonic acid am.d-, Sere sulfonic acid monoalkylam.d- or> m, phenylres? optionally by methyl or methoxy groups or chlorine atoms substituted sulfonic acid

phenylamide groups, R an alkyl group having 11 to 6 carbon atoms and R ₁ a hydrogen, chlorine or bromine atom or a methyl or methoxy atom. sruppe, a process for their preparation, in which one diazotized amines of the general formula

45

in which X, Y and Z have the meanings given above have, with azo components of the general formula

55

wherein X, Y and Z have the meanings given in claim 1, with azo components of general formula N — CO

CH ₃ CO-CH ₂ -

N CO

CH ₃ CO-CH ₂ -CO-NH

R.

ι ι ._ r> .._ j D λ; » aforementioned Be 6s in weicnci rs. unu ^ v ₁ «... · t.

have interpretations, as well as the use of these compounds as pigments. You have particularly advantageous properties

Men moiioazo compounds of the above formula • where Y is a group of the formula R ₂ HNOC

S d R ₄ OOC- means in which

or

R and R3 are ^a hydrogen atom, a lower alkyl group ^{or the} optionally substituted phenyl radical as indicated above and R _{4 is} a lower alkyl group.

The compounds according to the invention are distinguished from those from DT-AS 12 81606 and US Pat. No. 3,109,842 known structurally related Compounds are characterized by their considerably improved lightfastness.

Suitable amines of the formula (2) mentioned for the preparation of the compounds according to the invention are, for example: chloroanilines, such as 2-chloro-, _5- niline, 2,4-dichloroaniline, 2,5-dichloroaniline, 2-chloro-5-methyianiline, 2- Chloro-4-methoxyaniline, 4-chloro-7-trifluoromethylaniline, NUraniline, like 2-nitro-aniline, 2- nitro-4-chloro-aniline, 2-nitro-4-methyl-aniline, 2-nitro-4-acetylamino-aniline, after all Aminobenzoic acid esters, such as methyl 2 - aminobenzoate, butyl 2 - aminobenzoate, dimethyl 1 - aminobenzene - 2,5 - dicarboxylate, dimethyl 1 - aminobenzene - 3,5 - dicarboxylate, methyl 4 - aminobenzoate, and furthermore such as amides, arylamides or aminobenzoic amides, for example 4-aminobenzoic acid amide, 4-chloro-3-aminobenzoic acid amide, 4,6-dichloro-3-aminobenzoic acid amide, 3 - amino - 4 - methoxybenzoic acid phenylamide. 3-Amino-4-methyl-benzoic acid methylamide, 3-Ami- 3c _n0 . 4 - carbomethoxybenzoic acid - (2 ', 5' - dichloro) -phenylamide, finally aminobenzenesulphonic acid amides, -alkyiamides or -arylamides, such as 3 - amino - 4 - methoxy - benzenesulphonic acid butylamide, 3 - amino - 4 - methylbenzenesulphonic acid methylamide 'and S-amino ^ -chlorobenzenesulfonic acid isopropylamide, 2,5-dimethoxy-4-aminobenzene-sulfonic acid methylamide and 2,5-dimethoxy-4-aminobenzene-sulfonic acid phenylamide.

The compounds used as azo components can be prepared by known processes, for example by reacting 2,4-dinitrochlorobenzenes with an amine of the formula R — NH ₂ , in which R has the meaning given above, to give the corresponding 2,4-dinitroaniline, whose partial reduction, for example with sulfhydrate liquor, to the corresponding 4-nitro-o-phenylenediamine, reaction with urea or phosgene to give the corresponding nitrobenzimidazolone, reduction to the corresponding aminobenzimidazolone and addition of diketene to the corresponding 5-acetoacetylaminobenzimidazolone according to the following scheme, where Ri has the meaning given above :

55 O ₁ N

O ₁ N

CH ₃ COCH ₂ CONH

C = O

N-C = O

NO

40

Examples of suitable amines R - NH ₂ are methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine or iso-butylamine.

