DE1447643A1 - Process for the production of a photographic relief image and photographic material for carrying out the process - Google Patents

Description

Double piece

PATENT ATTENDERS 7 STUTTGART I? ^5. *

7 STUTTGART DR.-ING. WOLFF, BARTELS, DR. BRANDES 17/51/25/49 long street si

TELEPHONE: 296310 and 297295 TELEPHONE: 0722312

Reg.

Eastman Kodak Company, 345 State Street, Rochester State New York, United States of America

Process for producing a photographic relief image and photographic material for carrying out of the procedure.

The invention relates to a method for producing a photographic relief image and to a photographic one Material for carrying out the procedure.

The production of relief images by developing an exposed silver halide emulsion layer by means of certain Developer compounds which harden the colloid of the emulsion layer in the developed areas are known. In a known method an exposed gelatin-silver halide emulsion layer is, for example, Pyrocatechol is developed, whereupon the unexposed areas are washed away with warm water, creating a relief image is obtained. With this procedure, however, it is

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not possible to make gelatin insoluble at greater distances from the point of development, because catechol Gelatin only to a distance of less than about 0.01 mm from the point where the catechol is oxidized, makes insoluble. As a result, it is not possible to use gelatin or similar colloids in a layer free of silver halides by the action of developing an exposed SiI overhalide emulsion layer to make the oxidation products obtained insoluble. If this were the case, it would be possible to arrange the silver halide-free layer on the support, on which the relief image is to be formed. The relief image could for example be formed on a metal plate and further processed into a relief printing plate by etching will.

The invention was based on the knowledge that tanning developer compounds, namely 1,4-dioylbenzene compounds, are able to gelatin or similar colloids at a distance of more than 0.01 mm from the point where the oxidation of the developer compound is going on to make it insoluble. This made it possible to provide a method for producing a photographic relief image in gelatine or similar by » to develop permeable colloids, which is based on the imagewise transfer of diffusing oxidation products of these developer compounds from a developing,

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exposed silver halide emulsion layer to one of The colloid layer separated from the emulsion layer is based

The invention therefore relates to a method of manufacture a photographic relief image in which a nivor imagewise exposed light-sensitive and essentially uncured silver halide emulsion layer Developed with a tanning developer compound. The method is characterized in that the emulsion layer is in contact with a layer disposed on a support preferably pigmented, silver halide-free colloid layer treated with a 1,4-dioxybenzene compound becomes, whereupon the layers separated from each other and

in _n the unhardened areas of the colloid layer / known per se are removed by washing.

Accordingly, an exposed silver halide emulsion layer becomes according to the invention developed with a developer whose oxidation products are capable of producing a colloid such as To harden gelatine etc. also at greater distances from the development site. As suitable for this only quite certain tanning developer compounds, namely 1,4-dioxybenzene compounds such as hydroquinone, chlorohydroquinone, bromohydroquinone, toluhydroquinone, morpholine methylhydroquinone etc. proved. Other tanning developer

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like £ »B« Srenskateohin »Chiorbrenzkatechin» Xethylhrene catechol »Phenylbrenekateehin, Morpholinbrenskateohin« pyrogallol and gallic acid and on the other hand unsuitable for surfing the process of the invention.

eohicht 2rfindu & g * ge »äJ3 the Eaulaion / geaäS is a precaution th execution form during the development for a time, which stands out from gelatine with the oxidation products of the developer formed during the development reaction su harden "pressed against a gdlatineeehiefat arranged on a special support, whereby the Celatineeo layer is hardened imagewise * The no silver halide containing layer is then stripped from the silver halide emulsion and treated with warm water to remove the unhardened areas as shown below, revealing a relief image in the gelatineechioht which does not contain silver halide *

According to the invention, the oil coating is preferably on a different support than the one on which the Silberhalegenidemulflisnseehioht is arranged. In order to get stronger gelati & ereliefe than is usually the case However, it is also possible to use a material in which an egg halide-free selatin layer under the silicon

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Over halide emulsion on the same support

arranges let · If the Silberhalogenidemulsionaechieht "then developed as the Gelat! neunterschicht just case" imagewise hardened "is In this embodiment, the amount of silver halides _y needed to make a strong gelatin relief au receive less than that required for an ordinary photographic relief image set where the silver halide pervades the entire gelatin structure * However, in this embodiment, both layers should consist of essentially unhardened gelatin «

The uncured oleatin layer containing no silver halide can also be arranged as a coating layer over the silver halide emulsion layer. For example, starting from an appropriately sensitized photographic material, single color images can be produced without that expensive color films are required. In graphic work it often happens that colored line or halftone images are produced without the need for costly and tedious development of photographic color materials should be. For this purpose, the silver halide-free colloid layer can simply be pigmented, or it can be an * -. medium and contain a dye. The from the developing emulsion «migrates into the silver halide-free gelatin layer.

