DE1249683B - Photosensitive copying material with p-phenylenediamine derivative diazotized on one side as a photosensitive substance - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .: G 03 c

German KL: 57 b-12/05 /4 Z Ct / [Q

Number: 1 249 683

File number: K 51880IX a / 57 b

Filing date: January 18, 1964

Opened on: September 7, 1967

The subject of the main patent 1226 879 is a light-sensitive copying material which, as a light-sensitive substance, contains at least one derivative of Contains unilaterally diazotized p-phenylenediamine, which is characterized in that the derivative of general formula

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

Addendum to the patent: 1 226 879

^l \

O - (CH ₁ ) * - (CO) »- Z

Γ Λ- N ₉ Y

R,

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 to which they are attached form a heterocyclic 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

- N

Applicant:

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

Named as inventor:

Dr. Herbert Rauhut,

Dr. Oskar Süs, Wiesbaden-Biebrich

is characterized in that the derivative of the general formula

R ₁ ,

O - CH ₂ - CHOH - CH ₂

)> - N ₂ Y
X

in which R ₄ and R _{5 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 copy material that is very good Light sensitivity is characterized by particularly good stability.

The subject matter of the invention is based on a photosensitive copying material which contains as photosensitive substance at least one derivative of the unilaterally diazotized p-phenylenediamine with an alkoxy group in the m-position to the diazo group, at least 1 heteroatom in the form of ether groups or tertiary amino groups being introduced into this alkoxy group is, according to patent 1,226,879, and corresponds, in which R _{1 is} an alkyl group with a maximum of 4 carbon atoms, R _{2 is} an alkyl group with a maximum of 4 carbon atoms or an aralkyl group with a maximum of 10 carbon atoms or R ₁ and R ₂ together with the nitrogen atom N, to which they are bound form a heterocyclic group which may have one or more substituents, and Z is an alkoxy group, an arylated alkoxy group, an aryloxy group, an alkyl mercapto group, an aryl mercapto group or the group

- N

means in which R _{3 is} hydrogen, an alkyl group with a maximum of 4 carbon atoms, a hydroxyalkyl group with a maximum of 4 carbon atoms, R ₄ an alkyl group with a maximum of 4 carbon atoms, a hydroxyalkyl group with a maximum of 4 carbon atoms

709 640/500

represents atoms or an aralkyl group with at most 10 carbon atoms or R ₃ and R ₄ together with the nitrogen atom to which they are bonded form a heterocyclic group which can carry one or more substituents.

As an alkyl mercapto group, Z preferably represents a lower alkyl mercapto group and, as an aryl mercapto group, preferably represents the phenyl mercapto group, which can optionally be substituted by reaction-inert substituents, for example by lower alkyl groups or chlorine atoms. R ₃ and R ₄ as hydroxyalkyl groups preferably represent monohydroxyalkyl groups, but can also contain more than one hydroxy group. As an aralkyl group, R ₄ preferably represents the benzyl group, which may optionally contain lower alkyl radicals or other nuclear, reaction-inert substituents.

This diazotype material is identified like the diazotype material of the main patent 1,226,879 very good light sensitivity due to particularly good stability and is with additives and stabilizers, such as B. citric acid, thiourea, zinc chloride, naphthalene-l, 3,6-trisulfonic acid, well tolerated. It like this, it can be used for both the drying and the semi-wet process.

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 epichlorohydrin etherified in the presence of alkali and the epoxy ring in the ether side chain through suitable agents in which the desired radical Z is present, e.g. B. alcoholates, thiophenolates or amines, split up and substituted. Then the nuclear chlorine atom becomes a secondary one Nitrogen atom-containing heterocyclic base is exchanged, the nitro compound is reduced and then the Reduction product diazotized.

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 manner indicated above. The resulting nitro compound is reduced and dialkylated in a known manner. The introduction of the Amino group in the p-position to the dialkylamino group is then achieved by coupling with a diazo compound and subsequent reductive cleavage of the azo dye formed or by reduction the corresponding nitroso or nitro compound, which has previously been obtained in a known manner is. 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 annex shows the formulas of some of the new diazonium salts used according to the invention. The melting points in degrees Celsius of the nitro compounds on which these diazonium salts are based (nitro group in p-position to the -NR ₁ R ₂ group) are:

1) 94 °, 2) 92 °, 3) 92 °, 4) 198 ° (as HCl salt), 5) 108 up to 109 °, 6) 131 °, 7) 78/79 °, 8) 101 °.

Numbers 1) to 8) match the numbers in the formulas in the system.

example 1

A layer support made of paper, which is common in the diazotype, with a precoat of colloidal Silica and polyvinyl acetate is provided,

ίο is coated on the pre-painted surface with a solution which, in 100 parts by volume of water, 4.0 parts by weight of citric acid, 5.0 parts by weight of thiourea, 3.0 parts by weight of aluminum sulfate, 3.5 parts by weight of 1,3,6-naphthalenetrisulfonic acid, sodium 2.4 Parts by weight of 2,7-dihydroxynaphthalene-3,6-disulfonic acid sodium, 1.0 part by weight of zinc chloride, 2.3 parts by weight of the diazo compound from 1 - amino - 4 - pyrrolidino - 3 - (γ - hydroxyäthylamino - /? - hydroxy-propoxy) - contains benzene in the form of the hydrochloric acid zinc chloride double salt (formula 6).

