DE1472882A1 - Photographic development process - Google Patents

Description

v-opy

DR. BRANDES, DR.-ING. HERO '

1472882 8 MÖNCHEN 22, Th: ors * slr. 8 | ΠΙ

TELEPHONE 293297 Reg. No. 120 034

Eastman Kodak Company, 3M3 State Street, Rochester, New York State, United States of America

Photographic development process

The invention relates to and to a dry photographic processing method photographic materials suitable for the process. In particular, the invention relates to photographic materials, which carry out photographic diffusion transfer processes and photographic colloid transfer processes enable in a dry way.

In the usual photographic development process, an exposed light-sensitive silver halide emulsion * layer in a liquid way by treatment with an alkaline one Developed reducing agent, which converts the silver halide to silver. This creates a negative Image. ^

In the diffusion transfer photographic process, such as it is, for example, in US Pat. No. 2,352,014.

i'.l

80981 1 / 10U

is written, the exposed silver halide emulsion layer becomes during development in the presence of a silver halide solvent with a receiving sheet brought into contact, which contains development cores. The undeveloped silver halide is replaced by the Silver halide solvent bound in complex, allowed to diffuse onto the receiving sheet and there under formation of a positive image is reduced with the help of the development nuclei.

At the Bog. Colloid transfer processes, such as those described in U.S. Patents 2,596,756 and 2,716,059 is described, an uncured silver halide emulsion layer and a tanning silver halide developer compound used. During development, the exposed areas of the layer are hardened and the unexposed areas and areas of the emulsion layer that have remained uncured are applied by pressing the emulsion layer on transfer a receipt sheet to the latter.

Liquid developers are used in conventional photographic development processes. Because bypassing As is known, has disadvantages with liquid developers, there has been no shortage of attempts to use dry development processes to develop.

It is known, for example, from the photographic

Adding hygroscopic compounds to the emulsion layer, 809811/1014

absorb water from the atmosphere and release it again when heated. However, the use of these dry-developable photographic materials has the
Disadvantage that they can only be used with a certain degree of humidity in the atmosphere, because only then
can be developed when they have absorbed a certain minimum amount of water.

Another known dry development process is
a material is used which, when heated, releases ammonia or an amine. This dry development process also has the disadvantage that it can only be carried out when water is present, since the liberated amines or the liberated ammonia only in the presence of water
bring about a development.

The development of a dry development process in which
a photographic material by the application of heat only
can be developed, therefore encounters difficulties in particular because light-sensitive silver halide emulsions are extremely sensitive to the addition of. conduct a development-inducing compounds. Most additives cause desensitization, fog and the like. In other words, it is extremely difficult to find compounds which are added to the emulsions when heated
cause a development without the silver halide emulsion

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-H-

bad to affect adversely.

The invention was based on the surprising finding that photographic materials of various constructions can be developed dry in a simple manner if dry development is used using a substance that is solid at room temperature, but becomes liquid when heated and in the liquid state, a solvent for photographic silver halide developing agents and silver halide reducing agents It has been found that these compounds, which will be described in more detail later, with silver halide

emulsions are excellently compatible and either in silver halide emulsion layers can be used themselves or in special layers.

It has been found, in other words, surprisingly that catfish Photographic material developed dry in the simplest way if either in a layer of the photographic light-sensitive material itself or in a A special welcome tea accommodates a substance which is a non-aqueous, polar solvent for organic developing agents that is used at room temperature is solid, but melts on heating and when the material is in the presence of a developing agent or a silver halide reducing agent and optionally a silver halide solvent is heated to a temperature that is at least necessary to liquefy the non-aqueous, solid substance

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The invention therefore relates to a photographic developing agent drive, in which a charged photographic silver halide mulalon layer arranged on a support is developed with the aid of a developer compound activated by heating, which is characterized by that the development by heating in the presence of a solid at room temperature, but melting below 140 ° C, Substance dissolving silver halide developer compounds through to be led.

The invention also relates to photographic materials for carrying out the method. Substances suitable for carrying out the method of the invention consist in particular of compounds or mixtures or complexes odeij eutectics of compounds that are solid at room temperature but liquid below about 140 ° C., have a high dielectric constant and contain -CO- or S0 ₂ groups.

