DE1232822B - Photosensitive material and method of making it - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY Int. Cl .: G03c

GERMAN WJfW PATENT OFFICE

EDITORIAL

German class: 57 b-10

Number: 1232 822

File number: N 24646IX a / 57 b

1 232 822 Filing date: March 18, 1964

Opened on: January 19, 1967

Photosensitive material and process

The invention relates to a photosensitive device for the production of this material
Layer with a cyclotetraisoindolenine (endoiso-

indolenine) cobalt complex and at least one re-

reducing agent containing the cyclotetraisoindolenine (endo applicant:

isoindolenine) cobalt complex to a phthalocyanine 5 _. ,, ,, ..

reduced. Vlisco Textieldrukkerrjen,

It is known in a photosensitive layer Helmond (Netherlands)

with a mixture of iron (HI) salts and representatives
Potassium Iron (III ) Cyanide Forming Turnbulls-

blue to use for the production of pictures (blue io Dr. H. G. Eggert, patent attorney,

pause procedure). Cologne-Lindenthal, Peter-Kintgen-Str. 2

Furthermore, a blueprint approach

mendes negative process, the so-called Van Dijke- _A j _{g Er} f _mder named-process known, in which also an iron (III) - _,, '
salt, e.g. iron (III) ammonium citrate, applied 15 CornellsGeerhardVermeulen,
which under the influence of light into an iron (II) - Stiphout (Netherlands)

connection is transferred, the one in the light

sensitive layer present light-insensitive- Claimed priority:

Liches metal salt, mostly silver nitrate, can reduce to metal Netherlands from March 19, 1963 (290 386). 20th

From U.S. Pat. No. 2,915,392 there is a Nega- 2
tiwerfahren known in which the light sensitivity of the inherently weakly yellow-colored complex RongaIit C in an alkaline medium (see, for example, from a copper compound, l-amino-3-iminoiso-Melliand's textile reports, 39, 7/1958, 773), indolenine and oxalic acid , an alpha-hydroxycarbon- 25 acid or a salt thereof is used from the acidic solution at room temperature. From the complex the insoluble cobalt phthalocyanine, the complex arises on exposure which form in water.

and organic solvents insoluble copper In experiments it has been shown that the Anferphthalocyanin. Both the application of the grain turning of such a cobalt complex in the plexes as well as the washing out of the unexposed 30 process according to the US Pat in complete tion for longer than 1 hour there is only an extremely weak absence of water, because it gives a small and completely unusable picture.
Amounts thereof to precipitate the copper phthalocyanine, object of the invention is to provide a lichtempfindso that then provide a sufficient penetration into the 35 Liehe layer, it can be achieved at substrate with the aid of. The exposure times, which are not customary for exposure, are extremely lightfast, and parts of the image can also be obtained with the help of an acid.

be decomposed. The object of the invention proceeds from a In the textile industry, an analog complex light-sensitive layer is formed with a Cyclotetraisobenutzt, the blue cobalt phthalocyanine containing 40 indolenine (endoisoindolenin) cobalt and at least slightly darker than the Kupfeiphthalocyanin and a reducing agent to Cyelotetraisoindoetwa same light fastness properties Has. The lenin (endoisoindolenin) - cobalt complex to a complex consists of cobalt, l-amino-3-iminoiso- phthalocyanine reduced, and is thereby gekennindolenin and a polyamine, z. B. ethylenediamine. characterized in that it comprises a complex of Cyclotetraiso-to dyeing of textiles are -cobalt latter with a 45 indolenine (endoisoindolenin) and treated with a PolyBrei containing in addition to an acidic solution of the amine and an iron (III) salt.
Complex a reducing agent, e.g. B. Hydroquinone Suitable polyamines which the complex contains or contains formic acid. Advertising can, after drying, are ethylenediamine, diethylenetriamine, y, y to the fabrics treated with steam, wherein at diaminopropyl methylamine, 1 - aminopropane dimethyl influence of the elevated temperature and the existing 50, l-diethylamino-4 - amino - 3 amino-n-pentane, to which moisture the complex is reduced to cobalt phthalo- hexamethylenediamine or y, y - diaminodipropyl cyanine. Some reducing agents, such as ether.

