Zweikomponentendiazotypiematerial

FtlrdieHerstellung of Zweikomponentendiazotypiematerial, which contains a Diazoverbindung and a one to the Knpplung with this qualified connection, and by which borrowing breaks with red and braunmten colours can be manufactured after the Tmekenveffahren, to have as Diazoverbindungen diazotierte p-Phenylendiamine with tertiary Sticl toffatom and as clutch components of amides of the 3, 5-Dihydroxy-bermoesäure (Resorcylsäure) works satisfactorily. To the Verbauerung of the water firmness of the breaks manufactured with this material one suggested to see 3, 5-Dihydmxy-benzoesäureatylamide, to e.g. 3, 5-Dihydmxy-benzoes ureanilid. The use of these connections for the production of the photo-sensitive layers from aqueous Lööungen is however difficult by their bad water solubility. It winds now found that this disadvantage is to be repaired and - on use in the Diazotypie common Diazoverbindungen - much it strengthens Lich ausen with red colours is producible, if in liehtempfindlichenSclüeht as clutchable connection, if necessary as salt available, substituted 2 [3 ', 5 ' - Dihydroxyphenyl] - benzimidazol the general forms! HO [OH I I I I blank or a mixture of several of these connections is present, whereby in the formula g 1 hydrogen, a low Alkylgmppe or a substimierte low Alkylgtuppe, RZ hydrogen, a low alkyl group, a low alkoxy group or a halogen atom with a Atomgewieht of highest 80, and Rn hydrogen or bromine mean. Blank is prefers an alkyl group with highest 3 Kohlensmffatomen. If blank is substituted, one or more amino groups are appropriate for hydroxyl group or substituted amino groups forwards as substituents prefer. Suitable ones substituted Aminograppen are particularly low alkylated amino groups, in addition, dialkTIierte Aminagruppm, in those the two allyl groups over a KoMemtoff, Sauerstoffbzw. Is, as for example the Pyrrolidino, Piperidinooder Morpholinogruppe preferably interconnects nitrogen atom to one to 8oder 6-gliodrigen ring. Blank represents prefers methyl, Methoxyoder Äthoxygruppe or as halogen atom a chlorine atom. The formulas of some according to invention used of the 2 [3 ', 5 ' - Dihydroxyphenyl] - benzimidazole are the Tabolle to be taken. The connections are again and draw by grolle stability both in substance and in solution and in the photo-sensitive layer to. In form of its salts this substituted Benzimidazele is water soluble. The salt screen end group of X0 is in the heterocyelischen ring. The basicity of this ring can be strengthened by the substituents specified above ftir the remainder of blanks, because a further salzbfldende group is then present. For the Salzbildung are suitable see natural both anorganiseh¢ acids, and hydrochloric acid and sulfuric acid, and organic acids, like vinegar, äure, Zirronemäure or Weimäum or also mixtures dieser8äuren. It is not necessary always to isolate the salts. .qie forms for example also with addition of the free bases to the Semibilisierungflösungen containing the Diazoverbindungen, which contain acids as Stabflisatorcn llberschtlssigc. To the production according to invention of the used of the 9 - [3 ', 8 ' - Dihydroxyphenyl] - bermimidazole one can do of the underlying acylierten, usually aoetylierten 3, 5-Dihydrexy-benzoesäureehloriden to go out. These can substitute on the two following because of into the gewtlmchten Benzimidazole to be over-granted: a) One semt the acylierten 8 halogenmbstituierten if necessary, 5-Dihydroxy-benzoe äurechlorid “with o-Phenylendiaminen over, in which the substituents blank are already present tmd blank, soaps the aeylierten Hydmxygruppen, for example with