Examples of suitable azo components of the formula (3) mentioned are:

l-methyl-5- (acetoacetylamino) -benzimidazolone, 1-ethyl-5- (acetoacetylamino) -benzimidazolone, 1 -n-propyl-S-iacetoacetylaminol-benzimidazolone,
l-iso-propyl-S-iacetoacetylaminoJ-benzimidazolone,
l-iso-butyl-S-lacetoacetylaminoJ-benzimidazolone,
ln-butylö-iacetoacetylaminoJ-benzimid'izo'on,

!, o-Dimethyl-S ^ acetoacetylaminoj-benzimidazolon,

l-methyl-o-chloro-o-iacetoacetylaminol-benzimidazolone,

l-methyl-T-bromo-S-facetoacetylaminol-benzimidazolone,

l-methyl-T-chloro-S-iacetoacetylaminoj-benzimidazolone,
1-methyl-o-methoxy-S-lacetoacetylaminoJ-benz · imidazolone.

The diazonium compounds are prepared in a known manner. In some cases they are Diazonium salts are sparingly soluble in an aqueous medium and separate out. You can isolate it and use it as a Bring moist paste to the coupling. However, the diazotization can also be carried out in a suitable organic Carry out medium, for example in glacial acetic acid, alcohol, dioxane, tetrahydrofuran, formamide, Dimethylformamide or dimethyl sulfoxide, and the resulting solution of the diazonium compound with the Combine azo component.

The dyes can be used in bulk or on a substrate, e.g. B. barite produce.

The preparation in substance takes place according to methods known per se, for example by association of the diazonium compounds with the azo components in an aqueous medium, advantageously in the presence of a union-active, Kalionaktivui or s nonionic dispersant or ii · presence of an organic solvent.

The dyes obtained in this way are often of hard grain and must then be used to achieve the full The color strength and the optimal fastness properties are subjected to an aftertreatment. For example heated the dried and ground or moist dyes in pyridine, dimethylformamide or other organic solvents such as dimethyl sulfoxide. Alcohol or chlorobenzene some Zeil under reflux or at higher temperatures under pressure. In some cases the transfer succeeds into a grain-soft form by heating with water under pressure, if necessary under Addition of dispersants.

The dyes obtainable by the present process are water-insoluble pigments. They are suitable for the production of colored paints. Lacquer formers, solutions and products made from acetyl cellulose, natural resins or synthetic resins such as polymerization or condensation resins such as Aminoplasts or phenoplasts, as well as from polystyrene, polyolefins, such as polyethylene or polypropylene, polyacrylic compounds, polyvinyl compounds, for example polyvinyl chloride or polyvinyl acetate, polyesters, rubber, casein or silicone resins.

The dyes according to the invention are also suitable for pigment printing on a substrate, in particular on textile fibers as well as on other flat structures such as paper. They can also be used for other purposes, e.g. B. in finely divided form for dyeing rayon made of viscose or cellulose ethers or esters, polyamides or polyurethanes in the spinning mass or used for coloring paper.

Due to their favorable rheological properties, the dyes can be classified in the named Process media well. They then have good light, weather and migration fastnesses. You are still heat-resistant, strongly colored and in many cases show pure, brilliant shades. Against the influence of Chemicals e.g. B. of solvents, they are resistant, especially to acidic and alkaline Actions. example 1

20.9 parts by weight of 5-amino - isophthalic acid dimethyl ester are stirred with 80 parts by volume of 5N hydrochloric acid for about one hour and then diluted with 300 parts by volume of water. Diazotising at 10 ⁰ C with 20 parts by volume of 5N Natriumnitrillösung, clears with diatomaceous earth and eliminates a possible excess of nitrous acid with a little amidosulfonic acid.

This diazo solution is allowed at about 20 ⁰ C with good stirring to an acetic acid suspension of the azo component flow, which was prepared in the following way:

25.5 parts by weight of 1-methyl-5-acetoacetylaminobenzimidazolone are stirred with 200 parts by volume of water at room temperature and dissolved by adding 60 parts by volume of 5 η sodium hydroxide solution. This Solution is clarified with activated charcoal and the clarified

55

60

65 solution in the course of about 30 minutes with stirring into a solution of 300 parts by volume;) water, 41 parts by volume of glacial acetic acid and 80 parts by volume of 5 η-sodium hydroxide solution at room temperature.

The coupling is terminated immediately. The coupling mixture is brought to the boil, suction filtered and washed thoroughly with water and dry at 60 C. The yellow pigment obtained is powdered and in 450 parts by volume of dimethylformamide heated to 130 ° C. for 4 hours. Subsequently, the Washed out dimethylformamide with methanol and dried the dye. You get a yellow one Soft grain pigment, good color strength and pure shade. In polyvinyl chloride, a varnish, if a printing ink or a dispersion paint is incorporated, higher yellow colorations are obtained Fastness to light, perfect fastness to overcoating and heat resistance and very good fastness to bleeding in polyvinyl chloride.

