DD220427A1 - SILVER-FREE INFORMATION RECORDING MATERIAL - Google Patents

Abstract

THE TASK ON SILVER FREE INFORMATION RECORDING MATERIALS TO CREATE WHAT UV AND BLUE LIGHT SENSITIVE IS A GOOD THERMAL STABILITY HAVING AND ITS MADE IMAGE DYES IMPROVED LIGHTFASTNESS OWN IS SOLVED BY THE SILVER FREE INFORMATION RECORDING MATERIAL COMPRISING DOCUMENT AND LIGHT SENSITIVE LAYER diazonium, IN THE LIGHT SENSITIVE LAYER OF DIAZONIUM COMPOUNDS OF THE GENERAL FORMULA, IN WHICH 1 LOW HYDROGEN, ALKYL, ALKOXY, ALKOXYCARBONYL, ALKYLSUFONYL, HALOGEN, CYANO, PHENYL, PHENOXY, BENZYL, CARBONYL; R DEEP 2 R DEEP 3 ALKYL, PHENYL, BENZYL, TOGETHER A HETEROCYCLUS; X HIGH - ANION MEANS, INCLUDES.

Description

Silver free infotation recording material

Field of application of the invention

The invention relates to a silver-free material for recording information

Characteristic of the known technical solutions

The benzenic diazonium compounds are of outstanding importance in the field of azo dye synthesis and as a major component in silver-free informational recording materials (reviewed by K.H. Saunders, The Aromatic Diazo Compounds and their Technical Applicants, Edward Arnold & Co. London 1947). A number of properties of these diazonium compounds greatly affect both the quality of the azo dyes formed with couplers and the qualitative parameters of the reprographic information recording materials, for example the thermal stability of the diazonium compounds, their coupling activity to dyes and the intensity of absorption of these dyes formed.

- '. - 2 -

In the application of the benzenic diazonium compounds as so-called diazotized azo base in the preparation of azo dyes, particular attention is paid to such properties as the stability of the azo dyes formed and high extinction coefficients thereof (top view in H, A. Lubs, The Chemistry of Synthetic). Dyes and Pigments, Reinhold Publishing Co. NY 1955). To achieve these goals find as diazotized azobases mainly those primary aromatic amines application, which are substituted by strong electron acceptors, for example, by 4-nitro- _< 4-sulfo, 3-trifluoromethyl or 3-nitrosubstitution (FR-PS 767,953 ).

A disadvantage for such diazotierbäre Azobasen proved to be the relatively short-wavelength absorption of the azo dyes formed, in particular this, which are prepared with hydroxybenzene or hydroxynaphthalene as a coupler. Bathochrome absorbing dyes can be generated when the diazotizable azo base In. 4-position to the diazotizable amino group containing another substituted amino group, for example the Phenylcarbamoyl or p-Anisidinö group The longer wavelength absorption, with couplers of the type 2rHydroxy-3-naphthoesäureamide violet to blue dyes can be achieved with a loss of fading resistance connected. The introduction of these substituted 4-Xminogruppen also changes the absorption of the diazotized azobase, it absorption maxima are achieved in the range of 350 to 450 nm. Based on this property and its photosensitivity to ultraviolet and blue light, such diazonium compounds can be used in reprographic information recording materials (reviewed by M "S. Dinaburg, Photosensitive Diazcj Compounds, Focal Press, London -NY_1964). ^

The main field of application is the diazotype. Such diazotype materials consist of photosensitive diazonium components which have been placed on or in a solid matrix and are capable of being reacted with couplers, either in the layered state or in the development bath, under the influence of bases to give colored azo compounds No further coupling is possible in exposed areas (review at 3. Munder in G. Haase (Ed), Wissenschaftliche Grundlagen der Reprographie, Hannover 1975. pp. 120 ff and R, A. Mchitarov, Usp. nnuchn, photograph 21, 5 ff , 1978) The essential parameters of diazotype materials, photosensitivity, thermal stability, coupling speed, spectral behavior and stability of image dyes are mainly determined by the nature of the diazonium compounds used.