diluted caustic soda solution, and verkoeht the received 8, 5-Dihydmxybenzoesäure-o-aminophenylamide with center more tarker to more strongly, for example about 30% iger SalzeS acid, whereby under Wasserabspaltung of the Benzimidazolring one forms. If necessary kölmen the Entacylierung and the Ringschlußreaktion with strong Salzsäme in a stage to be durchgeftthrt. b) One converts the acylierten 3, 5-Dihydroxy-benzoesäurechloride with o-Nirxanilinen, halogemubstituierten if necessary, in which the substituents blank and blank are already present, and reduces DL “received O-acylierten 3, S-Dihydroxy-benzeesäure-o-nitmphenylamide to the concerned -, set free into this through soaping with verdilnntcr caustic solution, usually caustic soda solution, dic both hydroxyl groups o-aminophenylamiden and close then the Imidazolring appropriately by cooking with glacial acetic acid in presence of small quantities more concentrated. %hwefelsäum. A specification of these two Herstellnngsmethoden is given to 1 in example for the method A and in example 3 of the method b. Suitable p-Phenylendiamine, di “in diazotierter form as well as the 9 the according to invention - [3 ', 5 ' - Dihydmxyphenyl] - to be used, are primarily such benzimidazolen, at the nitrogen atom two low Alkylbzw p-constant to the Diazogruppe. Hydroxyall lgmppen contained, whereby also here the Alkylgmppen over a Kohlemtoff, Sauerstoffbzw. Nitrogen atom zn one 5oder 6-gliedrigen ring to preferably be connected know. Diazotierte p-Phenylendiamine with tertiary nitrogen atom, which additionally still contains two z each other in the core or preferably p-constant low alkoxy groups, particularly Methoxyoder Äthoxygruppen, is particularly suitable. Genarmtseien for example the salts of X-Diazo-4-diäthylaminobenzol, I-Diazo-4-dipropylamino-bermol, 1-Diazo-9-äthoxy-4-diäthylamino-benzol, 1-Diazo, 4 [hydroxyäthyl äthylamino] - benzene, 1-Diazo-2, 5-dimethoxy-4-inorpholino-benzol, 1-Diazo-9, 5-diäthoxy-4-morpholino-benzol. According to invention used the 2 [3 ', 5 ' - Dihydroxyphenyl] - benzimidazole are suitable together with genarmtcn the diazotiertenp Phenylendiaminen both for the Semibilisierung of normal Lichtpampapiere and for the production of photo-sensitive layers on Tramparentpapieren and foils. In the first case one brings the subsrätuierte Benzimidazol from purely aqueous solutions on the carrier, in the latter case is the use of L'Osungsmitteln, in particular to low aliphatic alcohols, preferably Impropylalkohol, necessary. In the solutions can be used into the Diazotypie usual additives, which increase the stability of the layers and cause a antivergilbenden effect. The greater technical importance is attached to the Diazotypicmatcrial manufactured with transparent slow-acting one. Panen manufactured of it shows in practice desired saving. One uses such copies for colored projections, for example for Lehrzweoke, particularly in the school teaching. They are further suitable for the production of well visible zwischenoriginalen intended for the Weiterpanen. In the latter case it is necessary to along-use a second Azokomponeme which results in a yellow coloring material with good cover strength against fnr the exposure the used kind of light. The invention becomes by the following examples and the table erll'tnterr. In the table r of the formula of the substimierten Benzimidazols concerned is the Hemtellungsmethode A) and/or, b) (see above) as well as the point of decomposition indicated in °C. The Formelunmmein indicated in the Beispinlen corresponds to those the table. In the examples 1 valley is considered as unit volume, if as Gewichrseinheit 1 g is taken. Example I: On, which is provided Polyvinylacerat, a solution of 4 thread - parts of Zitmnensäure 2 thread - becomes more l.