4261 4265.output

* GB784668 (A)

Description: GB784668 (A) ? 1957-10-16

Process of dyeing and printing textiles and foils of organic esters

Description of GB784668 (A)

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DE1051786 (B) FR1140533 (A) DE1051786 (B) FR1140533 (A) less Translate this text into Tooltip

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The EPO does not accept any responsibility for the accuracy of data and information originating from other authorities than the EPO; in particular, the EPO does not guarantee that they are complete, up-to-date or fit for specific purposes.

PATEN SPEF - PATENT' SPECIFICATION 784,668 Date of Application and filing Complete Specification: Jan 3, 1956. No 196/56. Application made in Switzerland on Jan 5, 1955. ERRATA SPECIFICATI O Ni 1 N O 784,668 Page lz line 5, for N 1-amino-3-t read it 1-anlno-4-t. Page 5, line 35, for h 1, 2,11 read li: 2,". THE PATENT OFFICE, 11th April, 1958 DB 04130/1 ( 10)/ 3600 150 4/58 R fibres, bands, and fabrics and foils of cellulose organic acid esters or of linear aromatic polyesters. It is known to dye or print articles (e g. filaments, fibres, bands, fabrics, foils) of cellulose organic acid esters or of linear aromatic polyesters with disperse acetate dyestuffs in the presence of swelling agents for these products.

These processes using disperse acetate dyestuffs have however various drawbacks Thus, for instance, finely disperse acetate dyestuffs required for the preparation of printing pastes, dyeing solutions and padding liquors can be obtained only with considerable difficulties It is further difficult to obtain level dyeings with disperse acetate dyestuffs when dyeing, for example, balls of the ester material in a circulating liquor since the balls have a filtering effect on the liquor In addition to the known processes of dyeing and printing cellulose ester textiles with disperse acetate dyestuffs, there are also known processes where water-soluble dyestuffs are used But the dyeings obtained by the said processes generally show a moderate, sometimes even poor fastness to light and an unsatisfactory fastness to washing It was therefore of importance to find a simple process for the dyeing or printing of cellulose ester or linear aromatic polyester articles with water-soluble dyestuffs which does not show the aforesaid drawbacks. It has now been found that textiles or foils of cellulose organic acid esters or of linear aromatic polyesters can be dyed or printed in level shades fast to light and washing by allowing the water-soluble dyestuffs, defined lPric R tl of the reducing agent in the hot, thereby becoming water-insoluble and being drawn on to the base in a molecular dispersion. According to the invention a process of dyeing or printing textiles or foils of cellulose organic acid esters or of linear aromatic polyesters with water-soluble dyestuffs from aqueous dyebaths at an elevated temperature or by means of aqueous printing pastes or padding liquors with subsequent steaming of the prints or paddings with, if desired, the application of pressure, is characterised in that as the water-soluble dyestuff an acid dyestuff of the anthraquinone series having as the only water-solubilising group a sulphonic acid group in the 2-p Gsition of the anthraquinone nucleus is used, said sulphonic acid group being splittable in the hot by the action of reducing agents, and the dyeing, printing or padding of the said textiles or foils being carried out in the presence of the required reducing agent and, if desired, of an agent having a swelling effect on the said textiles or foils. A feature of the invention is to provide dyebaths, printing pastes or padding liquors suitable for the process according to the invention for the dyeing or printing of the textiles or foils of cellulose organic acid esters or of linear aromatic polyesters They are characterised by a content of one or more dyestuffs of the above defined kind, of a reducing agent and, if desired, of an agent having a swelling action on the cellulose ester or linear aromatic polyester. As the cellulose ester dicellulose pentaacetate (acetate rayon) or

cellulose tri-acetate Ind Inht PATENT SPECIFICATION 784 668 o Date Application and filing Complete Specification: Jan 3, 1956. (&( i II 2 N o,196 /56. Application made in Switzerland on Jan 5, 1955. Complete Specification Published: Oct 16, 1957. Index at acceptance:-Class 15 ( 2), B 2 K( 1 A: ID: 2 B 1: 2 82: 2 88), B 2 L( 3: 5 A: SD). International Classification:-DO 6 p. COMPLETE SPECIFICATION Process of Dyeing and Printing Textiles and Foils of Organic Esters We, SAN Doz LTD, of Basle, Switzerland, a Body Corporate organised according to the laws of Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to a process of dyeing or printing textiles such as filaments, fibres, bands, and fabrics and foils of cellulose organic acid esters or of linear aromatic polyesters. It is known to dye or print articles (e g. filaments, fibres, bands, fabrics, foils) of cellulose organic acid esters or of linear aromatic polyesters with disperse acetate dyestuffs in the presence of swelling agents for these products. These processes using disperse acetate dyestuffs have however various drawbacks Thus, for instance, finely disperse acetate dyestuffs required for the preparation of printing pastes, dyeing solutions and padding liquors can be obtained only with considerable difficulties It is further difficult to obtain level dyeings with disperse acetate dyestuffs when dyeing, for example, balls of the ester material in a circulating liquor since the balls have a filtering effect on the liquor In addition to the known processes of dyeing and printing cellulose ester textiles with disperse acetate dyestuffs, there are also known processes where water-soluble dyestuffs are used But the dyeings obtained by the said processes generally show a moderate, sometimes even poor fastness to light and an unsatisfactory fastness to washing It was therefore of importance to find a simple process for the dyeing or printing of cellulose ester or linear aromatic polyester articles with water-soluble dyestuffs which does not show the aforesaid drawbacks. It has now been found that textiles or foils of cellulose organic acid esters or of linear aromatic polyesters can be dyed or printed in level shades fast to light and washing by allowing the water-soluble dyestuffs, defined lPlicc l below, which contain a single sulphonic acid group per molecule, to act on these products in the presence of a

reducing agent and, if desired, of an agent having a swelling effect on these products Experiments have shown that the dyestuffs applied on to the base are free from sulphonic acid groups The dyeing process may therefore be explained in that in the dyeing liquor or printing paste the dyestuff splits off its sulphonic acid groups by the action of the reducing agent in the hot, thereby becoming water-insoluble and being drawn on to the base in a molecular dispersion. According to the invention a process of dyeinw or printing textiles or foils of cellulose organic acid esters or of linear aromatic polyesters with water-soluble dyestuffs from aqueous dyebaths at an elevated temperature or by means of aqueous printing pastes or padding liquors with subsequent steaming of the prints or paddings with, if desired, the application of pressure, is characterised in that as the water-soluble dyestuff an acid dyestuff of the anthraquinone series having as the only water-solubilising group a sulphonic acid group in the 2-po Gsitian of the anthraquinone nucleus is used, said sulphonic acid group being splittable in the hot by the action of reducing agents, and the dyeing, printing or padding of the said textiles or foils being carried out in the presence of the required reducing agent and, if desired, of an agent having a swelling effect on the said textiles or foils. A feature of the invention is to provide dyebaths, printing pastes or padding liquors suitable for the process according to the invention for the dyeing or printing of the textiles or foils of cellulose organic acid esters or of linear aromatic polyesters They are characterised by a content of one or more dyestuffs of the above defined kind, of a reducing agent and, if desired, of an agent having a swelling action on the cellulose ester or linear aromatic polyester. As the cellulose ester dicellulose pentaacetate (acetate rayon) or cellulose tri-acetate 2 784,668 is preferred, and as the linear aromatic polyester a higher molecular product of a polyalkylene glycol and an aromatic dicarboxylic acid is obtainable on the market, for example under the names "Dacon" or "Terylene" (Registered Trade Marks), is preferred. The process may be carried out in various ways The dyeings of the cellulose ester may thus be effected, without the addition of a swelling agent, at 80 C in the case of acetate rayon, or at 100 C in the case of cellulose tri-acetate fibre, whilst the dyeing of the linear aromatic polyester fibre at the boiling temperature of water requires the presence of an agent having a swelling effect on the fibres of said polyester Swelling agents of this kind which are suitable for the process of the invention are, for example, "Tetralin" (Registered Trade Mark), trichlorobenzene, benzoic acid and 2 or 4-hydroxy-1,11-diphenyl The dyeing of the linear aromatic polyester

