DE1249682B - Photosensitive copying material with p-phenylenediamine derivative diazotized on one side as a photosensitive substance - Google Patents

Description

UNION REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

G 03 c

German class: 57 b-12/05 ΊZ> Q ή Ο

Number: 1 249 682

File number: K 51523 IXa / 57b

Filing date: December 3, 1963

Opened on: September 7, 1967

The subject of the main patent 1266 879 is a light-sensitive copying material which, as a light-sensitive substance, contains at least one derivative of contains unilaterally diazotized p-phenylenediamine with an alkoxy group in the m-position to the diazo group, characterized in that the derivative of the general formula

0 (CHJn (COV-Z

in which R _{1 is} an alkyl group with at most 4 carbon atoms, R _{2 is} an alkyl group with at most 4 carbon atoms or an aralkyl group with at most 10 carbon atoms, or R ₁ and R ₂ together with the nitrogen atom N to which they are attached are a hererocyclic group which can carry one or more substituents, and also Z is an alkoxy group, an arylated alkoxy group or an aryloxy group or the group

Photosensitive copying material with p-phenylenediamine derivative diazotized on one side as
photosensitive substance

Addendum to the patent: 1 226 879

Applicant:

Kalle Aktiengesellschaft,
Wiesbaden-Biebrich, Rheingaustr. 190-196

Named as inventor:

Dr. Herbert Rauhut,

Dr. Oskar Süs, Wiesbaden-Biebrich

R ₄

—N:

in which R ₄ and R _{6 are} each an alkyl group with a maximum of 4 carbon atoms or, together with the nitrogen atom to which they are bonded, form a heterocyclic group which can carry one or more substituents, X is hydrogen, halogen or the methyl group, Y the Anion of an acid, η is an integer from 1 to 4 and m is 0 or 1, and in which the sum η - \ - m is at least 2.

The object of the present invention is to provide a diazotype material that is very good Light sensitivity is characterized by particularly good stability.

The subject matter of the present invention is based on a copy material according to patent 1,226,879, and is characterized in that, according to general formula 1, an alkyl mercapto group or the group

denotes in which R _{3 represents} hydrogen or a hydroxyalkyl group with at most 4 carbon atoms and R _{4 represents} an alkyl group or hydroxyalkyl group each with at most 4 carbon atoms.

This diazotype material, like the diazotype material of the main patent, is very good Photosensitivity is characterized by particularly good stability and, like this, can be used for both dry and can also be used for the semi-wet process.

If Z is an alkyl mercapto group, the alkyl group is preferably a lower alkyl group and m is preferably 0.

The diazo compounds are new and are generally available as diazonium chlorides in the form of Double salts with metal halides, for example zinc chloride or cadmium chloride, are used. Other Salts, e.g. B. sulfates, phosphates or boron fluorides can also be used.

The diazo compounds can be prepared in a simple manner using methods known from the literature Methods especially when compounds are desired which are in the p-position to the diazo group have a heterocyclic ring. In this case, e.g. B. 2-chloro-5-nitrophenol with an o-bromodialkylthioether reacted in the presence of alkali, the chlorine atom of the resulting thioether against a secondary nitrogen containing heterocyclic

709 640,499

Exchanged base, reduced the nitro compound and then diazotized the reduction product.

If a p-dialkylaminodiazo compound is to be used in the diazotype material according to the invention, so one can start from o-nitrophenol, which is etherified in the desired manner. the The resulting nitro compound is reduced and dialkylated in a known manner. The introduction of the amino group the p-position to the dialkylamino group is then achieved by coupling with a diazo compound and subsequent reductive cleavage of the resulting azo dye or by reducing the corresponding nitroso or nitro compound which has previously been obtained in a known manner. This is followed by the reaction with nitrous acid to form the diazo compound.

In the examples, the unit of volume is 1 ecm if 1 g is selected as the unit of weight. The appendix shows the formulas of some of the new diazonium salts used according to the invention. The melting points of these diazonium salts underlying nitro compounds (nitro group in the para position to - NR ₁ R ₂ group) are: 1) 81 ⁰ C, 2) 42 ° C, 3) 54 ° C, 5) 117 ⁰ C, 6 ) 92 ° C.

