DE1597631C3 - Process for making copies of images - Google Patents

Description

The invention relates to a method for producing image copies using two-component diazotype materials, in which the respectively exposed diazotype material is wet developed.

Known wet-developable diazotype materials normally contain in the photosensitive layer only one color forming component, namely a diazonium compound. Such one-component diazotype materials are developed after exposure with a coupler-containing developer liquid. As a result of coupling of the coupler with the diazonium compound during the development process is formed an azo dye image. The disadvantage of the use of one-component diazotype materials is that the in the required developer liquid coupler contained during its application or storage for a

ι »Oxidation by air is susceptible and that an oxidized Coupler is a colored component that makes the developer liquid cloudy. For this reason the developer liquid cannot be stored for a long period of time. Also provides an exposed, with

i ^; . A diazotype material developed with such a contaminated developer liquid will not produce a spotless, sharp image copy.

They are already two-component diazotype materials became known for the dry development carried out with the help of ammonia gas. When making copies of images with the aid of such diazotype materials, the color development reaction must be carried out be completely expired at the precise point in time at which the material contained the ammonia gas Has gone through the developer tank. For this reason, it is more sufficient to obtain a copy of the image Image density required that the photosensitive layer of the two-component dry developable diazotype material compared to the diazonium

.? ^u bond contains at least 4 to 6 times the molar amount of coupler.

In the case of a photocopier or two-component diazotype material, its photosensitive layer, for example, only a very small amount of about 0.5 to 2.0 moles of coupler per mole of diazonium compound contains, the color development reaction with ammonia vapor is difficult to perform in a single pass expire completely. Even after repeated development processes, something still remains unreacted diazonium compound back, so that a satisfactory image copy is not obtained.

From US-PS 21 41 103 is a type of wet development of exposed two-component diazotype materials known. The development process known from the above-mentioned US Pat however, a very special development technique, whereby the aqueous-alkaline developer solution is mandatory exclusively to those facing away from the light-sensitive layer of the two-component diazotype material Side, d. H. must be applied to the substrate. Through this special development technique of the US-PS 21 41 103, however, you only get copies of relatively low image density. In addition, the warns US-PS 21 41 103 before that, two-component diazotype materials by immersion in aqueous alkaline Liquids to develop, as this is a more or less large mixing of the chemicals in the non-exposed and exposed ^ districts takes place, which leads to the formation of blurred copies or to what is known as bleeding.

DT-PS 5 28 317 also describes a type of wet development of two-component diazotype materials known. The known method works (to distortions of moist cellulose films during

ή 5 Avoid drying) with aqueous alcohol solutions in which the alcohol ^{content is expediently at least 70%.} Although it says aaO on page 1, right column, lines 45 to 49 that the quantitative

The ratio of alcohol to water can also be reduced, although care should be taken in this case must that the film is given as little time as possible to absorb water. Here, too, is a pronounced prejudice against the use of exclusively aqueous developers for two-component diazotype materials. In addition, there would be development of two-component diazotype materials with (mainly used in this field) paper backings with aqueous Aiko- ιυ Hollow solutions of the known composition are not possible at all, because the alcohol because of its strong affinity to paper make such paper backing so soft immediately after its exposure would that the finished copies would be unusable.

The invention is based on the object of a real wet development process for To create two-part diazotype materials.

The invention relates to a method of the type described at the outset, which is characterized is that the exposed, in its photosensitive layer, a diazonium compound consisting of a zinc chloride double salt of

l-diazo-4-benzoylamino-2,5-diethoxybenzene, l-diazo-4- (4'-methoxy) benzoylamino-

2,5-diethoxybenzene,

1-diazo-4- (4'-methoxy) benzoylamino

2,5-dimethoxybenzoI,

1 -diazo-4- (4'-methyl) benzoylamino-2,5-diethoxybenzene,

4-diazo-2,5-dibutoxyphenylmorpho! In,

4-diazo-2,5-diethoxyphenylmorpholine,

4-diazo-1-benzylmethylamino-

2,5-diethoxybenzene or is

4-diazobenzylmethylaminobenzene,
in combination with per mole of diazonium compound 0.5 to 1.5 moles of coupler, consisting of the sodium salt of,

l-naphthol-4-sulfonic acid or 2-naphthol-3,6-disulfonic acid,

2-hydroxy-3-naphthoic acid hydroxyethyl

amide,

2-Hydroxy-3-naphthoic acid diethyl

aminoethylamide, 2-hydroxy-3-naphthoic acid

morpholinoethylamide,

Resorcinol,

l-MorpholinoacetyIamino-7-naphthol,

Ä-Resorcylic acid, the sodium salt of resorcinol monosulfonic acid,

«-Naphthol,

1 -Biguanidino-7-naphthol,

jJ-hydroxynaphthoic acid morpholinopropylamide

or / J-hydroxynaphthoic acid dimethyl

aminopropylamide,

containing two-component diazotype material by applying a coupler-free solution of a alkaline developer compound in water is developed on its layer side.