may, moreover, be carried out at a temperature above C, e g 125 C with the application of pressure, by a known method, e g in a hightemperature dyeing apparatus, whereby the addition of at swelling agent is not required. The above-mentioned dyestuffs may also be added along with the reducing agent to printing pastes or padding solutions which consist of the usual thickeners and further additives. The printing or padding is, carried out by conventional methods, the prints or paddings on fabrics of polyester being preferably steamed at 115-120 C under elevated pressure The prints on fibres of acetate rayon may be steamed at 100 C, and the prints on fibres of cellulose triacetate or linear aromatic polyesters may be steamed at a temperature above 100 'C under pressure. The textiles or foils of cellulose ester or linear aromatic polyester dyed or printed according to the process of the invention mainly show a very good penetration, particularly with closely woven fabrics and balls cf the ester material as well as very level dyeings and prints The dyeings and prints are moreover usually fast to light and washing. As reducing agents for the present process there are preferably suited zinc or sodium formaldehyde sulphoxylate, or sodium formaldehyde bisulphite, the first named being used with advantage in the dyeing from an aqueous liquor, a reducing sugar in alkaline medium, e g glucose, galactose, fructose, or lactose, or sodium cellulose xanthogenate Other reducing agents, for example, alkali metal hydrosulphites, stannous chloride or zinc dust in ammoniacal medium generally yield byproducts. The water-soluble acid dyestuffs of the anthraquinone series which may be used for the process according to the invention must meet the above-mentioned requirements, for instance, of containing in the 2-position of the anthraquinone nucleus a sulphonic acid group splittable off by the action of the reducing agent, but otherwise being free from watersolubilizing groups, particularly from further sulphonic acid groups or carboxylic groups 70 Dyestuffs of this kind belong to the most varied classes of the anthraquinone series and are already known, such as for example, the salts of 1 4-diamino-anthraquinone-2-sulphonic acid, 1-amino 4 hydroxy-anthraquinone-2 75 sulphonic acid, 1-amino 4 phenylaminoanthraquinone 2 sulphonic acid, 1-hydroxy4-phenylamino anthraquinone 2 sulphonic acid, 1-hydroxy-4-( 41-methoxy)-phenylaminoanthraquinone-2-sulphonic acid, 4 4 '-diamino 80 1.11 dianthrimide 2 sulphonic acid, 3 Ycarbethoxy 4 ( 21-cyano) propylamino-l 9anthrapyridine 2 sulphonic acid, 3 '-carbethoxy-4-( 4 '-methoxy or 41-chloro)-phenylamino-1 9-anthrapyridine 2 sulphonic acid 85 and 1-amino 4 N pentyl-sulphonylaminoanthraquinone-2-sulphonic

acid. The following examples illustrate the invention without limiting it Therein the parts denote parts by weight and the temperatures 90 are given in degrees Centigrade. EXAMPLE 1. parts of a linear aromatic polyester fibre are introduced at 60 into a dyebath containing 3000 parts of water, 4 parts of sodium 95 31-carbethoxy 4 ( 21-cyano) propylamino1.9-anthrapyridine-2-sulphonate, 1 5 parts of zinc formaldehyde sulphoxylate and 1 5 parts of 2-hydroxy-1 11-diphenyl, whereupon the bath is heated to boiling temperature within 100 minutes The fibre is dyed at this temperature for 60 minutes, removed from the dyebath, rinsed with water and dried The polyester fibre is thus dyed in a level yellow shade of gcad fastness to light and washing 105 EXAMPLE 2. parts of a linear aromatic polyester fibre are dyed in a high-temperature dyeing apparatus under pressure at a temperature of above 110 for 30 minutes with a dyeing 110 liquor consisting of 3000 parts of water, 4 parts of potassium 1-hydroxy-4-phenylaminoanthraquinone-2-sulphonate and 1 5 parts of zinc formaldehyde sulphoxylate After this time, the polyester fibre is dyed in a level 115 violet shade of good fastness to light and washing. EXAMPLE 3. parts of acetate rayon are introduced at about 60 into a dyebath consisting of 3000 120 parts of water, 4 parts of ammonium 1hydroxy-4-( 4 '-methoxy) phenylamino-anthraquinone-2-sulphonate and 1 5 parts of zinc formaldehyde sulphoxylate The dyebath is heated to 80 within 20 minutes and main 125 tained at this temperature for a further 60 minutes The dyed acetate rayon is thereupon removed from the bath, rinsed and dried It is dyed in a level, pure violet shade of good fastness to light and washing 130 784,668 784,668 EXAMPLE 4. parts of cellulose triacetate fibre are introduced at about 60 into a dyebath containing 3000 parts of water, 2 parts of lithium 1-amino-3-n pentylsulphonylamino anthraquinone-2-sulphonate and 1 5 parts of zinc formaldehyde sulphoxylate The dyebath is heated to 100 within 20 minutes and kept at this temperature for 60 minutes The dyed cellulose triacetate fibre is thereupon removed from the bath, rinsed with water and dried A level, bright bluish red dyeing is obtained of good fastness to light and washing. EXAMPLE 5. 100 parts of a linear aromatic polyester fibre are introduced at 60 into a dyebath of 3000 parts of water, 2 parts of sodium 1-amino-4phenylamino-anthraquinone-2-sulphonate, 1 5 parts of

2-hydroxy-1 11-diphrnyl, 1 5 parts of a 30 % caustic soda solution and 2 parts of fructose, whereupon the bath is heated to boiling temperature within 20 minutes The fibre is dyed at 100 in the course of 60 minutes, removed from the dyebath, rinsed with water and dried The polyester fibre is dyed in a 25 blue shade of good fastness to washing. EXAMPLE 6. parts of acetate rayon are introduced at about 60 into a dyebath consisting of 3000 parts of water, 2 parts of sodium 1-amino-4 30 ( 4 '-amino) phenylamino anthraquinone-2sulphonate, 2 parts of glucose and 2 parts of sodium carbonate The dyeing bath is heated to 80 ' within 20 minutes After 60 minutes at the dyed acetate rayon is removed from 35 the bath, rinsed and dried It is dyed in a level greenish-blue shade of good fastness to washing. Examples 7 to 14 are set down below in tabular form; the procedures adapted for each 40 of these examples are as set forth in the preceding examples: 784,668 Example No Fibre Product Reducing Agent Shade a linear aromatic polyester a linear aromatic polyester a linear aromatic polyester a linear aromatic polyester acetate rayon acetate rayon acetate rayon cellulosetriacetate sodium 31-carbethoxy-4phenylamino-l 9anthrapyridine-2sulphonate sodium 1-hydroxy-4cyanamylaminoanthraquinone-2sulphonate sodium 1.4-di-p-(methoxy)ethoxyethloxyanilinoanthraquinone2-sulphonate sodium 4.41-diamino-1 11dianthrimide-2sulphonate sodium 1-amino-4-hydroxyanthraquinone-2sulphonate sodium 1-amino-4-phenylamino-anthraquinone2-sulphonate sodium 1-amino-4-hydroxyanthraquinone-2sulphonate sodium 1-amino-4-( 41hydroxy)-phenylamino-anthraquinone2-sulphonate EXAMPLE 15. A cheese of 100 parts of a linear aromatic polyester fibre is dyed in a high-temperature dyeing apparatus with a circulating liquor in the following way: a liquor consisting of 4 parts of sodium 3-carbethoxy-4-( 4 L-chloro)phenylamino 1 9-anthrapyridine-2-sulphonate, 1.5 parts of zinc formaldehyde sulphoxylate and 4000 parts of water is made to circulate in the apparatus and rapidly brought to boiling temperature The temperature is then increased so that it reaches 125 within 60 minutes Thereafter the cheese is dyed in a level orange shade fast to light and washing. EXAMPLE 16. A fabric of a linear aromatic polyester fibre zinc formaldehyde suiphoxylate do. galactose glucose zinc formaldehyde sulphoxylate zinc formaldehyde sulphoxylate sodium cellulose xanthogenate zinc formaldehyde

sulphoxylate orange red-violet green grey red blue red blue is printed with a printing paste having the following composition: parts of patassiumr 31-carbethoxy-4-( 2 'cyano)-propylamino-1 9-anthrapyridine-2-sulphonate, parts of thio-diglycol, 450 parts of crystal gum 1:2, parts of sodium formaldehyde sulphoxylate, parts of potassium carbonate, 390 parts of water 1000 parts The print thus obtained is dried at 50 % 30 II 784,668 5 steamed during 30 minutes at a normal steam pressure (temperature 100-105 ) and for 10 minutes at an excess pressure of 0 8 atm (temperature 120 ), it is then rinsed with cold water, soaped at 50 with a fatty alcohol sulphonate, again rinsed and finally dried A level yellow print is obtained of good fastness to light and washing. EXAMPLE 17. 10 parts of sodium 1-amino 4 phenylamino anthraquinone 2-sulphonate, parts of thiodiglycol 450 parts of crystal gum 1: 2, s 15 80 parts of sodium formaldehyde bisulphite, parts of potassium carbonate, 340 parts of water 1000 parts are worked up to a printing paste A fabric of a linear aromatic polyester fibre is printed with this paste The further treatment of the print is carried out according to the data of Example 16 A level bright blue print is obtained of good fastness to light and washing. EXAMPLE 18. A fabric of a linear aromatic polyester fibre is padded on a padding machine with a padding liquor having the following composition: parts of sodium 1-hydroxy-4-phenylamino anthraquinone 2 sulphonate, parts of thiodiglycol 200 parts of crystal gum 1,2, parts of sodium formaldehyde sulphoxylate, parts of potassium carbonate, 655 parts of water, 1000 parts The padding is steamed according to the data of Example 16 and finished A level violet dyeing is obtained of good fastness to light and washing. EXAMPLE 19. A fabric of a linear aromatic polyester fibre is padded according to the instruction of Example 18 with a padding liquor of the following composition: 20 parts of potassium 3 '-carbethoxy-4( 4 '-chloro) phenylamino 1 9anthrapyridine-2-sulphonate, parts of thiodiglycol parts of crystal gum 1: 2, 80 parts of sodium formaldehyde bisulphite, parts of potassium carbonate, 580 parts of water 1000 parts The padding thus obtained is treated according to the instruction of Example 16 A level orange dyeing is obtained of good fastness to light and washing. In the following examples the printing compositions only are given They are used for printing fabrics of cellulose acetates and linear aromatic polyesters After printing, the fabrics are dried The prints on fabrics of acetate rayon are steamed for 30 minutes at 100103

