DE1571897A1 - Printing inks or paints or dispersible materials - Google Patents

Description

FATINTANWHLTe OIPL-INÖ. H. BOHR ■ minor * · * · * -si ■■ '... DIPL.4NQ. S. STAEGER

FaramJi »24 * 41.

M 20 756

Case Ho. & 18 407

Description see »Patent application

the flxaa BCFE & XAI »CHEMICAL INDUSTRIES LBSXTED _t

London,

concerning

besiehuagewelee drinking. or dtspea? - vases "

Priority · »s 1 · June 1965 ■ - ■ Great Britain 6, Mid 186S

The Etf indtiBg defeated see on Azo & cylacetamide _t the al® BIepeargieraiittel beslehissgsweiee ^ flocculants for pigments of value sUad.

Ea was set on the feet that certain Aeylaoetaaide sdt Xflaaoni amau Aioaojlacetaalden, which is used as a blepergiex agent as a flocculating agent for use in

are useful, dome ».

009831/1947

According to the invention, therefore, azoacylacetamides are new compounds the formula

χ. f_ _K -HOOH

wherein X is an aryl radical or heterocyclic radical, which may optionally be substituted, 7 is a Denotes alkyl radical, aryl radical or substituted aryl radical, 2 hydrogen or an alkylreci; or substituted Alkylrasä represents, A for an alkyl radical, alkenyl radical or substituted alkyl radical with more than 10 carbon atoms or an alkyl radical with a secondary or tertiary amino group; and η is an integer.

Examples of aryl radicals for which X can stand are phenyl-, 3> 3 * -Mchlor-4,4'-diphenylene-, 4-methyl-2-nitrophenyl- and ^ -Chlor ^ -nitrophenylreste mentioned "

As an example of heterocyclic radicals, for which X can stand, the 7-chloro «-2-hydro3Ey-4-methylquinol3ji-6-yl radical may be mentioned.

Examples of the best that X can stand for are alkyl radicals, such as the methyl radical, aryl radicals, such as the rhenyl radical, and substituted Aryl residues, as by a group of the Pormel

009831/1947

- 3 ■ ·

C-N-N-I substituted phenyl radicals, mentioned *

c -

As an example · for best, for which Z can stand »be rest ·, such as the methyl and ethyl radicals, and substituted alkyl radicals, like the 2-Hydroocyäthylreet mentioned.

Examples of best "for which A can stand are alkyl radicals, such as octadecyl, hexadecyl and! Eetradecyl radicals, .substituierte alkyl radicals, such as the 12-hydroxyoctadecyl radical, alkenyl radicals, such as the oetadecenyl radical, and alkyl radicals from a secondary or tertiary amino group, such as 2-Dimethylaminoäthyl- and 3- -Diaethylaainopropylreste mentioned.

η is preferably 1 or 2.

Examples of azoacylaoetamides according to the invention are those made from tetrasotated 3 »3'-dichlorobensidine and aoetoacet-5-disethylaainopropylajnid (2 UoI), from tetrasotated 3,3'-1-dichlorobenzidine and acetoacet-3-octadecylamijaopropylajnid (2UoI) and tetrazotlertea 3,3 ^f -I> iciilorbenzi & in und Acetoacetoleylaaid (2 Hol) / 3,3 * "diohlorobenaidine ? ace toacet-5-dimethylaminopropylamide (2 mols.) t 3« 3'-dichlagdbengidine ^ acetoacet ^ -octadecylaminopropylamide (2 mole.) and 3.3 * -dichlorobenzidine ^ acetoaQQtolayl · - amide (2 mols.) λ mentioned.

"bad original - 4 -

009831 / 19A7

The Azoacylacetamide of the invention may be prepared by coupling a suitable Diazoxiiumvorblndung be made with a "matching acylacetamide by a conventional method, you · coupling reaction can be, for example, at temperatures tone ■ be carried out at a pH of preferably 4 to 6, preferably O to 40 ⁰ C and · The acylacetamide can, for example, be in the form of a solution, emulsion or dispersion in dilute acetic acid or buffered mineral acid · Di · Asoacylacetamides are insoluble in water and can be isolated, for example, by filtration.

