DE2323742A1 - IMAGE RECORDING MATERIALS FOR THE SILVER SALT DIFFUSION TRANSFER PROCESS AND PROCESS FOR THEIR PRODUCTION - Google Patents

Description

DR. E. WIEGAND DipL-ING. W.

DR-M. KOKLER DIPL-ING. C.OERNHARDT -

MÖNCHEN HAMBURG 2323742

TELEPHONE 55 5474 '8000 MONKS 2

TEtEGRAMMEiKARPATENT -.,. ",,, '

MATHILDENSTRASSE 12

W 41 602/73 - Ko / DE May 10, 1973

Fuji Photo Film Co., Ltd., Minami Asbigara-shi, Kanagawa / Japan

Image receiving materials for the silver salt diffusion transfer process and methods of making them

The invention "deals with imaging materials for the Sirber salt diffusion transfer process and one Process for their production and concerns in particular those which consist of a carrier and at least two layers, which include a cellulose ester layer, the at least contains a fluorescent brightening agent, and a hydrolyzed cellulose ester layer, the silver deposition nuclei contains, include, the two layers lie on top of each other on the surface of the carrier.

According to the invention, an image recording material for the silver salt diffusion transfer process specified, w & lches a support and at least two on the surface of the carrier has superimposed layers, which consist of a cellulose ester layer and a hydrolyzed Cellulose ester layer exist. The former cellulose ester layer contains at least one fluorescent whitening agent and the hydrolyzed cellulose ester layer contains the silver deposition nuclei. Likewise a process for the production of the same is given.

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. ibei which .a silver salt, such as a silver halide is applied _l5 Photcgraphisehe diffusion transfer process are! known. In these methods, a photographic photosensitive member which is obtained by applying a dispersion in which fine particles of a photosensitive silver salt such as silver halide in a hydrophilic binder such as oilatin, polyvinyl alcohol, carboxymethyl cellulose, polyvinylpyrrolidone, methyl cellulose, and the like are dispersed, on a support , such as paper, baryta paper, or films made of high molecular weight substances, for example polyethylene terephthalate, cellulose diacetate, cellulose triacetate, cellulose nitrate, polycarbonate, polyvinyl chloride and the like, with the formation of an image in the photosensitive layer of the same selected and the element exposed in this way through Contacting the same with a treatment solution containing a developer.

During this development, the exposed silver halide is formed in the photosensitive layer with the formation of non-diffusible silver deposits are reduced or developed. Simultaneously or subsequently when the photosensitive element is coated with a water-soluble silver complexing agent is contacted, the silver halide which has not been exposed becomes with the complexing agent to form a water-soluble silver complex compound implemented. When an image pickup element which is a layer (• Image receiving layer) has »a dispersion of a substance that acts as a catalyst for the reduction of the water-soluble Silver complex compound is used, (Silberabsebeidungskerne, i.e. so-called physical3 development cores) in contains a hydrophilic binder, closely related to * .er photosensitive ^ borrowed layer is contacted, diffuses in the photosensitive layer formed by the action of the processing solution and the silver complex compound

309848/0909.

transported from the light-sensitive layer into the image-receiving layer and to silver deposits in the image-receiving layer ^. layer 'reduced by the action of the development core.

If these appearances from the point of view of the whole Surface of the image recording layer can be viewed, a silver image is formed as if the image is attached to the image receiving layer from the photosensitive layer would be transferred. This photographic process is therefore correspondingly as a silver salt diffusion transfer photographic process designated.

Various studies have been made on silver salt diffusion transfer materials, for example with the image recording materials used in the process carried out. For example, silver separation cores generally metal sulfides or metal selenides used, soft at most slightly soluble in Are water, or colloidal heavy metals or precious metals are used. However, it is favorable if the silver deposition cores have high activity in the imaging materials.

With these requirements in mind, U.S. Patent 2,693,237 describes a method of manufacture high activity silver deposition cores by mixing a water-soluble metal salt and a water-soluble sulfide in fine particles of silica for the formation of precipitates of a water-insoluble metal sulfide. Further, it is published in Japanese Patent Publication 32754/69 describes an image recording material which can be produced according to the following steps; after this the silver deposition core subsides into an alkali impermeable Polymers coverage by means of the vacuum evaporation coating Process was incorporated, the substance treated in this way is in a solvent for the polymer substance dissolved and the resulting solution applied to a support and dried and then the surface of the polymer layer chemical treatment, e.g. hydro

lysis, subjected to the surface for alkaline substances to make permeable.

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In Japanese Patent Act ^ tg ^ S ^ G ^ TT isitein

Process for the production of image receiving materials for proposed the silver salt diffusion transfer process, in which a cellulose ester layer which is free of silver deposition cores is formed on a paper support becomes the surface layer of the cellulose ester layer is hydrolyzed and silver deposition nuclei in the hydrolyzed Layer are incorporated.

In these image receiving materials, it is preferred to use one or more fluorescent brightening agents or To incorporate whitening agents into the cellulose ester layer to improve the whiteness of the support.