without excess pressure; the prints on fabrics of cellulose triacetate and linear aromatic polyesters are steamed for 30 minutes at 102-104 without excess pressure and for minutes at 110-112 at excess pressure of about 0 5 atm After steaming, the prints are rinsed with water, soaped at 60 for 3 minutes, again rinsed and then dried It is to be understood that " excess pressure " indicates a pressure greater than atmospheric pressure wherever mentioned in the specification. EXAMPLE 20. parts of sodium 3 ' -carbethoxy-4mesidino 1 9 anthrapyridine2-sulphonate 85 parts of thiodiglycol 330 parts of water 450 parts of crystal gum 1: 2 parts of potash parts of sodium formaldehyde sulph 90 oxylate 1000 parts on a linear aromatic polyester fibre: orange. EXAMPLE 21. parts of sodium 1-amino-4-isopentylsulphonylamino anthraquinone2-sulphonate parts of thiodiglycol 375 parts of water 450 parts of crystal gum 1: 2 parts of potash parts of galactose 1000 parts on a linear aromatic polyester fibre: bluish red. EXAMPLE 22. parts of sodium 1 amino 4 panisidino anthraquinone 2sulphonate parts of thiodiglycol 340 parts of water 450 parts of crystal gum 1: 2 parts of potash parts of lactose 1000 parts on a linear aromatic polyester fibre: blue. 784,668 6 784,668 p EXAMPLE 23. parts of sodium 1 amino 4-( 4amino) phenylamino anthraquinone-2-sulphonate 100 parts of thiodiglycol 340 parts of water 450 parts of crystal gum 1: 2 parts of potash parts of glucose 1000 parts on a linear aromatic polyester fibre: greenishblue. 1 2 1 EXAMPLE 24. parts of sodium 4 41 diamino 1 1dianthrimide-2-sulphonate, parts of thiodiglycol 260 parts of water parts of crystal gum 1:2 parts of potash parts of dextrin 1000 parts on a linear aromatic polyester fibre: grey. - EXAMPLE 25. parts of sodium 1-amino-4-hydroxyanthraquinone-2-sulphonate parts of Tetracarnit (Registered Trade Mark) 375 parts of water 450 parts of crystal gum 1:2 50 parts of potash parts of hydrosulphite conc (Nahyposulphite) 1000 parts on a linear aromatic polyester fibre: red. "Tetracarnit" is an agent for dissolving dyestuffs and for levelling on the basis of heterocyclic bases. EXAMPLE 26. parts of sodium 1-hydroxy-4-phenylamino anthraquinone 2-sulphonate parts of thiodiglycol parts of Tetracarnit 370 parts of water 450 parts of crystal gum 1:2 parts of potash parts of zinc dust 1000 parts

on a linear aromatic polyester fibre: violet. EXAMPLE 27. parts of sodium 1-aminoanthraquinone-2-sulphonate parts of thiodiglycol 360 parts of water 450 parts of crystal gum 1:2 parts of potash parts of sodium formaldehyde sulphoxylate 1000 parts on acetate rayon: orange. EXAMPLE 28. parts of sodium 1-amino 4 -phenylamino-anthraquinone 2 sulphonate parts of thiodiglycol 320 parts of water 450 parts of crystal gum 1: 2 parts of potash parts of fructose 1000 parts on acetate rayon: blue. EXAMPLE 29. parts of sodium 31 carbethoxy-4-( 4 'methoxy) phenylamino 1 9anthrapyridine-2-sulphonate parts of thiodiglycol 360 parts of water 450 parts of crystal gum 1: 2 parts of potash parts of sodium formaldehyde sulphoxylate. 1000 parts on cellulose triacetate fibres: orange. EXAMPLE 30. parts of sodium 1 hydroxy 4-( 4 'methoxy)-phenylamino anthraquinone-2-sulphonate parts of thiodiglycol 360 parts of water 450 parts of crystal gum 1: 2 parts of potash parts of glucose 1000 parts on cellulose triacetate fibres: violet. EXAMPLE 31. parts of sodium 1-amino-4-( 4 '-methoxy)-phenylamino anthraquinone-2-sulphonate parts of thiodiglycol parts of Tetracarnit 360 parts of water 450 parts of crystal gum 1: 2 parts of potash parts of sodium hyposulphite 1000 parts on cellulose triacetate fibres: blue.

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* GB784669 (A)

Description: GB784669 (A) ? 1957-10-16

Improvements in the production of amphoteric finishing agents fromcarboxylic acids and hydroxyalkyl amines which agents are stable to hightemperatures and the hardnessin water



BE544600 (A) FR1140215 (A) BE544600 (A) FR1140215 (A) less Translate this text into Tooltip



PATENT SPECIFICATION 784,669 Date of Application and filing Complete Specification: Jan 17, 1956. Application made in Germany on Jan 26, 1955. Complete Specification Published: Oct 16, 1957. No 1533/56. Index at acceptance:-Classes 2 ( 3), C 2 B 2 (A 1:A 2:D:GC 10:J:K), C 2 83 (A 1:E: F:C 1), C 2 837 (A 1:A 2:J:K); and 15 ( 2), CA 18, GB( 2 A 1:2 A 2: 2 B 1:4 D:5 A:5 B:5-C), CC 2 A 12 (A 1:A 5:B 11), C 2 C( 2:3:4: 5:9). International Classification:-C 07 c, D 006 m. COMPLETE SPECIFICATION Improvements in the Production of Amphoteric Finishing Agents from Carboxylic Acids and Hydroxyalkyl Amines which Agents are Stable to High Temperatures and the Hardness in Water We, BADISCHE ANILIN & SODA-FABRIK AKTIENGESELLSCHAFT, a Joint Stock Company organised under the Laws of Germany, of Ludwigshafen on Rhein, Germany do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:It is already known that valuable softening agents for fibres and fabrics are obtained by the reaction of trihydroxyalkyl dialkylene triamines with

high molecular weight fatty acids These softening agents are cationactive and are therefore soluble only in neutral or acid media Moreover they may cause change in shade in the case of dyed materials It has also been proposed to prepare anion-active softening agents by semiesterification of dicarboxylic acids with fatty acid alkanolamides which do not contain basic nitrogen atoms These, as anionactive compounds, are soluble only in neutral or alkaline media and are very sensitive to the salts causing hardness in water. We have now found that valuable softening agents are obtained by reacting condensation products from high molecular weight fatty acids and trihydroxyalkyl dialkylene triamines with dibasic aliphatic or aromatic carboxylic acids to a product which still contains unreacted carboxylic groups The products obtained are amphoteric and are therefore soluble equally well in the acid and alkaline regions Moreover they are largely inert to the salts causing hardness in water. They impart to the treated goods a soft, pleasant handle which does not change even during the drying and treatment of the goods at elevated temperature such as is frequently necessary in further processing. Suitable initial materials for the new softening agents are the reaction products containing acid amide groups and acid ester groups derived from high molecular weight natural or synthetic, straight-chained or branched fatty acids which contain 10 to 20 carbon atoms in the molecule with trihydroxyalkyl dialkylene triamines, such as trihydroxethyl diethylene triamine or trihydro 50 xyethyl dipropylene triamine As fatty acids there may be mentioned for example lauric acid, coconut oil fatty acid, stearic acid, oleic acid, linoleic acid and fatty acid mixtures such as are obtainable from natural fats, 55 such as beef tallow and palm oil About 1 to 2 mols of fatty acid are used for 1 mol of trihydroxyalkyl dialkylene triamine Instead of trihydroxyethyl dialkylene triamine, trihydroxypropyl dialkylene triamines, for ex 60 ample, are also suitable The products prepared according to the process of the British Patent Specification No 680,688 are especially suitable as initial materials As dibasic acids there may be used maleic acid, 65 succinic acid, adipic acid and phthalic acid. The reaction with the dibasic acids is carried out in the absence of water, if desired in the presence of solvents such as benzene, at 100 to 200 C, preferably at 120 to 150 C 70 The reaction is preferably discontinued when about half of the carboxyl groups of the added dicarboxylic acids have been reacted; this can readily be determined by titration. The products obtained, depending on the 75 nature of the initial

