DD224419A1 - diazotype - Google Patents

Abstract

The object of providing a blue light-sensitive diazotype material having high coupling activity and thermal stability and low tendency to gel is achieved by dissolving the diazotype material consisting of a base, diazonium salt, coupler, binder and optionally further additives, one or more diazonium salts of the general formula ## STR1 ## Aralkyl, together a heterocycle; R3H, alkyl; R5alkyl, aralkyl, haloalkyl, alkoxy; R6alkoxy, aryloxy, halo; R7H, halo, hydroxy, alkoxy, -NH2, -NR1R2R8ArylX0Anion, contains.

Description

diazotype

Field of application of the invention

The invention relates to a diazotype material for recording

of information.

Characteristic of known technical solutions Diazotype materials consist of light-sensitive diazonium components which, when not irradiated, are capable of reacting 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), "" Issenscha ft Liehe Basics of Reprography, Hanover 1975, p.120; M.S.Dinaburg, Photosensitive Diazo Compounds, Focal Press, London-New York, 1964;

 Mchitarov, Usp.naucn. f otogr. _2JL, 5 1978.)

The most important characteristic parameters of diazotype materials are photo-sensitivity, thermal stability, coupling speed, maximum and minimum density, gradation, spectral behavior and stability of image dyes

 The photosensitivity is determined essentially by the type and concentration of the diazonium salts used

 Dt: "Disadvantage of the diazo materials compared to silver halide systems is mainly in the low sensitivity (E ± 10 0 · cm) and the lack of colorability, since all monosubstituted aryldiazonium salts absorb in the UV region and thus largely stable to visible light

are.

... a ( ο κ ·

An improved sensitivity, combined with a bathochromic shift of the absorption maxima, is achieved by the introduction of substituents carrying free, nonbonding electron pairs, which are able to conjugate in mesomeric position with the nonbonding electron pairs of the diazo group. This is most easily achieved by the introduction of substituted amino groups in the 4-position to the diazo group (DE-PS 884 733). Targeted introduction of additional substituents makes it possible to further improve various parameters. A 3-methoxy group improves the coupling speed (DE-AS 1 092 767), a 3-trifluoromethyl group also improves the thermal stability (DE-OS 1 244575).

Such doubly substituted 4-NR ₂ -diazonium salts are bathochromated in their absorption maxima up to the 430 nm range. If one wishes to achieve full blue light sensitivity of the diazo materials, ie to absorb light in the wavelength range from 440 to 480, orange-colored diazonium components are required.

The 2-nitro-4-morpholino-5-methoxybenzendiazoniumsalz described in DE-OS 2,202,251, which absorbs at 471 nm in the maximum causes, due to the 2-nitrosubstitution, at the exposed areas the structure of a yellow haze. This can be avoided, one starts from the 4-NO ₂ ^su ~ bstituierten diazonium salts of the above 2-substituted ₍₁ H Böttcher, Journal f. Prakt. Chemie Vol 325, S.725 ff) but .The absorption maxima are only in the region from 400 to 440 nm. Additionally introduced acceptors at the 5-position, as described in DD-IVP 159 730, do not affect the absorption maximum positively; the 2-piperidino-5-cyanobenzendiazonium salt absorbs at a maximum at 428 nm. However, the spectral region of interest can be achieved by annealing or aromatics bridging, so pyrendiazonium salt -2 at 460 nm (U.S. Patent 3,486,900) absorbs 4-dimethylaminofluorendiazonium salt at 470 nm (Tsunoda, Nippon Ga / -kkai Kaishi vol. 29, p.27 ff). However, these multiple aromatic systems are extremely poorly soluble. Vinylogous diazonium compounds such as coumarinyl

- (DD-WP 154 402) and Ca rbazoloy Ideriva te (DD -VVP 157 940) are also suitable in terms of spectral Absdrptionseigenschaften, but their photosensitivity is too low.

Object of the invention

The aim of the invention is to produce copies of documents in a simple manner with blue light. "

Explanation of the V.'esens invention

The known diazotype materials, which are built up from diazonium salt, couplers, stabilizer acids and other additives in the binder, do not meet the requirements of an ouplication with blue light.

It is therefore an object of the invention to provide a blue light sensitive diazotype material with high coupling activity, thermal stability and low tendency to scold. According to the invention the object is achieved by the diazotype material, consisting of base, diazonium salt, coupler, binder and optionally further additives, one or more diazonium salts of the general formula

identical or different, alkyl having 1 to 6 carbon atoms, aralkyl having 7 to 10 carbon atoms, together the necessary for the completion of a heterocyclic ring alkyl groups, which may optionally contain a further heteroatom, such as oxygen, nitrogen, sulfur;

H, alkyl of 1 to 8 carbon atoms;

OO ^7: O

R 1 is alkyl of 1 to 6 carbon atoms, aralkyl of 7 to 10 carbon atoms, optionally substituted, haloalkyl of 1 to 4 carbon atoms, alkoxy of 1 to 5 carbon atoms;

R _{β is} alkoxy having 1 to δ carbon atoms, aryloxy, optionally substituted, halogen;

RH, halogen, hydroxy, alkoxy of 1 to 18 carbon atoms, -NHp ₁ -NR ₁ R ₂ ^

-N-f \, optionally substituted,

R ^ aryl, optionally substituted ^

X. anion

mean,

contains.

