DE2734659A1 - DISAZOPIGMENTS, PROCESS FOR THEIR PRODUCTION AND USE - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. E. Assmann - Dr. R. Koenigsberger Dipl.-Phys. R. Holzbauer - Dipl.-Ing. F. Ki'ngs Eisen - Dr. F. "Lumstein jun.

PATENTANWmLTL TELEPHONE: COLLECTIVE NO. 239341

TELEX 539979 TELEGRAMS: ZUMPAT

CHECK ACCOUNT: MÖNCHEN 91139-809. BLZ 7001008O

BANK ACCOUNT: BANKHAUS H. AUFHÄUSER ACCOUNT NO. 397997. BLZ 7OO 306 00

8 MUNICH 2.

BRAUHAUSSTRASSE 4

Case 3-10647 / -

CIBA-GEIGI AG, CH-4002 Basel / Switzerland

Disazo pigments, process for their production and use

The invention relates to new valuable disazo pigments of the formula

n-1

CH ₃ COCHCONh

: NHOCCIIOCCH

worxn

X is a hydrogen or halogen atom,

Y is an alkyl or alkoxy group with 1 to 6 carbon atoms Z is an alkoxycarbonyl group with 2-6 carbon atoms

m is the number 1-5

η the number 1-4

709886/0833

ρ is the number 1-3, where trH-n-fp is 5,

Q is an oxygen or sulfur atom

V represents a hydrogen or halogen atom or the group

R is an alkyl group containing 1-4 carbon atoms

Formulas

Of particular interest are disazo pigments

CH ₃ COCHCONh-

NHCOCHCOCH.

wherein R has the meaning given, X-, and Y-, H-, Chlcratoine or methyl groups and Z denote an H or chlorine atom, a methyl group or an alkoxy group with 1-4 C atoms.

709886/0833

The pigments according to the invention can be obtained if the diazo compound of an amine of the formula

X Y,

m _v , η-1

H ₂ N

Vi

with a bis-acetoacetylphenylenediamine of the formula

OR

CH ₃ COCH ₂ CONH - ^ (J) V-NIIOCCk ₂ OCCH ₃

OR

couples in a molar ratio of 2: 1.

The diazo components used are, in particular, those of the formula

H ₂ N

CF.

709886/0833

where X ,, Y ^ and Z ^ have the meaning given.

Examples are the following known diazocoraponents called:

2-amino -4- tr if luortne thy 1 -diphenyl ether 2-amino-2'-chloro-4-trifluoromethyl-diphenyl ether 2-amino-3'-chloro-4-trifluoromethyl-diphenyl ether 2-amino-4'-chlorine -4-trifluoromethyl-diphenylether 2-amino-2 ', 4 ¹ -dichloro-4-trifluoromethyl-diphenylether 2-amino-2', 5'-dichloro-4-trifluorocethyl-diphenylether 2-amino-3 ', 4'- dichloro-4-trifluoromethyl diphenyl ether 2-amino-2 ', 4', 5'-trichloro-4-trifluoromethyl diphenyl ether 2-amino-2 ', 4', 6'-trichloro-4-trifluoromethyl diphenyl ether 2-amino -2'.3 ', 4', 6'-tetrachloro-4-trifluoromethyl diphenyl ether 2 ~ amino-2 ', 3', 4 ', 5', 6'-pentachloro-4-trifluoromethyl diphenyl ether 2-amino- 2'-chloro-6'-methy1-4-trifluoromethyl-diphenyl ether 2-amino-4'-chloro-2 ¹ -methyl-4-trifluoromethyl-diphenyl ether 2-amino-4'-chloro-3'-methyl-4- trifluoromethyl diphenyl ether 2-amino-2'-methyl-4-trifluoromethyl diphenyl ether 2-amino-3'-methyl-4-trifluoromethyl diphenyl ether 2-amino-4'-methyl-4-trifluorroethyl-diphenyl ether 2-amino-3 ', 5'-dimethyl-4-trifluoromethyl-diphenyl ether 2-amino-2', 4'-dimethyl-4-t rifluoromethyl diphenyl ether 2-amino-2'-methoxy-4-trifluoromethyl diphenyl ether 2-amino-3'-methoxy-4-trifluoromethyl diphenyl ether 2-amino-4'-methoxy-4-trifluoromethyl diphenyl ether 2-aroino-4 '-carboethoxy-4-trifluoromethyl-diphenyl ether 2-amino-4-trifluoromethyl-diphenylthioether 2-amino-4'-chloro-4-trifluoromethyl-diphenylthioether 2-amino-5-chloro-4-trifluoromethyl-diphenylether 2-amino-2 ', 5-dichloro-4-trifluoromethyl diphenyl ether