materials, are pale coloured solid masses of soft to brittle nature which dissolve very well in water in the form of their alkali salts, are not separated from the solution by acids and are substantially 80 stable to the salts causing hardness in water. Suitable bases for the formation of salts are for example caustic soda solution or organic bases, such as ethanolamine or triethanolamine The condensation products 85 can be used as such or as salts with the said or other bases. The products obtained according to this invention are suitable as preparing and softening agents for textiles of natural fibres and 9 @ 784,669 man-made fibres of all kinds, as for example wool, cotton, spun-rayon, acetate rayon, polyamide fibres, polyacrylonitrile fibres and polyester fibres The treated yarns, fabrics and the like acquire a smooth and very full handle The products also have a special importance in the dyeing and softening of yarns in the form of cheeses and in subsequent rapid drying In this way ease of winding is considerably improved The softening effect on synthetic fibres, as for example polyamide fibres, which have been softened with agents prepared according to this invention is retained even after heat-setting, by reason of the high stability to heat of the finishing agents. Approximately I to 12 grams of the products per litre of treatment liquid are used depending on the nature of the fibrous material and the properties desired for the goods The treatment of coloured textiles is preferably carried out in the last rinsing bath. The treatment agents prepared according to this invention are employed alone or together with other textile assistants, as for example in combination with urea-formaldehyde resins, melamine-formaldehyde resins or dispersions of plastics, as for example of polyacrylic acid esters The combination with urea-formaldehyde resins is eminently suitable for the schreiner finishing of cotton and spun rayon fabrics The -goods acquire a soft and flowing handle similar to the handle of natural silk. The following Examples will further illustrate this invention but the invention is not restricted to these Examples The parts are by weight. EXAMPLE 1. 1,410 parts of the reaction product of 1 mol of N N' N"-trihydroxyethyl diethylene triamine and 1 mol of stearic acid are melted under nitrogen 348 parts of maleic acid are added and the melt is stirred at 130 to 145 C. When a sample which has been removed and titrated uses up only half as much alkali as a sample withdrawn at the beginning of the reaction (which is the case after several hours), the desired degree of reaction has been reached The pale brownish product is neutralised

with 512 parts of 25 % caustic soda solution and adjusted with water to a content of 30 % 6,280 parts of a pale paste are obtained which may readily be dispersed in warm water and upon further dilution gives a 55 clear solution which is stable in acid and alkaline regions and is substantially inert to the salts causing hardness in water. EXAMPLE 2. 470 parts of the initial material used in 60 Example 1 are reacted in the same way as in Example 1 with 118 parts of succinic acid. A brownish product is obtained which has the same properties as that obtained according to Example 1 65 148 parts of phthalic acid may be used instead of the 118 parts of succinic acid. EXAMPLE 3. 620 parts of a reaction product of 1 mol of N.N' N"-trihydroxyethyl diethylene triamine 70 and 2 mols of stearic acid are fused with 116 parts of maleic acid while stirring and leading through nitrogen and then kept for about 6 hours at 135 ' to 145 'C After this period the titratable acid content has fallen to about 75 half After neutralisation with 194 parts of % caustic soda, water is mixed therewith until there is a total amount of 2 6 parts A pale coloured 30 o paste is obtained which dissolves well in water


* GB784670 (A)

Description: GB784670 (A) ? 1957-10-16

Heterocyclic quinones



CH339207 (A) DE1041500 (B) CH339207 (A) DE1041500 (B) less Translate this text into Tooltip



I A S-:. } -y^ i > ec a N 'PATENT SPECIFICATION 4 C Applic Date of Applic No 2045156. Application mi 784,670 ation and filing Complete Specification: Jan 20, 1956. 2 ade in Germany on Jan 24, 1955. SPECIFICATI Oi NO 784,670 Index at a Thle Inventor of tils invention in the sense of being the actual deviser thereof within the meaning of Section 16 of the Patents Act, 1949, Is Hans-Bodo Kon 14, of Internatiox Farbenfabriken Bayer A tiengesellschaft, 'ikppertal-Elberfeld, Germany, of German nationality. W( GESE TE PATWNT OFFICE, unde: ist;governber, 1957 Gem which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to a process for the synthesis of heterocyclic quinines and more particularly to a process for the synthesis of phenazine quinones. According to the present invention 1,4-dihydroxyphenazine is oxidised to the corresponding phenazinequinone by using as oxidising agent the oxide or oxygen-acid of a halogen, preferably bromic acid or its salts If instead of the unsubstituted 1,4-dihydroxyphenazine, its derivatives substituted with halogen atoms, hydroxy-, alkoxy-, acyloxyand/or alkyl groups, are used, 1,4-phenazinequinones are obtained which are correspondingly substituted. The bromic acid preferably used according to the invention as oxidising agent is advantageously employed in the form of one of its stable alkali metal salts in concentrated aqueous solution. The dihydroxyphenazines may be used as such or as a suspension or solution in a diluent such as for example glacial acetic acid. In carrying out the process an aqueous solution of the oxidising agent may be added to a mixture of dihydroxyphenazine with glacial acetic

acid, with stirring, at temperatures ranging from 0-100 C, but preferably at room temperature The di'hydroxyphenazine not immediately dissolved goes into solution after a short time whereupon the corresponding phenazinequinone precipitates in welldefined, fine, almost analytically pure crystals. The precipitation may be completed by the addition of water and by cooling the reaction mixture, The invention comprises the compounds obtainable by the process They may be used as dyestuffs, drugs, pest control agents or as DB 000 oooe 6/1 ( 5)/i 593 oo 100 10 o/57 o R-CX 3) II 0 in which R is hydrogen, a halogen atom, or an alkyl-, hydroxy-, alkoxy or an acyloxy group. The following Example is given for the 55 purpose of illustrating the invention. EXAMPLE. 0.5 Grams of 1,4-dihydroxyphenazine are dissolved or suspended in 25 millilitres of glacial acetic acid To this mixture there is 60 added, in one portion, with stirring, a solution 0.5 grams elf potassium bromate in 7 millilitres of water, at room temperature The reaction mixture is stirred at room temperature for 10 minutes whereupon 10 millilitres of water are 65 added and after 4 minutes another 10 millilitres of water The mixture is then cooled with ice and after 5 minutes treated again with 10 millilitres of water After 6 minutes the precipitate thus formed is filtered off with 70 suction, washed with water and dried Yield: 0.43 grams ( 87 per cent of the theoretical) of fine light-brown crystals B p above 2800 C (decomposition between 150-200 C) (Kofler heating bloc) 75 In like manner, derivatives of 1,4-dihydroxyphenazine substituted as aforesaid, may be oxidised to the corresponding phenazinequinone.


* GB784671 (A)

Description: GB784671 (A) ? 1957-10-16

Fibrous products comprising fibres bonded with dextran xanthate

Description of GB784671 (A) Translate this text into Tooltip



PATENT SPECIFICATION Inventor: LEO J NOVAK 784,671 Date of Application and filing Complete Specification Jan 23, 1956. No 2206/56. Complete Specification Published Oct 16, 1957. Index at acceptance: -Classes 2 ( 3), T 5; 96,'B( 1: 11 A: IB:: 13: 13 H: 14 H: 19: 23); 121, C; and 140, G. International Classification: -C 08 b C 09 k D 04 j D 21 h. COMPLETE SPECIFICATION Fibrous Products Comprising Fibres Bonded with Dextran Xanthate We, THE COMMONWEALTH ENGINEERING COMPANY OF O Hio, a Company organized under the laws of the State of Ohio, United States of America, of 1771, Springfield Street, Dayton, Ohio, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates in general to fibrous products and, in particular, to so-called "nomiwoven fabrics " formed from discontinuous or short fibers and in which the fibers are bonded together in a coherent structure without benefit of weaving, knitting or other conventional textile processing. It is known in the art to make fibrous products from mixtures of two types of short or discontinuous fibers one of which is rendered adhesive by heat or solvents so that, while those fibers are in the adhesive condition, and usually with the application of pressure, the adhesive and non-adhesive fibers are autogenously bonded together by adhesion of the adhesive fibers to the remaining fibers Such fibrous products, in diverse forms, have found acceptance in the trade as

