DE2028368A1 - Process for creating a direct positive metal image - Google Patents

Description

Eastman Kodak Company, 343 State Street, Rochester, New York State, United States of America

Process for the production of a direct positive metal image

The invention relates to a method for producing a direct positive metal image in a light-sensitive Layer of a photographic material.

The previously known photographic processes for the production of photographic images are based on the use of photographic recording materials with silver halide emulsion layers. In these proceedings, it is used by Exposing a photosensitive silver halide emulsion layer produces a latent image. It will the silver halide bearing the latent image by selective reduction evolved to silver while that after evolving remaining unreduced silver from silver halide solvents including those substances that make the non-reduced silver chemically insensitive or transparent can make is removed. If necessary, more necessary treatment measures are reinforcement «reduction, Toning and dyeing. However, the primary or first step in imaging in this type of process is always one selective reduction and is based on a silver halide material limited.

009882/1426

A recently become known another photograph ladies method is that _ß © © in specially prepared © silver halide emulsion is used which contains a certain amount of an organic compound which changes the solubility of the Siiberhalogenids § © ,, that the SiI-berhalogenidkörnchea under the Einwirlcimg Loosen the ^one organic compound in the usual Silberhalegenidlöstragsmittela slower than usual "One such emulsion layer exhibiting photegraphisch @ s Aufzeichaisagsraaterial is imagewise exposed and unexposed areas can'll then treated in © iner solution of Silberhalogenidlösungsiitittels" to give a positive Silberhalogenidbildesv

Task der_vorliegend @ n invention was © s mm, © is further _e 'of the known gj & BROAD-ätzlich different und'verbessertes anzugeben- method for producing metal images diirelctpositiver ₁ in which the photosensitive layer dms w @ \ photo ns®mä®t®n = graphic display, gssiat @ slals Ic © Ise Silb®thalQg®nidpaX " tikel 2u needed

The invention has been approved by a direct positive metal image with a light-sensitive layer of a photographic recording film which is characterized by ₈

a) the light-sensitive layer, which sends a «s @ eat © r continuous metal! or is made of particles, a metal © that of an oxide, sulfide, selosside or halogsmids © ia @ s metal d ©? Groups Ib ₉ HB ₈ UIa, IVa _s Va and VIII "feg Periodic System of the Elements" with the exception ¥ @ a silver halide ^ with an adsorbi @ rtea ₉ © iae Me? Captss & v @ rbindusig un-d-a o, ^ - Unsaturated compound consists of thai tend © light © i ^ £ inalichen mass, which d © n ch © miscfe®a Ä handle it φϊώ. Bleaching agent and the physically © development <i © ir light-sensitive layer voy the Baliclifaag inhibits ₀ aiit -octi-. aischer radiation imagewise 'exposed

b) for the removal of the exposed areas of the brings light-sensitive layer into contact with a chemical bleach.

The advantage of the method of the invention is readily apparent and is primarily that it is no longer thereafter it is necessary to use a photographic recording material containing silver halide. Rather, the subject matter of the present invention is primarily a V drive for the production of direct positive metal images from substances other than silver halides. In this respect, the method according to the invention differs significantly from the previously known methods for image generation, which primarily based either on a first selective reduction step or on the use of a silver halide-containing photographic recording material.

üie photosensitive mass, which the chemical attack by a bleach and inhibits the physical development of the photosensitive layer prior to exposure to actinic radiation, a photosensitive sulfur compound, especially a mercaptan compound, and an α, β-unsaturation must be used Connection included.

According to a preferred embodiment of the process of the invention, the photosensitive mass adsorbed on the photosensitive layer contains, in addition to the important sulfur and α, e-unsaturated compounds also use a spectral sensitizing dye for the purpose of inducing the photoreactivity of the sulfur compound in the visible region of the Spectrum. A preferably used spectral sensitizer The dye is rose bengal. It has also been found that when using spectral sensitizing dyes the 'Sensitivity of the procedure is improved.