Suitable light-sensitive iron (III ) salts are iron (III) chloride, iron (III) oxalate, iron (III) ammonoxalate, iron (III) ammonium citrate or iron (III) citrate. If iron (III) oxalate or iron (III) ammonium oxalate is not used, it is advisable to add a little oxalic acid to accelerate phthalocyanine formation.

A photosensitive recording material can be prepared by having a Layer carrier z. B. from textiles, paper, glass or ceramic material with an acetic acid solution of the cobalt complex, a solution of the iron (III) salt and a solution of the reducing agent or coats and then dries.

The application of the light-sensitive layer to textiles is best done with the help of a matting roller done, which presses the layer on evenly. If desired, the penetration of the To restrict the coating liquid in the substrate as much as possible, a thickener, z. B. gelatin or tragacanth, are added. Drying takes place at temperatures below of 80 ° C, because otherwise decomposition of the complex is possible.

Because the complex itself is not photosensitive, rinsing the exposed recording material with water is sufficient to remove the ferric salt to obtain a light-insensitive blue-yellow image. The unexposed complex can easily removed with a weakly acidic solution. When a blue picture on a white surface is desired, it is advisable to use a weakly acidic rinsing liquid that a little ethyl alcohol and sulfuric acid are added. This becomes the unexposed complex practically immediately completely removed.

The photosensitive layer according to the invention means that significantly shorter exposure times are achieved than required by the method of U.S. Patent 2,915,392. The received Images, including excellent halftone images, have particularly good lightfastness.

The production of images is carried out as usual by imagewise exposure and subsequent washing out with water or diluted acid and rinsing with water. Due to the minimal number of processing steps and the cheap raw materials is particular for the textile industry all of the use of the photosensitive layer according to the invention superior to known photographic printing processes. Because the cobalt phthalocyanine temperatures Can withstand up to 450 ° C without noticeably decomposing or discoloring, can be used as a layer support a non-glazed ceramic material can also be used. After applying a picture to this it can be provided with a glaze layer at temperatures up to 450 ° C, so that e.g. glazed tiles with photographic images can be obtained. Another advantage of the good temperature resistance of cobalt phthalocyanine consists in textiles with photographic images finished or otherwise treated at elevated temperature.

For example

5 parts by weight of a complex of cyclotetraisoindolenine (endoisoindolenine) cobalt with triethylenetetramine with 5 parts by weight of diethylene

glycol rubbed into a paste. The addition of 2.5 parts by weight of glacial acetic acid results in a clear, dark brown solution which is diluted to 100 parts by weight with water. With this coating liquid, white typewriter paper (80 g / m ² ) is treated on one side. The paper is then dried at a maximum of 50 ° C. In the same way, a coating liquid composed of 13 parts by weight of ferric ammonium citrate, 20 parts by weight of oxalic acid and 80 parts by weight of water is applied under subdued artificial light. After drying, the recording material is exposed imagewise to a strong light source. Depending on the exposure time, a light blue to dark blue image is created. After exposure, the unreacted cobalt complex is washed out with a dilute aqueous acetic acid solution. After rinsing with water, the picture can be dried. The washing out of the unexposed parts of the image can be significantly

zo nigt if a liquid is used which consists of 50 parts by weight of ethyl acetate, 20 parts by weight of glacial acetic acid and 180 parts by weight of water.