As anions to the diazonium cations, it is preferred to use those complex anions which thermally stabilize the cation, for example BF ₄ ", ZnCl ₄ ² ", HSO ₄ ", SbCl _g ² ", CdCl ₄ ² ",

The couplers commonly used in the diazotype, such as pyrocatechol and resorcinol derivatives, acetamides, resorcyl derivatives, pyrazolones, 2-naphthols, hydroxynaphthoic acid derivatives, oxybenzotriazoles and the like. can also be used for the material according to the invention.

Suitable stabilizers are organically readily soluble, low-volatility acids, such as, for example, 4-toluenesulfonic acid, sulfosalicylic acid, oxalic acid, tartaric acid, citric acid, trichloroacetic acid and the like.

Suitable binders are all those film-formable, transparent matrix-producing, water-swellable, as permeable as possible polymers, such. Cellulose derivatives, vinyl polymers, copolymers of vinyl chloride and vinyl acetate, polystyrene, copolymers of alkyl acrylates and acrylic acid and polyethylene oxides.

Support materials for the photosensitive layer may include polymeric films, papers, glass and metal foils.

As other additives, plasticizers (Oiethylphthala t, Oibutylphthalat, Dioctylphthalat, tricresyl phosphate), image dye stabilizers (sterically hindered phenols, aromatic substituted amines, hydroquinone dialkyl, Phosphorsäurephenylesterderivate) or antifoggants (Stilbenderivats) are introduced.

In order to prepare a diazotype casting solution, the components are incorporated into the solution of a binder which, when combining diazo component and coupler, must have a sufficient acid strength to prevent a pre-coupling.

Suitable solvents include, for example, the readily volatile lower aliphatic alcohols, ketones and chlorinated hydrocarbons, including mixtures of said solvents.

The material of the invention is sensitive to blue light, has a high coupling activity and thermal stability and a low tendency to tarnish. The resulting image dyes are characterized by a high brilliance.

- 6 examples

Example 11

In 10 ml of a 10% cellulose acetate solution in methylene chloride / methanol, which is cast on 1.2 π ^ subbed substrate of polyethylene terephthalate, a diazo system of the following composition is introduced: ... '..

12 g of 2-pyrrolidino-5-acetylaminobenzendiazonium tetrafluoroborate. '

10 g β- naphthol 2.5 g sulfosalicylic acid

After casting and drying, a yellow-orange transparent film is obtained. After imagewise exposure behind an edge filter 440 nm and development in a moist ammonia atmosphere, a violet positive image of the original on a light background is obtained. The absorption maximum of the dye image is 532 nm.

Example 2

If a diazotype material according to the example is changed only in that the amount of 3-naphthol is replaced equimolar with other couplers, and the processing according to Example 1 is carried out, then image dyes which are summarized in Table 1 are obtained.

Sheetl

Coupler. ... > 1 of the image dye in

¹⁷¹ cellulose acetate film

Resorcinol 513 nm

OC naphthol 529 nm

2-hydroxy-3-naphthoic acid 550 nm

anilide

2-hydroxy-3-naphthoic acid 553 nm

2'-änisidid

- "7 -

Example 3

The following diazo system is introduced into 100 ml of a 7.5% polyvinyl butyral solution in methyl chloride / acetone:

15 g of phosphoric acid phenyl ester di - (- 3-diazonium tetra-chlorozinc-4-pyrrolidino) -anilil

8.2 g of 2-hydroxy-3-naphthoic acid 2'-anisidide

4.0g resorcinol

3.2 g acetoacetanilide

2.0 g sulfosalicylic acid

After being cast on substituted polyethylene terephthalate substrates and dried at 40 G, a yellow-orange transparent film is obtained. After exposure and development according to Example 2, a brown positive image of the original is obtained.

Example 4

A diazo system of acetone / methanol (2: 1) is rinsed in 100% of the strong cellulose acetate film and, per 2.5 l of acetone / methanol mixture, 30 g of 2-pyrrolidino-5-N-butylacetylaminobenzendiazo

ammonium tetrafluoroborate and

20 g sulfosalicylic acid contains.

After image-wise exposure to blue light and development in an aqueous solution of phloroglycine, pH 9.5, a reddish osmotic image of the precursor is obtained.

Claims (1)

invention claim in the
R ₁ , R ₂ identical or different, alkyl having 1 to 6 carbon atoms, aralkyl having 7 to 10 carbon atoms, together the alkyl groups necessary for completing a heterocyclic ring, which may optionally contain a further heteroatom, such as oxygen, nitrogen, sulfur; H, alkyl of 1 to 8 carbon atoms; R 0 CR. Il ^; 0 -P II * -S-R 3 0 Alkyl of 1 to 6 carbon atoms, aralkyl of 7 to 10 carbon atoms optionally substituted, haloalkyl of 1 to 4 carbon atoms, alkoxy of 1 to 5 carbon atoms; Alkoxy having 1 to 5 carbon atoms, aryloxy, optionally substituted, halogen; H _{1 is} halogen, hydroxy, alkoxy of 1 to 13 carbon atoms, -NHp, -NR ₁ R ₉ , optionally substituted, R. © θ Aryl, optionally substituted anion mean, contains.