009882/1426

2028388

According to a preferred embodiment of the invention Silver seeds are used as metal particles in the process. The use of silver particles has proven to be particularly advantageous proved, since it is possible to use it as a direct positive Generate silver image.

According to a further preferred embodiment of the invention after contacting the photographic material with a chemical bleaching agent as the active centers for physical development, which is the photographic Recording material is subjected to further stages, also particles of metals or metal compounds used with the exception of silver halide. Thus, the photographic material can be made according to the method of the invention exposed to actinic radiation, for example, in order to destroy the inhibiting effect of the photosensitive mass adsorbed on the remaining, previously unexposed germs and then the photographic recording material can be contacted with a solution of a metallic compound, thereby causing physical development

an ee «· metal image is positive

In carrying out the method of the invention, the photosensitive mass attached to a continuous metal layer or adsorbed on a layer of particles of metal or a metal compound other than silver halide is, are applied by the photographic recording material, which consists of a support and a There is a metal layer with the photosensitive mass, for example by bathing the layer support with the layer applied thereon Layer of metal particles in a solution of the photosensitive mass brings into contact »The photosensitive Mass can also be incorporated directly into a layer on the substrate «whereby this layer is both silver»

009882/1426

halide-free metal particles as well as the light-sensitive ones Contains mass. A non-polymeric photosensitive composition is preferably used.

Since the photographic process of the invention is based on a new photographic principle is the present invention Of course, not even on a special class of photosensitive compounds, chemical bleaching agents or metallic substances Particles limited.

In the case of the sulfur compound contained in the photosensitive composition it is preferably a thiophenol compound. Particularly preferred thiophenol compounds are those represented in at least one form by the following general formula can be represented! .

R - S - H

where R is an organic group with a directly attached to the sulfur atom-bonded carbon atom means

Compounds of this class of preferred used include heterocyclic mercaptans, dimercaptans, and aliphatic and aromatic mercaptans.

Other preferred sulfur compounds used are e.g. B «t

7,13-dithianonadecane-T, 19 "bis" pyridinium-p-toluene% sulfo3iatr

3-mercapto-1,2,4-triazole,

1-octyl-1,2 »3,6-tetrahydro-1,3,5-triasin-4-thiol" t-decyl-1,2,3 _# 6-tetrahydro "» t, SjS-triazin ^ -thiol, 1-Hexyl.1 ₉ 2a3 _t 6-tetrahydro-1 | 3 "S-triazine-4" thiol ₉ 1-propyl-1,2,3,6-tetrahydro "! _f 3,5 »triazine-4-thiol, 1-iUhyl-1,2,3 _i .6-tetrahydro» 1,3, S »triazine-4-thiol _f

.009882 / 1428

»6 ™

1-Cyclohexyl «· 1, 2,3,6-tetrahydxo» 1 ' _s 3 _t S *> triazine-4-thiol ₉ 1 -ΜβΛο-sec.-Butyl-i j2 _# 3 ₉ 6 ° «t®trahydro- 1 eSpS-triazine ^ piperidinylmethyl-Z-tfeio-oxazolidine, 2-mercapt © benzimidazole

3,9-Dithiaundecan-1, 1T-bis (N-methyl-morpholinium) -p-törluol, "Mercapto-5-methyl-1 _{8 2} g 1 4" tria2ol ₉

2-benzoxazole thioI ₀
1 «(3-aminophenyl) -S-me? Capteitrazolhyd ¥ ochloTid ₉ 1- (3-MethyIsulfonamidopheuyl) -5» me reaptot® trazol _f ■ J- (4-CaproylaminopHieayl) -S-mercaptoteirazol ^ 1- (3- Acetamidophenyl) -5-mercaptotetrazole.

