DE1569784A1 - Process for the production of pigments - Google Patents

Description

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00982-7 / 15.30

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consist in which the rings X and Y are replaced by halogen atoms, Liethyl or alkoxy groups with a maximum of 5 carbon atoms can be substituted or carry condensed benzene rings. These mixtures are characterized by that their X-ray diffraction diagrams TOn are the sum the X-ray diffraction diagrams of the individual quinacridone components differentiate. In the shark ptpatent is also a process for the preparation of the new 1igmont dye mixtures described, which is characterized in that a finely divided mixture of two or more linear ones Quinacridones of the general formula

in. the X and Y have the meaning given above, with an organic liquid of high dielectric constant is treated.

According to the present invention that is an improvement or a modification of the method used by the master sponsor ta represents is a process "ur production

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the new Pigraentfarbstoff provided geraisch ©% & η 'Verfügmag which is characterized in that ₀ © ia @ © aqueous die'zwei odes * mete feinverteilt® Ilxwsis © ¹ of the general formula

in the dl © ring © X - and Y by 'halogen atomQ ₀ methyl «= · © of the alicoxy groups with a maximum of 5 carbon atoms can be so-titled, so that aluminum is heated with organic solution.

The organic solvent used according to the invention can be a liquid or solid substance that maintains! the temperature of the heating melts. The organic solvent preferably has a boiling point above 100 O ₉ and the following solvents are preferably selected:

-Alcohols, z, B _e kmyl- _g ■ Hes: yl-j ß-phenylethyl, ß-Ihenoxylithyl-, Benayl or? Urfuryl alcohol, cyclohexanol, methylcycloheianol, glycerine, uono-, di- and triethylene glycols and their! onoalkyl ethers;

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1563784

Ether, e.g. Anisole, phenetol, phenyl ether, dioxane and Ethyleneglykoldialky lather;

Esters, for example Carbonsäureester such as amyl acetate, ß-Äthoxyäthylacntat, diethyl oxalate, Äthylbenaoat, _t üethylealioylat phenyl salicylate, dimethyl phthalate, and lüloheäareäthylester Eater inorganic S.iuren as Tritoutyl-, triphenyl- and Tricreaylphoapliat and Diathylcarbonatj

Lactones, e.B. Butyrolactone;

Ketones, 2.B. Ethyl-n-butyl ketone, eesityloxyd, Cycloheranone, Methylcyolohexanone, Acetophenone, Diaeetone Alcohol (4-hydroxy-4-methylpentanone);

Kohlwaaeratoffe (preferably aromatic) and their halogen and nitro compounds, such as xylene, dichlorobenzene, Kltrobenzol, tetrachloroethane

Phenols, such as phenol, o-, m- and p-Kreaol, o-, m- and p-chlorophenol and the xylenols;

Aromatic and heterocyclic amines, such as aniline, N-L-ethylaniline, Ιί, Κ-dimethylaniline, o-, m- and p-toluldines, Pyridine, quinoline, morpholine, picoline, lutidine, Piperidine, collidine, quinaldine and lopldine;

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1553784

Amides (such as Acetamid _f Propionamid, Diine thy! Acetamid, Oiiaethylfcriasjaid, Diethy Iformamid, .N-Methylpyrrolidonj

Carboxylic acids, propionic acid, butyric acid and yfie Benzoic acid;

Nitriles, such as benzonitrile, benzyl cyanide, acetonitrile, Propionitrile and i "-luethoxypropionitrile;

Alipfcatischo and cyclic sulphoxides "and sulphones, such as dimethyl sulfoxide and uramethylene sulfone.

The beyorsugt vorwendetentösungaiaitteJ ^ lm procedure of the invention are phenol, dimethylformamide, Simethyleulfoiyd, letraittethylene sulion, dimethyl acetamide, H-kethyl 1-pyrrolidone, Oyclohexanone, Butyrolactone, Benzyl Alcohol and A.oetophenon.

V / ä333? Igß pastes containing2 or more finely divided linear Quinacridones} contain, and which are useful in the process of the invention, can be prepared by mixing ^ white. or more aqueous pastes of finely divided quinacridones or by mixing the dried quinacridones, e.g. in crystalline form, and processing d-ea Gremischae in well-known Yelsö for the production of finely divided solid Substances are obtained in pasty Porm. Preferably one can also use dry, crystalline quinacridones

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in sulfuric acid or polyphosphoric acid dissolve the Missing solution with V / aaser and the precipitated finely divided Filter off the quinacridones and add • Wash Yasser 3 acid-free. You can also use a mixture Grind the dry crystalline quinacridones with SaIa y and wash out the salt by washing with a viaser.

