US3498790A

US3498790A - Diazotype material

Info

Publication number: US3498790A
Application number: US547799A
Authority: US
Inventors: Oskar Sus; Heinz Schafer
Original assignee: Keuffel and Esser Co
Current assignee: Keuffel and Esser Co
Priority date: 1965-05-08
Filing date: 1966-05-05
Publication date: 1970-03-03
Anticipated expiration: 1987-03-03
Also published as: BE680702A; SE326370B; GB1084487A; AT276082B; DK111472B; DE1693196B2; ES326442A1; FI44873B; DE1693196A1; FI44873C; NL6606213A; CH475577A; FR1478912A

Description

United States Patent 3,498,790 DIAZOTYPE MATERIAL Oskar Siis, Wiesbaden-Biebrich, and Heinz Schiifer, Wiesbaden-Sonnenberg, Germany, assignors to Keuifel & Esser Company, Morristown, NJ.

No Drawing. Filed May 5, 1966, Ser. No. 547,799 Claims priority, application Germany, May 8, 1965, K 56,062 Int. Cl. G03c 1/58, 5/22, 5/34 US. Cl. 96-91 14 Claims ABSTRACT OF THE DISCLOSURE The present invention relates to diazotype material and more particularly to light-sensitive diazonium compounds useful in the preparation of diazotype compositions.

It is known to use, for the preparation of lightsensitive diazotype material, i.e. material for photocopying processes which comprises a coating support, for example paper, and a reproduction coating adhering thereto, sensitising mixtures which contain as lightsensitive substances unilaterally diazotised p-phenylenediamine derivatives. As light-sensitive substances in such diazotype sensitising mixtures, great practical importance has been attained by diazo compounds which are derived from p-phenylenediamine and in which the amino group in para-position to the diazo group is tertiary. The essential suitability of the p-aminobenzenediazo compounds concerned for the preparation of so-called two-component material for the dry-development process, or of socalled one-component material for the semi-wet development process, is determined in each case by the nature of the substituents which may be adhering directly to the benzene ring or to the nitrogen of the tertiary amino group.

For the preparation of one-component diazotype material, those sensitising mixtures are well suited which contain p-aminobenzenediazo compounds with a tertiary amino group which are substituted on the tertiary nitrogen atom by an aralkyl radical, for example (and preferably) the benzyl radical. The presence of the aralkyl group in the diazo compound increases its coupling energy quite substantially compared with the coupling energy of a diazo compound with a purely aliphatic alkyl group instead of the aralkyl radical. The colour deepening which shows in photocopies prepared from one-component material sensitised with such diazo compounds is also attributable to the presence of the aralkyl group in the tertiary aminobenzenediazo compound. For the preparation of black copies by the diazotype process, material sensitized with l-N-(benzylethyl)-amino-4-di azobenzene is therefore used which, after exposure under the original, is treated with developer which is soluble in alkalis and contains phloroglucinol.

As is known, the above-mentioned behaviour in respect of increased coupling speed and colour deepening shows still more strongly in one-component material whose light-sensitive coating contains tertiary p-aminobenzenediazo compounds in which the aralkyl radical on the tertiary nitrogen atom is replaced by a phenoxyalkyl 3,498,790 Patented Mar. 3, 1970 radical. If these diazo compounds substituted by a phenoxyalkyl radical in the tertiary amino group also bear on the benzene nucleus substituents such as an alkyl or alkoxy radical or a halogen atom, their water-solu bility in sensitising mixtures, which, as is known, contain stabilisers, e.g. salts of metals, such as zinc chloride, or of naphthalenepolysulphonic acids, is greatly reduced. The keeping qualities of the sensitising mixtures suffer and, as a result of turbidity and resin-like precipitates, their suitability for the formation of the light-sensitive coating on the coating support also suffers. The objects of the invention are to provide improved diazotype material and to provide improved sensitising compositions suitable for the preparation of diazotype material which are free from the disadvantages explained above.