According to the invention, particularly suitable solvents for organic Substances representing developer compounds can be represented by the following general formulas:

* - I. XCONRR

Z ^ II. YSO ₂ NH ₂

^ III. R'C

ι y ³⁰

° CH-O

co 2

IV. ZCONRR * »or

V. XCOH ₁ , V

where mean:

R is a hydrogen atom or a CH-- or HOCH-CH _{2 group} j R * is a hydrogen atom or a CH ~ group; R "'and Z together have a remainder of the formulas:

- (CH ₂ ) ^ - CO- or - (CH ₂ ) _fa -, where a * is 2 or 3 and bs is 3 »4 or 5;

X is a hydrogen atom, an alkyl group with 1 to 4 carbon atoms or an R ¹ NH, R "0 or - (CH ₂ J _n CONRR» group, where R and R 'have the meaning given, η - 1, 2, 3 or 4 1st and R ″ represents an alkyl group with 1 to 4 carbon atoms;

Y is an alkyl group with 1 to 4 carbon atoms, an NH ₂ , R ⁿ 0 or an optionally substituted aryl group, where R ″ has the meaning given and

W including the N atom to complete of a heterocyclic ring.

W preferably represents the atoms that form a 5- or 6-membered, heterocyclic ring, such as a Norpholln or Piperldln rings are required.

Particularly suitable substances are, for example, the following compounds:

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Formamide,

Acetamide,

Propionamide,

Valeramide,

N-methylacetamide, Ν, Ν-dimethylacetainld, N- (2-oxyethyl) acetamide,

N, N * -bis (2-oxyethyl) malonaraid, N, Nl-bis (2-oxyäthy1) adipamide,

N, N »-Bis (2-oxyethyl) -N, N · -dimethy14uccinamid,

Succiniraid, Glutarimide,

2-pyrrolidinone, 2-oxohexamethyleneimine,

Ethyl carbamate,

Urea,

N-methylurea, N.N'-diraethylurea,

SuIfamid,

Methyl sulfamate, Xth? Lsulfamate, Methylsulfonamide, Ethyl sulfonamide,

p-toluenesulfonamide,

Ethylene carbonate and * Propylene carbonate

Such .Compounds can either stand alone or can be used in the form of mixtures, complexes or eutectics. Are the compounds described liquid at room temperature, which is the case with some of the compounds falling under the formulas is the case, however, these form with other

80981 1 / 10U

to indungen, possibly such tier formulas I bli V, sub-

■ '■' ■■■ i

rods that are b «i room temperature feet and dl · desired j

Have properties

8o kfewen, for example, by heating hydroquinone old liquid formamide (Behmel point * 2 ⁰ C) or H-Methjlpjrrolldon, Aoetylaorpholln uiw. In one «g« «lgn * t« n Hllfelöiungieit-

·. ν ■

t «lb * l TT ⁰ C, btv« TO ⁰ C and 68 bit 90 ⁰ C ecle «li * ndt complex · hftrgtitftllt. Dlcit Xoapl «x · β · ΓΓ · 11 · η, if there is enough faoeh, ie from teaper doors about above the SehaelKpunktet In your bed end * Vlrd therefore a material, In des al ·" Subetene "" housed in such a Kovplex Let, "ur development warmed, eo form both the developer al" as well as the · non-aqueous, polar evacuating agents · On the other hand, if suitable solvent equipments have a xu high Sobmeli point, then a «wide connection through the lowering of the ecbmelapmkt · are mixed»

Xn are the following rebe11 "t _t different from mixtures tin" ν · 1 components existing Mubstaneen "on gefahrt * I

TaeeUe 1, see sewed felte.