Diazonium salts which have only a substituted amino group in the 4-position to the diazonium group (DE-PS 884 733) are often not. Coupling active enough to allow use on fast-working Diazoentwicklungsgeräten. By targeted introduction of additional substituents, especially in adjacent position to the 4-amino group , it is possible to improve a lot of properties. A 3-methoxy (DE-AS 1092767), 3-fluoro (DE-OS 1297468) or 3-phenyl group (GB-PS 1246254) improve the coupling activity, on the other hand negatively affect the thermal stability. A ⁹ 3-trifluoromethyl (DE-OS 1297468) or 3-carbonyl group (US Pat. No. 3,758,307) improve the coupling activity without lowering the thermal stability. A 3-sulfonic acid (DE-OS 1547944) or 3-cyano group (US Pat. No. 3,758,307) further enhances the extinction coefficients and the fade resistance of the image dyes. »Good thermal stability of the diazonium compounds is particularly necessary in such reprographic information recording media where their Decomposition triggers a modification of physico-chemical properties of polymers or prepolymers, ie in the fields

photopolymerization, photocrosslinking and photosolubilization (reviewed in VV.S. De Forest, Phsoresists Material and Processes, Mc Graw Mill Book Comp., NY 1975 and AF Bogenschuetz (Ed.) Photoresist Technique, Eugen G. Leuze Verlag, Saulgau 1975). ', _:

of the invention /

The object of the invention is to improve essential performance characteristics of reprographic information recording materials.

Explanation of the essence of the invention

The known silver-free diazotizable azobase-based recording materials do not simultaneously meet demands for good thermal stability, photosensitivity in the near ultraviolet and blue region, low fade rate and high extinction coefficient of the azo dyes formed.

It is therefore the object of the invention to provide a silver-free information recording material which is sensitive to UV and blue light, has good thermal stability and whose image dyes formed have improved fastness to light.

According to the invention the object is achieved by the silver-free information recording material consisting of sub-layer and photosensitive layer with diazonium compounds in the photosensitive layer, diazonium compounds of the general formula

in the .

R is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkoxycarbonyl, alkylsulfonyl, halogen, cyano, phenyl, phenoxy, benzyl, carbonyl;

R, R_ is the same or different, alkyl of 1 to 6 carbon atoms, phenyl, optionally substituted, benzyl, '.

together, the necessary to complete a heterocyclic ring alkyl groups, which may optionally contain a further heteroatom, such as S, N, O; y .

X ~ anion

mean, contains.

Preferred anions to the diazonium cations are those which thermally stabilize the cation, e.g. BF "

ZnCl ₄ ² ", HSO ₄ ", SbClg ", CdCl ₄ ".

The silver-free information recording material of the present invention may be used e.g. as Oiazoraikrofilm, Lichtpausmaterial, Diazo thermofilm and photopolymerization material can be used. Suitable binders for use in these materials are, for example, cellulose derivatives, vinyl polymers, copolymers of vinyl chloride and vinyl acetate, polystyrene, Copolyraera of alkyl acrylates and acrylic acid, polyvinylpyrrolidone, polyvinyl alcohols and polyethylene oxides.

As the support for the photosensitive layer, there may be used, among other polymer films, paper, glass, metal and semiconductor coated films.

Suitable couplers for use of the diazonium compounds in the diazotype are, for example, pyrocatechol and resorcinol derivatives, acetamides or acceptor-substituted 1-naphthols for the yellow image dyes, resorcyl derivatives, pyrazolones, guanidine derivatives or 1,2, for the range of red and purple image dyes. 4-triazolium-echelium, 2-naphthols substituted in the range of violet, blue and blue-green image dyes, hydroxynaph-

thioic acid derivatives, 2,3-dihydroxynaphtholenes, oxybenzotriazoles or in combination with e.g. Nickel salts as more complex benzaldehyde-2-pyridylhydrazones,

., In addition to the coupler types already mentioned here are suitable for the preparation of dyes aush those whose coupling is not started as in the diazotype by the influence of bases, such as aniline or substituted Aminobenzene and -naphthalenes. .

Further suitable additives are, for example, initiators, stabilizers, fading inhibitors, plasticizers, copolymers, monomers, pigments, UV absorbers and the like.

The advantages of the blue light-sensitive recording materials according to the invention lie both in their substantially improved thermal stability and in the improved lightfastness of the image dyes formed. Due to the high thermal stability of the diazonium compounds used, in addition to the use of these components in the diazotype, the use in photopolymerization

•, systems particularly favorable.

· '_. ·. , ι

Exemplary embodiments,.

 example 1

f | Synthesis of S-nitro-pyrrolidinobenzenediazonium tetrafluoroborate

After the synthesis of 3-nitro-4-chloroaniline from 4-chloroaniline with nitrating acid and subsequent acetylation of the amino group with acetic anhydride in benzene, 1 mole of 3-nitro \ A-chloroacetylaminobenzen be heated for 2 hours in 4 moles of pyrrolidine at the boiling point of the pyrrolidines. After completion of the ReaktiOn the reaction mixture is added to crushed ice, 3-nitro-4-pyrrolidinoacetylaminobenzen separates and can be filtered off. The precipitate is stirred into 20% hydrochloric acid and boiled under reflux for 1 hour.