According to the present invention diazotype material is provided which comprises, as light-sensitive component, a diazo compound having the general formula:

wherein:

R is a hydroxyalkyl radical containing 2 to 4 carbon atoms;

R is an aryloxyalkyl or aryl thioalkyl radical in which the aromatic component may also be substituted;

R is a hydrogen atom or an alkyl or alkoxy or betahydroxyalkoxy group;

R is a hydrogen or halogen atom or an alkyl or alkoxy group; and X is an acid anion.

For the p-aminobenzenediazo compounds with tertiary amino group which conform to the general formula stated and which characterise the sensitising mixtures according to the invention, the hydroxyalkyl radical adhering on the nitrogen of the amino group is characteristic. Compared with the tertiary p-aminobenzenediazo compounds previously mentioned, they are at least equal to these in respect of light-sensitivity, coupling speed and tinctorial power, but in respect of water-solubility, particularl in combination with the stabilisers usual in diazotype sensitising mixtures, are substantially superior. The sensitising mixtures according to the invention therefore permit the addition of stabilisers in such large amounts that the shelf life of the one-component material sensitised with them is excellent, even under tropical conditions.

A further substantial advance based on the invention is to be seen in the fact that the dyes which are formed on the photocopies prepared from the diazotype material prepared with the sensitising mixtures according to the invention are substantially more insensitive to changes in pH-value and therefore have a much lesser tendency to change of colour. The photocopies which are prepared with the use of the one-component material prepared with the sensitising mixtures according to the invention can be developed with alkaline solutions or, if the benzene nucleus of the diazo compound according to the invention which is present as lightsensitive substance bears substituents which accelerate coupling, also with a neutral or acid solution.

It may be advantageous to also add to the sensitising mixtures according to the invention diazo compounds which are already in use for the sensitising of one-component diazotype material. The coating supports on which the light-sensitive coating is formed with the sensitising mixtures according to the invention are the 3 ;supports with a hydrophilic surface which are commonly .used in diazotype processes.

The diazo compounds according to the above general formula which characterise the sensitising mixtures according to the invention are new. They are obtained according to known methods. In the table, the formulae of some representatives of these compounds are set forth as examples. Their preparation is described below.

PREPARATION OF THE COMPOUND OF FORMULA (I) 160.75 g. of l-N-(beta-hydroxyethyl-beta-phenoxyethyl)-amino-2-methoxy-5-chlorobenzene are dissolved in 1130 ccm. of 34% sulphuric acid. To this solution are added dropwise, at an initial temperature of 26 C., 20.8 ccm. of nitric acid (1.52). Towards the end of the dropwise addition, at 36 C. the nitro compound which is formed begins to crystallise out as sulphuric acid salt. As the temperature falls, the reaction mixture is stirred, then filtered with suction and well expressed under a press. The sulphate tends to split hydrolytically in the presence of water. The press cake is dissolved in about 1 litre of methanol (yellowish-red solution) and the solution rendered neutral with about caustic soda solution, with good stirring. Filtering with suction is effected from the precipitated salt, the salt is washed with a little methanol and Raney nickel is added to the weakly alkaline solution (pH 8). Reduction proceeds at between 20 and 40 C. The initially colourless amine solution is freed from nickel and to the 1-N-(beta-hydroxyethyl-beta-phenoxyethyl)- amino-2-methoxy-4-amino-S-chlorobenzene there are immediately added 150 ccm. of fluoroboric acid (35'38% The solvent is evaporated in vacuo. A thick, brownish syrup remains behind. This is dissolved in 1.5 litres of fluoboric acid (35-38%) and the solution, heated to about C., is filtered over 20 g. of animal charcoal. After the addition of 500 ccm. of water, the solution is again filtered over 20 g. of animal charcoal to be then diazotised. Diazotisation is effected by slowly adding dropwise 64 ccm. of 40% solution of sodium nitrite. By rubbing on the glass wall of the diazotisation vessel there is achieved the immediate solidification in crystalline form of the initially oily diazo compound. To keep the diazotisation mixture stirrable, 1 litre of water is added to it, stirring is continued for 1-2 hours, and the crystal mass filtered with suction and dried. The crude yield is about 150 g.=% of the theory, calculated on the tertiary base. Purification is effected by dissolving 50 g. in ccm. of preheated isopropanol, adding 5 5 0 ccm. of water of 8085 C. to the solution and filtering the mixture at 7075 C. over 10 g. of animal charcoal. Melting point: 116 C., with decomposition.