BAD ORIGINAL 'j

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Tftb «n« ι Part of the mixture 3ch «elipunkt
the sugeaets
ton Vtrbin
training 9 tu fet tt> ar «Congo from
B tu A tu * Horstoliun
from Miohtingon «it ei
ne »Scheoli point of
iOp ° C 04 * r wonlefi - M - 100 1 55 · SO I A * Suooinlaidj melting point, 123 ⁰ C 40 «100 y 30 «45 I. • Formamide 2 ⁰ C 15-100 y 517 x 100 j 13 · tt f B. Trilthanolein 21 ⁰ C 35-100 y 71-100 y BATH ORIGINAL B "N-MothyUootiMid 25 ⁰ O 22 - 100 y 61-100 y B xthylcarba * at »9 ° 0 25 - 100! 45 - 100 1 B · acetamide 79 ⁰ C 16-100] 86 - 100 1 B ■ N _f N * -Dinethylurate
B · N _t N * -Bii (2-Qxyethyl) adipamide 100 ⁰ C
130 ° C 25-95 y
* 8 - 70 1 40-100 y A · Ureaj Sohmolpunkt, 132 ⁰ O 30-100 j B · N- (2-oxyethyl) acetamide <25 ° C 50 - 100 y B ■ N-Hethylaootaaid 25 ° C 30 - 100 1 B * a-Ajilno-a-ethyl-1-propanol 25 ⁰ C 7a 15! B · 1,6-hoxandlol »2 ° 0 38 * 95 1 B x ethyl carbamate »9 ° c B · 2,2,2-trichloro-1-l-thoxyethanol 51 ° C B · n-butyl carbanate 53 ⁰ C B · n-Propionaeld 78 ⁰ C B Aoetaeid 79 ⁰ C B Ialdaiol 88 ⁰ C ft · Kothyluratoff 99 ⁰ C \ B »n-valeramide 102 ⁰ C \ U · 2-A »ino-2-ethyl-1,3-propanediol 109 ⁰ O 1 · 3uoeinleid f B · M, N '-bit (2-oxylthyl) adipa' ld { B * thiourea B · LUhive »nitr» t I. 123 ⁰ C
• In · «utektltsh · Mltthunf
■ it 70 IA un4 30 IB,
• ehailst Hol ill · C 13O ^e C Hl ⁰ C 255 ⁰ O

809911/1014

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In a preventive embodiment, the method of the invention uses a layer prepared by applying a dispersion of one of the described non-aqueous substances, in a "binder, in a thickness of about 0.025 to 0.076 ws ₉ on a" Document·

Particularly advantageous results are obtained with 1 to 2 g of the substances per about O ₉ O 9 »underlay, although larger and smaller amounts of it can of course also be used Part of the Sehloht is formed by the Substans. For example, ratios of binder to "substance" of 1 1 2 to 1 8 have proven to be useful :

As part of a DIffuslonsUbertragungsverfahrena sB such Sohicht is applied over a support containing development nuclei, but during the Sehloht under a colloid transfer process _k a non-pretreated support or a support is applied, which, to that of the transferred image Dlohte su larger, on its Surface, precautionary in a special layer, contains a fogging agent "

BtIsI diffusion transfers experience s.B. can the exposed photographic emulsion layer pressed against a face sheet warden, «among other things has developmental germs and a · oversight

IAO ORIGINAL

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with the Subetans and a silver halogen developer compound and a 318 oil solution. The formed Sandwich is heated to a temperature that is sufficient to keep the substances liquid until the development in the emulsion layer has taken place and see a positive one Image on the carrier of the Em * containing the development nuclei pang-leaf has formed «Since the non-aqueous which forms the substances Solvent, after the sandwich has cooled down to room temperature again, usually due to hypothermia * «» If there is still some liquid left in the tent, see the receipt sheet easily wipe off the emulsion layer again

In the colloid transfer process, the exposed photographic silver halide emulsion base, which preferably contains a tanning developer sandwich formed "uf" ine such a temperature it is hitst * daft the flubstans schallst, which in the silver "... hslogenidemulslonsschieht a tanning development occurs · After separation of Empfangabiattes of the emulsion layer remains on the topfangtblatt an image consisting of a fl-coated layer of the unhardened areas of the emulsion s * r (Uk

BATH ORIGINAL

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The method used in the case of diffusion transfer as a binder The colloid used for the photosensitive silver halide can be selected from any of the known swellable binders for silver halide, * »B» gelatin; Polyvinyl alcohol} nethyloellulose} Polyacrylamide} an xthylaerylate-acrylic acid mixture polymerJ a cellulose phthalate ether, albumin; Collodions and the like exist, while in the case of the colloid transfer process the binder for the silver halide consists of a colloid which can be hardened by means of a tanning developer exist mufc.

