DE1026170B - Process for the preparation of dye images and light-sensitive material for carrying out the process - Google Patents

Description

GERMAN

The invention relates to a new photographic process and a new light-sensitive material. object of the invention is a photosensitive material that can be easily processed and is insoluble Pigment images results. The invention also includes the method of producing photographic images from insoluble phthalocyanine pigments.

According to a feature of the invention, the photosensitive material consists of a base, e.g. B. a self-supporting film, foil, plate, paper or fabric or one of several These materials are layered support, on which there is a layer with a certain Solvent-soluble phthalocyanine intermediate complex and a reducing agent that can be activated by light Agent is in the form of one or more of the following substances: oxalic acid, a-oxycarboxylic acids and Ammonium and alkali metal salts, e.g. B. sodium or potassium salts.

The photosensitive material is made by coating the surface of the support with a solution of the in one Phthalocyanine intermediate complex dissolved in organic solvents and one which can be activated by light reducing agent in the form of one or more of the following substances: oxalic acid, cc-oxycarboxylic acids and said salts of these acids, and by subsequent drying of the recovered material manufactured.

The novel photosensitive material according to the invention can be obtained by simple, inexpensive treatment permanent and extremely lightfast color images, which consist of insoluble phthalocyanine pigments.

A group of α-oxycarboxylic acids useful in the invention and their salts correspond to the general formula:

R '

R "

C (OH) COOQ

in which Q is a hydrogen or an alkali metal atom or an NH ₄ group and R 'and R ", which can be the same or different, hydrogen atoms or alkyl (ζ. B. methyl, ethyl, propyl, isopropyl The radicals R 'and R "should be preferred contain no more than 14 carbon atoms each. Particularly preferred compounds according to this formula are glycolic, glyceric, lactic, α-oxyisobutteric, tartaric, lemon, almond, benzil, atrolactic, gluconic, sugar, mannonic, mucous and taloic acid and sodium -, potassium and ammonium salts of these acids.

Method of manufacture
of dye images and photosensitive material for carrying out the process

Applicant:

EI du Pont de Nemours and Company,
Wilmington, Del. (V. St. A.)

Representative: Dipl.-Ing. R. Müller-Börner,

Berlin-Dahlem, Podbielskiallee 68,

and Dipl.-Ing. H. H. Wey, Munich 23,

Patent attorneys

Claimed priority:
V. St. v. America April 20, 1955

Charles John Pedersen, Salem, NJ (V. St. A.),
has been named as the inventor

If desired, the surface of the support, especially if it is water-repellent, with a Layer of a water-permeable colloid, for example gelatin, polyvinyl alcohol, polyvinyl acetal, etc., provided be. Such a layer absorbs or sucks the solution of the complex and the reducing acid or the salt and, when the material is processed, serves as a carrier for the photographic result Image.

The solution of the phthalocyanine intermediate complex and the reducing acid or salt may be one aqueous solution or dispersion of a water-permeable colloid are mixed, whereupon the surface a support coated with the obtained dispersion for the purpose of forming a photosensitive layer and is dried.

In the production of photographic images according to the invention, the light-sensitive material is through a halftone, halftone or line negative on a transparent base exposed to actinic radiation and the proportions of the complex not changed thereby by treatment a) with a leucophthalocyanine dissolving solvent or b) removed with an aqueous solution of a strong acid, whereby a positive image is created from a phthalocyanine pigment. The image-bearing material is then washed in water and then dried.

709 909/353

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Various actinic light sources cannot have a coloring effect compared to the insoluble ones

used for irradiation. Suitable for this are phthalocyanines (which have an intense reddish-blue

are: sunlight, carbon arc lamps, mercury vapor to greenish-blue in color).