Optionally, you can use a mixture of two or more synthetic chloracridones, for example, if the following Yag herotellen:

(a) Cyclization of a mixture τοη two or more 2 "5-Bi3- (arylamino) -terephthalic acids or esters (prepared 8.B. by dehydrating a mixture TOn two or more 2,5-bis- (arylamino) -5 _f 6-dihydroterephthalic acid dialkyl esters and, if necessary, the ester groups) by heating with a dehydrating agent or condensing agent, or

(t) cyclization of a mixture of two or more 2,5-bis (arylamino) -3,6-dihydroterephthalic acids or dialkyl star by heating with a water-releasing agent Agent or a condensing agent and Dehydration of the product obtained «.

- Suitable for use in the method of the invention aqueous pastes can sometimes be obtained immediately by one of the processes a) or b),

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apielaweiae one can carry out the last stage a) In sulfuric acid or P ο Iy phosphorus β llure, precipitate the quinacridones by adding fiber and the obtained Filter off watery paats and wash out «,

. In dor Durohführungdea traversed the invention, the aqueous paste is preferably with the organic solvent in sufficient !! close to offset _p "in® stirrable mixture obtained eu ,, and heated under Rtthrea, Se iat often low, water by distillation to remove ^ Dao heating can then £ .B. .at 50 to 20O ⁰ C, .vorugswelse which 100 and 200 ⁰ G are continued for some time. If necessary, m & n des Srhitsea can be found under Druok in ®in © a varBohloeeenen B®Mlt®r äur-chf Uhren «When using the preferred soldering fluid, the process is usually finished in 2 to 6 hours. Longer heating times may be necessary if other solvents are used. Finally, you can pour the (Hinisoh in Jaaeer or in dilute acid or a low-boiling solvent such as KetMol (the particular diluent used depends on the type of organic solvent used). The rigmentg®ssiscii can then be filtered off, washed and dried » On the other hand, the solvent can also be separated off by distillation and the aqueous suspension of the pigment solution can then be filtered off and dried.

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According to the method of the present invention The pigment dye mixtures obtained give similar results like the Gemiaohe? arbtb'ne obtained according to the parent patent, which are brighter than those which cian with Use of the quinacridone components either individually or in a simple mixture with one another is obtained the Figaentfarbatoffgemiechen of the parent patent, the increased brilliance seems to be related to a Change in crystal form as the X-ray diffraction patterns of those obtained by the method of the invention Figment dye mixtures are different than those of the individual quinacridone components. Presumably are those obtained after the process according to the invention Pignent mixed crystals of the quinacridones.

The process according to the invention has Sahireich «

■ »iff. * Advantages over the method of Staampatents · Thus, the grinding is not an essential part of the new procedure. The method can be carried out in a simple apparatus and allows _t China ridon-Pignentgemisohe to be produced in a satisfactory physical form without the use of expensive balding devices. A wider range of solvents can be used in the new process. It is therefore practical to use a solvent which can be easily recovered, for example by steam distillation from the container in which the process is carried out

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is carried out. First of all, the procedure is the Finding advantageous as it is directly aqueous pastes can be used, * s «B. such as her direct can be obtained from reaction mixtures, and since they do not require drying or intermediate milling is.; ; : - ■■■ :. .v-

The invention is further illustrated by the following examples. Parts mean parts by weight. .

Example 1

Sine solution of 2.85 parts lln-Chinaeridon and 2.15 parts of 2,9-Bichlor-lin-chinaoridon in 91 Tellea concentrated sulfuric acid is added gradually with good stirring in 1000 parts of water of between 70 and 8O ⁰ C. The precipitate is filtered off and washed free of acid. The wet paste is rrührt with 30 parts of phenol ▼ • and heated in a bath at 130 to 14O ⁰ G is distilled off until the 'Jas3er. After Sntfernungdea Wässere the mixture is erhitst another hour to 130 bi · 140 ⁰ C. The mixture is cooled and diluted with methanol. The pigment mixture is filtered off xasA with methanol free of phenol. The pigment gel is then dried at room temperature. You get a bright blue-tinged red symbol. When incorporated into paints and varnishes, this plagination results in extremely light-emitting bluish tones

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red shades with excellent resistance to heat, solvents, light and, 7etteinflüase. The hues obtained are considerably brighter than those obtained when using lin-quinaeridone or 2,9-dichloroquinacridone either alone or in a simple mixture. The X-ray diffraction diagram of this pigment mixture shows lines which correspond to the following crystal plane abatements (in S).

Strong lines Medium lines Relatively weak L. 6.45; 3.21 5.9; 3.58 7.45; 4.9; 3.94;

3.33; 3.13.