insulation, for coat linings, and so on. While the "fabrics" comprising the two types of autogenously bonded fibers and obtained by commingling the two types of fibers, activating the one type to adhesive condition, and pressing the fibers together while the activated fibers are in the adhesive state, are generally less costly than fabrics obtained by subjecting masses of discontinuous fibers to conventional textile processing, including carding and/or combing, drafting, etc to form a yarn and then weaving or knitting the spun yarns, they do involve the production of the potentially adhesive fibers, usually from a thermoplastic fiber-forming material such as a synthetic resin The production of the resin or other thermoplastic, fiber-forming material, shaping thereof int Q continuous filaments, and lPrice 3 s 6 d 1 disruption of the filaments into fibers of the desired short length, are relatively costly steps all of which contribute to the expense of the fabric obtained and the ultimate cost of the same to the consumer. It is an object of this invention to provide fibrous products, particularly "non-woven fabrics" made of discontinuous or short fibers which are, in general, less expensive than available fibrous products of that type. Another object is to provide fibrous products, particularly "non-woven fabrics" made of discontinuous or short fibers in which the fibers are bonded together by a relatively inexpensive bonding agent and which do not depend on the use of expensive resin or thermoplastic fibers for coherence and strength. A further object is to provide a new and novel bonding agent for the fibers of a "nonwoven fabric" which can be applied to the fibrous structure in aqueous medium and which sets to bind the fibers together on drying of the treated structure. These and other objects of the invention which will become apparent hereinafter are accomplished by the use of dextran xanthate as binding agent for the discontinuous fibers. Dextran is a high molecular weight polysaccharide comprising anhydroglucopyranosidic units joined by molecular structural repeating alpha-1,6 to non-alpha-1,6 linkages, at least 50 % of tie linkages being, apparently of the 1,6 type. The dextran xanthated to obtain the bonding agent for the fibers may be obtained in any suitable way Usually, it is obtained by inoculating a sucrose-bearing nutrient medium with a culture of a dextran-producing strain of Leuconostoc mesenteroides or L dextranicum, or the enzyme filtered from the culture, and holding the mass until the dextran is biosynthesized from the sucrose in maximum yield, after which the dextran is precipitated from the fermentate as by the addition of a watermiscible aliphatic alcohol or ketone The

native dextran thus obtained is, under normal Prke <a 6 ( 784,671 conditions, characterized by a very high molecular weight, calculated to be in the millions. It may be used as such in the xanthation reaction, after suitable purification, reduction to particulate condition, and conversion to alkali dextran, or it may be partially hydrolyzed in any suitable way to dextran of lower molecular weight prior to being xanthated In general, the dextran xanthated to obtain the bonding agent may have a molecular weight of 5000 to 150 x 106, determined by light scattering measurements. The xanthate is obtained by reacting on the alkali dextran with carbon disulfide, the alkali dextran being formed when the dextran is dissolved or dispersed in an aqueous alkaline solution, preferably aqueous sodium hydroxide. By appropriate selection and correlation of the reaction conditions, dextran xanthates containing an average of from less than 1 0 up to 3 0 xanthate groups per anhydroglucopyranosidic unit may be produced. In accordance with one preferred method, the dextran xanthates are produced by the addition of liquid CS, to an aqueous slurry or solution of the alkali dextran, such as and preferably sodium dextran, at a temperature of C to 25 O C, and allowing the reaction to proceed at said temperature while subjecting the reaction mass to continuous agitation. The molar ratio of alkali dextran to C 52 may be between 1:3 and 12:1, the reaction time may be between 2 and 4 hours or even longer The reaction results, in the production of a rather viscous mass which may be precipitated in a water-miscible aliphatic alcohol to obtain the dextran xanthate in the form of granules which may be filtered and dried to obtain the dextran xanthate in the form of a white to light brown powder. Introduction of the xanthate groups into the dextran molecule may or may not appreciably alter the solubility characteristics of the starting dextran These characteristics vary depending on the microorganism used in the biosynthesis which evidently influences the structure of the dextran, i e, the proportion of 1,6 linkages therein and the water-sensitivity thereof Dextran which is inherently water-soluble even in the native, unhydrolyzed state, such as the dextran obtained using the microorganism (or their enzymes) bearing the following NRRL (Northern Regional Research Laboratory) designations: Leuconzostoc nesenteroides B-512, L m B-119, L in. B-1190 and L m B-1146, may be readily soluble in water, after xanthation, at low degrees of substitution up to an average of 1.0 to 1 5 xanthate groups per anhydroglucopyranosidic unit, but at higher substitutions, are usually less soluble in water or waterinsoluble but

dispersible therein. The xanthates of dextran which is, in native state, difficultly soluble in water or substantially water-insoluble under ordinary conditions, such as dextran obtained using the microorganisms (or their enzymes) bearing the NRRL classifications: Lcuconostoc mi Isente,'oid Les B-523: L m B-742: L m B-1191: L m B-1196; 70 L m B-1144: L mn B-1208: L m. B-1216: Streptobacterium dextranicum B1254 and Betabacteriumt vemzifci'ne B-1139 are also difficultly water-soluble or substantially water-insoluble but may be dissolved or 75 dispersed in aqueous medium under special conditions For example, xanthated L m. B-512 dextran is insoluble in water but soluble in aqueous alkaline solutions such as aqueous sodium hydroxide Such solutions 80 may be used to incorporate the xanthate with the fibrous product. The following is illustrative of the production of a dextran xanthate for use as bonding agent for the fibers 85 About 10 gins of particulate B-523 native (unhydrolyzed) dextran are slurried in 200 mls of hot ( 60 C) water A solution of 2 0 gins of sodium hydroxide in 10 mls of water is added and the mass is heated at 60 C with 90 constant agitation for one hour It is then cooled to 25 C and 2 0 mls of liquid carbon disulfide are added dropwise The mass is agitated for 2 hours at room temperature and then poured into methanol The granular pre 95 cipitate is separated by filtration and dried in a vacuum oven for about 12 hours at 60 C. The dextran xanthate (about 95 % yield) occurs as a light brown powder and has an average degree of substitution (D S) of about 100 0.5 The degree of substitution is the average number of substituent xanthate groups per anhydropyranosidic unit of dextran It is soluble in 2 % to 10 %, sodium hydroxide solution, but is insoluble in water, acetone, toluene, 105 morpholine and chloroform. The dextran xanthate, when wet, is characterized by pronounced adhesiveness and when associated with the fibers in solution or dispersion is deposited on the fiber surfaces as an 110 adhesive glaze which, on drying, serves to cement the fibers together at their contiguous surfaces or points of contact in the product. In making the fibrous products, according to one variant of the invention, the fibers are 115 deposited in any suitable way, and preferably non-parallel, that is not oriented in the same direction, and in the form of a web, met, or bat of desired thickness, the web or the like is treated with a solution or dispersion, prefer 120 ably aqueous, of the dextran xanthate, and the treated product is dried, with or without pressing, to obtain a product in which the dextran xanthate remains bonded to the fibers to secure them in a coherent structure which has good 125 strength Re-wetting of the fibrous

product increases the adhesion of the xanthate to the fibers, and thus paper products in accordance with the invention have good wet strength. The fibers may be deposited by drawing 130 Iz 784,671 them downwardly through a suitable chamber onto an endless, travelling foraminous collection surface by suction applied below the surface, or by blowing them through a chamber onto the collecting surface The resulting feltlike web or bat of fibers may be moved on the travelling surface from the zone of deposition to a zone in which they are sprayed or otherwise treated with the solution or dispersion of the dextran xanthate, and then to a drying zone in which they may be subjected to a current of hot air under pressure, or pressed between platens or the like heated to a temperature below that at which the fibers are damaged. According to another embodiment, the fibrous products are made on paper-making equipment, which permits of obtaining products of indefinite length and varying width. The fibers and dextran xanthate are distributed in the water in the beater, with or without beating of the fibers depending on the type of fiber used, the suspension is laid down on the screen, and the product is then dried and, optionally, calendared. Various types of fibers may be used in making the products and particularly natural fibers of textile-making, paper-making length, or of shorter length, including those of cotton, flax, jute and other vegetable fibers; wool, hair, silk and other animal fibers asbestos, glass, mineral wool; also artificial fibers comprising cellulose, such as regenerated cellulose or cellulose hydrate of all kinds, cellulose derivatives such as the esters, the ethers, mixed cellulose ester-ethers, hydroxy-alkyl and carboxyalkyl ethers of cellulose, xanthates of the cellulose ethers, cellulose thiourethanes, cellulose-fatty acids, dextran, and dextran ethers, and other fibers which are not rendered adhesive by heat without damage to the fiber structure and therefore cannot be used in making fibrous products of the type under consideration except in combination with more expensive resin fibers The products may be formed of fibers which are of shorter length than is normal for textile or paper-making. Thus, they may be formed of rayon waste or flock which comprises extremely short fibers or fibrils The fibers will usually not have a length greater than one-half inch. Synthetic fibers which are thermoplastic are not required for activation to adhesive condition to bind the fibers of the product together. However, there are instances in which it may be desirable to use such fibers alone or in combination with the natural or artificial