PREPARATION OF THE COMPOUND OF FORMULA (II):

13.4 g. of l-N-(beta-hydroxyethyl-beta-phenoxyethyl)- amino-Z-ethoxy-S-chlorobenzene are dissolved in ccm. of 34% sulphuric acid and to this solution 1.84 ccm. of

nitric acid (1.52) are added dropwise at room temperature. The temperature rises to 32 C. The nitro compound (sulphuric acid salt) which separates out of the solution in the form of yellow drops of oil is separated from the aqueous liquid. From this the free base is obtained by treatment with n-solution of caustic soda. The nitro compound is now reduced catalytically with Raney nickel in methanolic solution. After reduction the solution, which contains oxidisable l-N-(beta-hydroxyethylbeta-phenoxyethyl)-amino-2-ethoxy-4-amino 5 chlorobenzene, is filtered off from the nickel and 150 ccm. of fluoboric acid (35-38%) and 50 ccm. of water are immediately added to it. The methanol is distilled off and the remaining amine solution filtered twice over animal charcoal and then diazotised by the dropwise additon of 5 ccm. of 40% solution of sodium nitrite. When rubbed, the oily, yellow diazo compound solidifies in crystalline form. After filtering with suction, the crude product is, in order to purify it, recrystallised from a little isopropanol with the addition of water and in this way yellow, long matted needles of the diazo compound are obtained with a melting point of 116 C., with decomposition. Yield: g.

PREPARATION OF THE COMPOUND OF FORMULA (III):

18 g. of l-N-(beta-hydroxyethyl-beta-phenoxyethyl)- amino-2-hydroxyethoxy-5-chlorobenzene are dissolved in 130 com. of 34% sulphuric acid and to this solution 2.36 ccm. of nitric acid (1.52) are added dropwise at room temperature. The temperature rises slowly to 32 C. When water is added to the yellow solution the nitro compound separates as a yellow, greasy mass which becomes crystalline when rubbed. For purification, the crude product is dissolved in chloroform and reprecipitated by adding petroleum ether. Yellow crystals with a melting point of 103-104 C. are obtained. Yield: g.

12 g. of the nitro compound, dissolved in 200 ccm. of methanol, are reduced catalytically by means of Raney nickel. To the solution, filtered off from the nickel, are added 150 ccm. of fluoboric acid (35-38% The methanol is distilled off, the amine solution filtered over animal charcoal and, for diazotisation, 15 ccm. of 2 N solution of sodium nitrite are added to it dropwise. The diazo compound from l-N-(beta-hydroxyethyl-beta-phenoxyethyl)- amino-2-hydroxyethoxy-4-amino-5 chlorobenzene forms yellow crystals, which are filtered with suction and, for purification, recrystallised from about 200 ccm. of water at 60 C. Yield: 10 g. Melting point: 107l08 C., with decomposition.

PREPARATION OF THE COMPOUND OF FORMULA (IV):

30 g. of l-N-(beta-hydroxyethyl-beta-phenoxyethyl)- amino-2-methoxybenzene are dissolved in 300 ccm. of glacial acetic acid and, with stirring and cooling, slowly nitrated with 100 ccm. of 40% solution of sodium nitrite added dropwise. The time taken for the dropwise addition is about 4 hours. The nitrating mixture is then stirred for a further 10 hours. The oily nitro compound precipitates from the yellow solution when water is added, and is absorbed in methylene chloride. After the solution has been rendered neutral by shaking out with soda solution, the dried methylene chloride is evaporated. 33 g. of yellow, oily nitro compound remain behind, which are absorbed in 170 ccm. of methanol and reduced catalytically in the presence of Raney nickel. After it has been freed from the nickel, there are immediately added to the colourless amine solution 200 ccm. of fluoboric acid (3538% It is then, after evaporation of the methanol, diluted with 200 ccm. of water and filtered over animal charcoal. When diazotisation is effected with 50 ccm. of 2 N solution of sodium nitrite, the diazo compound from l-N-(beta-hydroxyethyl-beta phenoxyethyl) amino 2 methoxy-4-aminobenzene precipitates in crystalline form and, for purification, is recrystallised from a little isopropanol/water and then twice from water. Yellow crystals (yield: 15 g.) are obtained. Melting point: C, With decomposition.