Arc lamps, fluorescent lamps with special, ultra- Compared to the generally almost insoluble fluorescent substances emitting violet light, argon- 5 Phthalocyanine parent substances are the phthalocyanine

Glow lamps and photographic floodlights. These intermediate complexes in the usual organic solutions

actinic light sources emit medium in the range of 1800, for example in methanol, ethanol, chloroform,

up to 7000 Å and also strong wavelengths between acetone, 2-ethoxyethanol, ethylene glycol, monomethyl,

3000 and 4800 Å, which are probably the most effective monoethyl or monobutyl ethers, benzene, toluene and in emanations. You can easily dissolve the xylenes from various ent- ^{1 Q.} However, they are in water

distances are used, but they should not be soluble in all.

common distances of 18 to 50 cm from the surface While the exact reaction mechanism of the color

the layer to be exposed. education is not known, it is believed that the

Among the "soluble in a solvent phthalo-weakly reducing effect of oxalic acid or the cyanine intermediate complexes «are here the phthalo ± 5 α-oxycarboxylic acid or its salts by the ultra-

Cyanine intermediate complexes meant, which is increased from a higher violet light, so that the reduction of the

Oxidation stage of a phthalocyanine or from I ¹ Z ₂ mol phthalocyanine intermediate complex is made possible. in the

A phthalocyanine and the usual general is the reducing acid or its salt

organic solvents (for example in methanol, used in molecular excess, before ethanol, Acetone, toluene, chloroform, benzene, dioxane 20, preferably in amounts of 1 to 10 mol of the reducing

and in the monoethyl ether of ethylene glycol) soluble acid or salt to 1 mole of the phthalocyanine

are. These include the following classes of intermediate complexes.

bindings: Before use must be the photosensitive (I) The solutions from French patents 1,068,092 and the photosensitive material in full and 1,094,376 known compounds that are likely to be kept in the dark or must not be known to anyone 1.5 molecules of phthalocyanine are exposed to actinic light. To understand, where half the molecules spatially guard against unwanted exposure, the usual is sufficient right on the flat structure of the base phthalo darkroom safety light.

cyanine molecule. Suitable compounds Of course, the exposure time depends on the intensity These classes are obtained by adding a 30 of the light source, the sensitivity of each

Phthalonitrile, ammonia and an anhydrous phthalocyanine intermediate complex and the redox

Copper or nickel salt in an alcoholic potential of the reducing agent used

Solution to be made to react, whereby the pending. In general, an exposure time of

extracted compounds have the property that 0.10 to 10 minutes are required to produce an image Reduction a metal phthalocyanine to evoke a 35 of intensity.

To supply phthalonitrile and ammonia. Removal of the phthalocyanine intermediate complex

(II) A compound of the formula from the unexposed surface elements and the not

, QD, MV _C ν exposed parts of the originally light-sensitive

" ^Λ borrowed layer can be done by using a metal- or metal-free Phthaloplex solvent which dissolves the Comin of the MPc. If the cyanine molecule means X is chlorine or bromine, R an unexposed areas-removing bath acid uses an alkyl group and η does not mean than 1 and not to become, various aqueous acids can be greater than 4. The metal phthalocyanines that can be taken are those of Cu, Co, Ni, hydrochloric acid, hydrofluoric acid, silica fluorine-Cr , Fe, Mg and Na. 45 Hydrogen acid, sulfuric acid, organic sulfonic acids, (III) A compound of the formula phosphoric acid, partial ester of phosphoric acid, organic

ivrp _ / η r π RI phosphonic acid and perfluorocarboxylic acids. In space-

The acids a metal Odei metal-free phthalocyanine concentration ^ are common in a 5 to 50 ° / _o by weight of MPC Konin (based on the weight of the water) vercyaninmolekül and an alkyl radical COR 50 applies a. The aqueous acid solutions can not standard (based on the weight of the water) / ₀ not more than 7 carbon atoms, a water-soluble alcohol, for example methanol less than 2 and means 5 to 50 ° weight organic carboxylic acid having a total. and ethanol. In general, preference is given to the compounds of classes (II) and (III) and an alcohol concentration by weight of 1 to 2O ⁰ Z _0. Details of the process for their preparation are preferred.