nonthermoplastic fibers The synthetic fibers, and also artificial fibers of the type of regenerated cellulose, are characterized by smooth surfaces and normally cannot be used in the manufacture of paper, using conventional paper-making equipment. In making paper from the usual paper-making fibers, an aqueous suspension of the fibers is beaten in the paper beater and during such beating the fibers undergo fibrillation and when the suspension is laid down on the screen dependence is placed on interlocking of the fibrilles of contigous fibers to hold the paper 70 web together The synthetic and artificial fibers having smooth surfaces do not fibrillate on beating and therefore do not tend to interlock when an aqueous suspension thereof is laid down on the paper-making screen, even after 75 vigorous beating of the suspension Those smooth-surfaced synthetic and natural fibers may be used in making paper or paper-like products in the practice of this invention, by including the dextran xanthate in the suspen 80 sion in the beater with sufficient stirring (no beating required) to distribute the xanthate through the mass and then depositing the suspension on the screen, or by stirring the fibers in the water, laying the suspension down on 85 the screen, and then treating the deposited fibers with a solution or dispersion of the dextran xanthate, and processing the resulting web of adhered fibers in the usual way Preferably, when paper-making equipment is used, the 90 dextran xanthate is dispersed or dissolved in the water in the beater, before or after introduction of the fibers If an alkaline condition exists in the beater, or even if it does not, an alkali soluble dextran xanthate may be used, 95 such as dextran xanthate derived from an alkali-soluble dextran of the L m B-523 type, and may be introduced in the form of an aqueous alkaline solution, such as a solution in aqueous sodium hydroxide When dextran 100 xanthate soluble in aqueous alkaline solution of a given alkali concentration is added to the water in the beater, the dilution may reduce the concentration of the alkali to a point at which the dextran xanthate is not soluble and 105 precipitates on the surfaces of the fibers in the form of minute, discrete masses which form discrete bonds between the fibers on deposition of the suspension and drying of the web. Such products, in which the fibers are held by 110 the discrete mass or particles of dextran xanthate are characterized by increased porosity as compared to products comprising fibers the surfaces of which are more or less glazed or coated by the adhesive xanthate 115 Any of the natural or artificial fibers mentioned herein may be used, and may be used when the products are formed on paper-making equipment Synthetic fibers which may be used, particularly when the products are 120 formed on paper-making apparatus, include those of nylon, "Dacron

" (Registered Trade Mark), "Dynel" (Registered Trade Mark), " Teflon" (Registered Trade Mark), and fibers formed of various vinyl polymers and copoly 125 mers, including those of polyacrylonitrile and acrylonitrile copolymers. The amount of dextran xanthate incorporated in the fibrous product may vary and may be as low as 1 % or as high as 25 %, or even 13 Q 784,611 as high as 50 % on the weight of the fibers, depending on the relative flexibility or stiffness desired in the fibrous product. In general, these products in which the fibers are chemically bonded together by the dextran xanthate are characterized by good strength in all directions and sufficient flexibility to enable them to be manipulated They may comprise fibers pre-dyed to any shade of any color, or may be printed for decorative effects, and may be used for a variety of purposes such as "non-woven " interfacing, backing, lining, reinforcement or padding in the apparel, upholstery, and home-decorating fields The products are light in weight, may be more or less porous, have a smooth surface, and do not tend to ravel. The following examples are given to illustrate the invention, it being understood that these examples are not intended to be limitative. EXAMPLE I. Staple regenerated cellulose fibers are mixed with water in the beater of a paper-making machine to obtain a 10 % suspension Five per cent (on the fiber weight) of waterinsoluble dextran xanthate (derived from L m. B-523 (dextran and having a D S of about 2.0) is mixed with the suspension, together with 0 5 % of polyoxyethylene glycol monopalmitate as dispersing agent and the mixture is laid down on the paper-making screen to obtain a web of fibers adhesively bonded by the dextran xanthate The web is passed through the machine in the usual way The dried, calendared web has a smooth surface and good strength. EXAMPLE II. Regenerated cellulose flock consisting of extremely short fibers or fibrils is blown into an enclosed chamber the bottom of which is formed by an endless travelling foraminous screen The fibers are collected on the travelling screen in heterogeneous, random lay to a thickness of one inch, and are then carried on the screen under a sprayhead which projects an aqueous sodium hydroxide solution of the dextran xanthate of Example I downwardly against them The impregnated layer of fibers is then carried on the screen through a zone in which air under pressure and heated to a temperature of 100 C is blown against them. The product is thus dried, with compaction of the fibers by the force of the air impinging against them. The water-insoluble dextran xanthates are preferred for most purposes,

and may be applied in the form of aqueous dispersions or emulsions, in aqueous alkaline solution where appropriate, or in organic solvents such as formamide In preparing the aqueous dispersions or emulsions, various dispersing or emulsifying aids may be employed such as triethanolamine oleate, morpholine stearate and polyoxyethylene glycol stearate. Since certain changes in carrying out the above process, and various modifications in the article which embody the invention may be made without departing from its scope, it is intended that all matter contained in the above 70 description shall be interpreted as illustrative and that the invention is not to be limited except as defined in the appended claims.


* GB784672 (A)

Description: GB784672 (A) ? 1957-10-16

Improvements in or relating to the production of acid derivatives of ortho-naphthoquinone-diazide-carboxylic acids, particularly aromatic esters andaromatic amides



DE957392 (C) DE957392 (C) less Translate this text into Tooltip



COMPLETE SPECIFICATION Improvements in or relating to the Production of Acid Derivatives of Ortho-naphthoquinone-diazide-carboxylic Acids, particularly Aromatic Esters and Aromatic Amides We, KALLE & CO. AKTIENGESELLSCHAFT, a Body Corporate organised according to the Laws of Germany, of 25, Rheinstrasse, Wies- baden-Biebrieh, Germany, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement : This invention relates to the production of acid derivatives of ortho-naphthoquinone- diazide-carboxylic acids and especially to aromatic esters and aromatic amides. The above-mentioned compounds are referred to in the literature but only brief information is given concerning their preparation. It has been propose that the aromatic amides or aromatic esters of hydroxynaphthoic acids should be converted to azo dyestuffs by coupling with diazo compounds. On reduction of these azo dyestuffs, aromatic esters or aromatic amides of hydroxy-amino- naphthalene-carboxylic acids are obtained, from which the corresponding orthonaphtho-quinone-diazide-carboxylic acid esters and amides may be prepared by diazotization. This method of preparation, however, does not proceed smoothly in all stages of the reaction, and the production of the starting products also presents diEculties. The chlorides of hydroxynaphthalenecarboxylic acids are very difficult to obtain. The method of preparing the esters and amides by conversion of these chlorides with hydroxy compounds or amines in the presence of alkaline agents is therefore not advantageous. The amides of hydroxy-naphthalene- carboxylic acids with aromatic amines as well as the esters of these carboxylic acids with aromatic hydroxy compounds are very difficult to dissolve either in dilute alkalies or in organic solvents. Moreover, the production of these esters and amides itself presents diiculties, particularly when weak basic amines or higher molecular aromatic hydroxy compounds are to be condense with 2, 3-hydroxy-naphthoic acid. In the production of the azo dyestuffs from these carboxylic acid

derivatives by coupling with diazotized aromatic bases, it is necessary initially to work in suspension and in the presence of stronger alkalies. This has the result that, particularly in the case of carboxylic acid esters, a partial resaponifi- cation takes place, and considerable quantities of azo dyestuffs of the free carboxylic acids are obtained as undesirable byproducts. Owing to their limited solubility in organic solvents, it is very dimcult to obtain in pure form the azo dyestuffs of the aromatic hydroxy-naphthalene-carboxylic acid amides or or the corresptonding esters. For this reason ortho-hydroxy-amines obtained by reduction of such azo dyestuffs are also in an impure condition, and they in their turn are difficult to dissolve and therefore difficult to purify. While the amide group generally remains intact during reduction of the azo dyestuffs from the carboxylic acid amides mentioned above in the case of the azo dyestutfs from the-aromatic esters the phenolic component is largely split off during the reduction process, so that free ortho-hydroxy-amino naphthalene-carboxylic acid is obtained as the main product. Diazotization of the barely soluble aromatic a-hydroxyamino-naphthalene-carboxylic-acid-amides, which are only weakly basic, also results in only a poor yield, In order to dissolve the amines sufficiently during diazotization, a raised temperature is necessary and the nitrite must be added at this temperature. This results in partial decomposition of the diazo compound formed and byproducts results, removal of which is possible only through recrystallization of the impure diazo compound with high losses. The object of the present invention is to provide a method which makes the production of aromatic ortho-naphthoquinone diazide-carboxylic acid-esters and amides possible in a technically simple way and with a good yield. The present invention provides a process for the production of acid derivatives of ortho-naphthoquinone-diazide-carboxylic acids, which process comprises treating an ortho-naphthoquinone-diazide-carboxylic acid with excess thionyl chloride to form the corresponding ortho-naphthoquinone-diazide-carboxylic acid chloride. The acid chloride so produced may be reacted with aromatic hydroxyl compounds or aromatic amines in the presence of acid-combining agents, to form the corresponding esters or amides respectively. Acid-combining agents that may be mentioned as suitable for the carrying-out of the present process are pyridine, quinoline, and their basic derivatives, such as methyl pyridine, and also trialkylamines, such as for example trimethylamine, triethylamine, tripropylamine, and others. If the aromatic amine that is brought into reaction with the carboxylic acid chloride possesses sufficient basicity, the addition