PREPARATION OF THE COMPOUND OF FORMULA (V) To the solution of 17.3 g. of l-N-(beta-hydroxyethylbeta-phenoxyethyl)-amino 2,5 diethoxybenzene in 140 ccm. of approximately 16% hydrochloric acid is added dropwise a solution of 4-nitrobenzenediazonium chloride in hydrochloric acid. When the mixture is stirred and then stands in ice, a red dye precipitates in the form of the hydrochloric acid salt. This is filtered with suction and, for purification, recrystallised from glycolmonmethylether/ethanol. Yield: 21 g., melting point 190-191 C. By treatment of the dye with n-solution of caustic soda the dyes free base is obtained which is catalytically reduced in methanolic solution in the presence of Raney nickel, filtered off from the nickel after reduction, and freed from the solvent by evaporation. In order to remove p-phenylenediamine the oily amine which remains behind is shaken with water and then distilled in vacuo. Boiling point 241 C. (2 mm.). Yield of oily 1-N-(betahydroxyethyl-beta-phenoxyethyl) amino 2,5 diethoxy- 4-aminobenzenez 10 g. Of this compound, for diazotisation 6 g. are dissolved in com. of 16% hydrochloric acid, and 10 ccm. of 2 N solution of sodium nitrite are added to it. The yellow solution obtained is filtered over animal charcoal and the diazo compound precipitated by adding 5 ccm. of 50% solution of stannic chloride, filtered with suction and, for purification, dissolved in 700 ccm. of water with the addition of a little hydrochloric acid and filtered over animal charcoal. When 90 g. of sodium chloride and a few drops of stannic chloride solution are added the yellow diazo compound precipitates again and this is filtered with suction and dried. Yield: 5 g., melting point 102 C., with decomposition. Discolouration occurs at 70 C.

PREPARATION OF THE COMPOUND OF FORMULA (VI) 20.25 g. of l-N-(beta-hydroxyethyl-beta-phenylthioethyl)-amino-Z-methoxy-5-chlorobenzene are dissolved in a mixture consisting of ccm. of 34% sulphuric acid and 20 ccm. of glacial acetic acid, and nitrated by adding dropwise 2.75 ccm. of nitric acid (1.52). Upon the addition of water to the nitration mixture, the oily, yellow nitro compound is precipitated and this is separated with the aid of methylene chloride. From the dried solution there remains after evaporation of the methylene chloride 24 g. of oily, yellow nitro compound. 20 g. of this are absorbed in 200 ccm. of methanol and reduced in the presence of Raney nickel. The reduction mixture is filtered off from the nickel and the solvent evaporated from the filtrate. For the diazotisation, the oily l-N-(beta-hydroxyethyl-beta-phenylthioethyl)-amino 2 methoxy-4-amino- S-chlorobenzene is dissolved in 300 ccm. of approximately 8% hydrochloric acid. To this solution are added 20 ccm. of 2 N solution of sodium nitrite. The yellow diazo solution obtained is filtered over animal charcoal and the diazo compound precipitated out of the solution by the addition of 10 ccm. of 50% solution of stannic chloride and 50 g. of sodium chloride. The diazo compound is then filtered with suction and, for purification, dissolved in water and reprecipitated by adding sodium chloride. Yield: 10 g., melting point 9092 C., with decomposition.