Mixtures of two or more @T®n of this inheritance can also be used fertilize to be used »examples of suitable © heterocyclic Mercaptans are yerbiadui ^ ii of the following! Classes

2-mercapto-4-phenylthiazole - -

2-mercaptobenzothiazole _v 6-amiro-2 "Hiercaptobenzthias © l ₀

i-Phenyl-S-mercaptotetrasolg, 5- (2'-Hydroxybenzylid®n) -2- * thiohy4antoin 2-mercaptobenzimidazole, 2-mercapto-5-aminobenzisiidaz @ i ₀

2-mercaptobenzoxazole »

2-mercaptoquinine ₉

2-naphtho (1 ' ₉ 2 *> thiazol-thiol,

2-mercapto-5,6-dimethoxyboxynsthiazoles 6 »Acetylamino-2-mereapt © b @ ngtfeias © !,

o-Lauroylamino-Z-mercaptobenzothiazole » 4-Phenyl-t, 3,4-IhIaUXaZOUdIn-Z-UIiOH,

S.ö-Dihydrö ^ -phenyl ^ H-i ^^ - thiadiazin-Z-thiqh.

Examples of suitable dimercaptans are compounds of following class:

2,3-quinoxalinedithiol, 2,3-dimercaptopropanol,

Toluene-3,4-dithiol, Glycol dimercaptoacetate, Cyclohexane-1,1-dithiol,

2,5-uimercapto-1,3 _v 4-thiadiazole,

-i, 2-thiazole, N-cyanoimine-dikaliuBiditJiiolat »t, 1-dicyano-i, 2-disodium dithiolate ethylene, 2-cyano-3,3-disodium dithiolate acrylamide _t 2-cyano-3 _l 3-dipotassium dithiolate ethyl acrylate, catrisylethiol-dicyanoäthylacrylat, catris-thiol-dicyanoäthylacrylat , trans-dicyanodithiolate-ethyleneditetramethylammonium salt and 3, S-disodium dithiolate-4-cyano-i, 2-thiazole.

Examples of suitable aromatic mercaptans are compounds of the following class:

Thiophenols ß-naphthothiol, p-chlorothiophenol, 2-aminothiophenols 4-aminothiophenoi, p-bromothiophenol, ρ-nitrothiophenoi, Thiosalicylic acid, o-toluene thiol,

009882/1426

m-toluene thiol, p-toluene thiol, 4-t-butylthiophenol 4-nonylthiophenol and 4-t-butyl-o-thiocresol.

Examples of suitable aliphatic mercaptans are compounds of the following class:

n-propylmereaptane,

Isopropyl mercaptan,

n-butyl mercaptan,

Isobutyl mercaptan,

see.-Butylmercaptari, t-butyl mercaptan, n-amyl mercaptan, 2-pentanethiol, sec.-Ainylme reap tan, t-amylmereaptan _t n-hexyl mercaptan, η-heptylmereaptane, n-octyl mercaptan, t-octylinercaptan, 2-ethyl-1-hexanethiol, n-nonylmereaptane, n-decyl mercaptan, n-undecyl mercaptan, η-dodecylmereaptane, t-dodecyl mercaptan,

Benzyl mercaptan,

o-methylbenzylmereaptane, p-methylbenzyl mercaptan, o-ethylbenzy! mercaptan, p-ethylbenzyl mercaptan and p-methoxybenzy! mercaptan,

009882 / U26

Examples of suitable α, ß-unsaturated compounds and spectral sensitizing dyes, which according to a preferred embodiment of the invention on the photosensitive Compounds in addition to a photosensitive sulfur compound are given below. The expression "α, ß-unsaturated" means that between the carbon atoms, which are adjacent to a carbon atom substituted by a reactive group, an unsaturation is present. Preferred examples of α, s-unsaturated compounds that Serving as acceptors for the photosensitive sulfur compound are compounds of the following class:

Cellosolve acrylate,

Dirnethylaminoethyl methacrylate,

Phenylbutynol,

2,3-dibromo-2-butene-1,4-diol,

2-buten-1-ol (10 * in water),

3-butenenitride,

2-propyn-1-ol (10 * in water),

2-methyl-3-butyn-2-ol (10 * in water), Ethylene dicyclohexanol,

2,3-butyne-1,4-diol and

Acrylamide,

Preferred examples of spectral sensitizing dyes are dyes from the class bengal pink, eosin blue, eosin yellow, Tetraiodofluorescein, methylene blue, the pyrylium dye 2,6-bis (4-ethylphenyl) -4- (4-n-amyloxyphenyl) thiopyrylium perchlorate. It should be noted, however, that the choice of a particular sensitizing dye and a particular α, β-unsaturated compound, of course, partly from each photosensitive sulfur compound used to prepare the photosensitive composition depends.