from U.S. Patents 2,662,895, 2,662,896, The method is followed by the following, den

662 897 known. Non-limiting examples of the invention

The »phthalocyanine used according to the invention - further explained:
Intermediate complexes are also sometimes referred to as

Phthalocyanine precursors, propigments or with the example in 60
the common expression used in vat dyeing as

Leukophthalocyanine denotes; Four solutions A, B, C and D are made as follows, that during a leuko vat connection set:

The reduction product of the dye is the leuco-A: 4.5 g of the copper phthalocyanine propigment
phthalocyanine in a certain sense a higher 65 Cu Pc (Cl) (OCH)
Oxidation level as the corresponding phthalocyanines ³ "'
represent, since they give the latter on treatment with reducing agents (prepared according to Example 4 of the USA patent specification. These complexes are per se 2,662,896) are dyed in 150 ecm chloroform at space weakly (whereby in solution they have a yellow-brown, temperature dissolved and the solution have reddish brown or purple color by filtering), but have cleared 70.

B: 2.5 g of oxalic acid dihydrate are at room temperature dissolved in 300 ecm of a saturated solution of the propigment used in solution A in methanol. C: 50 ecm of concentrated hydrochloric acid (37% HCl)

mixed with 150 ecm methanol and 150 ecm water. D: 2% aqueous ammonia.

A # 1 Whatman filter paper is immersed in Solution A and hung to dry for 5 minutes. Then it is immersed in solution B and dried for 15 minutes. The treatments with A and B are carried out in a darkroom at room temperature. The dark yellow colored one thus produced Paper is placed under a high-contrast photographic negative under window glass for 6 minutes exposed to direct sunlight. The dark yellow color turns green when exposed to sunlight above. The exposed paper is immersed in solution C for 1 to 5 minutes until the yellow-colored portion disappears. The acid decomposes the unchanged propigment, with the blue positive copper phthalocyanine copy remains on the paper. The blue positive copy is first in solution D, then in Water washed and finally dried.

In a modified process, the copy is made after exposure in sunlight by dissolving the Unchanged propigmentes developed using acetone before being treated with solutions C and D. will.

Example 2

By dissolving 1 g of the metal-free phthalocyanine precursor (or of the leuco-calcium phthalocyanine) according to Example 2 of US Pat. No. 2,681,348 in 100 g Acetone is used to make solution E-I.

Solution E-2 is obtained by dissolving 2.5 g of oxalic acid dihydrate in 300 ecm of methanol.

In subdued daylight, a piece of filter paper is immersed in the solution E-I, after 5 minutes of drying air immersed in Solution E-2 and then air dried again for 15 minutes. That Paper is now covered with a piece of glass on which a pattern has been drawn with charcoal pencil, and then (about 5 to 10 minutes) with a 275 watt General Electric »Reflector Sun. «-Sunlamp exposed until the yellow color disappears. The paper is then with the solutions C and D described in Example 1 treated. The metal-free phthalocyanine pigment in the image of the pattern obtained in this way has a greenish-blue color Coloring.

Example 3

By dissolving 0.05 g of nickel phthalocyanine propigment (made from NiPc and tertiary butyl hypochlorite according to Example 3 of US Pat. No. 2,662,895) and of 0.04 g of oxalic acid in 5 ecm of methanol solution F is produced.

In subdued daylight, a sheet of filter paper is dipped into solution F, after 5 minutes of drying air immersed in Solution E-2 and then air dried again for 15 minutes. That Paper is then covered with a piece of glass on which a pattern has been sketched with charcoal pencil, and 105 minutes under with 275-watt General Electric "Reflector-Sun" sun lamp from a distance of 28 cm exposed. The copy is then developed by dissolving the unchanged propigment with chloroform. The color of the nickel phthalocyanine pigment in the image of the pattern is a greener blue than that of the image Example 1 obtained with copper phthalocyanine.