Ealls, however, a cellulose ester layer that has an or several fluorescent whitening agents or whitening agents contains, is subjected to a hydrolysis treatment, the following errors will occur: If any of the above Carrier in a hydrolysis solution, generally a methanolic aqueous solution containing an alkaline substance, for Hydrolysis of a portion of the cellulose ester layer is immersed, those contained in the hydrolyze layer fluorescent whitening agent in the hydrolyzing solution extracted. As a result, the hydrolysis is continuous is carried out, the extracted fluorescent brightening agents or whitening agents accumulate in the hydraulic lysing solution, so that sludge deposits appear therein or the accumulated fluorescent whitening o ^ er Whitening agents are re-applied to the surface of the support deposited, which gives disturbances to the whiteness of the support, i.e. the whiteness becomes uneven due to the redeposition.

In addition, the whiteness of the carrier is prior to hydrolysis different from that of the carrier after hydrolysis, so that it becomes difficult to determine the whiteness of the carrier.

8 / 090-9 · '

gers to control the manufacture of the same.

As a result of extensive research to avoid the above-mentioned defects, the image receiving materials obtained according to the invention, i.e. image receiving materials for the silver salt diffusion transfer process, which consist of a carrier and at least two layers, one of which consists of a cellulose ester, which is at least contains a fluorescent whitening agent or whitening agent, and the other consists of one hydrolyze Cellulose ester chictat, which silver absebeid cores ent- -_-. holds, with the two layers lying on top of each other on the surface of the carrier.

These imaging materials are grouped into the following Stages are produced: after a cellulose ester chic nt, which contains one or more fluorescent whitening agents, is applied to the carrier, another cellulose ester layer, which is free of fluorescent whitening agents, applied thereon to form a support and then the surface layer of the support is hydrolyzed and silver deposition nuclei incorporated and in the deposited hydrolyzed layer.

If the one containing the fluorescent solvents Layer and the other layer, free of fluorescent whitening agents, are applied separately to the carrier a portion of the fluorescent whitening agents may generally be from the layer containing them to the Layer that is free from this diffuse. If the quantity

It is large that the amount of the agents extracted into the solution for hydrolysis is harmful or the fluorescent one Whitening effect is lowered, creating unfavorable results would be obtained are such embodiments naturally included within the scope of the present invention.

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Since the carrier used in the image recording materials according to the invention only fulfills the known supporting function of the must meet like materials, 'the carrier is not in terms of the nature and quality, strength or exact characteristics of the same, as well as the manufacturing process and any known carrier can be selected. Photographic base papers are particularly preferred, pigment-covered papers, for example with barite, Titanium white or the like, polyethylene coated papers or films made of substances of high molecular weight such as - polyethylene terephthalate, cellulose acetate, cellulose nitrate, Polycarbonate, polyvinyl chloride and the like, art papers

and the same.

With regard to those formed on the paper carrier Cellulose ester layer and the cellulose applied over it Either way, this can be achieved in the following way; one or more cellulose esters are dissolved in a solvent for this purpose and the solution on the carrier, for example Paper, applied and dried; on the other hand A cellulose ester film can also be applied to the carrier, for example paper, by means of heat / pressure melting or with be made to adhere to an adhesive.

Examples of solvents typically used include esters such as methyl acetate, ethyl acetate and the like, ketones such as acetone, diacetone alcohol, polyhydric alcohols such as methyl celiosolve, ethyl cellosolve and the like. Typical Wärae / Bruck-Scbnielzverbindungsbedingungen are 60 to 80 ⁰ C and 4 to 8 · kg / cm ^2. Typical adhesives are Polyvinylacetatharzie, Poly es ternär ze, PoiylsöüjSHatbsrss

and the same.

Any method used must securely share a strong bond iind, provided a firm bond is given, is the method is not particularly limited.

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Illustrative examples of cellulose esters are for example cellulose esters of organic acids, such as cellulose diacetate, Cellulose triacetate, cellulose propionate, Cellulose butyrate, cellulose acetate butyrate and the like, Cellulose esters of inorganic acids vrie cellulose nitrate and the like or mixtures thereof.

The strength of the hydrolyzed cellulose ester layer, which contains the silver deposition nuclei is preferably about 0.1 "to about 20 microns, especially 0.5 to 10 microns, so that an image with excellent image quality ■ did can be obtained.

The thickness of the cellulose ester layer, which contains one or more fluorescent whitening agents, is preferably otv? A 0.5 to about 20 microns, especially 1 to 10 microii ^ so that the layer can serve as a waterproof layer against the penetration of the developing treatment solution and a sufficient " Get whitening effect

v / can earth.

üin therefore an image recording material with the above to produce the starches listed, a cellulose ester layer, which contains fluorescent brightening agents, to = next applied to the support to a thickness of about 0.5 to about 20 microns, preferably 1 to 10 microns, and then another cellulose ester layer is applied in a thickness to the carrier coated in this way, which corresponds to that of the desired hydrolyzed layer.

The strength of the hydrolyzed 5 chic-tit can be too; 5sdsr desired thickness of about 0.1 to about 10 microns Control of alkali concentration or alcohol concentration the hydrolysis solution or the period of the hydrolysis treatment as well as the temperature of the hydrolysis solution can be controlled. For example, more alkali or more Alcohol, for example, $ 30 to $ 50, and longer periods or higher temperatures increase hydrolysis *

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232374?

EaIls the thickness of the image receiving layer too low
is, ds is schv / ierig ₅ sufficient to tjbertragungskonzentration erhalten- Ealls other hand, the strength to
is large, a large amount of the treatment solution penetrates
inside the SchicU. Gin and, as a result, un-

■ favorable results on + reten, so that "for example the
BildaufnahEebogen -vfgrund of the oxidation of the developer

The storage stability of the formed egg is colored.