The azoacylacetamides can also be obtained by coupling the dlasonous junction with an acyl acetic ester in a conventional manner and subsequent reaction of the azoacylacetate obtained with a matching arnia. This latter implementation will expediently by heating a mixture of the ester and the amine alone or in a solvent such as ethanol borrowed Toluene, carried out at a temperature of 50 to tOO ° C.

The asoacylacetamides according to the invention are in organic solvents and easily soluble in the media used, for example, for printing inks or gravure inks and paints, but insoluble in water "

The asoacylacetamides are very effective dispersants In organic solvents, especially for azoacylacetarylamides or other pigments. As examples of such A «o-. acylacetarylamide are said to be the products of the coupling of the Dlazonlumverbindungen of amines, such as 3-nitro-4-toluidine, 5-chloro-o-toluidine

009831 / 19A7 bathroom original 5_

s & ehweise ^, 'P-dichlorobensidine, with acetoacetarylamides, such as aoetoacetaailid, acetoacet «^ ehIo3S-2 _y 4-diiethaz7anilide or terephthaloyl-bis-acetanilide, respectively.

The asoacyiaoetamide can be used as a dispersant for example sum azoacylacetarylamld in suspension in aqueous Media for the achievement of a product, which, for example, printing inks of better strength or strength and? leave properties, can be added · However, any another conventional method of mixing the asoacylacetamide can be used with the azoacylacetaryla & id. Preferred mixes contain the asoacylacetamide in amounts of 5 to 20% by weight, based on on the asoaeylacetaxylamide.

It is often useful to use the final stage in the production of the Combine asoacylacetamides with that in the preparation of the azoacylacetarylamides su, especially in those cases in which a common diasonium compound is used, the product then the desired mixture of the azoacylacetamide and the asoaeyl ~ contains acetarylamide. In this case, the acylacetamide and the Acylaoetarylanid mixed in the appropriate proportions and the solution the biasonium compound is mixed with the conventional Way coupled.

The invention is not intended to be limited to the following aufBUfaasenden. Examples explained in more detail, where all parts are weight * parts and all prosents are percentages by weight, unless otherwise specified 1st

BAD OR-Oc ^ -Ig -009831/1947

- 6 - Example 1

6 »5 ropes of 3,3'-dichlorobenzidine were tetrasotized by suspending them in 100 parts of 2 η hydrochloric acid at ⁰ ° C. and rapidly adding 13 parts of 2 η sodium nitrite solution. The mixture was then stirred for 30 minutes. The solution was clarified with activated charcoal or absorption charcoal, filtered and the volume was adjusted to 160 parts ^{with water at a temperature of 0 to 5 ° C.}

Se 20 parts Acetoaeetoleylamld were ß-Äthoacyathanol in 200 parts at 20 ⁰ G solved and then 500 parts and 50 parts Waeier Hatriumacetatkristalle added. The tetrazo solution was then added to the acetoacetoleylamide over a period of 2 to 3 hours until a weak permanent or constant excess was indicated by testing with an alkaline solution of H-3 acid. The yellow-brown solid was filtered off and washed with water until it was free of electrolytes

The paste product or the product paste can then through. Stir in a suspension of benzidine yellow (CI. Pigment Tellow 12) can be incorporated. Proportions of 5 to 20% by weight, • In relation to the benzidine yellow, printing inks give a better one

Strength or strength and a better one

t Flow.

The acetoacetoltoylamide used above was obtained by the following Procedure produced:

It was a solution of 16 parts of diketene in 21.6 parts of toluene

009831/1947 BATHROOM ⁰ ^ ^?

gradually at a Temperatnir 20-25 ⁰ C to a solution of commercially available 50! Beilen oleylamine (Armeen O) was added in 4 to 3.2 parts of toluene. The temperature was then raised to 90 to 95 ⁰ C and the toluene was removed under reduced pressure to give 65.β product, which was a waxy solid at tree temperature, left over.

Example 2

Ss were 2513 parts jS ^ '- dichlorobenzidine tetrasotiert as described in Example 1 and the clarified solution was adjusted with water at 0 to 5 ⁰ C to 800 parts.