009882/1426

The metal or metal compound particles which can be used as a substitute for silver halide particles include a wide variety of substances. For example, when carrying out the invention, preference is given to using the noble metals and those metals which are below hydrogen in the electromotive Spaainungsreihe. Examples of these metals are substances such as. B. copper, arsenic _β antimony, mercury, platinum, gold and silver. Other substances which can be used as substitutes for silver halide nuclei in the process of the invention are, for example, the sulfides and selenides. Examples of such substances are lead sulfide and lead selenide, zinc sulfide and zinc selenide, nickel sulfide and nickel selenide. In addition, substances such as. B. zinc oxide, zinc hydroxide and lead iodide can be used as a substitute for silver halide. It should also be pointed out that both light-insensitive and light-sensitive materials can be used as a substitute for the silver halide particles in carrying out the process of the invention, for example silver is light-insensitive while lead iodide is a light-sensitive substance.

In some £ By the invention uhrungsformen the particles used have an average diameter of above 25th A particularly expedient range of the particles is between approximately 25 and approximately 100,000 % . One or more of these materials can be used for the coating

The surface on the support of the photographic recording material used in the process of the invention can be a continuous metal layer of one or more of the metals suitable for carrying out the process of the invention. The metal layer can be self-supporting seia _# "for example a copper or aluminum foil. A particularly suitable recording material for lithography printing consists of one

009832/1428

thin even metal coating on a surface that has an ink-water affinity that is different from the corresponding affinity of the metal. For example an aluminum plating by a conventional method such as vacuum plating on a copper plate au be stored and this can be according to the method of the invention are etched to form a useful lithographic printing plate. Particularly suitable metal layers have a thickness of 0.01 to 1.0 mm.

According to a further embodiment of the invention, a Stencil can be made by applying a thin layer of metal to a porous substrate. The solubilizing The effect of the inhibitor is in such areas delayed in which the inhibitor has not been exposed.

Regarding the implementation of the method of the invention Usable chemical bleach should be noted that too for this purpose the most diverse chemical bleaching agents including solvents for the metals and other chemicals which are able to remove the unexposed germs in a chemical manner and / or they can be used to make it transparent. Accordingly, the method of the invention does not apply to silver halide solvents and chemicals Limited bleach for silver. The essential feature of the chemical agents which can be used according to the invention is that that the chosen chemical agent must be able to remove the particular non-silver halide material being used or to make it transparent. As a result, the choice of bleaching agent used will depend on the particular non-silver halide used away.

009882 / U26

A chemical bleaching agent which is preferably used according to the invention and which can be used when silver is used as the non-silver halide material is a ferricyanide bleach bath. Such a bleach bath is from "Kodacolor Manual", October 1955, Chemistry of Mixing Formulas, page 1, no. 2623. In general, it should be noted that a large number of different chemical bleaching agents are known which can be used in practicing the method of the invention. These include, for example, permanganate, persulfate and ferricyanate.

That used in the manufacture of the photographic materials used in the process of the invention Support material can be any of the following, if desired be known support materials, for example a film support made of z. B. cellulose nitrate or cellulose ester, a plastic seal carrier made of z. B. polyethylene or polyethylene terephthalate, paper, metal and glass *

As a binder used to incorporate the in the process of Invention used silver halide-free particles (non-silver halide particles) are suitable, any water-permeable materials, for example gelatin or others hydrophilic substances, e.g. B. collodion, albumin, cellulose derivatives, certain synthetic resins and polyvinyl alcohol are used will.

The invention is illustrated in more detail by the following examples. example 1

A strip of a uniformly exposed photographic Recording material was made by an ordinary method developed to produce a metal silver image. D "= 1.5.