^ The silver image is reduced. Ξ

Of course, the invention also includes the following Z.

Agende embodiment: hydrolyzed layer with silver deposition cores; unhydrolyzed layer free from Aaf-

i ^ brighteners; unhydrolyzed layer, the whitening

Emitt & l contains.
} If necessary, a Schichx can be made from an acidic

^ Substance to neutralize the alkaline components in __ 73of the solution for the development treatment and the like _; ^ between which the fluorescent brightening agents contain- ~

-tenden Cellulos ees ters chicht and the Silberabscheidungs- ^ "_ cores containing hydrolyzed Celluloseesterschlcht pre- ₌ £ be -handen In general, all of the layers act, j welch® an acidic." compound containing, as layers of - acidic substances. "The polymers are particularly preferred
Acids, for example homopolymers or copolymers of
Maleic anhydride and phthalic acid.

Various types of commercially available fluorescent whitening agents which can be used in the present invention can be used
fluorescent whitening agents are used and
these remedies are not special as to species
limited, although preferably soluble in solvents
are for cellulose esters. Of course, other fluorescent whitening agents which are insoluble in solvents for cellulose esters can also be used and these are generally added to a dispersion. Illustrative examples of fluorescent whitening agents are given below
listed. The following are in Color Index Volume 2 (2.

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Edition, 1956, The Society of Dyers and Coloriats) (American Cyanamid Co.) give: II 57 C.I. Fluorescent Brightening Agent 4 (Ciba Ltd.) CaIcofluor Yellow HEB »69 tr (Sandoz) Uvitex W “70 Il (Geigy) Leucophor DC »72 Il (Geigy) Tinopal PCR it 73 11 (LB HoHiday Zc Co., Ltd.) Tinopal S. ¹¹ 76 If (General Aniline) Blancol SS ti 91 ir (llippon Kayaku KK) Eluorol OB Il Kayalight B

C.I. Fluorescent Brightening Agent 128

Hiltamine Arctic White DlCL (Hilton Ü3vid Chemical Co.)

ι · »130

Calcofluor vmite LD (AmericanCyanaaid Co.)

Other fluorescent WeiSungsinlttel, which are going aicht in the Color Index may also be used becoming They are available in the Hanlsisinfer rfölgenden designations "

Whitefluor TSR Sunitomo Kagalcu Kogyo, SK

B G

Uvitex OB Ci-ba Ltd. .

Kayalight Ä Hippon Kayaku KK

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-I
- 10 - NiasO Vf.. If Kaycoll C Kako KK "E. Bayer Blankophore DCB It 11 E200SK

It is preferred to have one or more of these fluorescent Whitening agents in quantities of about 5 to about 500 mg / m, especially 10 to 200 mg / m of the pushes it contains, to be incorporated. If the amount added is too small, a sufficient effect cannot be obtained will. On the other hand, if too much is added, occurs the yellow-brown color of the fluorescent whitening agents even up. The appropriate amount of the fluorescent whitening agents to be added varies depending on the Species and it is necessary to use the most effective and optimal amount of each fluorescent detergent Case by case, taking into account the above two Factors to choose.

In addition, fluorescent curatives described in the following publications can also be used can be used according to the invention:

Japanese Patent Publications 6442/65, 7709/66, 6616/65, 11338/67, 21016/67, 26135/67, 20456/67, 25336/63, 9928/68, 21220/69, 12035/69, 37194/70, 22557/69, 38986/70, 823/71, 3529/71, 322/71, 34939/70, 8782/71, S784 / 71, 11152/71, 6515/71, 40552/71, 19714/71, 30586 / 71, 23518/71 and 28995/71, IB patents 3,575,996, 3,586,673, 3,575,866, 2,639 and 3,447,942, British patents 1,234,544, 1,243,060, i 223 089 * 1 18? 679, 1 222 97O ₉ 1 072 916, 1 072 914 and 1 159 180.

Can dance as Silberabscheidungskernsubs the usual materials used as Silberabscheiduagskerne known eind, according to the invention uses werdea since this ma- must satisfy only his usual known function ^ * ^r TERIAL

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ir

? 323742

Examples of these include heavy metals such as sink, mercury, Blsi, cadmium, iron, chromium, nickel, tin, cobalt, Copper and the like, precious metals such as palladium, platinum, Silver, gold and the like or sulfides, selenides, tellurides and the like of these metals. These silver deposition core substances are, for example, by reducing the corresponding metal ion in an aqueous solution a water-soluble polymer called a protective colloid such as gelatin, polyvinyl alcohol, carboxymethyl cellulose, methy! cellulose and the like to form a colloidal metal dispersion or by mixing a solution of the metal ion with a solution of a soluble sulfide, selenide or telluride to form a colloidal dispersion of the water-insoluble metal sulfide, metal selenides or Ketalltellurides produced.

Various methods can be used to hydrolyze the surface the cellulose ester layer and the incorporation Silver deposition cores applied and some embodiments for this are given below.

Method 1) The cellulose ester layer is immersed in a hydrolyzing solution bath or the solution is applied to the surface of the layer, this solution reacting with the ester and then the surface layer of the cellulose ester layer is hydrolyzed, the layer is immersed in a dispersion containing the silver deposition cores or the dispersion is applied is applied to the surface of the layer, whereby the silver deposition nuclei are incorporated into the hydrolyzed layer.