A two-component diazotype material used in the context of the method according to the invention contains in its light-sensitive layer, compared to a dry-developable two-component diazotype material, only about 0.25 to 0.33 times the molar amount of coupler per mole of diazonium compound. Because of this small amount of coupler, couplers with higher coupling speeds can be used, without increasing the risk of an undesired pre-clutch. A dry development of such a low coupler content two-component diazotype material is not possible.

The development of two-component diazotype materials by means of a coupler-free aqueous alkaline solution, the same is applied on the layer side of the respective diazotype material. This can be done, for example, by applying the developer liquid or immersing the diazotype material in the developer liquid. It should it just has to be ensured that the layer to be developed will continue through for a while after the development the alkaline liquid remains moistened. This ensures that the coupling reaction in this Time runs out completely, resulting in a very sharp copy of the image.

As an alkaline compound in the developer liquids used according to the invention, for example Potassium carbonate, potassium hydroxide, sodium carbonate, potassium metaborate or potassium tetraborate or mixtures of which are used. The best color development is achieved with pH values (of the developer liquid) of between 11.5 and 12.0.

The photosensitive layer of the two-component diazotype materials which can be used according to the invention can, to prevent bleeding of the dyes, 1 to 3 wt .-% thiourea, cadmium sulfate, Contain cadmium sulfide or the like. In addition, inorganic substances can be used in the photosensitive layer or organic acids such as oxalic acid, sulfuric acid, tartaric acid, citric acid or maleic acid or Mixtures of these should be present. By adding 0.5 to 1.0% by weight of boric acid to the photosensitive layer the diazotype material can be given an even further improved shelf life.

The two-component diazotype materials used according to the invention have a better shelf life than the known commercially available dry developable products Two-component diazotype materials and almost as good as the commercially available wet-developable diazotype materials.

Because of their very low coupler content in the photosensitive layer, lies in time and after very few unreacted couplers before development. For this reason there is hardly any There is a risk that the copy of the image will be damaged if the coupler is oxidized on its surface if it is stored for a long time becomes blotchy or faded. So far it has always been accepted that those with wet-developable diazotype materials produced image copies generally have a strong tendency to color fading and therefore do not suitable for those image copies that are to be kept for a longer period of time.

example 1

A photosensitive coating solution made up of the following ingredients:

water 1 1 concentrated sulfuric acid 4 ml citric acid 20 g Boric acid 5g Thiourea 10g Cadmium sulfate 10g Caffeine 10g

2-hydroxy-3-naphthoic acid

hydroxyethylamide · HCl 3 g

4-diazo-2,5-dibutoxyphenyl-

morpholine · '/ 2ZnCl 7 g

. Methylene blue (C.I. No. Basic Blue 9) 0.05 g s

Saponin 1 g

is applied to a prepainted sheet-shaped support and dried. The precoating of the substrate is by means of a suspension of 10 g of colloidal silica of a particle size of 1 to ₀ 5 μίτι and 100 g of corn starch of particle size of 5 μπι been generated in 60 g of vinyl acetate emulsion having a solids content of 50%. The resulting diazotype material is covered on its photosensitive layer with an original, then exposed in a ι =, copier using a 60 W fluorescent lamp against the original and finally developed in a 5% aqueous potassium metaborate solution, a blue-tinted copy of high image density being obtained . The image copy can be filed in a file and kept for 6 months at a temperature of 30 ^° C. and a relative humidity of 80% without its surface becoming stained.

Example 2

By applying a coating solution of the following composition:

Water 1 1 y,

Oxalic acid 20 g

Thiourea 10 g

Cadmium chloride 10 g

1-biguanidino-7-naphthol · HCl 8.5 g

1-Diazo-4- (4'-methoxy) benzoylamino-2,5-; s

dimethoxybenzene / 2ZnCb 18 g

Saponin Ig

Patent Pure Blue (c. S. 42 045) 0.1 g

A diazotype material is obtained on the surface of a white support. ■

The diazotype material obtained is against a template by means of a high pressure mercury vapor lamp exposed and then with an aqueous alkaline 2 wt .-% potassium carbonate solution and 2% strength by weight potassium tetraborate solution, a high-contrast, blue-violet image copy being obtained.

Example 3

A suspension of 20 g of colloidal silica with a particle size of 1 to 5 μm and 40 g Vinyl acetate emulsion with a solids content of 50% in 1 1 of water is used as a primer on one side of a white applied sheet-like support.

A photosensitive coating solution of the following composition is applied to the primer: Water 1 I.