The specific surface area of the pigment, measured according to the Smaet ¹ nitrogen absorption method, is 120 a ² / «·

Example 2

1.82 parts of 4,11-dichloro-lin-chlnaoridone and 3.17 parts of lin-quinacridone are pasted together from sulfuric acid as in Example 1. The Fast "is mixed with 30 parts of phenol in a bath between 130 and 14O ⁰ C, is distilled off until the water. The Geai3oh is then increased to 140 ⁰ O for a further 6 hours. The mixture is then cooled and diluted with methanol. The pigment mixture is filtered off, washed and dried, lian is given a bright scarlet-red segmentation, which has a special surface

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111 a / g. When Einrerleiben in paints and coatings · Plgiaentgendach this gives extremely _bright:; scarlet color tones old excellent resistance to light,. "poor. solvents and Vettere infliis3e. The hues obtained are considerably brighter than they are obtained with lin-shinaeridone or 4,11-diohlor-lin-ohlnacridone alone or in a mixture "Own lines which correspond to the following crystal plane intervals (in S)! -

Strong lines Putty lines *

6.7 | 3.35 6.9 »3.7» 3.48

These «/ erte ontersoheiden each other τοη the sum of the X-ray diffraction adlagraame of the 4 «11-Dlohlor-lin-ohinaeridctie (strong lines at 6.9; 3.95 · 3.3 · middle lines at 6.0» 4.65; 3.15 Jt) and of the <* -, S. - or o (-Chinacridone.

Example 3

An Oemlsch of 2.85 parts of 11n-quinacridone and 2.15 parts of 2,9-dichloro-lin-quinaoridone is rerpasted as in Example 1 from sulfuric acid. The old Chamfered is $ 0 parts diethylene glycol * piioätbyΙο ther voraieoht and the mixture is erhitst in an oil bath at 5O ° G 4 and is stirred until the carcasses distilled off * Then the Gemieoh vrird 6 hours at 190 ⁰ C.

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• rhitit, left to cool and old!. 'Ethanol diluted.

The pigment mixture is filtered off, the bit of methanol is washed and dried, and the lian becomes a luminous one bluish red pigment with the same X-ray · » diffraction diagram and similar properties as Mixture of example 1.

Example 4 A mixture of 2.1 parts of 2,5-Bie- (2'-ohlor-

phenylamino) terephthalic acid and 3.5 parts of 2,5-bis- (phenylamino) terephthalic acid is gradually added to 30 parts Polyphosphorsfiure at 15O ⁰ O with stirring. The mixture is then heated for one hour at 15O ⁰ O, cooled then diluted with Y / carcasses. The quinacridone mixture which has precipitated out is filtered off. The feuohte fast is mixed with 40 parts of phenol

is - and stirred in a bath at 130 to 140 ⁰ C until

The mixture is then further distilled. Erhitst 6 hours at 140 ⁰ C. Oils suspension is diluted with and the Feststubetans filtered off, with methanol

Hethanol / phenol-free washed and dried

Ilen receives a bright scarlet pigment, that has a similar hue and also a similar X-ray diffraction diagram as the product of the example * having.

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Example 5

0.8 parts of 4,11-dimethylquinaeridone and 4.2 parts of lin-quinacridone are pasted together using the method described in Example 1 from sulfuric acid. The paste is stirred in a bath for 6 hours at 145 ⁰ C with 50 parts of phenol, is distilled off until the ater?. The product is then diluted with methanol as described in the previous examples and isolated; A bright red pigment is obtained, the X-ray diffraction _{diagram of which is different from the sum of the X-ray diffraction diagrams of 4 t} 11-dimethylquinaeridona and rf-, β- or T ^ -quinacridone.

Example 6

iian receives a bluish red pigment with the same X-ray diffraction diagram as that of the products of Example 1 and 3 »if you replace the phenol or diethylene glycol monoethyl ether an equal! One of the following solvents is used and heating at the specified temperatures and for the times indicated

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Cyclohexanone 6 3td. at 140 0 Butyrolactone 3 3td. at 15O ⁰ C and 2 hr. at 16O ⁰ C Benzyl alcohol 6 3td. at I70 ⁰ C Pyridine for 20 hours at 130 -. 14O ⁰ C Dimethylformamide 2 hours at 140-15O ⁰ C and

4 hr. At 17O ⁰ C

! Freeze sy lpho spha t 3 hrs. at 160 ⁰ O and

4 otd. at 20O ⁰ C

Acetophenone 3 3td. at 160 ⁰ C and

3 hrs. At 19O ⁰ C Dixactliy! Aniline. 6 hours at 19O ⁰ C.