Method 2) by treatment of the surface of the Celluloseesterschicht with a Hydrolysierbad, the deposition of silver cores, the surface layer of the hydrolyzed Celluloseesterschicht and simultaneously ⁱ ^, the deposition of silver core in the hydrolyzed Pushes einverleibt- In this method, the hydrolysis of; Celluloseesterschicht and the incorporation ' The silver lining cores are carried out in one bath at the same time.

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The method 2) is more advantageous than the method 1) because there the silver deposition nuclei siersehlcht uniform in the Celluiose ^ can penetrate ^ particularly if a Hetallsulf-id is used as the silver deposition nuclei _r is the procedure more preferably 2), as metal sulfides in alkaline oxidation baths and are stable in the hydrolysis treatment and the deposition of the silicon deposition cores can be carried out at the same time.

Wenii, however, the silver precipitation nuclei as colloidal Dispersion obtained, other specific procedures are required in addition to procedures 1) and 2). The cause lies in the fact that the in a polymeric protective colloid formed silver deposition cores are stably protected therein are and soait just with difficulty in the bydrolyzed layer penetrate. There are the following for this Procedure:

The hydrolysis conditions are not particularly limited, however, excellent products in accordance with the following information are obtained: Alkali (vorzugsv / else alkali hydroxide) etv / a 1 to 30 wt .- $$ Lösungsnr ^l tel (alcohols, preferably methanol and / or ethanol) is about 10 up to about 60 io and H ₂ O corresponding to about 90 to about 40% by weight? Glycerin about 10 to 50 g / 100cc HpOi silver deposition core: a) Heavy metal or noble metal 0.001 to 0.1 g / 1 1 hydrolyzing solutionj b) Soluble sulfide 1-300 times the chemical equivalent of a). The same basic conditions are used for all procedures 1) to 4).

Method 5) A water-soluble metal salt and a>. . water soluble sulfide. Selenide, telluride or a sulfur-containing compound, preferably an organic sulfur-containing compound, are dissolved in a solvent containing glycerine or a glycerine derivative to form a water-soluble metal sulfide, selenide or telluride.

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Method 4-) A water-soluble metal salt and a reducing agent are mixed in a solvent containing glycerine or a glycerine derivative to form a colloid.

Typical ones that can be used in the above methods Metals are zinc, cadmium, lead, iron, nickel, cobalt and zirn in the form of water-soluble metal salts such as acetates, Hit rates, borates, calorates, sulfates, hydroxides, Formates, citrates and the like.

Typical examples of sulfides, selenides or tellurides or organic sulfur compounds are the sulfides of alkali metals such as sodium, potassium, ammonium sulfide, Ammonium polysulfide and the like, tellurium compounds and selenium compounds of alkali metals and the like, ■ Thiourea, potassium thioeyanate, thioacetamide, sodium thioiosulphate and the like are also advantageous. All reducing agents that make up the components in the process 4) reduce, can be used v / earth, with dextrin, urodium borohydride, hydroxylamine and hydrazine being particularly good due to the decreased pollution problems.

The hydrolysis conditions are virtually the same as given above for the case of the general hydrolysis Toggle _=.

Temperature and time are not particularly critical in any of the above hydrolysis processes and generally the cellulose test material is only contacted with the hydrolyzing bath at ambient conditions for a few minutes, which is sufficient to achieve the desired depth of hydrolysis Eintauehen, spraying or the like with the Celluloseesterschicht for about 20 seconds to 100 seconds ^ abei a bath temperature of about -6 to about 10 ⁰ C (20 to 50 ° ^P), conveniently -1 to -4 ^ S ¹³ C (30 to 40 ⁰ F) contact is made.

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By sub-atmospheric pressure or above-atmospheric pressure little is gained if they can also be used "

Glycerin or glycerin derivatives are among the above listed method 3) or 4) effective for introducing the silver deposition nuclei into the bydrolyzed Cellulose ester rail. It is also possible to have a add another stage, i.e. after the sirber cut-off kernels in a liquid other than glycerine or glycerine derivative, for example water or a polymer in the form of a liquid, for example a liquid Polymer or a polymer solution, the glycerin or glycerin derivative becomes the liquid added.

In general, the silver deposition core substances have the defect that they are easily oxidized. The use of glycerin and the like is effective for Preservation of the silver deposition core substances during a long period of time in that glycerin and similar materials have antioxidant properties »Furthermore For example, glycerin and similar materials are the preferred medium for the dispersion of fine core substance colloids and thus are effective to keep the colloids in the state of stable fine particles. When the core dispersion colloid is formed in glycerin, core substances, which are very fine and highly active are obtained. This is a very beneficial advantage.

Examples of glycerin and glycerin derivatives are. Polyglycerin HO (CH ₂ CH (OH) CH ₂ O) _n H (trade name polycerin, .Manufacturer Nippon Yushi KK. The material is available in two., Qualities, one with a molecular weight of 1300 and one with a molecular weight of 2000), diglycerin , organic acid esters of glycerin and polyglycerin such as glycerin sonoate, glycerin diacetate. Glycerine triacetate, glycerine

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nonooleate, glycerol monolaurate, glycerol monostearate, monostearins acid esters from polyglycerine, monolauric acid ester of polyglycerin, eaterlura glycerophosphate, potassium glycerophosphate and the same.

In the processes 3) and 4) listed above, the glycerol solutions prepared in this way are wherein the silver deposit nuclei are dispersed, and the above-mentioned alcoholic aqueous solutions containing an alkaline agent mixed with one another.