of a special acid-combining agent may be omitted ; in such a case, the basic reaction component is used in excess. The ortho-naphthoquinone-diazide-carboxylic acids used as starting materials are easily obtainable. For example, the naphthoquinone- (1, 2)-diazide- (1)-carboxylic acids may be produced by coupling free 2-hydroxy-naphthalene-carboxylic acids with a diazo compound to form an azo dye which is then reduced to form the l-amino-2-hydroxy-naphthalene-carboxylic acid, which is diazotized. The naphthoquinone- (l, 2)-diazide- (2)-carboxylic acids may be produced from the 1-hydroxy-naphthoic acids by nitrosation, reduction and diazotization. The intermediate products can easily be purifie as the presence of free carboxyl groups ensures aood solubility even in weak alkalies. It is therefore possible to dissolve these intermediate products in an alkaline solution, and to reprecipitate with dilute acid almost without loss. The conversion of the orthohydroxyamino-naphthalene-carboxylic acids to the ortho-naphthoquinone-diazide-carboxylic acid results in an almost quantitative yield. The hitherto unknown ortho-naphthoquinone diazide-carboxylic acid chlorides are easily obtainable according to the invention by the action of thionyl chloride on the carboxylic acids. This is very surprising, considering the instability of the diazido compounds used as starting products and the reactivity of the diazide group in relation to inorganic acid chlorides. It was to be expec- ted that compounds incapable of coupling or compounds coupling in a different way would be formed, having no longer the properties of ortho-quinone-diazides. Such decomposition and conversion rections do in fact occur through the action on ortho-naphthoquinone-diazide-carboxylic acids of other chlorinating agents normally used in the production of organic acid chlorides, for instance phosphorus oxychloride, phosphorus trichloride and phosphorus pentachloride. A smooth course of the reaction using thionyl chloride in their place could therefore not be foreseen. An excess of thionyl chloride is used, so that at the same time it acts as a solvent. When t ? le reaction is completed the acid chlorides crystallize out in an almost pure state. For the reaction of the carboxylic acid and the thionyl chloride it is expedient to select temperatures below the boiling point of thionyl chloride, and those carboxylic acids which show a marked tendency to decompose during melting point determinations should be reacted for only a short time. With carboxylic acids which, during this test, give oS the diazide-nitrogen only after a period, reaction temperatures up to the boiling point of the solvent may be used without elimination of

nitrogen occurring, which has the avantage that the reaction can be effected more quickly. The ortho-naphthoquinone-diazide-carboxylic acid chlorides are relatively stable and very reactive, so that they can be reacted even with higher molecular aromatic hydroxy compounds, the hydroxyl groups of which do not react easily, and weak basic amines, to produce the corresponding esters and amides respectively. The aromatic esters and amides of orthonaphtho-quinone-diazide-carboxylic acids are technically valuable compounds. They y are suitable for the production of lightsensitive layers, particularly on metallic carriers. From the pre-sensitized material, which has an excellent shelf life, printing plates of high quality can be produced by photo-mechanical means. Several embodiments of the invention by way of example are set forth in the following examples, with reference to the chemical formulae shown in the accompanying drawings. EXAMPLE I 40 gms naphthoquinone- (l, 2)-diazide- (l)- carboxylic acid- (3), a compound known from the literature, is heated for 30 minutes with stirring, in 100 cc of thionyl chloride, to a temperature of 50 C.-60 C. The reaction mixture is then cooled and the naphthoquinone- (1, 2)-diazide- (1)-carboxylic acid chloride- (3) which has crystallized out. is filtered off, washed with a mixture of benzene and petroleum ether, and dried. Yield 38 gms, which is 87. 5% ouf the theoretical. The acid chloride forms brown crystals which, when heated rapidly, melt at 155C.-160'C. with decomposition. 5. 8 gms of this acid chloride, together with 2. 5 gms phenol and 5. 2 gms finely ground potassium carbonate in 30 cc benzene, are stirred for two hours at 50 C.-60 C. After cooling the reaction mixture, the liquid is filtered off. The residue is washed with water and dried. Yield 3. 0 gms which is 41% of the theoretical. Recrystallized from benzene, the naphthoquinone- (1, 2)- diazide-carboxylic acid ester, corresponding to formula 1, forms light brown crystals, melting at 148'C.-152'C. with decomposition. EXAMPLE II 9. 3 gms naphthoquinone-(1, 9) diazide-(l)- carboxylic acid chloride- (3), the preparation of which is described in Example I, is added to a solution ouf 5. 1 gms 7'-hydroxy-N(n-propyl)-C-(2)-ethyl naphtho-1', 2', 4, 5- imi- dazole in 40 cc pyridine and stirred for two hours at 40 C.-50 C. The reaction mixture is stirred into 1 : 1 hydrochloric acid. NaphthoquinoneP-diazide-(l)-carboxylic acid ester corresponding to formula 2, separates out, and is filtered off, washed and dried. Yield-4. 5 gms. which is 50% of the theoretical. The reaction product forms yellow crystals which have no well defined melting point.

EXAMPLE III 3.'oms naphthoquinone-(l, 9 iazide-(l)- carboxylic acid chloride- (3) (as produced, for example, as in Example I) are added to a solution of 2 gms C-naphthol in 20 cc pyridine and stirred for two hours at 45 C. The precipitate is filtered off, washed with sodium carbonate solution and subsequently with water, and then dried. Yield 3. 0 gms which is 64% of the theoretical. The reaction product, which corresponds to formula 3, is recrystallized from ethylene diichloride. Brown-yellow crystals are obtained, which melt at 181 C.-185 C. with decomposition. The esters which correspond to formula 4 and formula 5 may be produced in an analogous way by reacting naphthoquinone- (1, 9)-diazide-(l)-carboxylic acid chloride- (3) with p-nitrophenol or 4, 4'dihydroxydiphenyl. The compound corresponding to formula 4 forms yellow crystals melting at 153 C.- 155 C. with decomposition. The compound corresponding to formula 5 forms green-yellow crystals, melting at 184 C.-186 C. with decomposition. EXAMPLE IV l-amino-2-hydroxy-6-naphthoic acid is produced by coupling 2-hydroxy-6-naphthoic acid with diazotized aniline and subsequent reduction of the azo dyestuff thus produced (melting point 282 C. with decomposition) with sodium dithionite in alkaline solution. 10. 15 gms of this acid are dissolved in 90 cc dimethylformamide and, while stirring and cooling 32 cc of 16% hydrochloric acid are slowly added. The hydrochloride which precipitates is colourless and finely divided, and when 25 cc 2N-sodium nitrite solution are added dropwise, goes temporarily into solution. The green-yellow coloured naphthoquinone- (1, 2)-diazide- (l)-carboxylic acid (6) which soon precipitates is filtered off after two hours, washed with water, and dried at 40 C. After recrystallization of the reaction product from dioxane the naphthoquinone- (1, 2)-diazider-carboxylic acid-(6) is obtained in the form of a yellowish-brown coloured micro-crystalline powder, which melts at 166 C. with decomposition. 25 gms of this carboxylic acid are heated in 100 cc thionyl-chloride, with stirring, for 1--hours at a temperature of 50 C.-60 C. The reaction mixture is cooled and the naphthoquinone-(l, 9)-diazide- (1)-carboxylic acid chloride- (6) which crystallizes out is filtered off, washed with a mixture of benzene and petroleum ether and dried. Yield 20 gms which is 74% of the theoretical. The acid chloride forms light yellow crystals, melting at 165 C.-167 C. with decomposition. 4. 65 gms of this acid chloride are introduced into a solution of 1. 9 gms phenol in 40 cc of pyridine and the mixture is stirred for two hours at 40 C.-50 C. The reaction mixture is then stirred into 100 cc