PREPARATION OF THE COMPOUND OF FORMULA (VII) 22.6 g. of l-N-(beta-hydroxyethyl-beta-naphthoxy ethyl)-amino-2-methoxy-5-chlorobenzene are dissolved in 300 ccm. of glacial acetic acid and to this solution are added dropwise 50 ccm. of 40% solution of sodium nitrite. The nitro compound, which precipitates in oily form, is separated, freed from the glacial acetic acid by shaking with water and then reduced catalytically with Raney nickel in 200 ccm. of ethanol. After the solution has been filtered oil from the nickel, the solvent is evaporated from it and the l-N-(beta-hydroxyethyl-betanaphthoxyethyl)-amino-2-methoXy-4-amino chlorobenzene which remains behind is, as crude product, absorbed in 300 ccm. of 16% hydrocloric acid and diazotised by adding dropwise 20 ccm. of 2 N solution of sodium nitrite. When 5 ccm. of 50% solution of zinc chloride are added, the diazo compound precipitates out of the yellow solution as zinc chloride double salt, which is purified by dissolving it in 700 ccm. of water and precipitating it with sodium chloride. Melting point: 100- 120 C., with decomposition.

PREPARATION OF THE COMPOUND OF FORMULA (VIII) 20.1 g. of 1-N-(beta-hydroxyethyl-beta-phenoxypropyl)- amino-Z-methoxy-S-chlorobenzene are dissolved in 120 ccm. of 34% sulphuric acid and nitrated by dropwise addition of 2.75 ccm. of nitric acid (1.52). In the course of this being done the temperature rises from 25 C. to 32 C. The initially oily nitro compound becomes solid (melting point 8488 C.) during further stirring. It is filtered with suction and dissolved in 200 ccm. of methanol. By neutralisation of the solution with N solution of caustic soda, sodium sulphate is precipitated from which the soluiton is filtered off and reduced catalytically with Raney nickel. After filtration from the nickel, the solvent is evaporated. The l-N-(beta-hydroxyethyl-betaphenoxy-propyl)-amino 2 methoxy-4-amino-S-chlorobenzene is dissolved in 250 ccm. of 35-38% fluoboric acid and diazotised with 25 ccm. of 2 N solution of sodium nitrite. The initially oily diazo compound becomes solid during further stirring. It is filtered with suction and, for purification, recrystallised from 600 ccm. of water. The yellowish-orange coloured product has a melting point of 112-l14 C., with decomposition. Yield: 10 g.

PREPARATION OF THE COMPOUND OF FORMULA (IX) By reaction of 30 g. of beta-phenoxyethyl-aniline (Clemo, Perkin Chem. Soc., London, volume 121, page 645) with propylene oxide, advantageously at an initial pressure of 5 atmospheres gauge nitrogen, 3.3 g. of 1- N- (beta-hydroxypropyl-beta-phenoxyethyl)-aniline is obtained which boils at 178-181 C. (1.5 mm.). 33 g. of this tertiary base are dissolved in 80 ccm. of glycolmonomethylether and 250 ccm. of 30% sulphuric acid. To this solution 26.4 ccm. of 40% solution of sodium nitrite are added dropwise at 10 C. in the course of one hour. The nitro compound formed remains in solution and is reduced by addng a total of 31 g. of Zinc dust at 2530 C., with ice cooling. The colourless reduction solution is filtered and then rendered strongly alkaline with 10 N solution of caustic soda. The l-N-(beta-hydroxypropyl-beta phenoxy- 8 PREPARATION OF THE COMPOUND OF FORMULA (X) of methanol. The solution is rendered neutral with 10 N solution of caustic soda and filtered off from the precipitated sodium sulphate. Raney nickel is added for the the catalytic reduction of the nitro compound. After reduction, the solution is filtered off from the nickel, the solvent evaporated and the oily l-N-(beta-hydroxyethylbeta-4-chlorophenoxyethyl) amino-2-methoxy-4-amino- 5-chlorobenzene absorbed in 300 ccm. of 16% bydrochloric acid. Diazotisation of the last-named compound is eifected by dropwise addition of 23 ccm. of 2 N solution of sidium nitrite. The diazo compound precipitates out of the yellow solution when 5 ccm. of 50% solution of stannic chloride are added. For purification it is reprecipitated by dissolving it in water and adding sodium chloride. Yield: 16 g. Melting point: C., with decomposition. Sintering occurs around 75 C.