According to the various methods listed above, a cellulosic sea ester layer, the surface of which is hydrolyzed and contains silver depositing cores, is formed on a support such as paper, and after the layer is formed, it may be washed with water if necessary, or if an excess is present the alkaline substance contained in the alkaline solution which was used in the hydrolysis has remained, has been neutralized with an aqueous solution of an acid, the layer can then be washed with water and dried Image recording material _: and a photosensitive silver halide material, which has been exposed imagewise, are superimposed so that the image receiving layer and the exposed layer are face to face, with a treatment solution being introduced between the two layers and then after the two Shifts during a certain Z have been in close contact with each other, are the image recording material and the negative material separated _? wherein a positive silver image is formed on the image receiving layer of the image receiving material.

Contains the above treatment solution usually a thickener that gives a highly viscous solution, for example cellulose derivatives such as Carboxymethyl cellulose * Λthy! Cellulose, hydroxyethyl cellulose, Methyl cellulose, hydroxypropyl cellulose and the like

'. ^ 09848/0909

precisely, vinyl polymers such as polyvinyl alcohol and the like, acrylic acid polymers such as polymethacrylic acid, polyacrylic acid and the like, inorganic polymers such as water glass and the like, inorganic silver complexing agents such as thiosulphate, "for example sodium, potassium or Aaiaoniuiulathiosulfat, thiocyanates, ^ Rx for example sodium, potassium or ammonium thiocyanate and the like, organic cyclic imides such as uracH, barric acid, urasol, hydantoin and the like according to TB patent 2. G57 or hasic nitrogen-containing compounds such as ethylamine, ethanolamine and the like according to DS patent 3 343 958 ₄ developers such as hydroquinone, Hydroquinone derivatives, for example toluhydroquinone, tert-butylhydroquinone, pheny! Hydroquinone and the like, p-aminophenolj p-ainophenol derivatives, for example N-ilethy 1-paminophenol, srimethyl-p-aminophenol, and the like, hydroxylamine, hydroxylamina he iva te, for example IT dimethoxyethyhyd roxylamine, IT-diethoxyethy / hydroxylamine, diethy / hydroxylamine, and the like, 3-pyrazolidone, 3-pyra-kiolidone derivatives, for example i-phenyl-3-pyrazolidone. and the like, ascorbic acid and the like and an alkaline agent such as an inorganic alkaline agent such as sodium carbonate, sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia and the like, or amines such as ethanolamine, diethanolamine and the like. In some cases, some or all of the solvent for the silver halide, thickener, developer and alkaline agent may be incorporated in the silver halide photosensitive element or in the image-receiving element.

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-Π- 7i 7323742

It is preferred that the treatment solution be strong is viscous, especially when the image receiving material for use in a so-called camera of the Pclaroid-Laiid type is suitable wherein a treatment facility for development is included. The reason is that, if the treatment solution is very viscous, its » The amount used can be small and the total amount thereof can be effectively used. Furthermore, the Treatment solution in a specific position due their high viscosity can be maintained. In development treatment the solution can easily between the silver halide photosensitive element and the image receiving element can be expanded without loss of any solution. This results in various advantages in the Use of such highly viscous treatment solutions. In the case of the photosensitive element and the image pickup element are separated from each other after development, it is preferred to use the surface of the image receiving member to smooth or a thin separation-enhancing layer, for example gum arabic, hydroxyethyl cellulose, cellulose acetate phthalate and the like on the image receiving layer to apply so that the highly viscous treatment solution does not remain or adhere to the image pickup element.

The photosensitive silver halide layer contains one or more silver halides, for example silver chloride, Silver bromide, silver iodide, silver chlorobromide, SiI-beriodobromide or silver chloroiodobromide, however, are used for For the purpose of a photographic material for taking an image, silver bromide and silver iodobromide emulsions are preferred.

Silver halide ^ with an average grain size 0.1 microns to 10 microns will give the best results. Light sensitizers, chemical sensitizers, Antifoggants, gelatin hardeners and surface

30984S / 0SQ9: '- | _;

active agents can be added if desired and meet their known punctures. These silver halides are in 5 protective substances, such as natural: Polymers, e.g. gelatin, collodion, agar agar and the like, or in synthetic polymers, e.g. Polyvinyl alcohol, diapered.

Such elements are described in detail by P. Glafkides, "Chimie et Physique Photographique", 3rd edition, Publication Photo Cinema Paul licntel described in 1367.

In those embodiments where the silver halide layer trained directly on the Cr-llulose ester layer is (a carrier, multilayer element), v / ground best results obtained when the amount of silver is 5 to 50 mg / 100 cm and the gelatin is present in an amount of 10 to 300 mg / cm. These areas are not limiting, include however, the technically important silver halide systems as

such.

Instructions for using the image recording materials

according to the invention have already been given above and the most preferred use is in cameras from • ^ olaroid-Iand type. In this preferred pail, the image is on took emat ial according to the invention into the interior of the Zamera in the form of a bow or a roll together with one incorporated silver halide photosensitive material. Possibly The two materials can be fed into the camera in the form of a layered sheet of some pairs of the two materials includes ^ or in the form of a long roll that consists of composed of a pair of the two materials, and the photographed part is pulled out of the camera and cut off every time a picture is taken. While pulling the photographed part, the stick two materials close to each other in such a state,. that they touch face to face with a treatment solution spread therebetween and development

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is executed in this state. ^

The image receiving materials for the silver salt dif- ';!

fusionsüliert ^ agungsverfahren according to the invention have ^

^ various advantages. For example, the J

high mechanical strength and further- 2 These materials are excellent for use in Polaroid Land type cameras because they are easily drawn and can be cut and can also be easily rolled up due to the good flexibility.