Ea 32.5 parts of acetoacetanilide were dissolved in 300 parts of water, to which an amount of caustic soda, which was light enough to give titanium yellow a pale red color, was added. A solution of 5.2 parts of acetoacetdimethylaminopropylamide in Water added. The mixed solution was acidified with dilute acetic acid to give an acidic reaction to blue litmus, and then 50 parts of sodium acetate crystals were added. The tetrazo solution was during 1 sugegeben to 2 hours at 20 ⁰ C ssur Anilidsuspension, during which addition of an excess was avoided at the tetrazo compound. When the coupling was complete, the suspension was heated to 90 ° C., kept at this temperature for -g hours and then filtered, washed with water and dried.

The product yielded pigments with excellent strength behavior.

009831/1947

wise strength and excellent plied properties in printing inks.

This figment can advantageously be combined with bar »or Kolophoniua are stretched by treating old resin soap or neutralize Kolopnoniuaaeife and the following or by pelleting the Harsee or rosin as a metal sheet.

Bas above used aoetoacetdimethylaialnopropylamide was made by, obtain the following procedure:

It was stirred a solution of 226 parts of 3-Diaethylamlnopropylaain 1 000 parts of water at a temperature below 2O ⁰ C with 168 parts of diketene was added. It was implemented quickly. The resulting aqueous solution of the product can expediently be used directly for the preparation of asoderivates as described above.

Example 3

In the procedure of Example 2, the acetoacetdiaethylaminopropylamide was replaced by 8.2 parts of acetoacetoctadecylamino propyl amide. In this case the amide was used as a solution in 100 parts of 4 η acetic acid, which can be added during the precipitation of the acetoacetanilide, are added.

· - · "S The acetoacetoctadecylaminopropylaaid used above was made by

'.4

009831/1947 ^8AD original

Äie. following procedure:

It was "a solution of 12.9 ropes of diketene in 21" 6 parts Toluene gradually su one at a temperature of 23 to 2? ° C Solution tob 50 parts of commercially available octadecylaainopropylamine (Duoaeen τ) sugar added in 8616 parts of toluene. The temperature was then up 50 ° 0 increased and the toluene was removed under reduced »pressure * The resulting amorphous product was. soluble in 4 η acetic acid.

Example 4

Ee were 16.2 parts of 2,5-dichloroaniline by dissolving in 250 parts of 2 η hydrochloric acid at 95 ° C, cooling by adding 400 parts of you and rapid addition of a solution of 7.0 parts of hatriunite in 50 Divide diasotized water. The solution was stirred for 10 minutes, filtered and the volume was increased with water at a temperature 0 to 5 ⁰ C set to 800 parts

The dialysis solution became a solution in 2 to 3 hours from 70 parts of those prepared as described in Example 2 above Solution of acetoacet & imethylaalnopropylamide, 68 parts of sodium acetate crystals, 150 parts of acetic acid and 1200 parts of water suggest.

After coupling, dilute sodium hydroxide solution was added to to release the free base which precipitated as tar · you was washed by decantation and dried in a vacuum desiccator.

^ BAD ORiGiNAJ- 10-- ■

009831/1947

Se was added a suspension of 10 parts of the red pigment Index Pigment Bed Ho. 12 in 200 hone water Bit treated a suspension of 1 part of the above product in 10 ropes glacial acetic acid, erhitst to 80 ⁰ C, ait ammonia solution basified, filtered, washed and dried. Aue to the dried product was a printing ink in IdLthographen varnish (lithographic varnish), which proved to be less viscous in a wide shear range than a Bruok color from the untreated pigment, measured with a viscometer with a cone and plate according to Ferranti-Shirlegr (Terrantl-Shirley cone and-plate viscometer) at 25 ⁰ O, manufactured:

Shear coefficient Viscosity (in poise) Uh-treated
pigment (in seconds * " ¹ ) Treated
pigment 2 030 1 910 820 5 520 306 20th 142 2 * 0 70 112

