DD206003A1 - diazotype - Google Patents

Abstract

The invention relates to a slide material for recording information. The aim and object, a DIAZOTYPIENMATERIAL TO CREATE whose image DYES ABSORBANCE maxima above 620nm comprise is achieved by DAS DIAZOTYPIENMATERIAL COMPRISING diazonium salt, blue couplers, binders and optionally further PHOTOGRAPHIC additives such as combination of blue couplers of the general formula R1-NH-N = CH-R2 IN THE R1 SUBSTITUTED UNSATURATED N-HETEROCYCLES WITH THE HYDRAZINE SUBSTITUTION IN 2-POSITION TO THE HETERO-CYCLIC NITROGEN OR IN THE 8-POSITION OF A CHINOLINE SYSTEM, OR IN 7-POSITION OF THE INDOLSYSTEM; R2 SUBSTITUTED AROMAT; MEANS AND CONTAINING CU (II) SALTS AND / OR NI (II) SALTS AND / OR CO (II) SALTS OF ORGANIC CARBON SAWS.

Description

VEB Filmfabrik Wolfen Wolfen, 25. 3. 82

, PN 944 Wa / Br

Prof. Dr. Becker Int. Cl. : G 03 C 1/80

Dr. Marx Schikowski DC. Grisohin DC. Porstendorfer

Dr. Epperlein ^

z4 U 4 b ö 4

diazotype

Field of application of the invention

The invention relates to a diazotype material for recording

of information.

Characteristic of the known technical solutions Diazotype materials generally consist of light-sensitive diazonium salts which react at the unexposed areas, couplers under the influence of bases to give image dye.

According to the choice of the coupler component, image dyes having a wide variety of absorption characteristics can be obtained with the diazonium compounds of the substituted aonodiazotized 4-phenylenediamine type usually used in diazotype materials. Thus, for example, yellow image dyes by the use of alkylamino-substituted phenols (DE-AS 1285305}, Brertzkatechin- (DE-AS 825203) and resorcinol derivatives (DE-OS 1547921), acetamides (DE-OS 1923115), Cyanessigsäureamiden (DE AS 1597619) or acceptor-substituted 1-naphthols (DE-AS 1068555).

Orange, red and purple image dyes are obtained by the use of Resoroylsäurederivaten (ÜS-PS 3695885), pyrazolones (US-PS 3944422) or Guanidinabkömmlingen (US-PS 3653903).

Substituted 2-naphthols (DE-PS 697051), hydroxynaphthoic acid amines (DE-AS 1169293), 2,3-dihydroxynaphthalenes (DE-PS 922390) or oxybenzotriazoles (DE-PS 83869) are known blue couplers.

The absorption maxima of the blue Bildfakbstoffe are usually between 580 and 620 nai. Uses raan instead of the commonly used substituted iuonodiazotierten 4-phenylenediamines as Diazokoraponenten such.

4-Methoxybenzendiazoniumsalze (DD-WP 103 740) , diazotized 4-Anilinozimtsäurederivate (DD-WP 148910) or substituted monodiazotierte 2-Phenylendiaaine, so obtained with these couplers image dyes with Absorbtionsmaxiraa below 600 nm.

Object of the invention

The aim of the invention is to improve the performance characteristics of diazotype materials.

Presentation of the essence the invention

The known diazo blue-coupler materials have absorption maxima up to about 620 nra and are unable to produce cyan image dyes. It is therefore an object of the invention to provide a Diazotypiematerial whose image dyes Absorptionsmaxiina over 620 na have.

According to the invention, the object is achieved by providing a diazotype material consisting of diazonium salt, blue coupler, binder and optionally further photographic additives, a combination of blue couplers of the general formula

R _{1 is} -NH-N = CH-R ₂ ;

-3 -

in the

R substituted unsaturated N-heterocycles with the Hytirazinsubstitution in 2-position to the heterocyclic nitrogen, or in the 8-position of a Chinolinsysteras, or in the 7-position of an indole system;

Rp substituted aromatic;

mean, and Cu (II) salts and / or Nl (II) salts and / or Co (II) salts of organic carboxylic acids.

Inventive metal compounds are salts of unbranched saturated aliphatic monocarboxylic acids (eg capric acid), branched saturated aliphatic (eg isobutyric acid), unbranched unsaturated aliphatic (eg propiolic acid), branched unsaturated aliphatic (eg methacrylic acid), aromatic (eg salicylic acid), araliphatic (eg mandelic acid ) cyclic aliphatic (eg cyclohexane-1-carboxylic acid), heterocyclic monocarboxylic acids (eg isonicotinic acid), saturated aliphatic dicarboxylic acids (eg adipic acid), unsaturated aliphatic (eg maleic acid), aromatic dicarboxylic acids (eg phthalic acid), hydroxycarboxylic acids (eg lactic acid) of the halocarboxylic acids (eg <The>> o -chloropropionic acid), the keto acids (eg pyruvic acid) and the tricarboxylic acids (eg citric acid), the metal salts are readily available and are prepared in a known manner (Gmelin's Handbook of Inorganic Chemie),

As a blue coupler according to the invention can z.3. Benzaldehyde-2-pyridylhydrazone, 4-methoxybenzaldehyde-2-pyridylhydrazone, vanillin-2-pyridylhydrazone , 3-nitrobenzaldehyde-2-pyridylhydrazone, benzaldehyde-S-quinolylhydrazone, benzaldehyde - (4-methylquinolyl) -2-hydrazone or benzaldehyde (2-Methylthio-5-methylpyriflidyl) -2-hydrazone.