* Max

0098 82 / U28

This developed photographic material was then under IA safety light conditions in a 3 ml one 1% methanolic solution of phenyl mercaptotetrazole (a heterocyclic mercaptan as a light-sensitive compound), 9 ml of a SOIigen ethanol / water solution of acrylamide (90 parts Ethanol, 10 parts of water) and Z ml of a Higeh aqueous solution of the spectral sensitizing dye Bengal pink Solution immersed.

After immersing the photographic material for 30 seconds in the above solution it was dried and for 10 seconds at a distance of 46 cm with a photo lamp / exposed .. The photo graph is before recording material was then immersed in a ferricyanide bleach bath for 30 seconds immersed, and then washed

The procedure described above led to the result, that the photosensitive sulfur compound was removed in the imagewise exposed areas. The imagewise exposed Silver nuclei were preferably bleached and in the unexposed areas where the light-sensitive sulfur compound was still firmly adsorbed on the surface of the silver nuclei, the effect of the chemical bleach on the Silver nuclei effectively inhibited and a good direct-positive silver image was thus obtained,

Similar results were obtained when using the sensitizing dye Bengal pink through the spectral sensitizing dyes eosin blue, eosin yellow, tetraiodofluorescein, Methylene blue and the pyryloxy dye 2,6-bis (4-ethylphenyl) -4- (4-n-amyloxyphenyl) thiapyrylium perchlorate has been replaced,

/ "Nitrophot lamp

009882/1426

Example 2

In this example, the procedure of Example 1 was repeated, this time, however, as a film-forming material Copper foil 0.0254 mm thick was used. The film was made by immersion in the sensitizing agent described in Example 1 Solution sensitized. After imagewise exposure and bleaching in an aqueous, 50 g of potassium ferricyanide per Liter containing solution, the copper foil was preferably etched in the exposed areas.

Example 3

The procedure of Example 1 was repeated, this time however, instead of the photosensitive sulfur compound used in Example 1, a dimercaptan, 2,3-dimercaptopropanol, is used became. In this case too, a satisfactory direct positive silver image was obtained.

Example 4

The procedure of Example 1 was repeated, but this time instead of the photosensitive ones used in Example 1 Sulfur compound an aromatic mercaptan, IMophenol, is used became. In this case, too, a satisfactory direct-positive silver metal image was obtained,

Example 5

The process of Example 1 was repeated, but this time an aliphatic mercaptan, n-butyl mercaptan ₉ , was used as the photosensitive sulfur compound. A satisfactory direct positive silver image was obtained »

009882/1428

Example 6

as .

In this case, a strip of pliotojraphic film with metallic silicones was used for the photographic recording material. In this case, however, the photosensitive composition contained only the photosensitive sulfur compound, plienyluercaptotetrazole, and the α, β-unsaturated compound, acrylamide, i.e. The ρ lotographic recording material was immersed under IA safety light conditions in a solution which contained 3 ml of a methanolic solution of phenyl mercaptotetrazole and 9 ml of a SOUgen ethanol / water solution of acrylamide. After immersing the silver-containing strip in this solution for 30 seconds, it was dried and imagewise exposed to ultraviolet light for half an hour at a distance of 46 cm. The photographic material was then immersed in a ferricyanide bleach bath for 30 seconds. A satisfactory direct positive silver metal image was obtained in the examples described above Light reaction of the photosensitive sulfur compound required long exposure to ultraviolet light.

Example 7

In this example, a strip of film support was used used with colloidal copper seeds on it. the The mean grain size of the colloidal copper used was about 1000 S. This film had a uniform density of about 0.1. The photographic material was then immersed in a solution under IA safety light conditions, which was identical to the solution used in Example 1.