With dimethylformamide, the same weight amounts of pyridine or glacial acetic acid can be used. In this case, the mixture is refluxed for 4 hours.

Is used in the above example instead of 1-methyl-S-acetoacetylamino-benzimidazolone the equivalent amounts of l-methyl-o-chloro-S-acetoacetylamino-benzimidazolone, 1-methyl-T-chloro-S-acetoacetylaminobenzimidazolone, 1 -Methyl-7-bromo -5-acetoacetylamino -'benzimidazolone, 1-methyl-6-methoxy-5-acetoacelylamino-benzimidazolone or 1,6-dimethyl-5-acetoacetylaminobenzimidazolone, yellow pigments with good fastness properties are likewise obtained in this way.

The processing in polyvinyl chloride takes place, for example, according to the following process: 16.5 parts by weight of a plasticizer mixture consisting of equal parts of dioctyl phthalate and dibutyl phthalal are mixed with 0.05 parts by weight of dye and 0.25 parts by weight of titanium dioxide. Then 33.5 parts by weight of polyvinyl chloride are added. The mixture is rolled for 10 minutes on a two-roll mill with friction, the skin that forms being continuously cut up with a spatula and rolled up. Here, the one roller at a temperature of 4O ⁰ C, the other kept at a temperature of 14O ⁰ C. The mixture is then peeled off as a skin and pressed between two polished metal plates at 160 ° C. for 5 minutes.

Example 2

24.6 parts by weight of 1-amino-2,5-dimethoxybenzene-4-sulfonic acid methylamide are mixed with 50 parts by volume of water and 45 parts by volume of 5N hydrochloric acid Stirred for several hours, the hydrochloride of the amine used being formed. After that is diluted with 100 parts by volume of water at 15 ° C diazotized with 20 parts by volume of 5N sodium nitrite solution, a possible excess of nitrous acid eliminated by adding a little sulfamic acid and finally clarified with kieselguhr.

This diazo solution is allowed at 20 ⁰ C with good stirring to an acetic acid suspension of 25.5 parts by weight of 1-methyl-S-acetoacetylamino-benzimidazolone, prepared according to Example 1, to run. After the coupling has ended, the dye is filtered off with suction, washed and dried. The ground dye is refluxed with 600 parts by volume of glacial acetic acid for 3 hours, then it is suctioned off,

_lin , y _n

Gc rjl \ _n j _n

csf; h Γ e r 1 e r.

Washed indefinitely with methanol, then with water and dried. A yellow pigment is obtained, which in polyvinyl chloride, a varnish, a printing ink or a dispersion paint incorporated, red-tinged yellow tones of high lightness. flawless s Black paintwork and very good blood pressure in polyvinyl chloride. If you work the pigment into an oil-in-water emulsion or a water-in-oil emulsion one then obtains printing tubes with which one can produce textile fabrics, for example made of cotton or polyester fibers, in yellow tones with good light and dry cleaning properties can color.

B e i s ρ i c I 3

17.1 parts by weight of 1-amino ^ -chlorobenzene-carboxylic acid camide are dissolved with 50 parts by volume of 5N hydrochloric acid and 175 parts by volume of water and hot diazotized after addition of ice at 5 with 20 parts by volume of 5N sodium nitrite solution. The diazo solution is clarified and with a suspension prepared according to Example I of 25.5 parts by weight I - methyl - 5 - acetoacetylamino - benzimidazolone coupled. When the coupling is complete, the dye is vacuumed, washed and dried. The ground dye becomes glacial acetic acid with 600 parts by volume Heated under reflux for 3 hours, then filtered off with suction, first with methanol, then with water washed and dried.

A yellow pigment is obtained which, in polyvinyl chloride, is a varnish, a printing ink or a dispersion paint incorporated, reddish yellow colorations of high lightfastness, perfect fastness to overcoating and very good resistance to bleeding in polyvinyl chloride. Works m; on the pigment in an oil-in-water emulsion or a water-in-oil emulsion one, so one obtains printing pastes, with which one textile fabrics, for example made of cotton or Polyester fibers, dye in yellow shades with good lightfastness and good dry cleaning properties can.