Suitable binders are, for example, cellulose derivatives, vinyl polymers, copolymers of vinyl chloride and vinyl acetate, polystyrene, copolymers of alkyl acrylates and acrylic acid and polyethylene oxides.

Polyurethane films, papers, glass and metal foils may be used as support materials for the photosensitive layer.

Substituted raonodiazotierte 4-phenylenediamines, substituted monodiazotierte 2-Phenyiendiamine, diazotierte 4-Anilinoziratsäurederivate are examples of the diazonium compounds which can be used in the diazotype material. The copper, nickel and cobalt salts are used to prepare a casting solution with the hydrazones according to the invention and optionally other coupling components, diazonium salts, binders, stabilizer acids and optionally further additives such as inhibitors, plasticizers and the like. dissolved in a polyester solution or a solvent and applied to a support. The ratio of hydrazone coupler to metal salt is 1: 3 to 3: 1, while the other components are used in amounts customary for diazotype *

The metal salts in combination with the hydrazones and known diazonium salts used in the diazotype material according to the invention in the basic development step form metal-complexed formazan dyes which absorb in their absorption maxima much more bathochromically than 520 nm and have good light fastness. So it is possible to produce sufficient color depths and a neutral gray tone.

Exemplary embodiments Example 1

In 1000 ml of a 10% CeJkiloseacetatlösung Diazosy.Sifceme from diazonium salts, coupler, 4-toluenesulfonic acid and cupric or cobalt (II) - or nickel (II) - <= b1z an organic carboxylic acid introduced. These diazo casting solutions are cast on 10 to 15 m polyethylene terephthalate pad and dried. The result is a transparent Filffl, which is developed by the action of basic media, mainly ammonia. The absorption maxima of the formed blue to blue-green image dyes are determined spectroscopically.

As diazonium salts are used in the embodiments:

(I) 4-Methoxybenzendiazoniofluorotarfluoroborate

-N ₂ ⁺ BF ₄ -

(II) 4-diethylarainobenzendiazonium tetrafluoroborate

^H 5 ^C 2 H ₅ C ₂ ^

(III) 4-piperidinobenzendiazoniourate tetrozorozincate

(IV) 2,5-Dxetboxy-4-fflorpholinobenzendiazoniuratetrafluoroborate

OC ₂ H ₅

(V) 2,5-O-diethoxy-4-pyrrolidinobenzenediazonium tetrafluoroborate

? ^C 2 «5

, N- / XN ₂ ⁺ BF ₄ "

GC ₂ H ₅

(VI) 2-piperidinyl-5-cyanobenzendiazonium tetrachlorozincate CN

- *

/ 2 ZnCl ₄

(VII) X- (4-phenyldiazonioflitetrafluoroborate) - / 3 - (4-diethylaminophenyl) -acrylic acid nitrile

N - / ^ VcH = C-

The synthesis of diazonium salts from the corresponding aromatic amines is described, for example, by Organikura, VEB Deutscher Verlag der Wissenschaften, Berlin 1967, page 514 ff.

As coupler components are used in the embodiments;

(A) Benzaldehyde 2-pyridylhydrazone

/ \ -NH-N- CH- / Y

(B) 4-methoxybenzaldehyde-2-pyridylhydrazone

_k -NH-N = CH-

(C) Vani 1-lin-2-pyridylhydrazone

/ OCH ₃

-OH

(D) S-Nitrobenzaldehyde Z-pyridylhydrazone / Y-NH-N = CH

(E) Benzaldehyde e-quinolylhydrazone

-NH-N = CH- \

(f) Benzaldehyde - (- 4-methylquinolyl) -2-hydrazine

-NH-N = CH- \ (G) benzaldehyl - (2-hydroxyethio-5-methylpyriraidyl) -2-hydrazone

9C

μ -.

-NH-N = GH- / \ V-- t

CH-

The synthesis of hydrazone coupler components is described, for example, in Austral® Chem. Vol. 22, p. 7181 ff (1969), that of the most commonly used starting material 2-hydrazinopyridine, in the 3.0rg. Chem. 31, p. 257 ff / 1966),

The results are shown in Tables 1 to 3. Table 1: Diazo systems with copper (II) salts