PREPARATION OF THE COMPOUND OF FORMULA (X1) 107 g. of 2-toluidine are heated to the boil together with 60 ccm. of water and 0.5 g. of sodium diisobutylnaphthalenesulphonate. 110 g. of bromoethylphenylether are added dropwise to the mixture in 2 hours, with stirring, and stirring is continued for a further 15 hours. The reaction mixture formed is twice shaken out with water, with the addition of methylene chloride. After separation of the aqueous layer, the solvent is evaporated from the reaction product and the oily residue which remains is distilled in vacuo. The yield of 1-N-(beta-phenoxyethyl)- amino-2-methylbenzene is 70 g., and the boiling point at 2 mm. pressure is 168-171 C.

35 g. of l-N-(beta-phenoxyethyl)-amino-2-methylbenzene together with ccm. of methanol and 62 ccm. of ethylene hydroxide are heated for 4 hours to 100 C. at an initial pressure of 5 atmospheres nitrogen in a /2 litre rocking autoclave. The solvent is evaporated from the reaction mixture and the oily residue distilled in vacuo. The l-N- (beta-hydroxyenthyl-beta-phenoxyethyl)- amino-2-methylbenzene obtained boils at -187 C. at a pressure of 2 mm. The yield is 36 g.

23 g. of the above-mentioned tertiary base are dissolved in 160 ccm. of 16% hydrochloric acid and coupled to form a dye with diazotised p-nitroaniline in the presence of pyridine. By catalytic reduction of the dye obtained, 1 N (beta-hydroxyethyl-beta-phenoxyethyl) amino-2- methyl-4-aminobenzene with a boiling point of 232- 234 C. at a pressure of 2 mm. is arrived at.

6 g. of this mono-tertiary diamine are dissolved in 100 ccm. of 16% hydrochloric acid and diazotised with 10 ccm. of 2 N solution of sodium nitrite. The yellow diazo solution obtained is filtered over charcoal and 4 g. of cadmium chloride are added to it. The diazo compound separates in greasy form and, for purification, is filtered as aqueous solution over charcoal and precipitated with sodium chloride. The crystals melt at 155l57 C., with decomposition.

The diazo compounds of the present invention may be used in the normal manner as diazo components of diazotype compositions and diazotype material prepared therewith. Numerous available azo coupler components may be used to prepare developer solutions normally employed with one-component diazotype materials. The following examples set forth a few embodiments of the present invention.

beta-hydroxyethyl-beta-phenoxyethyl) amino 2- hydroxylethoxy 4-amino-5-chlorobenzene (Formula III) 1.8

and dried. After exposure of the sensitised paper under an original, a solution of Trisodium citrate 4.0 Trisodium phosphate 2.0 Borax 2.0 Phloroglucinol 0.6 Resorcinol 0.6 Sodium diisopropylnaphthalenesulphonate 0.1

in 100 ccm. of water is applied as a thin coating, approximately 10-15 g./m. A copy is obtained which shows strong, brown lines on a White background.

EXAMPLE 2 Transparent paper is coated with an aqueous solution which for each 90 ccm. of water contains:

Citric acid g 0.5 Sodium 1,3,6--naphthalenetrisulphonate g 3.5 Fluoboric acid salt of the diazo compound from 1 N (beta hydroxyethyl beta phenoxyethyl)- amino 2 methoxy 4 aminobenzene (Formula IV) g 3.2 Triglycol ccm 2.5 Isopropanol ccm 5.0

and, dried. After exposure of the sensitised paper under an original the latent image which is formed is developed with the solution stated in Example 1 containing phloroglucinol and resorcinol. Copies with dark brown lines on a transparent background are obtained. The copies are suitable as intermediate originals for further photocopying.

, EXAMPLE 3 White photocopying base paper with a precoat consisting of colloidal silicic acid and polyvinyl acetate is coated with an aqueous solution which in 95 ccm. of water contains:

Tartaric acid g 0.5 Sodium 1,3,6-naphthalenetrisulphonate g 3.5 Saponin g 0.02 Fluoboric acid salt of the diazo compound from 1- N (beta hydroxyethyl-beta-phenoxyethyl)-amino 2 methoxy-4-amino-5-chloro-benzene (Formula I) g 1.8 Zinc chloride double salt of the diazo compound from 1- (4-rnethylphenyl -mercapto-2,5-diethoxy- 4-aminobenzene g 0.2 Isopropanol ccm 5.0

The dried, sensitised paper, after exposure under an original, is developed with a solution of:

Sodium benzoate 2.4 Sodium adipate 2.0 Trisodium citrate 9.0 Adipic acid 0.2 Sodium chloride 5 .0

Phloroglucinol 0.35

in 100 ccm. of water, Photocopies with deep black lines on a white background are obtained.