ächrpauspapter parts of O, 5 VOL. - Parts of 4 thread - parts of 3 thread - parts of 1 thread - Teü 2 thread - parts of 100 VOL. - T flen me a pre-coating of colloidal silicic acid and boric acid konz. Hydrochloric acid Thioharmtoff 1-Naphthalin-3, 6-trisulfosäure Diäthylaminobenzol-4-diazoniumchlorid (when double salt with Zinkchlorid) l-7-Morpholinopropyl-2 (4 ' - bmm-3', 5 ' - dihydmxyphenyl) - benzimidazol (formula 14) and water applied, as usual dried and under a transparent collecting main exposes. One receives high-contrast copies with blaustichig red lines on purely white underground after the development with ammonia gas. The breaks to draw look by high Lichtechrheit and good tempering properties. In place of dessubsfirtüerten Benzimidazols of the formula 14 somewhat less advantage knows the 1-Ärhyl -2 (8 ', 5 ' - dihydmxyphenyl) with - 6-merhyl-benzimidazol (formula 12) to be used. The connection forms! 14 manufactured as follows… 33, 5 thread - parts of 4-Brom-3, 5-diacetoxT-benzoylcklorid become in 100 VOL. - Parts of Dioxan solved and under agitating with 30 - 40° (: slowly to a solution from 21, 6 thread - parts of n (7-Morpholinopropyl) - - o-phenylendiamin in 40 VOL. - Parts of Dioxan and 8 VOL. - Parts of Pyridin dripped. After the conversion the Dioxan is evaporated, according to which sirupöser arrears remain. To the Abspalmng of the Acetylgmppen and cleaning the conversion product is solved in verdfinnter warm 2n-Nauonlauge and the Verseifungsprodukr by addition from acetic acid ones again ausgePälh. In such a way received free base melts after preceding Sinrerung with for instance I15°C under decomposition. For the Ringschlußreakflon thread become - parts of this base with 100 VOL. - Heats parts for instance 30%iger up Salzstlum 80 min with 90oc and afterwards still 10 min with Siedetemperarur. With the Abkilhlen the hydrochloride of the l crystallizes? - Morpholinopropyl-2 (4 ' - brom-3', 5 ' - dihydroxyphenyl) - benzimidazols. For cleaning the raw product is recrystallized several times from water. One receipt colorless crystals, which melt after preceding sintering with 255oc under decomposition. The free base will receive by loosening of the hydrochloride in 2-normaler Natrenlauge and neutralizing of the solution with Essigsäurc. From Chlorbenzol umktismllisierr it melts with 208 - 209°C under Zersemung. The connection of the formula 12 can be supposed in similar way. Fuel element i s p i e 1 2: In a mixture of 50 VOL. - Parts water and 50 VOL. - Parts isopropanol 8 thread become - parts of Zintroneusäure 2 Gew. - Parts of Bersäme 2 Gew. - Parts of Thiohamstoff 6 Vo1. - Parts of Ärhylenglykol 3, 5 thread - parts of 1-Morpholino-2, 5-diäthoxy-benzol-4-diazoniumchlorid (when double salt with Zinkchlorid) and 4 thread - Teüe 1-1 - Hydroxyärhyl-2 (4 ' - brom-3', 5 ' - dihydroxyphenyl) - benzimidazol=hydrochlo - rid (formula 13) solved and with this solution a Baryrpapier, which is painted with acetyl cellulose, coated. The blueprints manufactured with this material after example 1 show strongly red lines on purely white underground. Equal good results one obtains with the connection of the formula I0, the 1-Me yI-2 (4 ' - bromine -3 ', 5 ' - dihydroxyphenyl) - benzimidazol. With smaller advantage one uses the connection of the formula 11, the 1-Methyl-2 (4 ' - brom-3 ", 5 ' - dihydroxyphenyl) - 5-merhoxy-benzimidazol. One receives the connections of the formulas 10.10 and 11 similar to the manufacturing method for example 3* 2 Gew, indicated in example