No. Diazoniumsal2 9 I copper 9 A Cu ( II )-salt Extinction maxima of the longest wavest absorption band of the image dye / nra 1 8th 9 I 8th 9 e 1.5 9 CuII-oleate 660 2 8th 9 IV 11 9 A 6.5 9 CuII-capronate 645 3 12 9 IV 8th 9 A 6.0 9 CuII butyrate 690 4 12 9 IV 8th 9 A 7 9 CuII-benzoate 690 5 12 9 IV 8th 9 A 7.5 9 CuII citrate 690 6 12 9 V 8th 9 A 6.5 9 CuII maleate 690 7 12 9 VI 8th 9 A 12 9 CuII-oleate 695 8th 10 9 VI 8th 9 B 6 9 CuII butyrate 680 9 10 9 VII 8.5 9 C 6 9 CuII-butyrate 690- 10 12 9 6.5 9 CuII-pivalinate 730 · I

240 4 58 4

Table 2: Diazo systems with cobalt II salts

No. diazonium salt pimp Co (II) salt Extinction maxima of the longest wavelength absorption band of the Bildfabrstoffs nra 11 SGI 8 g A · 5.5 g of Co (II) propionate 755 12 12 g IV 8 g A 5.5 g of Co (II) propionate 740 13 12 g IV 8 g A 7 g CoI (II) pivalinate 740 14 ' 12 g of V 8 g A 7 g of Co (II) - pivalinate 750 15 IO g Vi 8.5 g B 7 g of Co (II) - pivalinate 740

Table 3. DiazosysteuB with 5.5 g of Ni (II) propionate

No. DiazoniiUBsalz pimp Absorbance aaxiaiuaj of the longest wavelength absorption coefficient of image dye / nm 16 8 g I 8 g A 620 17 9.5 g II SGA 660 - 18 9.5 g II 8.5 g B 665 19 9.5 g II 12 g of F 645 2 NC 9 * 5 g III 8 g A 665 Ϊ21 9.5 g III 9 g C 675 | 22 12 g IV 8 g A 635 23 12 g IV 8.5 B 650 24 12 g IV 9 g C 645 25 12 g IV 8.5 g D 605 26 12 g IV HGE 710 27 10 g VI 8.5 g B 650 28 12 g VII 8 g A 695 29 12 g VII 8.5 g 8 700 30 12 g VII 9 g c 720 31 12 g. VII Bg 720 32 8 g I 10 g 625

240458 4

Example 2

In 1OG ml of a 10% solution of cellulose butyral in methylene chloride / methanol, a diazo system is introduced, consisting of

800 mg 2,5-oiethoxy-4-morpholinobenzonediazurate tetrafluoroborate 700 mg 4-methoxybenzaldehyde-2-pyridylhydrazone 1000 mg 4-toluenesulfonic acid 1200 mg Niokel II pivalinate

This casting solution is poured onto 1.2 m polyethylene terephthalate underlay and dried to give a transparent film.

By development to moist NH ₃ atmosphere at ca 6O ⁰ C, a blue dye image having a Extinktionsraaximura of 650 nm is formed.

The light fastness of this image dye was compared with that of a diazo material rait naphthol AS as a blue coupler. In the case of the use of the above hydrazine koraponenten in conjunction with Ni-II pivalinate an approximately 100 % ± ge improvement in light fastness is achieved.

Example 3

In 100 ml of a 10% solution of cellulose acetate in methylene chloride / methanol, a diazo system is introduced , consisting of

800 mg of 2,5-oiethoxy-4-raorpholinobenzendiazaniusntetrafluoroborate

700 mg benzaldehyde-2-pyridylhydrazone

1000 mg of 4-toluenesulfonic acid

1200 mg of cobalt II propionate

This casting solution is poured onto 1.2 m polyethylene terephthalate underlay and dried to give a transparent film.

- 10 -

-ίο-

By development under moist NH ₃ -At; Biosphere at about 60 C, a blue-green image dye is formed with an extinction maximum of 740 nm.

The fastness to appearance of this image dye was compared with that of a diazo material with naphthol AS as a blue coupler. In the case of the use of the above hydrazone component in conjunction with Co-II propionate a ca> 80% improvement in the durability is achieved.

If one waives the use of cobalt (II) propionate, an image dye is produced during the development process with an extinction maximum of 525 nm> which fades 15 times faster than the comparative diazo material with naphthol AS,

Example 4

In 100 ml of an IG% solution before Polyvinylformal a diazo system is introduced, consisting of

750 mg 4-Oiethylarainobenzendiazoniumietrachlorazincate 600 mg Vanillin 2-pyridylhydrazone 600 mg Cyanoacetic acid pyrrolidide 1000 rag 4-Toluene sulfonic acid 1006 mg Ni-II-pivalinate

This casting solution is spread on glass plates and dried to give a transparent film with an average layer thickness of 7 μm,

After imagewise exposure to a high pressure mercury burner and development with humid ammonia, a green positive illumination of the original is obtained.

Claims (1)

Invention, claim 1, diazotype material »consisting of diazonium salts blue coupler, binder and optionally other photographic additives * characterized by a combination of blue couplers of the general formula in the R ₁ substituted unsaturated N-heterocycles rait of Hydrazinsubstitution in 2-position to the heterocyclic nitrogen, or in the S position of a quinoline system> or in the 7-position of an indole system; R ₂ substituted Aroraat; mean and Cu (II) -salzewi and / or Ni (II) salts and / or Ga (II) salts of organic carboxylic acids.