Example 4

By dissolving 1 g of dodecachloro-leuco-calcium-phthalocyanine and 0.8 g of oxalic acid in 100 g of acetone, solution G is prepared. (The leuco connection will from phthalonitrile, ammonia and calcium oxide by the method according to Example 1 of the USA patent 2,681,348 except that 99 parts of 4,5-dichlorophthalonitrile were used in place of that in this example 64 parts of phthalonitrile used are taken.)

A sheet of filter paper is filled with the leucophthalocyanine and oxalic acid solution G, dried, then immersed in the solution E-2, and thereafter dried again as described in Example 3. After covering part of the treated On paper, this is done for 105 minutes with a 275-watt General Electric -> Reflector-Sun "sun lamp 28 cm from the paper exposed. The copy is developed with solutions C and D as described in Example 1, after which the exposed part has a green coloration.

Example 5

Solution H is prepared by dissolving 2 g of copper phthalocyanine precursor, Cu (C ₈ H ₁ Ng) ₆ -NH (which is known from French patents 1,068,092 and 1,094,376) in 150 ecm chloroform. Solution I is obtained by dissolving 2.5 g of ammonium almondate in 100 ecm of water.

In dim light, a sheet of filter paper is dipped in solution H and dried, then in the Solution I immersed and dried again. The paper treated in this way is placed under a negative for 30 seconds Long exposure to direct sunlight and continue with solutions C and D, such as in Example 1, treated. The copy obtained shows a positive image with blue tint.

Example 6

Example 5 is repeated with the exception that the solution I by one of 2.5 g of mandelic acid in 100 ecm of water is replaced. The photoreduction is even faster than in example 5. In both Examples give similar results.

Example 7

Example 6 is repeated with mandelic acid and benzilic acid as photo-reducing agents. The exposed and developed Papers show clear images, although the image produced with benzilic acid has a greater density and has a stronger contrast than that evoked with mandelic acid.

Example 8

Example 5 is repeated with the exception that the solution I by a solution of 2.5 g of atrolactic acid in 100 ecm of water is replaced. The copy obtained is similar to the copy produced according to Example 5.

If the ammonium salt of atrolactic acid is used instead of the free acid of this example, achieved similar results.

Example 9

When the light is subdued, a piece of "Dacron" fabric made from polyethylene terephthalate fibers in a saturated solution of sodium chromate is immersed in methanol, taken out of the solution and dried. The tissue is then immersed in solution H, dried and finally in solution I according to example 5

immersed and then dried again. The fabric is then partially opaque Cover material and apply it to a 275-watt General Electric from a distance of 11 inches for 5 minutes. "Reflector-Sun" irradiated. The exposed Copy is developed with solutions C and D as described in Example 1. Those exposed to the light Parts of the fabric that have been in the past are colored blue, and the parts that have not been exposed are almost white.

Following the procedure of this example, other fabrics such as cotton, silk, wool and also paper, successfully printed with patterns using copper phthalocyanine.

Example 10 ¹ p

In dim light, a piece of cotton fabric is immersed in a solution of 1 g of the copper phthalocyanine precursor according to Example 5 in a mixture of 25 ml of chloroform and 25 ecm of methanol. After air drying the fabric is impregnated with a l ° / _o aqueous solution of Di-ammonium oxalate. Excess moisture is squeezed out and the fabric is placed between two glasses, the top glass bearing a pattern drawn in charcoal. The whole thing is exposed to direct sunlight for 5 minutes. The fabric is then removed, immersed in solution C according to Example 1 for half a minute, rinsed thoroughly in water, neutralized with dilute aqueous ammonia and finally dried. A blue pattern of copper phthalocyanine was obtained on the fabric.

This example is repeated with the modification that the cotton fabric is replaced by a piece of silk fabric will. The process is also applied to a piece of cotton fabric dyed yellow with a real color. The result shows a blue image on a yellow background.