Is used in the above example instead of 25.5 parts by weight I-methyl-S-acctoacetylamino-benzimidazolone the equivalent amount of 1-ethyl-5-acctoacetylamino - benzimidazolone or I - isopropyl - 5 - acetoacctylamino-benzimidazolone or l-isobutyl-5-acetoacctylamino-benzimidazolone, in this way one also obtains similar pigments with similarly good properties,

According to Examples I to 3, the slide / o- and Use A / O components. The shade of the on this. Pigments made in graphic art Dtuc.k is given in the right column;

!component

45 l) iii / oki> mpiiiirnlc

2,5-dichloro-4-nitroaniline

I-methoxy-S-ncelylaminoaniline

5-methyl-2-chloro

aniline

2-trifluoromethyl

aniline

4-chloro-2-trilluor-

methylaniline

2-amino-5-chloro

benzonilril

2-aminobenzoc-

acid methyl ester

4 - ('chloro-2-amino-

benzoic acid methyl

4-bromo-2-amino

bcnzoic acid methyl

5-chloro-2-amino-

benzoic acid methyl

cst he

.VChlor-4-amino-

benzoic acid methyl

2.4-dichloro-5-amino-

bcnzoic acid methyl

5-nitro-2-amino

bcnzoesä u remct h y I-

4-trifluoromethyl

2-aminoheiv / oesäurc.-

methyl ester

I-Aminohcnzol-

2,5-dicarboxylic acid

dimethyleslcr

I-aminobenzene-

. "'■ carlvinsihiircnielhyl ·

.A / nknmpniirnir

I, ti I -Aniinobcir / ol-

? -i; u-bonsäi'ireiUhyl

esl (M "-5-earbonsiuiiv-

l-aniinoben / ol

A / okomporunk

the same
the same

the same
the same
the same
the same
the same
the same

the same
the same
the same
the same
the same
the same
the same
the same

drsgl

.k'sut

. \. VDir.hloraniline

butyUislor -. 'i-i'arbon ·

'iiiut'eiimid

I -Aminobcnzol

Isobiilyl

I methyl-5-MC (Mo- iiclb
acelylaminoben /
iniidnzolon
■ l- ('hlor,' .- nilroimilin desgl. Oraii) « ¹