If necessary, it is possible gnwünschtenfalls in the Celluloseesterschicht containing the fluorescent whitening agent, other additives, for example plasticizers, Bläuungsfarbstoffe, additives neutralize the prevention I of the fading of the SilberbilclPT, for example, compounds having a mercapto group, tinting agents, acidic compounds, the alkali, and the like to- | abide. | The invention is explained in detail below with reference to the | Examples explained. ϊ

Comparative example |

1. Hers division de "carrier \

A solution of the following components was two- I

times in equal quantities on G-round paper on top of each other ϊ

applied, dried after each application (base paper- ϊ

weight 120 g / m, thickness 0.125 mm) and an egg with a f

10 micron thickness obtained after drying: I.

"z ~ ^ Cellulose Acatate ^ £ Her3teller 'Dalsjel ¹ KK, Ace-iylierungs- ^ {

'degree 55 - 0.5 $ »Designation" Cellulose acetate V-AC ") - \

. - ■ 20 g j

"CI- fluorescent brightening agent 91 (designation ■■ ^< \

Kayalight B, manufacturer Hippon Kayäku KK) '' ■ '■ "? 0.45 g ' ^} ~ ^: j

Methanol '50 ecm ^

Methylene chloride -450 ecm 1,

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-20- CM- 23237A2

2, making the image ufnatimemateria Is

The carrier obtained above according to i) was in a hydrolyzing bath having the following composition

'■ (solution temperature 35 ⁰ C) .. immersed for 40 seconds and then washed with running water for 4 minutes and dried.

Glycerine ¹⁵ ° ^g

Nickel Nitrate (6H ₂ O) ° ' ⁰¹⁷ S

Sodium sulfide (9 H ₂ O) 3.1 g

Sodium hydroxide ¹² ° ^g

Methyl alcohol 720 com

480 ecm

V / ater

The thickness of the hydrolyzed layer "was 2.5 microns. As a result, a cellulose acetate layer with a thickness of 7.5 microns, which was not hydrolyzed, acts as a waterproofing layer. The thickness was determined by coloring the layer with a dye ( Sumilight Blue FBGC ₅ manufactured by Sumitomo Kagaku KK Eogyo) is performed, which stains the hydrolyzed cellulose, cellulose acetate, however, not färht, whereupon ^e was observed in cross-section by means of a microscope. the fluorescent brightening agent was extracted into the Hydrolysierbad.

The amount of Kayalight B was measured using the TJltravio «

lettenspectroabsorption method, which is carried out using a Cary Spectrophotometer Model 15 was performed. It was found that about 25% of the applied fluorescent brightening agent in the hyd ^ j- " 'lysing bath' were extracted.

The whiteness of the surface of the obtained image _; The receiving material was very different from that of the coated carrier before hydrolysis and in condition

The application of the cellulose acetate layer could reduce the whiteness of the image recording material finally obtained is not completely

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be taken away constantly before- When the hydrolysis treatment was carried out continuously in the same hydrolyzing bath, the whiteness "of the obtained image receiving material unevenly. Furthermore, due to the accumulation of the fluorescent whitening agent, sludge separated ah,

3- Manufacture of the silver halide photosensitive material (negative element)

A corona discharge was applied to a support having a 20 micron thick polyethylene layer coated on paper weighing 100 g / m 2 to make the surface of the support hydrophilic, and then a gelatin-silver bromoiodide photographic emulsion containing 5 MoI- ^ silver iodide contained, applied to the support. The amount of the emulsion drawn onto the carrier was 12 mg / oil, stated as the silver content of the emulsion, and 50 mg / 100 cm, stated as the drawn gelatin. An aqueous gelatin solution was placed on the emulsion layer as a protective layer and then dried, the thickness of the gelatin protective layer being 0.5 micron / 13Cti Ο.ΘΊ: xX'uCkiniHg W32; ·

4 «Developmental Treatment

The silver halide light-sensitive material which image by image with an automatic exposure camera in daylight aaset and the imaging material

faced other and then became a treatment solution of the following ingredients inserted between the two materials at a thickness of 100 microns:

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- 22 -

Diethy! Hydroxylamine 1.6 g

Zinc chloride 0.1 g

Uracil "1.2g

Hydroxyätbylcellulo3e, 72 g

Potassium hydroxide 3.5 g

H ₂ O 15 ecm

The thickness of the solution was 100 microns held by applying a paper frame with a thickness of 100 microns to the surface of the image receiving material with the central hole corresponding to the image area * After the two materials were in close contact had been held for 30 seconds, they were separated » A positive image was formed on the image receiving material which had a high reflection density. Anyway the white part of the kichtbildteil was uneven in terms of Whiteness as listed above.

example 1
1. Manufacture of the carrier ^

ρ ^

A mixed solution of the following composition was applied to a baryta-soaked paper (weight 135 g / m 2: thickness of the baryta layer 25 microns) (formation of layer A). The thickness of the applied layer was' microns after drying %

Cellulose acetate (manufacturer Daisel KE, degree of acetylation 60.5 + 0-5% - designation "Cellulose acetate T-AC")