When using pyridine or dimethylaniline, the pigment can be filtered off by adding dilute acid and washing out the acid. Hit V? Aa-6 series miscible solvents such as dimethylformamide, IcUn- ' Thinning with drums and other solvents can be separated by dilution with methanol.

Example 7

50 parts of an aqueous Chamfered, the 3,10-Dichlorehinaeridon is prepared according to the procedure described in Example 1 from 1.3 parts of quinacridone and 3.7 parts are stirred for 4 hours in a phenol bath at 14O ⁰ C with 50 parts of water until the water is distilled off. The product is then isolated as described in Example 1. You get a bright red

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Pigment dye mixture with a specific surface area of 103 » ² / g (measured according to the Eometl-eohen 3tioctoffab3toffabsorption afflethode). The X-ray diffraction diagram of this Plgmontgcmieohes xelgt lines which correspond to the following crietal plane distances (in £):

Strong lines, medium lines. Relatively weak lines

6, β5 »3 x 57 3.65 7.4; 6.4 | 5.2 _S 4. If

5.21; 3.06

De. " Rntgeribeagungsdiiagfaan is essentially daa same as the τ on 3,10-dichlorohinacridon and es I find no references to the characteristic features Lines of the σί, 6 or AChinacridoo. While feeling sincerely this rigmentgeBiechee in anstriohfarben and varnish receives Ban paints in bright red shades old Excepted resistance to sleeves, leaches, lueungsBittel, d iVetteinfieuen. The figment is suitable also bob dyeing of plastics, such as polystyrene, Polyvinyl chloride and cellulose acetate.

Example β

Parts of a mixture of 2 _{tons of} 5-bis- (aryl-inoterephthalic acids (their Heretellong is described below) are converted into 55 parts of 15O ⁰ O hot tetraphosphoric acid within 20 minutes with stirring

registered. The mixture is at for an additional 2 hours

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Stirred 15O ⁰ C and then poured into excess water. The precipitated Gemiodh the quinacridones is filtered off and the fast is washed acid-free. The fast is then added to 200 parts of phenol and the mixture is ^{heated in a bath at 140 °} C. for 4 hours with stirring until the water has distilled off. The product is isolated as described in Example 1. Kan receives a bright bluish red Figmentgemisoh, whose Runtgen diffraction diagram is the same and with very similar properties as the pigment of Example 1.

The mixture of 2,5-bis- (arylamino) -terephthalic acids used in this example can be prepared in the following way:

A mixture of 10 parts of Suooinoylobernateineäuredi <methyl ester, 16 parts of aniline, 22 parts of p-ChI or aniline, 2.4 parts of concentrated saline and 83 parts of 86 iigern alcohol is boiled under reflux for 2 1/2 hours and stirred. A mixture of 3,6-dihydro-2 _t 5-bi- (arylaeino) -terephthalic acid dimethyl esters crystallizes out. After cooling, the crystals are filtered _v old 80 parts 86 tigern aqueous alcohol and then washed '/ Aseer washed with. And dried. 16.6 parts of the mixture of dimethyl terephthalic acid thus obtained are then dehydrated,

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by nan through a boiling suspension that 180 Parts of amyl alcohol and 1.09 parts of ghloranil, bubbling air through for 4 hours. The deep orange one The solution is cooled and the product, which separates out in orange crystals, is filtered off. 12th Parts of the mixture of 2,5-bis- (arylamine) -terephthalic acid diae thy! Ester obtained in this way are then boiled for one hour with a solution of 4 parts of potassium hydroxide in 10 parts of water and 125 parts of 86% saponified aqueous alcohol. The alcohol is distilled off and the residue is diluted with 500 parts of water. The free acid is concentrated by adding 10 parts or hydrochloric acid is precipitated. The precipitate is filtered off, washed and dried. ! .Tan receives 11 parts a blue-rustic red dust.

Instead of 16 parts aniline and 22 parts P- * The chloroaniline of Example 8 are the amines I and II mentioned in the table below in the the amounts specified there are used. Pigment dye mixtures of the specified color shades are obtained. Each this pigment mixture has an ophthalmic diagram, that differs from the sum of the X-ray diffraction diagrams which distinguishes the quinacridone components.

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Example Amin JT Amin II color shade of the pigment mixture.