709886/0833

- si

<\ 273A659

2-Amino-4 ', 5-dichloro-4-trifluoromethy1-diphenyl ether 2-amino-2', 4 ^l, 5-trichloro-4-trifluoromethyl-diphenyläi: ago 2-amino-2 ', 5', S-trichloro ^ -trifluoromethyl-diphenyl ether 2-amino-2 ', 4', 5 ', S-tetrachlor ^ -trifluoromethyl-diphenyl ether 2-amino-5-chloro-4' ~ methyl-4-trifluoromethyl-diphenyl ether 2-amino-5- chloro-4'-methoxy-4-trifluoromethyl-diphenyl ether 2-araino-4 ', 5-dichloro-6'-methyl-4-trifluoromethyl-diphenyl ether 2-a-naphthoxy-5-trifluoromethyl-aniline 3-amino-4 , 6-diphenoxy-benzotrifluoride, 3-amino-4,6-di- (para-chlorophenoxy) -benzotrifluoride.

The diazo components are obtained by reducing the corresponding nitro-trifluorodiphenyl ethers, which for example from nitro-trifluoromethyl-benzenes and phenols under alkaline conditions in dimethyl sulfoxide or dimethyl formamide were manufactured.

The coupling components, which are also known, are obtained in a simple manner by the action of diketene or acetoacetic ester to the corresponding known phenylenediamines such as e.g.

2,5-dimethoxy-1,4-phenylenediamine
2,5-diethoxy-1,4-phenylenediamine
2,5-dipropoxy-1,4-phenylenediamine
2,5-diisopropoxy-1,4-phenylenediamine

709886/0833

The coupling takes place preferably in a weakly acidic medium, expediently in contrast to conventional means which promote the coupling. Such dispersants may be mentioned in particular, for example aralkyl sulfonates, such as dodecylbenzenesulfonate, or 1,1'-dinaphthylmethane-2,2'-disulfonic acid or polycondensation products of alkylene oxides. The dispersion of the coupling component can also advantageously contain protective colloids, for example methyl cellulose or smaller amounts of inert, sparingly water-soluble or insoluble organic solvents, for example optionally halogenated or nitrated aromatic hydrocarbons, such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene or ¹ nitrobenzene, and aliphatic Halogenkohlenwasserstof- · fe, such as carbon tetrachloride or trichlorethylene, further water-miscible organic solvent such as acetone Methylä'thy _s! ketone, methanol, ethanol or isopropanol.

The coupling can also be carried out advantageously in such a way that an acidic solution of the diazonium salt is used continuously combined with an alkaline solution of the coupling component in a Mischdlise, with an immediate Coupling of the component takes place. It

care must be taken that the diazo component and coupling component Are present in equimolecular amounts in the mixing nozzle, it proves to be advantageous to one to use a small excess of the diazo component. The easiest way to do this is to control the pH of the liquid causes in the Mischdlise. There is also a mixing nozzle for

709886/0833

to ensure a strong vortex of the two solutions. the The resulting dye dispersion is continuously added to the Mischdlise removed and the dye separated by filtration.

Finally, the coupling can also be carried out in such a way that the diazo component is mixed with the coupling component suspended in an organic solvent in a molar ratio of 2: 1 and with a diazotizing agent, in particular an ester of nitric acid, such as methyl, ethyl, Treated butyl, amyl or octyl nitrite.

The pigments obtained are usually already precipitated in the heat and can be filtered off and optionally Can be isolated in pure form by washing with organic solvents.

The pigments obtained generally have a good texture and can mostly be used as raw products. If necessary or desired, the raw products can be converted into a finely dispersed form by grinding or kneading. Grinding aids such as inorganic and / or organic salts in the presence or absence of organic solvents are expediently used. After grinding, auxiliaries are removed as usual, soluble inorganic salts, for example with water, and water-insoluble organic auxiliaries, for example by steam distillation.