Example 11

40

The following three solutions are made: A: 1 g of the copper phthalocyanine precursor according to Example 5

is dissolved in 50 ecm chloroform. B: 0.008 g mole of glycolic acid in 20 ecm of methanol. C: 50 ml of concentrated hydrochloric acid (37 ° / ₀ HCl) in 150 ecm of methanol and 150 ecm of water.

A sheet of filter paper is immersed in solution A for minutes under dim light. The paper is then removed and air dried in the dark for 30 minutes. The reducing acid is then applied to the dried paper by placing a sheet of filter paper soaked with solution B on it is pressed. The original paper is then dried in the dark, in a cut out Mask frame placed and exposed to direct sunlight for 2 minutes. The paper is then out of the Frame removed, immersed in solution C for 5 minutes, then rinsed in water with diluted neutralized aqueous ammonia and finally dried.

By using an equivalent amount of lactic acid, cc-oxyisobutyric acid, tartaric acid or citric acid instead of the glycolic acid according to Example 11, similar results are obtained.

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Claims (11)

PATENT CLAIMS: 1. Process for the preparation of dye images by means of a photosensitive material which one irradiated with actinic light through a transparent image, characterized in that one uses a photosensitive material having a layer containing a solvent soluble Phthalocyamn intermediate complex and a photoactivatable reducing agent in the form one or more of the following substances: oxalic acid, α-oxycarboxylic acids and ammonium and alkali metal salts of these acids, and the material remains unchanged after exposure to one of these remaining phthalocyanine intermediate complex dissolving solvent or with a water-containing solvent Solution of a strong acid treated. 2. The method according to claim 1, characterized in that the light used for image generation contains a significant proportion of wavelengths from 3000 to 4800 Å. 3. The method of claim 1 or 2, characterized in that the acid is applied / ₀ by weight concentration by weight (based on the weight of the water) with a 5- to 50 °. 4. The method according to any one of claims 1 to 3, characterized in that the acid is used in an aqueous alcoholic solution with a weight of 5 to 50 ° / ₀ (based on the weight of the water) of a water-soluble alcohol. 5. Photosensitive material for carrying out the method according to claim 1 to 4, characterized in that that on a support a layer with a solvent-soluble phthalocyanine intermediate complex and a photo-activatable reducing agent in the form of one or more of the following substances: oxalic acid, cc-hydroxycarboxylic acids and ammonium and alkali metal salts of these acids is present. 6. Material according to claim 5, characterized in that the ct-oxycarboxylic acid or its salt of general formula: R ' R ' C (OH) COOQ corresponds, in which Q is a hydrogen or an alkali metal atom or an ammonium group and R ' and R ", which can be the same or different, hydrogen atoms or alkyl, aryl, carboxyalkyl, Are oxyalkyl, carboxyoxyalkyl, polyoxyalkyl or carboxypolyoxyalkyl groups. 7. Material according to claim 6, characterized in that R 'and R "do not have more than 14 carbon atoms each contain. 8. Material according to claim 6, characterized in that the a-oxycarboxylic acid or its salt Glycol, glycerin, milk, a-hydroxyisobutter, wine, lemon, almond, benzil, atrolactin, GIucon, Sugar, mannonic, mucic or taloic acid or a sodium, potassium or ammonium salt is one of these acids. 9. Material according to one of claims 5 to 8, characterized characterized in that the support is coated with a layer of a water-permeable colloid which is the intermediate phthalocyanine complex and the oxalic acid or the α-oxycarboxylic acid or a salt contains these acids. 10. Material according to one of claims 5 to 9, characterized in that it is a phthalocyanine 9 10 Contains intermediate complex that is in an alcoholic 11. Material according to one of claims 5 to 10, Solution by reaction between a phthalo characterized in that the oxalic acid or nitrile, ammonia and an anhydrous copper α-oxycarboxylic acid or a salt of these acids therein or nickel salt is obtained and has the property in an amount of 1 to 10 moles per mole of the in one in the case of reduction a metal phthalocyanine, a phthalocyanine intermediate to supply nitrile and ammonia. complex is present. © 709 909/353 3. 58