After the reaction, the cooled solution is neutralized and the red crystalline 3-nitro-4-pyrrolidinoanilin separated, 0.1 mol of this substituted aniline are diazotized with the equimolar amount of sodium nitrite at ^{0 0} C in 80 ml of 40% tetrafluoroboric acid to give a yellow diazonium tetrafluoroborate having an absorption maximum in ethanol of 383 nm.

Example 2 ^; , -

Synthesis of 3-nitro-4-piperidinobenzendiazonium tetrafluoroDe 3-nitro-4-chloroacetylaminobenzene prepared according to Example 1 is dissolved in the amount of 0.5 mol in 500 ml of pyridine, treated with 0.6 mol of piperidine and boiled for two hours in the boiling heat.

After the reaction, it is poured onto ice and extracted with ether. After removal of the ether is deacetylated and neutralized according to Example 1. The 3-nitro-4-piperidinoaniline is taken up in ether again, dried and precipitated by introducing HCl as the hydrochloride. 0.2 mol of the hydrochloride are dissolved in 80 ml of 30% hydrochloric acid and diazotized with the equimolar amount of sodium nitrite at 5 to 10 ^P C. After the carbonation, the 3-nitro-4-piperidinobenzediazonium salt is precipitated by addition of a concentrated aqueous solution of sodium tetrafluoroborate as tetrafluoroborate. Yellow crystals, λ in ethanol 384 nm.

Beispiel.3

Zweikoraponentendiazotypiematerial

The following substances are introduced into 1000 ml of a 10% strength solution of cellulose acetate in methylene chloride / methanol, it being important in the order of introduction that the medium be added when the diazonium compound is added to the coupler or when the coupler is added to the diazonium compound is in an acid state

'. , , ^ · '- ⁸ - ·''·

to prevent a pre-coupling.

3.8 g of 3-nitro-4-pyrrolidinobenzendiazoniuratetrachlorozincate

6.0 g of ^ -hydroxy-S-naphthoic acid-α'-methoxy-S'-nitroanilide. 2.0 g sulphosalicylic acid ,

  ο.

The casting solution is heated to 10 to 15 μm. subscribed polyethylene terephthalate pad, dried and gives a yellow transparent film.

After bildtnäßiger exposure behind a xenon lamp and development in a humid ammonia atmosphere gives a positive image of the original with the color impression blue to light yellow. The fastness to light of the formed blue image dye in the solid layer determined by Xenotest is more stable by a factor of 1.8 than a comparable diazotype material with the corresponding diazonium salt without 3-nitro group.

B e i s ρ i e 1 4

Two-component diazotype

In 1000 ml of a 10% Celluloseacetalbutyrallösung in methylene chloride / methanol, the following diazo system is introduced according to Example 6:

0.015 mol of S-chloro-pyrrolidino-S-nitrobenzene diazonium tetrafluoroborate

0.008 mole of 3-hydroxy-3-naphthoic acid 2-anisidide 0.025 mole of cyanoacetic acid piperidide

". 0 _# 0'05 mol of 4-toluenesulfonic _acid;, .15 g of diethyl phthalate

The diazo solution is cast according to Example 3 and processed.

After the development process, a gray-violet positive image of the original is obtained. The resulting image dyes are characterized by two absorption maxima, at 568 nm and 405 nm.

Compared to an analogous diazo material with the corresponding diazo component without 5-nitro groups, the

/ bleach resistance of the system described here to the. Factor 1.6 more stable. Due to the hypsochromic shift of the yellow dye absorption, the duplication behavior of this diazotype material is substantially improved to the same.

Since the dyes formed in the development process have significantly higher extinction coefficients than in the comparison, it is necessary to achieve sufficiently high optical

f "~> densities between D = 1.5 to D = 2.0 only about 50 % of the usual amount of diazo component, the sensitivity is therefore higher by a factor of 1.5.

example

Two-Diazotypeimaterial

In 1 l of a polymer solution according to Example 3, the following components are introduced:

10.2 g of 3-nitro-4-pyrrolidinobenzendiazonium tetrafluoroethane

borate 10.0 g of cyanacetic acid morpholide

2.0 g resorcinol

2.0 g β- naphthol

2.0 g of 4-toluenesulfonic acid

After exposure of a fine line grid and development in a humid atmosphere of anira ammonia, a transparent light brown positive image of the original on a yellow background is obtained *

The image dye is characterized by an optical density> 3 between 360 and 440 nm. The imaged image parts have a yellow color with an absorption maximum at 450 nm and an extinction between 0.6 and 1.0 and an absorption minimum between 350 nm and 400 nm, the preferred sensitivity maximum of photoresist materials. The thermal stability of the Diazoniurasalzes is so high that only measurements above 90 ° C, a thermal decomposition of the diazo component ^ document.

Example 6. , ..