709886/0833

By treatment of the crude pigments with organic solvents, preferably those boiling in liber 100 ⁰ C, often can be achieved an improvement of the properties. Benzenes substituted by halogen atoms, alkyl or nitro groups, such as xylenes, chlorobenzene, o-dichlorobenzene or nitrobenzene, and pyridine bases such as pyridine, picoline or quinoline, and ketones such as cyclohexanone, ethers such as ethylene glycol monomethyl or monoethyl ether, prove to be particularly suitable. Amides, such as dimethylformamide or K-methylpyrrolidone, and sulfoxone or water under pressure

The after-treatment is preferably carried out by heating the pigment in the solvent at 100 to 150 ⁰ C, in many cases, grain coarsening occurs, which affects gtinstig to light and migration fastness of the pigments obtained.

The new pigments can be used in finely divided form for pigmenting high molecular weight organic material used, e.g. cellulose ethers and esters, super - polyamides or super-polyurethanes or polyesters, acetyl cellulose, Nitrocellulose, natural resins or synthetic resins such as polymerization resins or condensation resins, e.g. aminoplasts, especially urea and melamine-formaldehyde resins, Alkyd resins, phenoplasts, polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, Polypropylene, polyacrylonitrile, polyacrylic acid ester, rubber, Casein, silicone and silicone resins, individually or in mixtures.

It does not matter whether the mentioned high molecular compounds as plastic masses, melts or in the form of spinning solutions, varnishes, paints or printing

709886/0833

-Z-

colors are available. Depending on the intended use, it proves to be advantageous to use the new pigments as toner or in form of preparations to use.

In addition to the pure pigment, the preparations can, for example, also contain natural resins, for example abietic acid or its Esters, ethyl cellulose, cellulose acetobutyrate, alkaline earth salts of higher fatty acids, fatty amines, for example stearylamine or Rosinamine, vinyl chloride-vinyl acetate copolymers, polyacrylonitrile or polyether resins or water-soluble dyes, for example dye sulfonic acids or their alkaline earth salts contain.

The pigments according to the invention are distinguished by good light, migration and weather fastness. They also show good dispersibility, transparency and brilliance, as well as high alkali resistance and high color strength. Opposite to the US-PS 2,591,470 and 3,872,078 they are characterized by better light and weather fastness.

In the following examples, unless otherwise stated, parts are parts by weight and percentages Percentages by weight and temperatures are given in degrees Celsius.

709886/0833

example

25.3 parts of 2-amino-4-trifluoromethyl-diphenyl ether are concentrated in 300 parts by volume of glacial acetic acid with 25 parts by volume. Hydrochloric acid is stirred up, forming the hydrochloride of the base. It is then cooled to -5 ° by adding 300 parts of ice and diazotized by adding 25 parts by volume of 4N sodium nitrite. The yellow diazo solution is stirred at 0-5 ° until only traces of nitrous acid can be detected. Then the Diazo solution is clarified by adding a little decolorizing charcoal. The filtrate is brought to pH 4 by adding 48 parts of sodium acetate. At the same time ins η 16.8 parts of 2, S-dimethoxy-l ^ -bis-acetoaeetylaminobenzoi with 12 parts by volume of 40% sodium hydroxide solution in 800 parts of water and 5 parts of n-butyl sulforicinoleate are added. This solution comes with 0.5 parts of decolorizing carbon clarified by filtration and then under good Stir in 1 - 1 1/2 hours to the diazo solution, added dropwise. The temperature of the reaction mixture rises to 15-20 °. After the end of the dropwise addition, no more diazo compounds can be detected in the mixture. The mixture is stirred for one hour at room temperature, then heated to 80-85 ° in 1 hour. filtered hot and washed salt-free with hot water. After drying at 95-100 ° in vacuo, 40.0 parts of a yellow dye of the formula are obtained

CH ₃ COCHGONh

-NHOCCHOCCH

OCI f.,

709886/0833

-Yl-

40 parts of the pigment thus obtained are in 600 parts by volume Dimethylformamide stirred for 8 hours at 145-150 °. The dye takes on a uniform crystalline form at. Fine orange particles with a length of 10μ can be seen under the microscope. It is filtered at 140 °, washed with boiling Cellosolve until the filtrate runs off colorless, then displaces the Cellosolve with ethanol. After drying, one obtains

35 parts of a bright yellowish-orange pigment dye. It colors plastics such as PVC in yellowish-orange tones with excellent migration fastness. Treatment in the organic Solvent can also be applied directly to the moist filter cake without prior drying. So can the damp Press cake stirred in picoline at 100-120 °, filtered, washed with methanol and then with dilute hydrochloric acid , or the moist presscake is stirred in chlorobenzene, o-dichlorobenzene or nitrobenzene and cooked through azeotropic distillation freed from water and then worked up as described above. The dye dyes polyvinyl chloride in yellowish-orange tones with excellent light, Weather and migration authenticity.