Sulfuric acid 5 ml

Boric acid 5 g

Sodium salt of resorcinol monosulfonic acid 3 g of 4-diazo-2,5-diethoxyphenylmorpholine · '/ 2ZnCl ₂ 10 g

Methylene Blue (C.I. No. Basic Blue) 0.06 g

Saponin 1 g

applied and dried to obtain a diazotype material. When exposing and developing of the same according to Example 1, a brown, high-density image copy is obtained.

Example 4

Two photosensitive coating solutions of the composition given in Example 1, of which but instead of 2-hydroxy-3-naphthoic acid hydroxyethylamide ■ HCl the one 4 g of 2-hydroxy-3-naphthoic acid morpholinoethylamide · HCI and the other 4 g of 2-hydroxy-3-naphthoic acid diethylaminoethylamide are used in the manner described in the preceding examples for the production of diazotype materials used. When exposing and developing according to Example 1, very sharp image copies are obtained, whose shelf life corresponds to the shelf life of the image copy according to B e i s ρ i e 1 1.

Example 5

A photosensitive diazotype material is produced with the aid of a photosensitive coating solution according to Example 1, in which the 4-diazo-2,5-dibutoxyphenylmorpholine · V ₂ ZnCb has been replaced by 7 g of 4-diazobenzylmethylamino-2,5-diethoxybenzene · V _{2 ZnCb} , which is exposed and developed according to Example 1. This results in a very sharp, sky-blue copy of the image.

Example 6

With the help of a photosensitive coating solution according to Example 2, but in which the l-Biguanidino-7-naphthol · HCl is replaced by 10 g of the sodium salt of l-naphthol-4-sulfonic acid, becomes a produced light-sensitive diazotype material, which is exposed according to Example 2 and developed. This produces a sharp, violet copy of the image.

Example 7

With the help of a photosensitive coating solution according to Example 1, but in which the

2-Hydroxy-3-naphthoic acid hydroxyethylamide · HCl by a mixture of 3 g of 2-hydroxy-3-naphthoic acid morpholinoethylamide and 1 g of 1-biguanidino-7-naphthol is replaced, becomes a diazotype photosensitive material produced, which is exposed and developed according to Example 1. Here you get a sharp, blue-violet image copy of greater image density than the image copy of Example 1 has.

Claims (4)

Patent claims: 1. Process for the production of image copies using two-component diazotype materials, in which the respectively exposed diazotype material is wet developed, thereby characterized in that the exposed, in its photosensitive layer, a diazonium compound, consisting of a zinc chloride double salt of l-diazo-4-benzoylamino-2,5-diethoxybenzene, 1-diazo-4- (4'-methoxy) benzoylamino 2,5-diethoxybenzene, l-diazo-4- (4'-methoxy) benzoylamino- 2,5-dimethoxybenzoI, 1 - Diazo-4- (4'-methyl) benzoylamino- 2,5-diethoxybenzene, 4-diazo-2,5-dibutoxyphenylmorpholine, 4-diazo-2,5-diethoxyphenylmorpholine, 4-diazo-1-benzylmethylamino- 2,5-diethoxybenzene or 4-diazobenzylmethylaminobenzene,
in combination with 0.5 to 1.5 moles of coupler per mole of diazonium compound, consisting of the sodium salt of 1-naphthol-4-sulfonic acid or 2-naphthol-3,6-disulfonic acid, 2-hydroxy-3-naphthoic acid hydroxyethylamide,
2-Hydroxy-3-naphthoic acid diethylaminoethylamide, 2-hydroxy-3-naphthoic acid morpholinoethylamide, resorcinol, 1-morpholinoacetylamino-7-naphthol, a-resorcylic acid, the sodium salt of resorcinol, monosulfonic acid or a-naphthoic acid-7-naphthyl-naphthol, 7-j-suanopropylic acid, a-naphtho-naphthol-7-j-suanopropyl-naphtho-naphthol, 7-j-suanopropyl-naphtho-naphtho-naphthol, monosulfonic acid, a-naphtho-naphthol -Hydroxynaphthoesäuredimethylaminopropylamid, containing two-component diazotype material is developed by applying a coupler-free solution of an alkaline developer compound in water to its layer side. 2. The method according to claim 1, characterized in that a diazotype material is used which also contains an acidic stabilizer and a das in its light-sensitive layer Contains an anti-bleeding agent. 3. The method according to claim 2, characterized in that a diazotype material is used which in its light-sensitive layer acts as an acidic stabilizer: oxalic acid, sulfuric acid, tartaric acid, Citric acid, maleic acid or boric acid and as a dye bleeding preventing agent Thiourea, cadmium sulfate, or cadmium chloride. 4. The method according to claim 1, characterized in that a diazotype material with sheet-shaped Substrate with a prepainted surface is used.