20 g

CiI. Fluorescent Brightening Agent 91 (designation Kayalight B, manufacturer Nippon Kayaku KK) 0.45 g Methanol 50 ecm

Methylene chloride 450 ecm

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- 23 -

The following solution was then applied to the getroclaiete Coating layer applied to the carrier (formation of layer B). The thickness of the newly applied layer was 5 microns after drying:

Cellulose acetate (manufacturer Daisel KK, acetylation degree 60.5 + $ 0.5, as above) 20 g

Methanol 50 ecm

Ξ: methylene chloride 450 ecm

JL Ξ ± Ξΐ2. Preparation of the imaging material

'"""'-": - The in the above step 1) carrier ΞΞΞΞΞΪΞ obtained ⁷¹ Ewurde in a hydrolysis ^ Kernsübstanzeinführungsbad selected from ^ - was "the f ₀ ig _en AEEN materials" for 60 seconds at a temperature of 35 ⁰ C immersed and then flow with - - ^; -; 7 "~ _{2 of the} water washed and dried for 4 minutes:

J = ^ E glycerine, 150g

M ^ Z ^:: - ^: nickel nitrate (6 H ₃ O) 0.017 g

fc ^ - Sodium Sulphide (9H ₂ O) 3.1 g

f - = H sodium hydroxide 120 g

I = - % methyl alcohol 720 ecm

water . 4-SO ecm.

The thickness of the saponified layer was 2.5 microns.

The amount of fluorescent, whitening agent (Kayalight E) ₁ which was extracted in the Hydrolysierbad of was about 1 i <> of the total amount initially present.

on the obtained image receiving material and the whiteness before the hydrolysis treatment. Even if the Hydrolysebehan% luBgköntinuieriich in ■ - * the stieletlen Hydrolysierbad was .fortgesetzt _t no trouble arose ^

30984870909

- 24 -

7323742

_When applying cueses image _{ΐ (ιΐΒν1β1} , became

Segati ^ teri.l like j »J- β- _Terglel ch _Sl ) el-

the same W «W» ^ _{bit elMI} fcofcen Ee-

_sple l -, a »guided. υ = S »^ * B ^ aaufBB ^ eBaterial erhaxflektionsdlcMe« uxde on the ^ -
_ΐβη . Expands "te", the - "^
tote and i ^ äBx

PjLelJL

1. Manufacture of the carrier Solutions, dl

. Boy,
_tG3t a _E den, «urden, ur

B. uses _ ^ v, ie in example ^ ne «^

SohicM A

elier

Methanol

45Ö

Brightening A

lungsinittel, Hers Splint B

_at

-, Λ Al

0.45 g

layer A) 20 g

50 ecm

Λ50 ccra

Me

ethylene chloride

₂ .

_{Dl8 use the} following Meong _iungS , ad), and

Game 1 performed, shift 2.5 Miteon was.

309848/0909

_a as in Be, - , " _ierselft en

Glycerin 150 g

Lead nitrate x 0.03 g

Hair sulfide in HgO) 3.1 g

Sodium hydroxide 120g

Methyl alcohol 720 ecm

Water 430 ecm

Even if the hydrolysis is continuous in the same The hydrolyzing bath was continued, no problems occurred on.

The negative material and development treatment were as in Example 1. A positive image of high reflection density was formed on the image receiving material and the background had high and even whiteness.

Example 3

A polyethylene layer paper which is made according to the following Procedure had been established instead of the Baryta paper used and the same procedure as in Example 1 for the production of a carrier and an image receiving material performed on this polyethylene layer paper.

Low-density polyethylene (Sumikasen L-402, product of Sumitomo Eagaku Kogyo KK) with a content of 12 wt the Ishihara Sangyo XK) was applied by extrusion, the thickness of the applied layer being 0.045 mm. The extrusion coating machine was equipped with a screw type extruder (caliber 60 ram) and an I-shaped nozzle 500 mm wide, and the coating speed was 30 mm / min. The surface of the cooling roll used for casting was smooth. The surface of the applied polyethylene layer was subjected to discharge treatment by a corona discharge device (Repel High! Frequency

3Q9848 / 090S

laboratories Co. Ltd.). The distance between The electrodes were 8 mm and the discharge strength was 250 W. ''

Formation of the image and observations

The development treatment was as in Example 1 carried out and a positive image of high reflection density was formed on the image receiving material, whose background had a high uniform whiteness.

Compared to the carriers of the preceding examples, the carrier of Example 5 was superior in terms of surface brightness. However, the adhesion between Her polyethylene layer and the Celluloseesterschieht was a bit weak in this Eeispiel so that it was necessary to carefully perform the Verseifungnbehandlung.

Example 4

A plastic material made according to your following procedure was used in place of baryta paper and the same procedure as in Example 1 was followed for the production of the carrier and the image recording material carried out.

Manufacture of the plastic film

The following mixture was prepared and applied Spread a glass plate to form a film 1-50 microns thick after drying.

Cellulose acetate (manufacturer Daisel KK, degree of acetylation 60.5 + °> 5 %) 100 g

Titanium white (trade name T ~ ipacue R-820, manufacturer Ishihara Sangyö ICK) (rutile type, average particle size 0.2 to 0.5 microns) 15 g > • Diethyl phthalate 10 g methanol 100 ocs.