The corresponding pigments with Chloratotnen instead of trifluoromethyl groups are described in US Pat. No. 2,591,470, but have poorer light and weather resistance in PVC coloring and lacquers.

The table below describes other dyes that are obtained by coupling the diazotized bases of the Column I can be obtained with the bisacetoacetic arylides of the diamines of column II. Column III gives the hue of the PVC film colored with 0.2% of these pigments.

709886/0833

E.g. Diazo component Coupling component Nuance in PVC 2 2-amino-4-trifluoromethyl-
diphenyl ether 2,5-diethoxy-1,4
phenylenediamine yellowish
orange 3 ti 2,5-Dipropoxy-1,4
phenylenediamine yellowish
orange 4th 2 "Amino-2 '~ chloro-4-trioluoro
methyl diphenyl ether -2,5-dimethoxy-1,4
pheny1end iamin yellowish
orange 5 Il 2,5-diethoxy-l _> 4-
phenylenediamine yellowish
orange 6th 2-amino-q'-chloro-4-tri-
fluoromethyl diphenyl ether 2,5-dimethoxy -], 4-
phenylenediamine orange 7th M. 2,5-diethoxy-1,4
phenylenediamine orange δ Il 2,5-diisopropoxy
1,4-phenylenediamine yellow 9 2-amino-2 ', 4'-dichloro-4-
trifluoromethyl-diphenyl- 2,5-dimethoxy-1,4
phenylenedi amine yellowish
orange 10 ather η 2,5-diethoxy-1,4
phenylenediamine yellowish
orange 11 2-amino-2 ', 4', 5'-trichloro-
4-tr i fluorine thyl-diphenyl
ether 2,5-dimethoxy-1,4
phenylenediamine orange 12th Il 2,5-diethoxy-1,4
phenylenediamine orange 13th 2-amino ~ 3 ^I -methyl ~ 4-tri-
fluoromethyl diphenyl ether 2,5-dimethoxy-1,4
phenylenediamine yellowish
orange 14th Il 2,5-diethoxy-1,4
phenylenediamine orange 15th 2-amino-3 ', 5'-dimethyl-
4-trifluoromethyl-diphenyl- 2,5-dimethoxy-1,4
pheny1end iamin orange 16 Il 2,5-diethoxy-1,4
phenylenediamine orange 17th 2-amino-2'-methoxy-4-tri-
fluoromethyl diphenyl ether 2,5-dimethoxy-1,4
phenylenediamine orange 18th It 2,5-diethoxy-1.4-
pheny1end iamin orange 19th 2-amino-4'-chloro-2 · meth
yl -4-trifluorme thyl -di
phenyl ether 2,5-dimethoxy-1,4
phenylenediamine orange 20th ti 2,5-diethoxy-1,4
pheny1end i amine orange

709886/0833

- ία -

E.g. Diazo component Coupling component Nuance in PVC 21 2-amino-5-chloro-4-tri-
fluoromethyl diphenyl ether 2,5-dimethoxy-1,4
phenylenediamine orange 22nd M. 2,5-DiUi; hoxy-1,4 ~
phenylenediamine orange 23 2-amino-4 ^f , 5-dichloro-4-
trifluoromethyl-diphenyl-
ether 2,5-dimethoxy-1,4
phenj ⁷ lenediamine yellowish
orange 24 Il 2,5-dietoxy-1,4
phenylenediarnine orange 25th 2-amino-2 ', 5 ¹ , 5-trichloro-
4-trifluoromethyl-diphenyl-
ether 2,5-dimethoxy-1,4
phenylenediamine orange 26th Il 2.5 ~ DiiiLhoxy-l, 4-
phenylenediamine orange 27 2-Amiiio-2 ', 4', 5 ', 5-tetra-
chlor-4-tr i fluorine thy! -di
phenyl ether 2,5-dimethoxy-1 / <-
phenylenediamine orange 28 Il 2,5-DiUtIiOXy-IZf-
phenyleadiamine orsiige 29 2-amino-2 ^f -niethoxy-5-chloro-
4-trifluoromethyl-diphenyl
ether 2, 5 -DimeUioxy-1,4-
pheny1end iamin orange 30th Il 2,5-DiMt.hoxy-l, 4-
phenylenediamine orange 31 2-amino-4 ', 5-dichloro-6'-
methyl-4-1ri fluoromethyl
dipheiiylUther 2,5-D imo thoxy-1,4-
phenylenediamine orange- 32 Il 2,5-Di.MLhoxy-1,4-
phenylenediamine orange 33 2-p-naphthoxy-5-trifluoro-
methyl aniline 2,5-dimethoxy-1,4
phenylenediamine orange 34 Il 2.5 «Di3tlioxy-l, 4-
phenylenediamine orange 35 3-amino-4,6-diphynoxy
benzotrifluoride 2,5-dimethoxy-1,4
pheiiy lend iamin yellowish
orange 36 Il 2,5-dia'thoxy-1,4
phenylenediamine yellowish
orange