9 aniline o-chloroaniline scarlet red (8 parts) (33 parts)

10 aniline m-chloroaniline red (S parts) (42.5 parts)

11 aniline. £ -Bromaniline reddish tint (16 parts) (18.4 parts) purple

12 aniline £ -Toluidine red (16 parts) (18.4 parts)

p-chloro-p-toluidine reddish aniline

(22 pieces)

^811111x1 (18.4 parts) purple

14 Aniline j> -Toluidine reddish

(16 parts) (18.4 parts) purple

Example 15

8.3 parts of 4,11-dimethoxy-lin-quinacridone and 1.2 parts of quinacridone are pasted together as described in Example 1, aue280 parts of 90% sulfuric acid. The paste was heated with 100 parts of phenol with stirring to 140 ⁰ C β hours, bie the 7aeser is distilled off via a column. The suspension is then cooled, diluted with methanol, filtered off, washed free of phenol and dried. A bright red pigment is obtained, the X-ray diffraction diagram of which is similar to that of 4 »T1-dimethoxy-lin-quinacrldone. In the diffraction diagram there is no reference to lin-quinacridone in the </ - _t ß- or A-crystal form. When incorporated into paints or

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κατ BJasse coloring τοη plastics results in the pigment ht '^

red shades of excellent real leather

Example 1.6

37 parts of an aqueous paste of 2.85 parts lia Chinaeridone and 2.15 parts of 2,9-dichloro-lin-ehinaori-

Those which are produced according to Example 1 by acidic pesting are mixed with 50 parts of teaser and 4 parts of phenol. The mixture is heated for 5 hours at 200 ⁰ C in an autoclave and stirred. After cooling, the solid substance is filtered off, gowashed? and dried. The product gives bright blue and big red shades similar to the pigment of Example 1 and it has the same X-ray diffraction diagram.

Example 17

A solution of 2.85 parts of lin-Chinaoridon In 51 parts of concentrated sulfuric acid is added gradually with stirring to "twa 500 parts of 80 to ⁰ C TOO heiBen Jaaser. In a similar manner, a solution of 2.15 parts of 2,9-dichloro-lin-quinacridone in 39 parts of concentrated sulfuric acid is added to about 400 parts / water. The two suspensions are combined, filtered and washed free of acid. The FiI

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terkuchen the mixed Figatente (43 weight part · β) is mixed with 40 parts of phenol and stirred for 6 hours at 140 ⁰ C, which Jaaser am abdestilllert let · Dae pigment is then isolated as described in Example. 1 L '. an receives a bright red pigment mass, whose x-ray diffraction8diagraxmn is very similar to that of the product in example 1

Claims

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Claims (13)

- 21 P a ten t a η a ρ r U ο he, 1.) Process for the production of new pigment dye mixtures according to patent ..... (patent application I 18 030 IVb / 22e) _t by using an aqueous paste containing two or more finely divided linear quinacridones of the general formula contains »in which the rings X and Y duroli halogen atoms Methyl or alkoxy groups with a maximum of 5 carbon atoms can be substituted »with an organic Solvents The method of claim 2 · _t ι characterized Eke β η η s η ei ο h e A, that the heating is carried out at a temperature between 50 and 200 ⁰ O. 3, method according to claim 1, characterized in that the heating is carried out at a temperature between 100 and 200 ⁰ C, 4. The method according to claim 1 to 3 »thereby g βλ: e η ή ζ ti ο h η e t that one is an organic with a boiling point above 10O ⁰ O ν 009127 / 1S30 - ■ BAD ^ 5. The method according to claim 1 to 4 »characterized in that the organic solvent Phenol is used. 6 _O Process according to Claims 1 to 4, characterized in that dimethylformamide is used as the organic solvent. 7. Method according to claims 1 to 4, characterized in that there is no that as an organic solvent Dimethyl sulfoxide is used. 8. The method according to claim 1 to 4 «characterized that tetramethylene sulfone is used as the organic solvent. 9. The method according to claim 1 to 4 »characterized g e, that diaethylacetanide is used as the organic solvent. 1Oe method according to claim 1 bia 4, characterized in that all organic solvents N-kethy! Pyrrolidone is used, 11; Method according to claim 1 ble 4, characterized in that g «- indicates that cyclohexanone is used as the organic solvent. 00982? / - .158 * 784 12. The method according to claim 1 bie 4, dadureh \ ge - It is worthwhile to use butyrolactone as an organic solvent. 13. The method according to claim 1 to 4, characterized in that all organic Löeungo ** is eliminated / ended with benzyl alcohol, 14 · The method of claim 1 to 4 characterized ge _t -Jcennzeio h η et, DAJ as organic Löaungaoittel acetophenone remendet. PATENT APPLICATION (XITE Bt-IM *. R flMCU, 0 * 1.-04 ·. H. lOHt WM.-IM ·. ·. tTAMOl 009827/1530