Gaydationaprcdnkte-promoting cure the Qelatineachicht then imagewise, Uo dag, when the unset areas are subsequently removed, aurückbleibt a pigmented or colored image.

In the embodiment of the invention in which the silver halide-free Selatin is arranged on a separate support, the gelatin should essentially be uncured. Also the gelatin of the silver halide emulsion layer should consist of essentially uncured material to avoid that if necessary any hardener present is transferred to the layer containing silver halide-free gelatin »Sas no Silver halide-bearing colloid can also be used from gelatin from any of the known alkali permeable colloidal substances that are used for photography purposes as binders for the silver halide will. The coverage of the silver halide emulsion is not critical and can vary depending on the intended use to be different. Expediently, about 50 - 500 mg of gelatin and about 100 - 300 mg are allotted to an area of 0.09 a Silver.

The silver halide emulsion layer can be selected from known ones Silver halide emulsions, including silver chloride,

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■ '"■■ ... ·. T

3ilfe «r» raaid ~ _# Silberehloridjodid-, eilberehlorldbroaid-, BilbertJhlsridbronidjodid-, Bilberbroaidjodideauleionen uew. produced «« la * Ua directly peeled pictures xu received, kOmien aaiaairtete, directly positive «lauleionen dft in dtr 9iA ~ £ at« ntaehrift 5 OfI i51 betchrtrtentn Typg Wstttit wtiv 4 «a * You lWAltlonui dl« atr Art can «la nloht hirttnd ·· Ytr- • eia «i« ruag * altt ·! «I · a * B *» tannoehltrtd, • aar · or 4 * rgl. You will be full of "tin"

DIt Intwl * kl «rT« rblziduftg kaan in di · ■ ione «« kloht or in the silver halidefr «i« see · ίη- T «rl« ibt w «rd« B «Di · Satwioklung can in di ·« · » If “through! • act with an“ in ”alkali-free actuator. The development can, however, also take place by immersing the exposed photographic liquid in an alkaline solution containing the developer.

Suitable actuator baths for photographic compositions containing the developer compound consist of B. an aqueous solution of an alkaline compound such as sodium carbonate, latriuah | 4rox7d _f potassium carbonate, laliuehydroiyd, mixtures τοη latriuahydroxyd and hatriun sulfite etc. "

ORIGINAL INSPECTED 909820/0946

-,he-

According to an advantageous embodiment of the method of the invention, an alkaline compound is brought into the silver halide-free layer and the egg-like compound is brought into the silver halide emulsion layer. It is then expedient to incorporate 3 to 5 moles of alkali metal salt or 3 to 5 moles of a corresponding alkaline compound per mole of silver halide into the silver halide-free layer. If the layers are then moistened, the development of the exposed silver halide takes place in the emulsion layer and the layer which does not contain silver halide is hardened in the corresponding areas.

Suitable activator solutions are described in U.S. Patents 2,596,754, 2,596,756, 2,725,298, 2,739,890, 2,763,553, 2,835,575, 2,852,371, 2,867,745.

It is also possible to use the known hydroquinone derivatives in the emulsion which contain groups that can be split off by alkali in order to stabilize the hydroquinone during storage, to add. It is known that these compounds are freed in the presence of alkali hydroquinone, etc., so that such Compounds the 1,4-dioxybenzenes or substituted derivatives in the silver halide emulsion layer, in the silver halide-free Can replace layer or in the developer solution in whole or in part.

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An auxiliary developer connection can also be used together with a 1,4-Dioxybenzene developing agent can be used to develop the To improve sensitivity without resulting in a disadvantage for the method according to the invention. Characteristic Auxiliary developers are e.g. the well-known 3-pyrazolidone developer i compounds such as N-methyl-p-aminophenol sulfate e.g. 1-phenyl-3 ~ pyrazolidone and 1-phenyl - 4,4-dimethyl-3-pyrazolidone.

Suitable supports for the photographic emulsion layer exist e.g. from cellulose ester films made from cellulose acetate butyrate, Cellulose acetate, cellulose acetate, cellulose acetate propinate, etc .; Polyethylene films, polypropylene films, polystyrene films, polyethylene terephthalate films and other polyester films, paper, polyethylene coated slassin paper, glass, metals, polycarbonate films, etc.

The silver halide-free colloid layer can also be on can be applied to a wide variety of layers. E.g. the colloid layer can be applied to a metal plate made of copper, zinc, Aluminum or the like. Be applied.