If the solvent, which is solid at room temperature, is used for the developer compound, ie. dlt Sübetan *, used in a special way "it is always applied to the desired substrate with a suitable film-forming binder" so that sufficient adhesion is achieved. «It t« B. XthyltnoMaUlnsäurtmlsehpolymtrisa.tt, Cellulose * esttr, such as Ctllultstaettett and Otllulostaeetatbutyrate silt "i-η" Asttylgruppabalt of about SS $ "4er Ctllttlottätntei s, B * Ithylst ^UultseHTl, poly. nnylpyt ^ · I rolidon-nnyUeetat ^ teniKiljrnerlsatt, fltyrti-lutaäitn ^ Ufhpo- 'frtttint, like κMtIn tu * «vttv * iM ν« «***

^ ■ · '«ts nltstwäskrigen Utungsmitteli 4 * 1» dtr iiikstan ·, thirsty (ptrmeabel) are. >

IAD OWGINAL

In the method of the invention, known developer compounds, such as s, B • N-methyl-p-aminophenol sulfate, ascorbic acid, hydroquinone, 3-pyrasolidones, such as l-phenyl-3-pyrasolidone, l-phenyl- ^, ^J l-di "Ethyl-3-pyra-olidone, etc. j p-phenylenediaalne; Pyrocatechin tin (II) octoate, dextrin, 3 »5-Dlamlno« · phenol · and the like, are used »

For the formation of soluble complexes with the silver halide suitable · silver halide solvents and for example! Thiourate compounds, thiosulfates, thiocyanates, sulfhydry groups containing compounds »such as i, B, mercaptoeaalgafiure, Polyanines, such as tetraftethylene pentamine and others

The silver halide of the silver halide build-up layers can from the usual silver halide shops "such as silver chloride, silver" chloride bromide, silver chloride iodide, etc., preferably silver helium rId, consist "

Get the Sübstansen on Bildeapfangeblittern sur application, so the carrier of the image reception sheets can, for example, be Paper; aiasi Hol «} metals} plastic» «1 · s» B, polyester fillings, Polyolefin films, etc. exist.

Venn dl · Substansen, d «| · dl · nlehtwAssrlgen solution waste production
If a developer solution is used, the solution is prepared before it is sugswelse at a temperature above the Sohmel point of the

non-aqueous solvent, whereupon it can be cooled and stored in a solid state. Will this solution then for the development of an exposed silver halide emulsion When used, it is melted by heating and used at a temperature above its melting point. Of course, such developer solutions can be used in a wide variety of » can be added to common ingredients in common, i.e. aqueous, developer solutions. The concentration of the non-aqueous solvent in these developer solutions are generally not critical if only complete dissolution of all constituents (in the liquid state) is achieved will·

If the non-aqueous solvent is placed in special layers, it should be used in such an amount that it contains all of the developer compounds present in the layers as well as any components that are present and involved in the development process. Becomes the non-aqueous solvent in a layer under or over an emulsion layer housed, it should be sweckable in quantities of at least 0 »* β P'O millimoles of silver halide used« earth *

If the non-aqueous solvent is placed directly in a silver bottle. Loyenldemulsionsschloht housed, so of this at least O ₉ I g per millimole of silver halide should be used «

809811/1014 mdor.ginal

Uni a wandering of the drainage connections from the non-aqueous Solvent-containing layer in a silver halide emulsion layer To prevent heat build-up, the Erauleion layer and the non-watery layer can puddle

LIe not mean

4M ** «· * · * · * containing layer» optionally a barrier layer to be ordered"

The temperature at which the exposed photographic material is developed, must in any case always above the melting point of the non-aqueous solvent used in the special case. If necessary, a considerably higher temperature can be used applied as the melting temperature of the non-aqueous solvent and "was especially when a special" rapid development is to be achieved

Xn the drawing is in Fig. 1 the process of a diffusion over Transfer method using the photographic material according to the invention and in Fig. 2 the sequence of the colloid transfer method using a photograph Materials shown near the invention *

QenäA Fig "i becomes a photographic material, bcttehteiA tu" elnesi carrier ti and one exposed * tllohen if and unbeliih-; tete flee 16 showing silver halide deeuleloneeohleht 18 pressed against a layer 13, the tin nlohtwtssriges L6tttAtl #

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60.9811 / 1014

1472682

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sattel gent * of the invention "nthält · Di" Sehlobt 13 also contains a developer and "in silver halide solution not old - t" l oär tin "" it silver halog "nld" a soluble complex * forming "compound" Dl "layer 13 is over an intermediate layer ik having EntloklungskelMe applied to the carrier 15. If the sandwich is heated to such an extent that solid, non-aqueous solvents are enameled, then a development occurs in the exposed areas if the emulsion layer 12, while the unexposed silver halide outside the areas 16 forms the soluble coaplexes which form superhalides Connection is released and Eu der Sehiaht ik "changes" where the silver complex 4 is reduced to form a positive formation of silver.

