DD223265A1 - diazotype - Google Patents

Abstract

The aim and the object of achieving a diazotype material with improved properties, in particular high coupling speed, good storage stability and brilliance of the image dyes, have been achieved. The diazotype material according to the invention, consisting of base and binder-containing layer, contains, in addition to couplers, stabilizer acid and optionally further additives, a diazonium salt of general formula R1, R2H, alkyl, alkoxyR3, R4 alkyl or R3 and R4 together form a Ringx anion for diazonium salts.

Description

VEB Filmfabrik Wolfen Wolfen, 08.03.1984

PN 1 086 RM / Mi

TLC, Waikoff IntCl, ³ : G 03 C, 1/58

DC. Fatzke * '.

Diazotype material Field of application of the invention

The invention relates to a diazotype material for recording information.

Characteristic of the known technical solutions

Diazotype materials consist of photosensitive diazonium components, which are free from radiation and are able to react with couplers, which are either in the layer system or in the development bath, under the influence of bases to form colored azo compounds. At the exposed areas no coupling is possible. / ~ 3rd Munder in G. Haase (Ed), Scientific Principles of Reprography, Hanover, (1975), p. 120; MS. Dinaburg, Photosensitive Diazo Compounds, Focal Press, London - New York (1964); RA Mhitarov, Usp.naucn. fotogr. 21 , 5, (1973) J?

The essential characteristic parameters of oiazotype materials are photosensitivity, thermal stability, coupling speed, maximum and minimum density, gradation, spectral response and stability of the dye dyes. The photosensitivity is essentially determined by the type and concentration of the diazonium salts used. " The disadvantage of diazotype materials is compared to SiI-. Berhalogenidsysteraen especially in the low sensitivity

- 1 - 2

(E f 10 3 · cm) and the lack of colorability, since all monosubstituted acryl diazonium salts absorb in the UV region and thus are largely stable to visible light * -

A first sensitivity improvement, associated with a bathochromic shift of the absorption maxima, is achieved by introduction of substituents bearing lone pairs of electrons that can conjugate with the lone pair electrons of the diazo group. This is most easily accomplished by the introduction of a substituted amino group (OE-PS 884 733) »By introducing additional substituents succeed in further improvement of various parameters · A 3-Hethoxygruppe improves the coupling ge _; , Speed (DE-AS 1 092 767), a 3-trifluoromethyl group, and also the thermal stability (DE-OS 1 244 575). Such doubly substituted 4-NR ₂ -diazonium salts are shifted to the range of 430 nm with respect to their absorption raaxiraa bathochroB, ₇

Their Kupplüngsgeschwindigkeit is low, by introduction of the substituents mentioned, it could be increased only slightly. The 2,5-dialkoxy-4-N, i- ^V -dialkyl-areno-benzene-diazonium salts contained in most of the marketed diazotylation materials leave much to be desired with their coupling speed. "

Object of the invention

The aim of the invention is to produce a diazotype material with improved properties in a simple manner,

Essence of the invention

The object of the invention is to provide a highly sensitive Diazotypiematerial with high coupling speed and good storage stability, which shows after processing brilliant image dyes. According to the invention the object is achieved by the diazotype material consisting of pad and bin. demittelhaltiger layer with at least one diazonium salts couplers, stabilizer acid and optionally other additives ·, at least one Diazoniurasalz the general formula

". ' ·. · '' ·. '.' '.- - 3 -

- 3 R ¹

.N

X ΝΞΝ -! ^ JL ~ y 'Χ,

R ¹ , R ² - = H, alkyl (C _{1 to 6} ). Alkoxy (C _{1 b ± 8 6} )

3 4 ¹ⁱ 3 4

R, R = alkyl (C ₁ .._ ₅ ) or 8, R together form a saturated 5 - or 6 - ring, the oxygen atoms

can contain

χ "= anion for diazonium compounds

mean, contains. ·

As anions to the diazonium cations, it is preferred to use those complex anions which thermally stabilize the cation, such as BFJ, Zn ClJ * HSO4V SbCIg _t CdCl ₄ ² ", Sn Cig ² " *,

The 2-N, N-Diaikylamino-benzthiazo'l-6-diazonium compounds according to the invention are thermally stable and can be isolated as Festestahzzz.

The synthesis can be carried out as follows:

Preparation of mercaptobenzothiazoles from the corresponding

anilines; FiAT Final Report, 1013, or BIOS Final Report, 661. -5 hours heating to 200 ⁰ C of Mercaptobenzthiazole with

a secondary amine and isolation of the 2-N, N-Dialkylarainobenzthiazole Nitration in the 6-position, Beilstein 27, 44th

- reduction of the nitro group

Diazotization of the amine in HCl with sodium nitrite and isolation of the diazonium compound,

In diazotization, no quinone formation occurs as a side reaction. To prepare a Diazotypiegießlösung the individual components are introduced into the solution of a binder, v / obei when combining diazo component and coupler sufficient acidity to prevent a pre-coupling must be present.