10 The same result is obtained with the fluoboric acid salt of the diazo compound from l-N-(beta-hydroxyethylbeta-phenoxyethyl)amino-2-ethoxy-4-amino 5 chlorobenzene (Formula II).

EXAMPLE 4 White photocopying base paper, which is provided with a precoat consisting of colloidal silicic acid and polyvinyl acetate, is coated with an aqueous solution which for each com. of water contains:

Sodium 1,3,6-naphthalenetrisulphonate g 4.0 Citric acid g 0.5

Of the diazo compound from l-N-(beta-hydroxyethyl-beta-phenoxyethyl)-arnino 2,5 diethoxy-4- aminobenzene (Formula V) in the form of its double salt with stannic chloride g 1.8 Isopropanol ccm 5.0

and dried. The paper, exposed under an original, is treated with the alkaline developer solution described in Example 1 containing phloroglucinol and resorcinol. A copy with very dark brown lines on a white background is obtained.

EXAMPLE 5 White photocopying base paper as used in Example 4 with a precoat of colloidal silicic acid and polyvinyl acetate is coated with an aqueous solution which contains for each 95 ccm, of water:

Sodium 1,3,6-naphthalenetrisulphonate g 4.0

Citric acid and g 0.5

Stannic chloride double salt of the diazo compound from 1 N (beta-hydroxyethyl-beta-phenylthioethyl)-amino-2-methoxy-4-amino 5 chlorobenzene (Formula VI) g 1.8 Isopropanol ccm 5.0

and dried. The paper, exposed under an original, is developed with the developer solution stated in Example 3. A copy with blue-black lines on a white background is obtained.

EXAMPLE 6 White photocopying base paper, which is provided with a precoat consisting of colloidal silicic acid and polyvinyl acetate, is coated with an aqueous solution which for each 95 ccm. of water contains:

Citric acid g 4.0

Zinc chloride double salt of the diazo compound from 1 N (beta-hydroxyethyl-beta-naphthoxyethyl)-amino 2 methoxy-5-chloro-4-aminoben- Zene (Formula VII) g 2.0

Isopropanol ccm 5.0

and dried, The paper, exposed under an original, is developed with the developer solution used in Example 3. A copy with blue-black lines on a white background is obtained.

If the developer solution described in Example 1, containing phloroglucinol and resorcinol, is used for the development of the exposed paper, a copy with very dark brown lines is obtained.

Equal results are obtained with photocopying paper which is prepared with the use (as light-sensitive substance) of the compounds with Formula VIII (borofluoride of the diazo compound from l-N-(beta-hydroxyethyl-beta-phenoxypropyl-amino-2-methoxy 5 chloro- 4-aminobenzene) or Formula IX, (stannic chloride double salt of the diazo compound from l-N-(beta-hydroxypropyl-beta-phenoxyethyl)-amino-4-aminobenzene) or Formula XI (cadmium chloride double salt of the diazo compound from l-N-(beta-hydroxyethyl-beta-phenoxyethyl)- amino-2-methyl-4-aminobenzene) EXAMPLE 7 V A white photocopying base paper loaded with baryta is coated with an aqueous solution which contains for each 95 ccm. of water:

Citric acid g 4.0

Stannic chloride double salt of the diazo compound from 1 N (beta-hydroxyethyl-beta-chloro-phenoxyethyl) amino-2-methoxy -chloro-4-aminobenzene (Formula X) g 2.5

Isopropanol ccm 5.0

and dried. From the paper, after it has been exposed under an original and developed with the developer described in Example 3 containing phloroglucinol, a copy with blue-black lines is obtained.

The foregoing examples have been presented for the purpose of illustration and should not be taken to limit the invention. It will be apparent that the described examples are capable of many variations and modifications which are likewise to be included within the scope of the present invention as set forth in the appended claims.