The numbers 1) to 6) agree with the numbers in the formulas in the system. The nitro compound according to 4) represents an oil.

example 1

30th

A layer support made of paper, which is common in diazotype printing, and which is coated on one side with a primer made of colloidal Silicic acid and polyvinyl acetate is provided with a solution on the pre-painted surface coated, which in 100 parts by volume of water contains 3.5 parts by weight of citric acid, 3.5 parts by weight of boric acid, 5.0 parts by weight of thiourea, 1.2 parts by weight of 3,5-dihydroxy-4-bromobenzoic acid amide, 2.3 parts by weight of the diazo compound from 1-amino-4-pyrrolidino-3 - [((3-ethylamino) ethoxy] benzene (in the form of the hydrochloric acid zinc chloride double salt) (Formula 1).

After drying, the sensitized base paper becomes imagewise under a transparent template exposed and developed with ammonia. You get red pictures on a white background. The copy papers have a very good shelf life.

The diazo compound used is obtained as follows: In a mixture of 560 parts by weight of ethylene bromide and 200 parts by volume of glycol monomethyl ether, a solution of 260 parts by weight of 2-chloro-5-nitrophenol in 150 parts by volume of NaOH (40 ° / ₀ ig), 350 parts by volume, is added at the boiling point with stirring Water and 550 parts by volume of glycol monomethyl ether were added dropwise within an hour. The mixture is kept at the boil for 1 hour while stirring, evaporated to dryness in vacuo, the residue is treated with water, filtered off with suction and recrystallized from methanol. This gives 232 parts by weight of 2-chloro-5-nitrophenyl / 3 bromäthyläther having a melting point of 77-78 ⁰ C. Of 120 parts by weight in 250 parts by volume of dioxane and treated within 3 hours in 360 parts by volume Äthylaminlösung (40%> aqueous ) and 150 parts by volume of dioxane were added dropwise with ice cooling and the mixture was stirred overnight at room temperature. It is then made strongly acidic with hydrochloric acid, separated from the undissolved material, concentrated in vacuo, made alkaline with NaOH and extracted with ether. The ether solution is dried and the ether evaporates from it. After recrystallization from gasoline, 65 parts by weight of 2-chloro-5-nitrophenyl - /? - ethylaminoethyl ether with a melting point of 64 ° C. are obtained.

65 parts by volume of the abovementioned compound are mixed with 65 parts by volume of pyrrolidine and 13 parts by volume of water, the mixture is refluxed for 3 hours and, after cooling, poured onto water. The residue is filtered off with suction and washed with water. Recrystallization from methanol. Yield 60 parts by weight with a melting point of 8I ⁰ C. 60 parts by weight of the 5-nitro-2-pyrro-iidino-phenol-ß-äthylarninoäthyläthers are dissolved in 200 ml hydrochloric acid (concentrated), reduced with zinc dust, brought to 800 parts by volume with ice water and mixed with 38 parts by volume of sodium nitrite solution (40 ° / ₀ ig) between 0 and 5 ° C diazotized.

There are 35 parts by weight of the diazo compound, which crystallizes very well, in the form of its hydrochloric acid Zinc chloride double salt isolated.

Example 2

A substrate made of paper, which is customary in the diazotype, is coated with a solution which is in 100 parts by volume of water, 0.4 parts by weight of tartaric acid, 0.4 parts by weight of aluminum sulfate, 2.2 parts by weight the diazo compound from l-amino ^ -piperidino-S - [(ß-ethylmercapto) -ethoxy] -benzene (in the form of the zinc chloride double salt) Formula 4) contains.

After drying, the sensitized paper is exposed imagewise under a transparent original and developed with a solution that in 100 parts by volume of water contains 2.5 parts by weight of borax and 3 parts by weight Soda, 2 parts by weight of table salt, 5 parts by weight of thiourea, 0.1 part by weight of sodium isopropylnaphthalene sulfonate, Contains 0.6 parts by weight of phloroglucinol, 0.6 parts by weight of resorcinol.