Ό '

Suitable solvents are, for example, easily volatile, short-chain, aliphatic alcohols, ketones and chlorinated hydrocarbons or their geroics. Suitable binders are all film-forming, transparent, water-swellable, preferably permeable polymers which produce a transparent matrix, such as cellulose derivatives, vinyl polymers, copolymers of vinyl chloride and acetate, polystyrenes, copolymers of alkyl acrylates and acrylic acid and polyethylene oxides.

Suitable couplers for the material according to the invention are brine catechol and resorcinol derivatives, acetanilides, resorcyl derivatives / pyrazolones, 2-naphthols, hydroxynaphthoic acid derivatives, oxybenzotriazoles, cyanoacetic acid amides and the like. use. , Suitable stabilizers are organically readily soluble, low-volatile acids, such as 4-toluenesulfonic acid, sulfosalicylic acid, oxalic acid, tartaric acid, citric acid and trichloroacetic acid. Other additives include Weiphraacher (diethyl phthalate, dibutyl phthalate, Oiöctylphthalat, tricresyl phosphate), image dye stabilizers (sterically hindered phenols, aromatic substituted amines, hydroquinone dialkyl, Phosphorsäurephenylesterderivate) or antifoggants (stilbene derivatives) are introduced. ^l ·

To prepare the diazotype material, the casting solution is cast on a base and the resulting layer is dried. Suitable underlays are other polymer films, paper, glass and metal foils.

The diazotype materials according to the invention have an excellent coupling speed and a good storage stability. These desirable properties are brought about by the use of new Z-N, N-dialkyl-aminobenzothiazole-diazonium salts, which have a high coupling activity and are remarkably thermally stable. The image dyes obtained after processing are characterized by high brilliance. .,. '·.; ..... , ,

Embodiment.

Synthesis Example -

Dissolve 458 g of 2-pyrrolidino-6-araino-benzthiazbl in a mixture of 600 ml of concentrated HCl and 600 ml H_0, add 500 g of cerium oxide.

jerked Eis.aj and passes under stirring for one hour 11 2 molar sodium nitrile solution under the surface of the reaction mixture. After 15 minutes, the diazonium salt is precipitated by adding saturated sodium tetrafluoroborate solution. After filtration with suction, it is washed with ice-water and dried in the air with the exclusion of light.

According to the 2-pyrrolidino ~ benzthiazol-6 ~ diazoniuratetrafluoroborat other derivatives are prepared. The following table contains some typical examples and characteristic data

rO>

-R Yield in % max / hm / NSN-stretching theory in methanol sc hwin g η g / c ηΓ ~ 7 Dimethylaraino 82 398 ' 2215 diethylamino 85 405 2210 pyrrolidino 80 405 2210 piperidino 80 402 2212 morpholino 88 395 2216

example 1

2 On an area of 10 to 15 m of a suitable support, 1 000 ml of a 7.5% solution of cellulose acetate in methylene chloride / methanol containing the following diazo-styrene:

9 g of 2-piperidinobenzothiazole-6-diazonium tetrafluoroborate

10 g Naphtol AS-OL

2 g of 4-toluenesulfonic acid

By exposing a black or yellow template and developing it with ammonia, you get a purple image.

Example 2

On an area of 10 to 15 m of a suitable support, 1 000 ml of a 7.5 % solution of cellulose propionate in methylene chloride / methanol containing the following diazo system is added:

12 g of 2-morpholino-benzothiazole 6-diazonium tetrachlorozincate

4 g of naphtha AS-Ol.

2 g of β-naphthol. ,

2 g of gyanacetic acid morpholide

2 g sulfosalicylic acid

After exposure of a black original and development in an ammonia pressure chamber, a brown image is formed.

Example 3

2. On an area of 10 to 15 m of a suitable support, 1 000 ml of a 7.5% cellulose butyrate solution in methylene chloride / methanol containing the following ozone system are poured; , ^v :; '' · " ,

4 g of 2-pyirolidino-4,7-diethoxybenzothiazole-6-diazonium tetra-

fiuoroborat

5 g of 4'-N, N-diisopropylamino-c, cyano-stilbene-diazonium, tetra-

fluoroborate 5g Naphtoi AS-OL 3g acetoacetanilide 2g oxalic acid

After exposure to a halogen lamp through a black or red template and subsequent development with ammonia, a brown picture is obtained »

Claims (1)

invention claim Diazotype material consisting of base and binder-containing layer with at least one Diazoniurasalz, couplers, stabilizer acid and optionally other additives, characterized in that it contains at least one diazonium salt of the general formula N = N - R ² R ¹ , R ² = H, alkyl (C _{1 to g} ). Alkoxy (C _{1 fais 6} ) R, R = alkyl (C, ₅ x or R, R together form one saturated 5- or 6-membered ring, which may contain oxygen atoms,
x "= an anion for diazonium compounds mean, contains *