Example 2

To a mixture of 100 parts by weight of 2.5% aqueous photographic gelatin solution, 10 parts by weight of iron (III) ammonium citrate, 20 parts by weight of oxalic acid are added to a solution, from 2 parts by weight of a complex of cobalt, l-amino-3-iminoisoindolenine and ethylenediamine, 4 parts by weight of methanol and 6 parts by weight of glacial acetic acid is yellowish milk-like liquid that is shaken well for a while to obtain a homogeneous emulsion. According to Example 1, it is used to coat paper and produce an image. After exposure the recording material can be mixed with 50 parts by weight of borax, 60 parts by weight of sodium tartrate, 1000 parts by weight of water moistened and then at a slightly higher temperature intermediate drying can be carried out, which deepens the blue color of the image. To Washed out and rinsed, the picture is dried at temperatures of 100 ° C.

"Example 3

A degreased ceramic tile is provided with a 10 [ µm thick gelatin layer. For this purpose, a solution of 8 g of gelatin in 50 cm ^{3 of} distilled water was soaked for 1 hour, 50 cm ^{3 of} distilled water were added and the mixture was heated on a water bath at 35 to 40 ° C. until a clear solution was obtained. 0.1 mg of saponin and 0.6 cm ^{3 of} 40% formaldehyde solution were added to this solution. The coating liquid was applied to the tile at a temperature of 30 ° C. After 40 hours, the gelatin was dried and sufficiently hardened. In the absence of light, a photosensitive solution was prepared by stirring 3 g of a complex of cobalt, l-amino-3-iminoisoindolenine and ethylenediamine with 10 cm ^{3 of} 96% ethanol, whereupon 5 cm ^{3 of} glacial acetic acid, 10 cm ³ diethylene glycol,

6s 90 cm ^{3 of} 96% ethanol and 10 cm ^{3 of} distilled water a solution was obtained. A second solution was made from IO g of ferric ammonium citrate, 20 g of oxalic acid and. 60 cm ^{3 of} distilled water

Claims (1)

represents. The ingredients were heated together until a clear solution was obtained. Shortly before use, both solutions were combined and then filtered. The clear solution thus obtained was applied to the coated tile. The tile was then air dried in the dark at a relative humidity between 40 to 60%. Immediately after drying, the photosensitive layer was contact-exposed through a negative master copy with the aid of a 125 watt lamp. At a distance of 10 cm between the lamps, the exposure time was 2.5 minutes. By using a light box with 12 of these lamps on a surface of 50-60 cm and a distance to the tile surface of 10 cm, the exposure time could be reduced to 1 minute. It has been shown that the exposure time is shorter when the tile is more humid. To avoid sticking to the master copy, a polyethylene or cellophane film can be placed between the master copy and the tile. After exposure, the tile was left to stand in the air in the dark for 1 hour. Any remaining iron (II ) salts were oxidized. The tile was then briefly rinsed in water and washed in a 30 % acetic acid bath for 8 minutes. After washing for 15 minutes in pure water, the tile was dried at 60 to 80 ° C. To protect the image, a curable acrylic resin was applied to the image and, after drying, cured at 140 ° C. for 30 minutes. Example 4 A fabric made of bleached and mercerized cotton was coated with a photosensitive solution according to Example 3, but in which 6 g of the complex were used instead of 3 g, impregnated. The fabric was air dried until it was slightly damp to the touch. Thereafter the fabric was exposed as in Example 3. It It is important that the fabric does not get warmer than 30 ° C, otherwise the surface may turn blue. The exposure time is 1.5 minutes. Immediately after exposure, the fabric was rinsed well in a water bath at room temperature and then the unreacted complex was washed out with stirring at 30% acetic acid at 60 to 70 ° C. for 5 minutes. The fabric was then rinsed in hot water and dried. Claim: Photosensitive layer with a cyclotetraisoindolenine (endoisoindolenine) - cobalt complex and at least one reducing agent which reduces the cyclotetraisoindolenine (endoisoindolenine) cobalt complex to a phthalocyanine, characterized in that it is a complex of cyclotetraisoindolenine and an (endo-iso-isoindolenine) iron III ) contains salt.