What is claimed is:

1. Diazotype material comprising a support and a light-Sensitive composition thereon comprising a lightsensitive diazonium component having the general formula:

wherein:

R is a hydroxyalkyl of 2 or 3 carbon atoms;

R is an aryloxalkyl or arylthioalkyl wherein the alkyl contains 2 or 3 carbon atoms;

R; is hydrogen, methyl, methoxy, ethoxy, or beta-hydroxy-ethoxy;

R is hydrogen, chlorine, or ethoxy; and

X is an anion of an acid.

2. Material according to claim 1 wherein said diazo component is 2 chloro 4-(N-B-hydroxyethyl-N-fl-phenoxyethyl) amino 5 methoxy benzene-diazoniumborofluoride.

3. Material according to claim 1 wherein said diazo component is 2 chloro 4 (N-fi-hydroxyethyl-N-fiphenoxyethyl) amino 5 ethoxy benzene diazoniumborofluoride.

4. Material according to claim 1 wherein said diazo component is 2 chloro 4 (N-fl-hydroxyethyl-N-[S- phenoxyethyl) amino 5 hydroxyethoxy benzenediazonium borofiuoride.

5. Material according to claim 1 wherein said diazo component is 4 (N ,8 hydroxyethyl-N-fi-phenoxyethyl) amino 5 methoxy benzene diazonium-borofluoride.

6. Material according to claim 1 wherein said diazo component is 2,5 diethoxy 4 (N-B-hydroxyethyl-N-B- phenoxyethyl) amino benzene diazonium chloride- 811014.

7. Material according to claim 1 whereinsaid diazo component is 2 chloro 4 (N f3 hydroxyethyl-N-fiphenylthioethyl) amino 5 methoxy benzenediazonium-chloride- SnCl 8. Material according to claim 1 wherein said diazo component is 2 chloro 4 (N-B-hydroxyethyl-N-B- naphthoxyethyl) amino 5 methoxy benzene diazonium-chloride ZnCl 2.

9. Material according to claim 1 wherein said diazo component is 2 chloro 4 (N-fi-hydroxyethyl-N-yphenoxypropyl) amino S-methoxy-benzene-diazoniumborofluoride.

10. Material according to claim 1 wherein said diazo component is 4-(N-fl-hydroxypropyl-N-fi-phenoxyethyl)- amino-benzene-diazonium-chloride-SnCl 11. Material according to claim 1 wherein said diazo component is 2 chloro 4-(N-fl-hydroxyethyl-N-fi-4'- chloro phenoxyethyl) amino 5 methoxy-benzenediazonium-chloride SnCl 12. Material according to claim 1 wherein said diazo component is 3 methyl-4-(N-fi-hydroxyethyl-N-fi-phenoxyethyl) amino-benzene-diazonium-chloride-CdCl 2.

13. Diazonium salt having the general formula:

wherein R is a hydroxyalkyl of 2 or 3 carbon atoms;

R is an aryloxyalkyl or arylthioalkyl wherein the alkyl contains 2 or 3 carbon atoms;

R is hydrogen, methyl, methoxy, ethoxy, or beta-hydroxy-ethoxy;

R is hydrogen, chlorine, or ethoxy; and

X is an anion of an acid.

14. Diazonium salt according to the formula in claim 13, wherein:

R is beta-hydroxyethyl,

R is beta-phenoxyethyl or gamma-phenoxypropyl,

R is methoxy or ethoxy,

R is H or Cl, and

X is the anion of fluoboric acid or the chloride ion in double salt combination with stannic chloride.

References Cited UNITED STATES PATENTS 2,529,464 11/1950 Von Glahn et a1. 969l 2,833,649 5/1958 Sus et a1. 9691 3,294,541 12/1966 Werner et al. 9691 FOREIGN PATENTS 711,390 6/1954 Great Britain. 867,630 5/ 1961 Great Britain.

OTHER REFERENCES Vander Grinten Bulletin, December 1962, pp. 1-7 relied on.

NORMAN G. TORCHIN, Primary Examiner C. BOWERS, Assistant Examiner US. Cl. X.R.