OemäA Fig. 2 is a photographic material "consisting of the carrier II as well as" exposed in the n areas If and unexposed in the fleece 16 "but unhardened silver halide, nldesiuleionetch it is coated against" a layer 13 " a non-aqueous "solvent" of the invention and dissolved in it in font of a fat soldering a tanned *** denickler hat * The layer 13 tit upper elncji "in Sehieier" means contains v tends "tvlsehensshleht lH" which they put on the rrttger i | befiMet, 0er ia «« # i «h itlr« gersendea developer etrthaIt «ate fette, ni

Will the sandwich

809811 / 10U

unexposed and consequently uncured areas 16 of the original Layer 12 on layer 14 on carrier 15 and there will be a, with addition to the image in the photographic material, received positive relief image

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

example 1

On a film base made of polyethylene terephthalate, which has a coating consisting of an Xthylacrylat-Aerylsäuremlschpolymerlsat had a dry measurement of about 0.013 nra (0.5 nil) thick layer of a mixture consisting of:

50.0 g of a 7 l solution of polyvinyl alcohol in an Oe * mix, consisting of 45 weight points isopropanol and 55 weight »share water,

3.5 g acetamide and

3 »5 g 50 $ aqueous · polyethylene imine solution

applied · After the layer had dried, this · «in ·, Measured wet, about 0.41 mm thick · Layer consisting of a mixture of

50.0 g of the 7 liter polyvinyl alcohol solution described, 20.0 g of aoetamide and
1.5 g thiourea

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A material consisting of a paper carrier and a silver chloride emulslon applied to it was used as the negative material. Half of the surface of this was barked, whereupon the entire negative material was developed in a Kodak D-72 developer, washed and dried at Rotlieht to H ¹ I ⁰ C, whereupon the seeds were separated again The receiving sheets then contained positive silver images The transfer of the unexposed silver halide from the emulsion layer by diffusion to the receiving sheet and the subsequent reduction of the halide su silver in the receiving sheet thus took place in a single Work gear *

Example 2

On a paper consisting of partially acetylated fibers, which has a gelatine-barite base that is common in photographic copier papers exhibited were one after the other

1 ·· one, measured dry, about 0.013 n °> thick layer of a mixture consisting of:

50 g of a 7 2-lgen polyvinyl alcohol solution, as described in Example 1,
3.5 g aoetamld and
7.0g yellow dextrin

and after the layer has dried on this “ _ιΛΙ ., _Α .

BATH ORIGINAL

Θ0981 1 / 10U "

2.) one, fire measured, about 0.81 is this Sohicht from one Mixture, consisting do '»/.

50 g of a 7% polyester alcohol solution, as in Example 1

deserve,
21 g acetamide and
2.5 g of tetrahedral pentamines

applied

The receiving sheet obtained was brought into contact with the emulsion core of a developed negative as described in Example 1, whereupon the formed saturation was bittered to a temperature of ItO ^{0 O for 15 seconds by means of an electric iron.} The receiving sheet, separated again from the negative, then contained the positive image of the Hegatlvs.

Example ι ■ ^{V: r.} Ϊ;, ;; "- ' ^f - | On "in sheet of paper, as in Example f, rubbed off

a solution consisting of t '' - ^ \ l. * ^'ϊ-; , ν-. ΐ'- ■ - '■■■■' - 'y ^{^:'} 'f ¥ ■■ ·: ■.''''■' ■■■ "■" λν-: '- ^ ;; v: - ^: ■, - ^ r * :. ; .- ..: ■ "·: ■ ■ -;' ^ ■■ ':.' - , p-

50.0 g of a 7% pure alcohol solution, as in the example

a »troeiten gestessen,« tva O ₁ OiS e »di« k «begs a» fg «trmg · * on which ·« ine, moist geMStui, «about 0.6 ■» dlek · tfhieh · «·