Methylene chloride 900 ecm

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"ti"

Formation of the image and observations

The same development treatment as in Example 1 was performed and a positive image with a high reflection density was made on a background of high uniform convexity formed.

The invention has been described above on the basis of preferred embodiments without being limited thereto is-

9 8 U S / 0 3 0 9- "- S- ^

Claims (1)

-28- 7323742 Pat en tans pr üch e Qy image recording material for the silver salt diffusion transfer process, which contains at least two layers, which consist of a cellulose ester layer, which contains at least one fluorescent whitening agent and a hydrolyzed cellulose layer, which contains silver deposition cores ₇ , the two layers being laid one on top of the other. Ξ 2. Image recording material according to claim 1, characterized in that the layers are superimposed on a carrier are laid. 3. Bildaufnahmemat-erial according to claim 2, characterized in that the hydrolyzed cellulose ester layer is ~ on the cellulose ester layer; Contains, which at least one fluorescently-Sziere ades Weißungs- or Aufnellungsisittel, befindete T 4. Image receiving material according to claim 1 to 3 _t · characterized [in that the Cellulosteester of cellulose acetate. Cellulose butyrate acetate, cellulose propionate or mixtures "There is sound here. 5- image receiving material according to claim 1 to 4, gekennseichnet characterized ₇ that the carrier is a photographic base paper, a pigment coated paper, a poly · äthylenübere-ogenen paper, a film of a substance of high molecular weight or a · art paper. 6. Bildaufnahmemateriai according to claim 5, characterized in that that the pigment consists of barite or titanium white. 7. Image recording material according to claim 5, characterized in that that the substance of high molecular weight consists of polyethylene terephthalate, a cellulose ester, polycarbonate or polyvinyl chloride. 8. Image recording material according to claim 1 to 7 _f, characterized in that a heavy metal, a noble metal or a sulfide, selenide or telluride of such a metal is present as the silver deposition core * 30S848 / 0909 -29- 7323742 9. Image recording material according to claim 8, characterized in that that the heavy metal of zinc. Mercury, lead, cadmium, iron, chromium, nickel, tin, or cobalt Copper and the precious metal consists of palladium, platinum, silver or gold. 10. Bildauf na hmematerial after .Anspruch 1 to 9, thereby characterized in that the strength of the hydrolyzed -Celltlose ester layer about 0.1 micron to about 20 microns i ^ r amounts. is "estersehicht 0.5 microns to 10 microns ΖΞ-.Ξ 12. Image receiving material according to claim 1 11, image recording material according to claim 10, characterized overall ££ Z3cennzeichnet that the strength of the hydrolyzing Gellulose - -"""": ~ ιΞΞΞ. to 11, da-If - ^£: 3lurch in that the strength of the fluorescent | i / - brightening agent about Zizzz ZZ ^r ^ Q 5 microns to about 20 microns containing Celluloseesterschicht?. ~ zSrzz ~ "ZZZL · 13. Image on suture material according to claim 12, characterized in that the thickness of the cellulose ester layer 1 Ji: ZZ. '" - to. 10 microns. Ξ ± ΞΞ ^Ζ Ζ ^ ^Ξ Ζ: Ξ 14. Image recording material according to claims 1 to 13? ds-Ξ £ -_ ί ^: Hcharacterized in that the fluorescent whitening agent or whitening agent is present in an amount of about 5 to about 500 mg / m ^. 15. Image recording material according to claim 14, characterized in that that the fluorescent brightening agent \ or whitening agent is present in an amount of 10 to 200 mg / m? j. I 16. Process for the production of image recording materials, ; j characterized by aaiä • | a) a cellulose ester layer which contains at least one fluorescent whitening agent or brightening agent, ^{1 is} applied to a .Träger., 1 b) "a cellulose ester layer, which at least initially is free of the fluorescent whitening agent on: this initial layer is formed, , 3088A8 / 0909 c) the surface of the support coated in this way
with a hydrolyzing bath and silver deposition cores
is treated to incorporate the cores in the bydrolysed cellulose ester layer. 17- method according to claim 16, characterized in that
that cellulose acetate, cellulose butyrate acetate, cellulose pro ^ ijnat or mixtures thereof are used as the cellulose ester
^ will. '%. 18. The method according to spoke 16 or 17, thereby nucleated ^ -I: indicates that a starch is hydrolyzed in cellulose- £ _:: |. Use an ester layer from about 0.1 micron to about 20 kilcron --.-; _-: '% - det will. - ._ ■. ::.! ■. | - "19" method according to address 16 to 18, .due to this, marked- i..z ':.' ~ Ξ % shows that a strength of the cellulose ester appears _{that -_:} \ -_- ■% -. - "that fluorescent whitening agents or whitening agents _ ..:.: h - contains, used from about 0 * 5 microns to about 20 microns ^: =; ^: - ϊ will. L '20. Method n & oh claim 19, characterized in: - that the fluorescent whitening agent or whitening --- ^ = - Medium applied in an amount of about "5 to about 500 mg / m will". ■ _- : '21 . The method according to claim 16 to 20, thereby germinated
f draws that a heavy metal, a precious metal or a Sulfide, selenide or telluride of such a metal as - Silver deposition cores are used. 22. The method according to claim 21, characterized in that
that zinc, mercury, lead, cadmium, iron,
Chromium, nickel, tin, cobalt or copper and as a precious metal
'Palladium' can be used as platinum, silver or gold. 30 9.8 U / 0909