Ί-Melliyl: ¹ . itilronnilin des | .'l. Red

spiky siliiraiinid azolon

GuIb ",, I Amino-bon / ol- I Methyl-5-Mcoto-

'I-Acelyliimino- ilcsi; l. "ot · '-cMibonsiiinio- aivtylsiminoheiv

- ¹ . uilioimilin si i ines η κ hy lost er-5-carbon-

(ίοΙΙι siiiircmo.lhvlnmid

I iirblnn

reddish yellow reddish yellow yellow

yellow yellow yellow yellow yellow

yellow yellow yellow yellow

reddish yellow pclb

yellow yellow

go Ib

lic Ib

9 Illuminated methylphenyl amide the same 18th 08 017 V? 10 l-'iirbti 4-methyl-3-amino- continuation bcnzoesiiiirciso- A / nkonipoiicnk ' yellow Azo components nronvlamicl Dia / okompoiKMitc Diazo component Fiirblon the same yellow 5 4-chloro-3-amino- the same benzoic acid ethylamide the same I-aminobenzene yellow 4-chloro-3-amino- 2-carboxylic acid methyl benzoic acid yellow ester-5-carboxylic acid 2'-methyl-3'-chloro- 2 \ 5 '-dichlorpheny 1- [O phenylamide the same amide the same 4-methyl-3-amino 1-amino-benzene yellow benzoic acid-2'-chloro- yellow 2-carboxylic acid methyl 5'-trifluoromethyl- ester-5-carboxylic acid phenylamide the same yellow 3'-trifluoromethyl- 15th 4-chloro-3-amino- phenylamide the same benzoic acid l-methyl-6-bromo
5-acetoacetyl- yellow 4-methyl-3-amino
benzoic acid methyl
ester the same yellow 20th n-butylamide
1-aminobenzene
3,5-dicarboxylic acid aminobenzimide
ii7olon 4-methoxy-3-amino yellow diamid l-ethyl-5-aceto- yellow benzoic acid methyl
f * ctf * r the same 1-aminobenzene acetylaminobenz-
imidazolone CMtL
4-chloro-3-amino- yellow 3,5-dicarboxylic acid
diamid ! -n-propyl- benzoic acid methyl the same ² 5 1-aminobenzene- 5-acetoacetyl-
aminobenzimide yellow CMCL
4-aminobenzoe yellow 3,5-dicarboxylic acid
diamid azolone acid amide the same 1-methyl 4-methyl-3-amino yellow 30th 1-aminobenzene 6-methoxy- benzoic acid meth y I- 3,5-dicarboxylic acid acetoacetylamino yellow amide the same di-monomethylamide benzimidazolone 4-methoxy-3-amino yellow l-methyl-5-aceto- benzoic acid amide the same 4-methoxy acetylaminobenz- 4-ethoxy-3-amino- yellow 35 3-aminobenzoic acid imidazolone yellow benzoic aniide the same 2'-methoxy-5'-chloro- 4-n-butoxy-3-amino- yellow phenylamide the same benzoic acid amide 1-methyl-6-chloro 4-chloro-3-amino- yellow 4-methyl-3-amino 5-acetoacetyl- yellow On benzene sulfonic acid benzoic acid amide aminobenzimide 4 ^U amide the same azolone 4-amino-2,5-di- yellow 1-isopropyl methoxybenzene 4,6-dichloro-3-amino o-chlor-S-acclo- yellow sulfonic acid amide l-methyl-6-chloro benzoic acid camide acetylaminobenz- 45 4-amino-2,5-di- 5-acetoacetyIamino- right- imidazolone methoxybenzene bcnzimidazolone 1-methyl sulfonic acid amide 1,6-dimethyl 2-Vmino-2 \ 4'-di- 5-acctoacctyl- yellow 4-amino-2,5-di- 5-acctoacctyl- chlorine diphenyl ether aminobcn / .imid- methoxybenzene aminobenz right 4-carboxylic acid amide a / .olon SO sulfonic acid amide imidazolone the same 1-methyl-6-meth- 2-amino-4'-methyl- yellow 4-amino-2,5-di- oxy-5-accto- diphenyl ether nicthoxybcn / ol acctylaminobcn / - valid 4-earbonic amide the same sulfonic acid methyl imida / .olon 2-amino-4'-chloro- yellow .S .S amide 1-n-l'ropyl- diphenyl ether 4-Aiiiino-2 ,. ^t i-di- 5-acctoacctyl- 4-carboxylic acid methoxybenzene aminobcn / .iniid- right niuthylaniid the same sulfoiü-urureniethyl- a / .olon 4-chloro-3-amiiH) - yellow f \ t \ amide l-ii-butyl-5-aceto- ben / .oesiiin c-2 ', 5-di- (»' 4-amino-2,5-di- acctylaminobenz- chlorop'icnylamide the same mcthoxybcn / .ol- imida / .olon gel ¹ 4-methyloxy-3-aniino- yellow siilfdiisiiiiremelhyl- ben / ocsiiuie-3'-tri- a in id 1-methyl-5-acelo ('S 4-aniino-5-melh- acetylaminobcn /.- oxy-2-nictliylbcn / .ol- imida / olon sulfonic acid ethyl ami'J

11th 18th 08017 T 12th continuation ■ ■ - ■ Azo component - - - Azo components Diazo component Diazo component larblon the same _. .. ... _ the same 4-amino-2,5-di- 4-amino-2,5-di- yellow ⁵ methoxybenzene methoxybcnzol- sulfonic acid-2 ', 5'-di- sulfonic acid ethylamide the same methoxy-4'-chloro- 4-amino-2,5-di- yellow phenylamide the same methoxybenzene 4-amino-2,5-di- sulfonic acid isopropyl methoxy benzene amide. the same su! fonsäure-2'-methyl- 4-amino-2,5-di- yellow phenylamide the same methoxybenzene 4-methyl-3-amino sulfonic acid n-butyl i ₅ benzenesulfonic acid atnid the same methylamide the same 4-amino-2,5-di- yellow 4-methoxy-3-amino methoxybenzene benzenesulfonic acid acid phenylamide methylamide

Shade of yellow

yellow yellow

Claims (1)

Patent claims: I. Monoazo compounds of the general formula R and R ₁ the Bc-S 'mentioned in claim 1 according to An ^ g compounds according to claim 1 for pigmenters, of plastics, rubber, natural or synthetic resins Textile fiber materials. Printing inks, colored paints or dispersion paints.