A particular advantage of the method according to the invention is that it is possible to use gelatin or the like

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Colloid on many surfaces to apply the impurities contain or release the sensitivity, fog level, etc. of a silver halide emulsion are capable of harmful influence. The gelatin can also be applied to a curved surface such as a The cylinder is applied and the developing silver halide emulsion is wrapped around the cylinder.

The J? Silver halide photographic developing emulsions may also contain additives such as chemical sensitizers, sensitivity-increasing compounds, reducing agents, sensitizing dyes, and the like. The emulsions can be blue sensitive or consist of orthochromatic, panchromatic, infrared sensitive, etc. emulsions.

Although gelatin is preferably used for the silver halide-free layer, other colloidal alkalipermeable compounds can be used if they are cured by the oxidized, gsrbenden Silberhalogenidentwieklem, such as casein, etc 2ain _e

Except for the production of photographic reliefs

represent

Ordinary carriers can use the 4Ä *. Invention too

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dacu used to make panels with the help of stencils provide·

Ou all over halide-free Sohioht is then on a porous applied like cloth, silk or highly porous paper and attach them to a developing one by pressing them exposed silver halide emulsion has been hardened, the unhardened areas are removed by washing with waraea Waeaer away. Clay of the stencil obtained will then be in particular positive prints produced in the way of using a low-viscosity ink, wherein a large number of prints can be obtained at a time.

Although Tor, sugewelse Carboxt lacquer is used as the pigment in the silver halide-free layer, any other pigment or dye can be used, including those which are inherently incompatible with a silver halide emulsion because of their effect on the silver halide. By "pigment" is fi any insoluble organic and inorganic material to be understood, through which the image obtained the required density.

An essentially unhardened gelatin is to be understood as meaning a gelatin which contains a maximum of about 0.7 g of formaldehyde

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(100 # ig) per 454 g gelatin or 7 g formaldehyde diluted 1: 3 with water) per 454 g of gelatin in freshly "coated Condition contains or about 0.5 g formaldehyde for 454 g gelatin in a sample stored for 3 to 6 months. in the rest can be the relief image with hardeners or other known Materials are treated to make the image more resistant to abrasion or the like when it is is used for printing purposes, or to better counteract the chemical action of an etching solvent or an etching solution to protect in the event that the (embossing on which the belief was formed is to be etched »

In the drawing, an advantageous embodiment of the method of the invention is shown.

Eb show:

FIG. 1 shows a carrier 10 on which an exposed photographic silver halide emulsion layer / with a latent image 14 is arranged}

FIG. 2 shows the same photographic material as in FIG. 1, but after development with a developer compound according to the invention;

FIG. 3 shows the transfer of the oxidized developer compound from the developed B41d areas 14 to corresponding areas

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12 of the colloid layer 13 on the support 15, FIG. 4 the support 15 which contains the colloid layer 13 with the hardened image areas 12 in the colloid after the silver halide-free layer 13 has been stripped from the emulsion layer 11, and

FIG. 5 shows the image area 12 in the hardened colloid after the untanned part of the colloid layer 13 has been washed out.

The following examples are intended to illustrate the method of the invention illustrate in more detail.

example 1

A film support was coated with a silver chloride emulsion containing uncured gelatin as a binder in such a way that that the carrier after drying 100 mg of silver

Chloride and 400 mg gelatin per 0.09 m support area.

Furthermore, a film support was coated with a dispersion of fine carbon particles in uncured gelatin in such a way that that there were 1,000 mg of gelatin on about 0.09 m of support surface and the gelatin layer contained enough carbon that after drying it showed an optical density of 2.0

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The exposed against a bar negative silver chloride emulsion coating was (to prevent excessive softening of gelatin) to 24 ° C for 60 seconds in a 1 $ hydroquinone and jfi sodium sulfate at approximately 23 ° down-containing aqueous solution. During this time, the man

material from the solution. 3 ₅ 6 g absorbed per 0.09 m of support surface. Excess solution was removed by squeezing

far away. At the same time, the carbon-containing coating at about 23 ° to 24 ° G also placed in an aqueous solution containing 5% sodium carbonate for 60 seconds.

2 During this time, 5.3 g of solution were absorbed per 0.09 m of support surface. Excess solution was also removed here by squeezing. The two sheets were then placed with their front sides on top of one another and brought into intimate contact by applying moderate pressure by means of rollers. The line image developed immediately. The two .blätter were left at about 23 ° to 24 ⁰ C for 60 seconds in contact, and then v / ieder separated juach rinsing with tap water, they were placed for 15 seconds a Säurestopbad and then washed in tap water at about 43 ⁰ O. The gelatin in the picture areas was very insoluble * while the rest was washed away. An insoluble mirror image was obtained on the gelatin-carbon coating.