After drying, the sensitized paper is exposed imagewise under a transparent original and developed with ammonia. You get blue images on a white background. The copy papers are very good shelf life.

The diazo compound used is obtained as follows: 173 parts by weight of 2-chloro-5-nitrophenol are dissolved in 250 parts by volume of methyl glycol, treated with 276 parts by weight of epichlorohydrin and up to almost heated to the boil. When 100 parts by volume of 40% sodium hydroxide solution are gradually added dropwise The solution then boils without further heating from the outside. After everything has dripped in, it will still be Heated under reflux for 1 hour. Then the still warm solution is filtered and 100 parts by volume are added Water, cools well and sucks off the resulting precipitate. This is dried and off Recrystallized methanol. Yield 183 parts by weight with a melting point of 93 ° C.

45 parts by volume of the 2-chloro-5-nitrophenylglycidether obtained in this way in 100 parts by volume of dioxane are converted into a solution of 120 parts by weight of ethanolamine in 100 parts by volume of dioxane while cooling with ice Stir dropwise within 2 hours. The solution is then left at room temperature for 15 hours stand, then pours it on water, sucks off the resulting precipitate and dries. Raw booty 55 parts by weight of l-nitro-4-chloro-3- (γ-hydroxyethylamino - /? - hydroxypropoxy) benzene from melting point 132 to 133 ° C.

55 parts by weight of this intermediate product are combined with 70 parts by volume of pyrrolidine and 10 parts by volume Water heated to boiling for 3 hours, poured into water, filtered off with suction and recrystallized from methanol.

Yield: 40 parts by weight of l-nitro-4-pyrrolidino-3 - (γ - hydroxyethylamino-β - hydroxy - propoxy) benzene with a melting point of 131 ° C.

40 parts by weight of l-nitro-4-pyrrolidino-3- (γ-hydroxyethylamino- β- hydroxy-propoxy) -benzene are converted into 1 - amino - 4 - pyrrolidino - 3 - in 86 parts by volume of concentrated hydrochloric acid and 40 parts by volume of water while cooling with ice with zinc dust. (γ - hydroxyäthylamino- / 3-hydroxy-propoxy) -benzene reduced. The filtered solution is then mixed with 37 parts by volume of hydrochloric acid and diazotized with 62 parts by volume of a 2N sodium nitrite solution while cooling with ice. The precipitated diazo compound is reprecipitated from water-common salt. Yield: 50 parts by weight.

Example 2

A layer substrate made of paper, which is customary in diazotype and which is provided on one side with a precoat of colloidal silica and polyvinyl acetate, is coated on the pretreated surface with a solution 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 - 2 '- diethylamino- ι ο anilide, 1.0 part by weight of zinc chloride, 2.2 parts by weight of the diazo compound of l-amino-4-pyrrolidino- 3 - (y - di - η - propylamino - β - hydroxy - propoxy) - benzene in the form of the hydrochloric acid zinc chloride double salt (formula 7).

The procedure described in Example 1 is followed and red images are obtained on a white background.

The diazo compound is obtained as follows: 45 parts by weight of 2-chloro-5-nitrophenyl glycidyl ether are heated with 60 parts by volume of di-n-propylamine on the steam bath for 3 hours. After that, on Given ice water and the precipitated product filtered off with suction and dried. Crude yield 55 parts by weight with a melting point of 41 to 42 ° C. Further processing succeeds in good yields in analogy to the manner described in Example 1.

Similar good results are obtained when using the compounds of the formulas 1 to 5 and 8, the can be prepared analogously to the compound of formula 6.

In formula 5 it is the N-n-butyl compound, in formula 7 it is the N-di-n-propyl compound.

Claims (1)

Claim: Photosensitive copying material which, as photosensitive substance, contains at least one derivative of p-phenylenediamine diazotized on one side with an alkoxy group in the m-position to the diazo group contains, in this alkoxy group at least 1 heteroatom in the form of ether groups or tertiary amino groups is introduced, according to patent 1 226 879, characterized in that the derivative of the general formula O - CH ₂ - CHOH - CH ₉ - Z N ₉ 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 may carry one or more substituents, and Z is an alkoxy group, an arylated alkoxy group, an aryloxy group, an alkyl mercapto group, an aryl mercapto group or the group - N means in which R _{3 is} hydrogen, an alkyl group with at most 4 carbon atoms, a hydroxyalkyl group with at most 4 carbon atoms, R _{4 is} an alkyl group with at most 4 carbon atoms, a hydroxyalkyl group with at most 4 carbon atoms or an aralkyl group with at most 10 carbon atoms or R ₃ and R ₄ together with the nitrogen atom to which they are attached form a heterocyclic group which can carry one or more substituents. Considered publications:
German interpretative document No. 1 117 387. 1 sheet of drawings 709 640/500 8. 67 © Bundesdruckerei Berlin