8tf9aiii / 1014 ⁸ ^ ^ORIÖINAL

■ - 20 -

a mixture consisting of »us

50.0 g of a 7 g polyvinyl alcohol solution, as in example

1 described »
28.0 g of N-Hcthylccetaald and
2 »5 C tetraithylene pentamine

Was applied

The apple leaf obtained was "tested as described" on the eeulsion surface of a negative, whereupon the formed sat was kept for 2 minutes by means of an electric iron at 80 ° C. Analysis of the silver content of the apple leaf from the positive image obtained determined that approximately 0 »09« s Flicht des Bapfangsblatt 15 $ mg of silver were present *

Because mixtures of other non-aqueous solvents A and B are used, "dl · within" a wide range of mixtures can form solid solutions. l & At the for the development bsw. Transmission required Teaperator betrlchtilch herabiet sen _t Suitable binary Systecw are ·· i "Dieethiriacetaeld-Acctssildi ronuuaid ^ Acetemldt Distethyifereaald-AectaaUi Pjrrrolidon-Aoetesüd and N-Mcthjrlacetcatld-acetamide · Ia of Table II are Sctacelspunkte of mixtures" he • uletKt sjenannten compounds indicated "

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Table XI Melting point % N-methylaoetaaid t Aoetaeid 80, O ⁰ C O 100 69, O ⁰ C 20th 80 67.0 ° C 40 60 43.0 ° C 45 55 27.5 ° C 50 150

Dl · second · layer of those described in the previous examples Collecting leaves was applied as an aqueous solution * In this process catfish is the drying time for The shift was relatively long because acetamide or substituted Aoetsjild · are known to be hygroscopic »On the other hand, amounts to dl drying cycle only about 15 to 20 seconds if, as described in the following example, the layer is applied according to a shell lining process

Example 4 On paper of the type described in Example 2 were

applied «

1 «) a, measured dry, about 0.013 *" thick "layer, consisting

47.0 g of a 7.4 S polyvinyl alcohol solution (solution · »ittel J.

Water-isopropyl alcohol la Oewlohtevernlltnie 55: 45), 5.0 g acetamide and_
2.5 g of tin (II) octoate, as well as

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2.) with a * knife spacing of about 0.30, a · layer, consisting of:

42.0 g of acetamide and
7 * 0 g cellulose acetate with an acetyl group content of 32.7 %

and
4.0 g tetralthylenepentamine,

at a temperature of 90 to 95 ° C

The receiver sheet was then pressed with its upper side on the emulsion layer of a negative, erhltxt whereupon the formed sandwich for 15 seconds with an electric iron at 110 ⁰ C · was the stripped from the negative Eajp start leaf contained then the positive image of the negative ·

Then hurdle the receiving sheet containing the positive image placed in an oven at a temperature of about 130 ° C for about 2 minutes, so the image became darker as it turned Acetamide evaporated and practically a picture consisting of silver dispersed in essentially pure cellulose acetate left behind on the sheet.

P In Examples 1 to 4, polymers were used as reducing agents, immovable links, as s.B. Polyethylene oil and dextrin used or dispersed in insoluble in a binder Reducing agents, such as β · Β · tin (II) octoate, which also

• AD ORIGINAL 809811/1014

was practically established «In the following example becomes a mobile reducing agent used in the negative material can migrate and on the reduction in the receiving sheet also that in the emulsion layer of the negative material Can reduce silver halide *

Example 5

On one made of partially aoethylated paper fibers Carriers were applied one after the other! 1 ·) a »measured dry, about 0.013 ■» thick layer, consisting from t

50.0 g of a 7 ff-lgen aqueous gelatin solution and 2.0 g of Dlmeth $ lamlnborat, "owl"

2 «), with a knife distance of about 0.3 mm and at a temperature of | 0 ° bla 95 ⁰ C an aust

42.0 g aoetamld,
7.0 g cellulose acetate and
4.0 g of tetraithylene pentamine

existing eyesight "

The receiving sheet obtained was obtained for 60 customers with a Silberohlorldnegatlv at a temperature of ItO ⁹ C. The receiving sheet, separated from the negative, contained a special “black silver positive image of the negative.