Example 5

15.2 parts of 5-nitro-2-aminotoluene were obtained by suspending in 500 ropes of 0.5 η hydrochloric acid at ⁰ ° C. and adding a solution of 7.0 parts of sodium nitrite in 50 parts of water at such a rate that au every time free nitrous acid was sugegen, diaeotized. The solution was filtered and the volume was adjusted to 800 parts with water at a temperature of 0: to 5 ^{° C.}

0098-31 / 19 * 7

. The diisol solution was added for 2 to 5 hours in a 70 layers of the lasting clay acetoacet dimethyl amiitopropylamide, prepared as in Example 2 above, 68 files of tatrlumaietate crystals, 15 layers of acetic acid and 800 lines of water. the Diabolosttng were 160 ropes denaföirlevfeer alcohol beslebungsveiee Mo ^ hyl ψ

(aetbylated spirit) sngesetyt. Vaeh the domes " the Suepeneion XxooJcene was dampened" · The fiQcJurtand was in a ¥ le

500 parts of water and 100 parts of I ^ ridin dissolved. Ss been mgesetst 200 parts chloroform, followed by the addition of a surplus · τοη diluted Itmaatronlöeung follows ·· shaking was · dl · Asorer * bond in the Ghlorofornsohioht überfuhrt and the latter ^one was separated · · The product words by evaporation dee Ghloroformos get "

Xs became a suspension of 10 parts of the yellow pigment Color Index Pigment Xellow Ho 13 in 200 parts of water with a Suspension τοη 1 part of the above product in 10 parts of glacial acetic acid treated by the procedure described in Example 4 and A lithographic Tarnish printing ink was produced from the dried product. The printing ink from the treated pigment was found to be less viscous than that from the untreated pigment, measured with a viscometer with Sonus and Plate after rerxfentl-Shlrlegr (Terranti-ahirley cone-and-plate Tiseometer) at 25 ° C:

BATH 009831 / 19A7

viscosity
*
Treated tea
pigment Example 6 1571897 - Shear coefficient
(in seconds " ¹ ) * ■ _€
4 620 ϊ (in Patie) ' 1 1 450 - pigment 5 410 13 840 20th 140 3,920 70 990 450

17.8 ropes of 5- <^ or-2 ~ e3ti & otoluene hydrochloride were diazotized by suspending in a mixture of 150 parts of nalic acid and 750 parts of water at ⁰ ° C. and adding a solution of 7% of latriuanitrite in 50 ropes of water. The solution was filtered and the volume was adjusted to 800 parts with water at a temperature from 0 to 5 ^{° C.}

The slide solution was added for 2 to 3 hours to a solution of 41 parts of lcetoacetoctadecyland.nopropylamide in 300 parts of 4B Sseigeäure and 68 parts of Vatriunacetatkrlstallen at 6O ⁰ O. The mixture was cooled and made alkaline with caustic soda solution. The aso compound was extracted with Chlorofore and evaporate the solvent isolated.

The viscosity of one obtained by grinding 0.9 part of the red Pignentes Color Index Pigment Bed Ho. 12 and 0.1 part of the above Aeo-compound with 5.25 parts of lithographic varnish (lithographic varnish) ink obtained was in a wide range of

009 831/1947

bath

- 15

Coefficients of approximation. lower than that of the corresponding printing ink from the pigment alone, measured with a viscometer with Komis and plate according to erranti ~ 8hirley (Ferranti-Shirley con - * nd-plate viscometer) at ⁰

Soherungskoeff issient Viscosity (in poise) Pigment alone (la seconds " ¹ ) Pigment + aeover- 4 010 1 980 5 1,650 315 20th 495 175 70 200 142

Example 7

There were 26.1 parts of p-dodecyl aniline at 85 ⁰ C au melted 100 parts. £ 26.1 Barts of p-dodecylaniline are melted in 100 parts at 85 ° o] and dissolved by adding 25 parts of 10 η salic acid. Bite, and water were sugeaetst in order to divide the volume to 400 parts at ⁰ ° C. The suspension was diasotized by adding a solution of 7.0 parts of sodium nitrite in 50 parts of water. The solution was filtered and the volume was adjusted to 600 parts with water at a temperature of 0 to 5 ^{0 O.}