High-contrast, brown images are obtained on a white background.

The diazo compound is obtained as follows: 125 g of 2-chloro-5-nitrophenot are dissolved in 400 ml of methyl glycol with 28 parts by weight of NaOH in 75 parts by volume of water and 122 parts by weight of 2-ethylmercapto-bromoethane added and heated to boiling for 3 hours with stirring. After cooling, the solution becomes Poured onto ice water, suction filtered and the residue dried. Yield: 148 parts by weight. The melting point of the resulting 2-chloro-5-nitrophenyl - /? - äthylmercaptoäthyläthers is 52 ° C.

48 parts by weight of this compound are combined with 80 parts by volume of piperidine and 10 parts by volume of water Poured over and heated to boiling under reflux for 24 hours. After cooling it is poured onto ice water poured, absorbed in ether, separated from the water and the ether evaporates. That from the oily Product obtained residue is purified by redissolving from HCl / NaOH. Yield: 38 parts by weight. The diazo compound can be prepared as usual from the nitro body after reduction and diazotization.

Example 3

A substrate made of paper, which is customary in the diazotype, is coated with a solution which is in 100 parts by volume of water, 4 parts by weight of citric acid, 5 parts by weight of thiourea, 3 parts by weight Aluminum sulfate, 3.5 parts by weight naphthalene-1,3,6-

sodium trisulfate, 2 parts by weight of 2-hydroxy-3-naplithoic acid / 5-aminoethylamide (in the form of the hydrochloric acid salt), 2.5 parts by weight of the diazo compound from l-amino-4-pyrrolidmo-3 - [(| S-dihydroxyäthylamino) ethoxy] benzene (in the form of the hydrochloric acid zinc chloride double salt) (formula 5).

The procedure described in Example 1 is followed and blue images are obtained on a white background. The diazo compound is obtained as follows:

115 parts by weight 2-0110 ^ 5-110 ^ x ^ 1161 ^ 1- / 3- ^ 0111-ethyl ether (see. Example 1) are heated with 130 parts by weight of diethanolamine and 40 parts by volume of water with stirring on the steam bath for 3 hours, then with water diluted, filtered off with suction, washed with water and recrystallized from dilute alcohol. Yield 78 g of melting point 113 ⁰ C. 61 parts by weight of 2-chloro-5-nitrophenyl / 3 dihydroxyäthylaminoäthyläther are heated in 80 parts by volume of pyrrolidine and 10 parts by volume of water for 3 hours boiling under reflux, then poured onto ice water, suction filtered, washed with water and recrystallized from methanol. Yield 67 g; Melting point 117 ° C.

From 32 parts by weight of 5-nitro-2-pyrrolidinophenyl - /? - dihydroxyethylaminoethyl ether 38 parts by weight of diazo compound are obtained after zinc dust reduction in hydrochloric acid solution by diazotization under the usual conditions.

Claims (1)

Claim: Photosensitive copying material which, as photosensitive substance, contains at least one derivative of unilaterally diazotized p-phenylenediamine with an alkoxy group in the m-position to the diazo group holds, being the derivative of the general formula
O (CH ₂ ) "(CO) _m -Z N ₃ Y in which R _{1 is} an alkyl group with at most 4 carbon atoms, R _{2 is} an alkyl group with at most 4 carbon atoms or an aralkyl group with at most 10 carbon atoms, or R ₁ and R ₂ together with the nitrogen atom N to which they are attached are a heterocyclic group which can carry one or more substituents, X is hydrogen, halogen or a methyl group, Y is the anion of an acid, η is an integer from 1 to 4 and m is O or 1 and the sum η + m is at least 2 , according to Patent 1226 879, characterized in that Z is an alkyl mercapto group or the group —N: denotes in which R _{3 represents} hydrogen or a hydroxyalkyl group with at most 4 carbon atoms and R _{4 represents} an alkyl group or hydroxyalkyl group each with at most 4 carbon atoms. Considered publications:
German interpretative document No. 1 117 387. 1 sheet of drawings 709 640/499 8. 67 © Bundesdruckerei Berlin