/ 'Then it was washed

009882 / U26

BAD ORIGINAL

After immersing the photographic material in the solution for 30 seconds, it was dried and dried Exposed for 10 seconds at a distance of 46 cm with a photolamp ^. The strip was then in for 30 seconds a chemical bleach for the copper nuclei, i. e. in ferricyanide, dipped, / Γη the image-wise exposed areas the photosensitive sulfur compound was removed and the image-wise exposed copper nuclei were preferably bleached and in the unexposed areas where the photosensitive sulfur compound still adheres to the surface of the When copper seeds were adsorbed, the effect of the bleach on the copper seeds was effectively inhibited.

After this treatment, the copper nuclei formed in the unexposed areas in which they were still firmly attached to the surface the pothead germs adsorbed photosensitive sulfur compound was present, a positive latent image and they established the active centers for physical development. To destroy the inhibitory effect of the previous ones the photosensitive sulfur compound adsorbed with the copper nuclei not exposed to actinic radiation became the stripe of the photographic material at a distance of 46 cm exposed for 10 seconds with a photolamp. In a final step, the strip of photographic material was then physically developed by making it brought into contact with an aqueous solution of dilute silver nitrate, immersed the film in a developing solution containing hydroquinone, and then the developed film ■ washed it with water to stabilize it, with the origin · lent unexposed areas a silver image was obtained. Corresponding results were obtained when the copper nuclei were replaced by silver or palladium nuclei.

/ + Nitrophot lamp

/ The recording material was then washed

009882/1426

Example 8

The procedure of Example 7 was repeated, this time however, instead of the copper nuclei, light-sensitive lead iodide nuclei were used. In this case too, the physical development of the strip of photographic material with a silver compound-containing one Solution obtained a positive silver image.

Although silver is used to produce a metal image in the above examples, the same can be done Other metals can also be used for this purpose. To this end Most suitable and commonly used are metals that are below hydrogen in the electromotive series as they are listed above. These metals too can be used to make metal images, although silver images are most preferred Represents embodiment of the method of the invention.

009882/1426

Claims (8)

Claims Process for the formation of a direct positive metal image in a photosensitive layer of a photographic Recording material, characterized in that one a) the photosensitive layer, which consists of a continuous metal layer or of particles of a metal or an oxide, sulfide, selenide or halide of a metal from groups Ib, Hb, IHa, IVa, Va and VIII of the Periodic Table of the Elements, with the exception of silver halide, having a photosensitive composition adsorbed thereon and containing a mercaptan compound and an α, β-unsaturated compound / which contains the chemical attack by a bleach and the physical development of photosensitivity * Borrowed south before exposure inhibits »exposed imagewise to actinic radiation and b) for the imagewise removal of the exposed areas brings the photosensitive layer into contact with a chemical bleaching agent. 2. The method according to claim 1, characterized in »that one a photographic recording material is used, the photosensitive layer of which additionally contains a spectral sensitizing dye 3. Verfahrenkiach claims 1 and 2, characterized in that that a photographic recording material is used whose photosensitive layer contains silver as the metal. 009882/1426 4. The method according to claim 3, characterized in that nan a photographic material used, its light-sensitive layer as a metal containing colloidal silver. 5. Process according to Claims 2 to 4, characterized in that a photographic recording material is used used its photosensitive layer as a spectral contains sensitizing dye bengal red, eosin blue, eosin yellow, tetraiodofluorescein or methylene blue. 6. Process according to Claims 1 to 5, characterized in that a photographic recording material is used used, the photosensitive layer of which is cellosolve acrylate, D! 2-butene-1 oil (as a 10% aqueous solution), 3-butenenitride, 2-propyn-1-ol (as 101% aqueous solution), 2-methyl-3-butyn-2-ol (as 10% aqueous solution), ethylenedicyclohexanol, 2,3-butyne-1,4-diol or a Acrylamide contains « 7. Process according to Claims 1 to 6, characterized in that a photographic recording material is used used, the photosensitive layer of which contains a mercaptan of the formula R-S-H, in which R is an organic bonded directly to the sulfur atom via a carbon atom Rest means. 8. The method according to claim 7, characterized in that one a photographic recording material is used whose photosensitive layer is phenylmercaptotetrazole as the mercaptan contains. 009882/1426 ORIGINAL INSPECTED