acqueous hydrochloric acid (1 : 1), the precipitate which forms is filtered off, washed and recrystallized from ethanol. The quinonediazide-carboxylic acid ester corresponding to formula 6 forms light brown crystals, which melt at 143 C.-145 C. with decomposition. Yield 3. 9 gms which is 67% of the theoretical. EXAMPLE V l-hydroxy-5-naphthoic acid is nitrosated in an acetic acid solution with an aqueous sodium nitrite solution and the 2-nitrose compound formed is reduced with sodium dSthionite, to form l-hydroxy-2-amino-5naphthoic acid. To a solution of 13 gms of this amino compound in 100 cc dimethyl formamide, 40 cc concentrated hydrochloric acid and 10 cc of water are added and the mixture is cooled to 10 C. To the suspension as it forms 20 cc 4N-sodium nitrite solution are slowly added dropwise. This reaction mixture is stirred for about two hours, filtered off, and the residue is washed with water until free of acid. The naphthoquinone- (1, 2)-diazide- (2)-carboxylic acid- (5) so obtained is recrystallized from a mixture of dimethyl formamide and water, when yellow needles result, which, in a pre-heated bath, melt at 180 C. with decomposition. 3. 9 gms of the carboxylic acid described above are heated with 15 cc thionyl chloride for 60-90 minutes to about 40'C. The thionyl chloride is then distilled off under reduced pressure and the resulting naphthoquinone - (1,2) - diazide - (2) - carboxylic acid chloride-(5) is recrystallized from ethylene dichloride. Yellow crystals are formed which melt at 128~C.-131~C. with decomposition. Yield 3. 4 gms which is 80% of the theoretical. 10 gms of this acid chloride are introduced into a solution of 4. 5 gms of phenol in 150 cc of anhydrous pyridine and the reaction mixture is heated for two hours at 40'C.-45'C. The reaction mixture is then stirred into 300 cc of ice-cold aqueous hydrochloric acid (1 : 1), whereupon the resulting ester precipitates and stirring is continued until precipitation is complete. It is then filtered off, washed with water, recrystallized from ethanol, and dried. Yield 10 gms of naphthoquinone- (1, 2)-diazide- (2)-phenyl carboxylic acid ester- (5) corresponding to formula 7 melting at 1435C.-145eC. with decomposition. EXEMPLE VI 4. 5 gms naphthoquinone- (1. 2)-diazide- (2)- carboxylic acid- (3), the preparation of which is known, are added to 30 cc thionyl chloride and heated for 1 1\2 hours, while stirring, to 70~C.-75~C. The thionyl chloride is then distille off under reduced pressure and the residue is recrystallized'from ethylene dichloride. The naphthoquinone- (1, 2)-diazide- (2)-carboxylic acid chloride- (3) forms light brown crystals, melting at 160~C.-162~C. with decomposition. Yield 2.2 gms

which is 47% of the theoretical. 1. 15 gms naphthoquinone-(1, 2)-diazisde- (2)-carboxylic acid chloride- (3) are introduced into a solution of 0. 72 gms -napthol in 10 cc pyridine and stirred for two hours at 55 C. The naphthoquinone-(1, 2)-diazide- carboxylic acid ester corresponding to formula 8 which precipitates is filtered off, washed with methanol and dried. The yellow crystals melt at 190~C.-192~C. with decomposition. Yield 1.1 gms which is 65% of the theoretical. EXEMPLE VII 1,-hydroxy-4-naphthoic acid methyl ester is converted by nitrosation with nitrous acid in glacial acetic acid to 2-nitroso-1-hydroxy4-napthoic acid methyl ester, which is saponified in an alcoholic solution with dilute sodium hydroxide solution by moderate heating and is subsequently reduced to the 2amino-l-hydroxy-4-naphthoic acid. The hydrochloride of this amine-carboxylic acid is isolated. 23. 9 gms of this hydrochloride are dissolved in 200 cc dimethylformamide while stirring, and 60 cc concentrated hydrochloric acid and then 30 cc 4N sodium nitrite solution are added dropwise to the solution at 5GC.-10'C. After leaving the reaction mixture to stand for 1-2 hours, the precipitated crystals are filtered off. washed with water and dried. 15 gms which is 70",, of the theoretical yield, of naphthoquinone- (l, 2)- diazide- (2)-carboxylic acid- (4) are thus obtained, which melts in a pre-heated bath at 150-C. with decomposition. To prepare the chloride of naphthoquinone-(1,2)-diazide-(2)-carboxylic acid-(4), 5 gms of the acid together with 40 cc thionyl chloride are heated in a bath at 70'C. until no further hydrochloric acid comes off. and the acid is completely dissolved. This should be completed within about 10 minutes. When the reaction mixture is cooled in ice, the acid chloride crystallizes out in the form of fine needles. The liquid is filtered off. the residue is washed with a petroleum ether benzene mixture, and 3. 5 gms which is 65~ of the theoretical yield of naphthoquinone- (1. 2)- diazide- (2)-carboxylic acid chloride- (4) are obtained, melting at 150'C. with decomposition. For the preparation of the 8-naphthyl ester of formula 9. 20 gms of ~-napthol are dissolved in 200 cc of anhvdrous pyridine and 32 gms of the acid chloride described above are introduced into the solution. The reaction mixture is heated for one hour to about 50~C., when a clear solution is formed. On stirring the solution into ice-cold aqueous hydrochloric acid (I : 1) the ester which is formed separates out. It is filtered. washed consecutively with sodium carbonate solution, water and methanol and dried. 20 gms which is 62% of the theoretical xield of naphtho-

quinone-d. 2)-diazid'*-e-naphthy ! ester- (4) are obtained. melting at 148-C. with decomposition. EXAMPLE VIII 23 gms naphthoquinone- (1. 2)-diazide- (l)- carboxylic acid chloride- (3) the preparation of which is described in Example I. are dissolved in 60 cc dioxane. 3. 66 gms N-benzylaniline. dissolved in I Oecdioxane are added to the solution at 40 C.-50 C. After about 15 minutes the reaction liquid is filtered off from the precipitated N-benzvlaniline hydrochloride. The reaction product is obtained from the nitrate by the addition of water. when the naphthoquinone-(1.2)-diazide-(1)carboxylic acid-N-benzylanilide-(31 separates out. The reaction product which is oily at first becomes crystalline when triturated. By re-crystallization from ethanol the compound corresponding to formula 10 is obtained in the form of yellow crystals. melting at 157 C. with decomposition. The yield of the pure product is 0. 8 gms which is 21 .'. of theoretical. EXAMPLE IX 7. 0 gms naphthoquinone-(l,')-diazide-(l)- carboxylic acid chloride-(6). the preparation of which has been described in Example IV, are introduced into a solution of 5. 1 gms diphenylamine in 20 cc pyridine. After stirring the reaction mixture for two hours at about 40 C.-50 C., the precipitated reaction product is filtered off and recrystallized from ethanol. It forms yellow crystals with a melting point of 154 C.-156 C. and corresponds to formula 11. The yield is 5. 2 gms which is 47% of the theoretical. EXAMPLE X 60 gms 1-amine-2-ethoxy-naphthalene are dissolved in 400 cc pyridine, and 70 gms naphthoquinone-(1, 2)-diazide-(2)-calboxylic acid chloride- (5) the preparation of which has been described in Example V, are added to the solution while stirring. After leaving the reaction mixture to stand for one hour, the liquid is fiAtered off. {The residue is washed with ethanol and dried. The naphthoquinone- (1, 2)-diazide- (2)-carboxylic acid amide- (5) of formula 12 is obtained as a yellow substance. The yield is 65 gms which is 58% of the theoretical. Melting point after recrystallization from ethylene chloride is 210 C.-215 C. with decomposition. The compound darkens at 155 C.-158 C. By a method analogous to that specified above for the compound corresponding to formula 12, the naphthoquinons- (l, 2)-diazide-(2)-3-carboxylic acid amide of formula 13 is obtained from naphthoquinone- (l, 2)diazide-(2)-carboxylic acid chloride- (3) (com- pare Example VI) and 1-amino-2-ethoxy- naphthalene. This forms yellow crystals and melts at 174'C.-176'C. with decomposition. EXAMPLE XI

20 gms naphthoquinone-(1, 2)-diazide-(1)- carboxylic acid- (4) in 100 cc thionyl chloride are stirred for four hours at 30 C.-40 C. with the exclusion of moisture. The conversion to naphthoquinone- (1, 2)-diazide- (l)-carboxylic acid chloride- (4) is effected in suspension. The precipitated reaction product is filtered off and washed with petroleum ether. The yield amounts to 15 gms which is 69. 5% of the theoretical. The carboxylic acid chloride melts at 123'C. with decomposition. 14 gms of this carboxylic acid chloride are introduced into a solution of 10 gms of diphenylamine in 180 cc pyridine, and the suspension then formed is stirred for three hours at 40 C.-45'C. with the exclusion of moisture. The reaction mixture is poured into hydrochloric acid containing pieces of ice and the naphthoguinone-(1, 2)-sliazide-(1)- carboxylic acid amide- (4) of formula 14 thereby settles out as a yellow precipitate. The carboxylic amide is filtered off, washed well and dried. It is a yellow substance melting at 135 C. The yield is 16. 5 gms which is 71. 4% of the theoretical. What we claim is :- 1. A process for the production of acid derivatives of ortho-naphthoquinone-diazide- carboxylic acids, which process comprises treating an ortho-naphthoquinone-diazide- carboxylic acid with excess thionyl chloride to form the corresponding fortho-naphthoquinone-diazide-carboxylic acid chloride.


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