I. - Parts of 1 thread - part of 9 Gew. - Parts of 2 thread - parts the connection of the formula 14. Citric acid boric acid Thiohamsmff 2 (4 ' - Brom-3', 5 '- dihydroxyphenyl) - 5-m ethyl benzimidazo! (Formula 7) and 3 Gew. - Parts of 1-Morpholino-2, 5-dimethoxybenzol-4-diazoniumdalorid (as double salt with Zinkchlorid) become with a mixture of 50 VOL. - Teüen water and 50 VOL. - Parts of Isopmpanol brought in solution. With this solution a Tramparentpapier, which is painted with acetyl cellulose, is coated. Like tiblich manufactured blueprints easily blaustichig red lines have. In the case of use einm well taking off Gelbkompenente, e.g. Monooxäthylbrenzcatechin, can be manufactured very kentrastreiche Zwisehenorigtnale. With geringemm advantage the connection of the formula 2, 2 (3 ', 5 ' - Dihydmxyphenyl) can - benzimidazol, the connection of the formula 4, 2 (3 ', 5 ' - Dihydroxyphenyl) - 6-methoxy-benzimidazol, the connection of the Fomael 5, 2 (4 ' - Brom-3', 5 ' - dihydmxyphenyl) - 5-äthoxy-benzimidazoI, the connection of the formula ö, 2 (3 ', 5 ' - DihydroxyphenyI) - 5-äthoxy-benzimidazol, those connection of the formula 8, 2 (3 ', 5 ' - Dihydroxyphenyl) - 5-methyl-benzimidazol or the connection of the formula 9, 2 (4 ' - Brom-3', 5 ' - dihydroxyphenyl) - -5-ehlorbenzimidazol to be used. The connection of the formula 7 is represented as follows: 152 thread - Divide 3-Nitro-4-amino-toluol become into 6O0 VOL. - Parts of Dioxan and 78 VOL. - Parts of Pyridin solved. Under Rflb.mn one lets this solution solved with 60 - 70°C to 335 thread - parts of 4-Brom-3, 5-diacetoxy-benzoylehlorid, in 1000 VOL. - Introduce parts Dioxan in drops. After 45 min becomes the Aeetylverbindung by addition of 100 VOL. - Parts and the solution with hydrochloric acid soaps 5n-Natronlauge neutrally posed. The received Carbonsäumamid is umgefällt for cleaning from caustic soda solution/hydrochloric acid. Yield 9,80 Gew. - Parts. Sehmeazpunkt 205°C. The reduction of the Nitrogruppe takes place catalytically in presence of Raney Niekel. From 2ö0 thread - parts nitro compound become 220 thread - receive parts amine. Fusion point l? 3°G under decomposition. Ftir the Ringsehlußreaktion become 110 thread - parts amine under Rflhmn with 500 VOL. - Heats parts glacial acetic acid up 2h for simmering. Then one gives 5 VOL. - And noch30 min. heats parts up of pure sulfuric acid in addition. After that. Cooling sucks one the rough brown crystals off, solves her in diluted caustic soda solution, sucks off again and places films with Essigstium neutrally. The cleaning of the raw Benzimidazols erfolg1 by repeated recrystallizing from Dimethylformamidf¢/asser. Yield 40 Gew. - Parts vorf Sehmelzpnnkt 282° (3 under Zetsetztmg. The production of the connections of the formulas 2, 4, 5, 6, 8 and 9 takes place in similar way. B e i s p i e 1 4: A foil from Aeetylcellulose becomes with a solution of 4 Gew. - Parts of Zintronensäure 2 Gew. - Parts aluminium sulfate 2 C-ew. - Teflen boric acid 2 Gew. - Parts of Thioharmtoff 4 Gew. - Parts of 2 (4 ' - Brom-3',5' dihydroxyphenyl) - 6-methexy-benzimidazol (formula 3) “and 43 3 Gew. - Parts of Dipropylaminobenzol-4-diazoniumchlorid (as double salt with Zinkchlorid) in a mixture of 50 VOL. - Parts water and 50 VOL. - Coated parts isopropanol. After the exposure one receives copies with strongly dark red lines. In place of the connection of the formula 3 can also, with somewhat smaller Vorteü, which Verbindun of the formula I, 2 (4 ' - Brom-3', 5 ' - dihydroxyphenyl) - benzimidazol to be used. The production of the connections of the formulas 3 and 1 is similar to that for connection 7 (vgl example 3).