Heat transfer baricidal two-component diazo-type terateriai

In 500 g of a 10% Poiyvinylchloridlösung in methylene chloride / ethylene chloride, 4.0 g of piperazine are dissolved and poured onto 5 m polyethylene terephthalate and dried. On the dry transparent layer, a 10% polyvinyl acetate solution is poured into methanol containing per 100 g of solution the following diazo system:

6.2 g of 3-nitro-4-morpholinobenzenediuronium tetrafluoro-

• <J- borate f. '

6.0 g β- naphthol

4.5 g of trichloroacetic acid

After drying, a transparent film results. After exposure of a template behind a high-pressure mercury larape the material is exposed to a temperature of 140 ⁰ C for 30 seconds. The result is a, red, murmur, s image of the original with a visual density of 1.5.

The unexposed material can be stored at room temperature, no fog can be observed after storage for 6 weeks. Since the diazonium salt etched in here is thermally more stable by a factor of> 2 than a comparable one without the 3-nitro group and O has good coupling activity at the same time, the use of the diazonium compound described here in thermally developable diazo materials proves to be very favorable.

B © i s ρ i e 1 7,

Zweikomponentenlichtpauspapier

In 1 1 0.2% xge solution of polyvinyl alcohol in ethanol / water, the following components are dissolved:

8.0 g of 3-nitro-4-morpholinobenzeridiazonium tetrachlorocin

-ii-

10.2 g of 1-methylbenzylamino-1-methyl-triazoliummetho-

Sulfate 2.0 g of citric acid

The coating solution is hydrophilized paper and dried. After imagewise exposure and development in a humid ammonia atmosphere, a strong purple positive image of the original with good lightfastness of the image dye is formed. ·

Examples

One-component diazotype material ^

A solution of acetone / methanol in a ratio of 2: 1, wherein 0.2 wt.% Cellulose acetate and 3.0 wt.% 3-nitro-4-pyrrolidinobenzendiazoniumtetrafluoroborat in addition to 0.8 wt.% Sulfosalicylsäure are solved by means of a Anspülwalze with a 140, in a strong cellulose acetate film brought into contact, wherein the components to about 12, to diffuse into the polymer film. After imagewise exposure, the piazomaterial is developed in a phloroglycine-containing aqueous soda solution, (pH 10-11), to which 2 % ammonium chloride has been added. It creates a brown positive image of the template,

Example 9

Use of the diazo component for the modification of the solution. properties of polymers'

The following components are introduced into 500 ml of a 5% strength acetone solution of OK lacquer:

20 ml glycidyl methacrylate

10.5 g of 3-nitro-4-diethanolaminobenzonium diazonium tetrafluoroborate

- 12 -

5.0 g of triacrylic

The casting solution is spread onto subbed polyethylene terephthalate backing to give a 8 to 10 μm clear transparent colorless film.

After exposure of a sharp edge behind a xenon lamp and development in chloroform gives a relief image negative to the original with good adhesion to the surface.

B e i s ρ i e 1 10

Use of the diazo component with organically modified anion to modify the dissolving properties of polymers

0.05 mol of S-nitro-morpholino-S-methylbenzendiazonium

tetrachlorozincate

are dissolved in 500 ml of water and slowly added dropwise at 5 ° C 0.07 mol of sodium tetraphenylborate in a little water with good stirring. Yellow 3-nitro-morpholino-S-methylbenzendiazonium tetraphenylborate precipitates, * * X max in ethanol: 394 hm.

The following components are then introduced into 100 ml of methylene chloride:

1.5 g of a copolymer of ethyl acrylate and acrylic acid

3.5 g of a cc -methylstyrene-maleic anhydride copolymer

3.5 g ' ^x pantaerythritol tetraacrylate,

1.5 g of - S-nitro ^ -raorpholino-S-methyl-benzidenediazonium tetra-

phenylborate _v

0.7 g of benzoin ethyl ether

0.5 g eosin

The casting solution is cast according to Example 9 and exposed, wherein the exposure time compared to Example 9 can be reduced by a factor of 5. After development in 2 * 10 molar aqueous solution of sodium hydroxide to obtain a relief image negative for presentation as.red image on a colorless surface.

Claims (1)

Inventory Free silver information recording material composed of support and the photosensitive layer with diazonium compounds, characterized as ^α: urch that the photosensitive layer diazonium compounds of general formula C. in the R _{1 is} hydrogen, alkyl having 1 to 4 carbon atoms, Alkoxy having 1 to 4 carbon atoms, alkoxycarbonyl, alkylsulfonyl, halogen, cyano, phenyl, phenoxy, benzyl, carbonyl, R, R_ the same or different, alkyl of 1 to 6 carbon atoms, phenyl, optionally substituted, benzyl in common, the necessary to complete a heterocyclic ring alkyl groups, which may optionally contain another heteroatom, such as S, N, 0; x " anion
mean, contains.