709886/0833

BATH ORIGINAL

- YES -

Diazo component

2-Airiino-4'-carbonethoxy-4-trifluoromethyl-diphenyl ether

2-amino-4-trifluoromethyl ■ diphenylthioether coupling component

2,5-dimethoxy-1,4-phenylenediamine

2,5-diithoxy-1,4-pheny 1 end i amine

2,5-dimethoxy-1,4-phenylenediamine

Nuance in PVC

yellowish orange

yellowish orange

yellowish orange

709886/0833

Example 40

2 g of the pigment prepared according to Example 1 are with £ Tonerriedehydrnt, 60 g linseed oil varnish of medium viscosity and rub in 2 g of l'obalt linoleate on the three-roll stool. the Yellow prints produced with the resulting color paste are strongly colored and excellent lightfast.

Example 41

0.6 l of the pigment prepared according to Example 1 are mixed together with 67 g of polyvinyl chloride, 33 g of dioctyl phthalate, 2 g of dibutyltin diatomate and 2 g of titanium dioxide: and processed on a roller mill at 160 ^° C. for 15 minutes to form a thin film. The yellowish-orange coloration produced in this way is strongly colored, migration, heat and lightfast.

Example 42,

10 g of titanium dioxide and 2 g of the pigment prepared according to Example 1 are mixed with 88 g of a mixture of 26.4 g of Ko kos alkyd resin., 24.0 g melamine-formaldehyde resin (50% solids content), 8.8 g ethylene glycol monomethyl ether and 28.8 g of xylene for 48 hours in one Grind ball mill.

If this lacquer is sprayed onto an aluminum foil, pre-dried for 30 minutes at room temperature and then baked for 30 minutes at 120 ⁰ C, then you get a brilliant orange paint, which is characterized with good color strength by a very good Ucberlackier ··, light and weather resistance.

709886/0833

\ BAD ORIGINAL

Claims (1)

Claims 1. Disazo pigments of the formula CH ₃ COCHCONh- Public transport OR in which X is a hydrogen or ualogenatoni, Y is an alkyl or alkoxy group with 1-6 carbon atoms, Z is an alkoxycarbony group with 2 - 6 carbon atoms m is the number 1-5
η the number 1-4 ρ is the number 1 - 4, where πΗ-n-'rp = 5 Q is an oxygen or sulfur atom V represents a hydrogen or halogen atom or the group ^z pi R an alley group containing 1 - hour carbon dioxide for. tome mean. 709886/0833 BAD OBiGiNAL yr -λ D: i sazo pigments according to claim 1 of the formula X, Y. CII ₀ COCHCOIi] I KHOCCHOCCH- wherein R has the meaning given, X, and Y, H or chlorine atoms or methyl groups and Z, a H or chlorine atom, a methyl group or an alkoxy group with 1-4 C atoms, 3. Process for the production of üisazo pigments the formula n-1 ; iI ₃ COCIICONH ÖHv. N1IOCCHOCCH 709886/0833 ORIGINAL INSPECTED - IS - X is a hydrogen or halogen atom, Y is an alkyl or alkoxy group with 1-6 carbon atoms, Z is an alkoxycarbonyl group with 2-6 carbon atoms m is the number 1 * - 5 η the number 1-4 ρ is the number 1-4, where ra + n + p = 5 Q is an oxygen or sulfur atom V represents a hydrogen or halogen atom or the group R is an alkyl group containing 1 - 4 carbon atoms, characterized in that one has the diaz over bond of an amine of the formula 709886/0833 with a bis-acetoacetylphenylenediamine of the formula OR CH ₃ COCH ₂ CONH - / QV- OR in the molar ratio 2: 1 couples. 4. The method according to claim 3, characterized in that that the diazo component is an amine of the formula used. 5. Process for pigmenting high molecular weight organic material, characterized by the use of ' of the pigments according to claims 1 and 6. High molecular weight organic material containing a pigment according to claim 1. 709886/0833