The diasol solution became in solution for 2 to 3 hours from 70 parts of the solution of acetoacetdiaethylaminopropyXamld prepared as described in Example 2 above, 68 parts

_, ._ - * · »14 <- 009831/1947

Files of sodium acetate crystals, 150 ropes of acetic acid and 1,200 Water specified 4

Dilute sodium hydroxide solution was added to the domes and the free base was released, which was extracted with diethyl ether. The solution was washed and the ether was evaporated. The product was dried in a Vakuumexaikkator at 20 ⁰ O.

This aso-compound was identified with the yellow Piginent Color Index Pigment Yellow Vo. 1? in lithographic? irale sur production of a printing ink by means of the 6% @ ecL * in the example; A flat procedure was used.Ss a printing ink was obtained which was less viscous in a wide range of shear coefficients. at 25 ⁰ C, wait

Shear coefficient Viscosity (in poise) Pigment alone Pigment + aso
link 20 400 11 100 4610 1 2,630 1 150 ' ITV 770 420 20th 380 70

Claims

009831/1947

Claims (1)

1.) Asoaeylaeetajdde the HO where Z stands for an Arjrlrest beslehungaweise heterocyclic constituent which can optionally be substituted, T stands for an alkyl radical, arylrea or substituted aryl radical, Z represents hydrogen or an allyl radical or substituted alkyl radical, _t A for an AUgrlreet alkenyl radical or substituted alkyl radical old more than 10 Carbon atoms or an alkyl radical from a secondary or tertiary aino group and η a whole look! is. 2 ») Asoaoylacetexide according to claim 1, characterized thereby, that T is a hetiy! group. f.) AsoaoarlaoetaMide according to claim 1 or 2, characterized in that η is 1 or 2. 4.) Method sur Berstellung the Asoacylacetanide according to claim Λ to 5, characterized gekennseictmet that one of an aroaatl- see Aain der Forael X- + -H *] derived Diasoniusrer- 009831 / 19A7 -JX- bond with an aeylacetamide of the formula 1571897 Ϊ - C - C - 0 - 1, where X, T, Zy A and η as in ^H X Proverb 1 are set, is coupled. 5 «) Method according to claim 4, characterized in that the Coupling "is carried out at a pH value of 4 to 6. 6.) Verfahr an ^ Ui- Heratelltssg dor Asea ^ Xaeetamide according to claim 3, characterized in that @ia Asiin of the formula H - H. with an Eupplungsprodu & t from a Beter one Acylesaiga acid of the formula T-O-O-O-QB and one of one H ₂ H ¹ nea Am In the formula X - «j— H ^) derived DiaBoniumver- bond, where Z, 7, Z, A and η as defined in claim 1 are heated. 7.) Method according to claim 6, characterized in that the heating is carried out at temperatures of 50 to 10O ⁰ C. 8.) Asoacylacetamides. according to claim 1 essentially as particularly described above 9 ·) Process for the preparation of aeoacylacetanides essentially as described above special. 009831/1947. ., 10.) A method of manufacturing ssur Asoacylssetamiden substantially as "besohriabenir in the above examples - - * _TTT BATH ORIGINAL 11.) Dispersible hats with a content of Asoacylaeetaniden naoh claims 1 to 5 and 8 « 12.) Dispersible masses according to the request 11 «which pigments ent keep. 13 ·) Dispersible compositions according to claim 11 or 12 «which contain Aaoaeylaeetaxylanide. 14 ·) Bispecgable masses essentially as above special be wrote. Process for the production of dispersible masses according to Anepruoh 11 to 14 essentially as described above in particular 16.) method sun dispersing pigments in organic solvents, characterized in that the pigment nit the solvent in the presence of an Asoacylacetanides after the invention is stirred or ground 17 ·) Printing ink or ink has a content of one AjBoaoylacetanid according to the invention. 18.) Printing ink or color produced by a process according to claim 16 has been produced. OIH.-ING. P. 8TAEGi * 009831/19 * 7 8AD Ο · ' ¹ - "''