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Example 2

The following coatings were produced:

Layer I.

Carbon BlaoJc gelatin egg

3.1 Jt Molacco-Carbon Slack and

Aqueous solution containing 4.8 pounds of gelatin 100.0 g

as

6.73 * Triton X-200 (p-tert.Ocylphenoxyethyl-

sodium sulfonate) solution 2 «0 al

102.0 g _

The dispersion was applied to a cellulose acetate film

p carrier applied so that 10.2 ml

were omitted »what an occupancy with 480 ng gelatine and 310 ag

2
Carbon per 0.09 m support surface.

Layer II

A chlorosilver gelatin emulsion was prepared which per 3 800 g one mole of Ag and contained the following components:

-fre-l

170 α gelatine 633.0 g

6.7% friton X-200 17.0 ml

1 liter aqueous solution of chlorhydroehinone .... 1 100 * 0 ml

1,750.0 ml This solution was applied over layer I in such a way that

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5 * 0 ml accounted for about 0.09 m of support area, which is a Silver coating with 54 mg, a gelatin coating with 85 mg

ρ and a chlorohydroquinone coverage of 30 mg per 0.09 m of support surface.

The obtained photographic material was exposed, activated and transferred as follows.

1. Contact exposure? One second with a reflector photoflood lamp against a line positive of high contrast.

2. Activation: Twenty seconds in a 4 $ potassium carbonate and 2 έ urea-containing solution at about 31 ⁰ C.

3. Transfer: Multiple transfers to regular colloid transfer recording sheets in a Regent Verifax device. About 20 copies were made by this procedure. The copies showed dense black images against a clean background. It is 3 to 4 times the number of copies that can be obtained by the process described in U.S. Patent 2,596,756.

Example 3

The procedure of Example 1 was followed with various developer connections repeated. In all cases where hydroquinone

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or cry derivatives used "a reflection of insoluble carbonaceous gelatin that have become ^ was formed, ie, wandered the oxidation product of the developing agent and made the gelatin 44" · ββϊβ * £ 'β in the carbon-containing gelatin layer insoluble. In all cases in which pyrocateohin or derivatives thereof were used, the gelatin only became insoluble in the image areas of the silver halide emulsion, while the gelatin in the gelatin-carbon layer did not become insoluble and no mirror image was formed, ie the oxidation product of catechol or the oxidation products of the catechol derivatives did not migrate.

In so far as a mirror image can be obtained by the method according to the invention, it may be desirable that no silver halide is used containing gelatin on a transparent support, so that the image either as a normal image or as a mirror image can be seen depending on whether the observation by the Carrier through or from above.

The method of the invention is particularly useful for producing images of almost any density or color, or in any particular medium obtained when the medium can be dispersed in gelatin or other polymeric material that can migrate through

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Oxidation products made insoluble by developer compounds will.

Example 4

A transparent film backing was made like an uncured one Gelatin-silver halide emulsion coated so that 400 mg of gelatin and 100 mg of silver in the form of silver halide to about

0.09 m of support area was eliminated. Over this layer was a finely divided titanium dioxide pigment, which is contained in uncured gelatin was dispersed, in an amount corresponding to 500 mg Ti

tandioxyd and 400 mg gelatine applied per 0.09 m support surface. Dae photosensitive material was exposed through the pad against an a line image having Hegativfilm and, in an aqueous alkaline solution, in addition to 5 $ sodium carbonate contained 0.4 $ hydroquinone 20 seconds at about 23 ° - developed 24 ⁰ C. Then it was rinsed for 3 seconds, 10 seconds in an acid containing 5% acetic acid.

Submerged in the stop bath and finally in water / about 43 C Washed and dried for 10 to 20 seconds. Through the film backing When viewed from the front, a black silver image could be seen, while when viewed from the front, the image appears to be shiny white titanium dioxide image appeared.

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In some cases it may be useful to remove the black silver. This can easily be achieved by rapid bleaching in a dilute ferricyanide or halide solution , which is then fixed and washed in a known manner.

Example 5

When a fogged silver chloride emulsion was used, a direct positive image was obtained as follows. The pH of a gelatin silver chloride emulsion was adjusted to a value of 8.5 by adding sodium hydroxide. Then, 10 mg of tin (II) - chloride (2 HgO), which were dissolved in 5 ml of methyl alcohol to which 1 mole of silver halide emulsion containing added * The emulsion was then heated for 7 minutes at 80 ⁰ C and then at 40 ° C cooled down. The pH was then adjusted to 6.0 with sulfuric acid.

To the fogged emulsion, which contained 1 mole of silver halide, the following components were added:

1. 2-ft> -Iitrostyryl) -6-ethoxyquinoline methio-p-toluene sulfonate 0.75 g in 75 ml

Methyl alcohol

2. 10 $ solution of gelatin 650.0 g

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iff

5 »15 # aqueous solution of saponin 100.0 ml

4. 0.14% solution of bromohydroquinone 680.0 g

5. Distilled water 2075 _f 0 ml

The emulsion treated in this way was applied to a cellulose acetate

2 carrier applied in such a way that on 0.09 m carrier area 250 mg of silver and 445 mg of gelatin were used.

At the same time, a film carrier was made with a carbon

2 gelatin dispersion coated that on about 0.09 m support-flat ^ 1000 mg of gelatin were omitted and this contained sufficient carbon particles so that the optical density of the layer was reduced drying was 2.0.

The previously exposed to a negative line and the silver chloride Emulsionsbesehichtung Kohleji-Gelatinebesch ^ ichtung were both immersed at 25 ° to 24 ⁰ C for 30 to 60 seconds in a 5 $> aqueous sodium carbonate solution. After removing excess solution, the sheets were brought into intimate contact by applying moderate pressure using rollers. The sheets of paper were placed on top of one another so that their front sides touched one another. A positive line image developed immediately. The leaves were left in contact at the specified temperature for 60 seconds, after which they were separated, rinsed with tap water, placed in an acid-stop bath for 15 seconds and

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At the end of the line, about 43 ⁰ C were washed away, while the remaining part was washed away. On the gelatin-charcoal coating, a dish in insoluble charcoal gelatin was obtained.

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Claims (1)

HA7643 Claim · ι 1. Terfmhren for the production of a photographic relief image by developing an image-wide exposed, light-sensitive silver halide emulsion layer with a tanning developer compound, characterized in that the emulsion layer in contact with a carrier arranged preferably pigmented, silver halide-free colloid layer is treated with a 1,4-diosybenzene compound, whereupon the layers are separated from one another and the in unhardened areas of the colloid layer / better known Way to be removed by washing. 2. The method according to claim 1, characterized in that the 1,4-bioxybenzene compound is hydroquinone, chlorohydroquinone, bromohydroquinone, toluhydroehinone or morpholirartthy! Hydroquinone is used" 3. The method according to claim 1, characterized in that an emulsion layer is used whose binder consists of uncured gelatin, 4. Process according to Claims 1 to 3, characterized. 909820/094 U47643 -.er- that the silver halide-free colloid refers to a τοη 4% of the silver substrate emulsion is provided with a separate, special carrier and the emulsion is pressed against the emulsion layer during development, so that the developer oxidized in the developed areas is transferred to the colloid layer; and that the colloidal layer is separated from the emulsion layer stripped before washing. 5 · Yerfahren according to claim 4, characterized in that the Colloid of the colloid layer consists of essentially unhardened gelatin. 6. The method according to claims 1 and 3, characterized in that that the silver halide emulsion layer consists of a direct positive emulsion consists) that the colloid of the colloid layer consists of essentially unhardened gelatin; and that the The emulsion layer and the colloid layer are arranged on the same support. 7. Yerfahren. according to claims 1 to 6, characterized in that an uncured gelatin layer is impregnated with an aqueous-alkaline solution and the still moist layer is impregnated with it a substantially uncured gelatin-silver halide emulsion layer in the presence of a hydroquinone developing agent. 909820 / OiHfi XH 8. Photographisohes, on a support a «light-sensitive Material having a silver halide emulsion layer sur Carrying out the procedure according to claims 1 to 7 «da» characterized in that the material susätslich a Layer of a torso white pigmented, silver halide " contains free colloids, which by the action of the oxidation products of a 1,4 ~ 2iexy-ensolentwiakler-blinding hard is f «Material mach Aaepruea ·, 4Mureh gekew & iolickt * that that On the side of the non-aged gelatine, there is a partial position in the field mi der slliertialegemidfrelMi KelUldeelilelit amf de «trager aageeraaet is " I ·· leiterlal MeH ämtfrUk ·, ta4mrwk g «k« e «m« l4k «et _f dU the lewlsleaasehicht über der silttrteelBgemldfrtiem Kslleideehiekt did« 11 "IiUiIaI s" e * lUra 4 "r 4M" f "" kt t Ms 10, "adarch gekem-Itetsiit" ie * IM I * U "t" the receipt "emi4f9" iem Ulleid mm "Mektrteter""Ifttis · reads. 909820 / 09A6