80961

The following is made up of the production of solid complexes Compounds of the general formulas I - V with hydroquinone described *

110 g hydroquinone, 91 g formamide and 250 ml ethyl acetate were warmed on a steam bath until complete dissolution occurred was * The solution was filtered while hot, whereupon the filtrate brought to crystallization at room temperature. was · The crystals were filtered off and dried · The Yield was 150 g * The melting point was 77 ° C,

Q) Acetmipld- Hr dro chlnon complex

1 mole of hydroquinone and 1 mole of acetamide were mixed with 700 ml of acetone heated until a solution was obtained. The solution then dried to dryness evaporated, the residue digested with ether and then filtered off 148 g of solid, white, crystalline complex compound were obtained obtained with a melting point of 105 ° C «

C) M-Methylpyrrolldinon-Hydrochlnonkpmpleχ

110 g of hydroquinone were dissolved in 250 ml of warm isopropanol »

whereupon 200 g of N-neliylpyrrolidinone were added to the solution « The mixture was cooled overnight, whereupon this crystallized out The product was filtered off and recrystallized from 250 ml of isopropanol »There were 212 g of the complex compound with get a point of view of about 70 ° C »

AAO OFUQJNAL 809811/1014

147288 *

D) Ethylmorpholine hydrochloride complex

110 g of hydroquinone were dissolved in 250 ml of warm isopropyl alcohol, whereupon 260 g of acetylmorpholine were added to the solution. The solution was filtered and cooled, whereupon the precipitated crystalline complex was filtered off with suction * 336 g of the complex with a melting point of 88-90 ^° C. were obtained.

Example 6

A solution of 15 g of the acetylmorpholine hydroquinone complex prepared as described and 10 g of 1-phenyl-3-pyrazolidone in 100 ml of methyl alcohol was placed in white paper with a square meter weight of about 2.8 g or 5 »6 g (Corinth brand) calmly. Sections of these papers were then pressed onto an exposed silver halide emulsion layer, whereupon the formed Sandwich was heated for 1 minute with a hot iron so much that the complex melted and hydroquinone released. The silver halide emulsion was thereby exposed in the Share developed.

In the same way, solutions containing l-phenyl-3-pyrazolidone were made and one of the other complex compounds contained, left sucked into the written paper, in each case a material very suitable for the dry development of photographic emulsions was obtained.

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The development process described in the previous examples of the invention, compared to known so-called dry development processes, which, like various, diffusion transfer processes performed at elevated temperatures Use small amounts of water as a solvent for the developer, essential benefits · While namely the The use of a solvent which is solid at room temperature does not result in any losses when the photographic material is stored such solvents can occur, e.g. Materlallen, which Trinatium phosphate, dodecahydrate as compounds that split off water contained, especially when the relative humidity is low, only kept under strict precautionary measures will. In addition, when the photographic material is heated, much water is lost through evaporation, i.e., water Water stands for the solution of the silver halide complex and therefore also as a diffusion medium in the development process no longer available. In contrast, the photographic material according to the invention has a stable diffusion medium which compared to aqueous media has the further advantage that it allows the use of higher development temperatures, whereby the development can be accelerated considerably.

Since acetamide dissolves hydrophobic binders such as cellulose acetate, when using such a non-aqueous Solvent easily silver images in matrices that are not water-soluble are to be preserved. Such matrices are below

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if

Stable conditions under which ordinary binders, how matrices containing gelatin on paper are destroyed.

The images produced according to the previous examples consisted of silver images. According to the method of the invention However, is it also possible to create Parbbilder in which In the case of an oxidized developer, a coupler is used to react. For example, a system with p-phenylenediamine can be used as a developer and dloxynaphthalene as a coupler. In this case, the exposed The silver halide image is developed and the oxidized developer dlffunidert into the receiving sheet, where it meets the coupler reacts to form a dye image. After such, at higher temperatures with solid at room temperature Polar solvents, in the absence of water, working processes, can produce color images even in copier can be obtained.

Belspfei 7

A solution consisting of 25.0 g of succinic acid imide, 5.0 g of urea and 25 ml of water was dispersed in 125 S 3 "5% ethylcellulose, whereupon the dispersion was applied over a silver chloride emulsion containing 4-phenylpyrocatechol, as used in the USA" U.S. Patent 2,716

8Ό981 1 / 10U

a '

is described, was applied at a distance of the coating knife from the emulsion layer of about 0.15 mm. The dried material was placed under a Ne-

j gative with a nltrophot lamp set up at a distance of 6l cm exposed, whereupon the exposed material was developed by heating at 140 ° C. for 5 seconds. The one black and material exhibiting white positive excellent sharpness was then immersed in water, thereby forming the top layer peeled off and the hardened image layer was exposed. The damp die was then pressed against an absorbent sheet, whereby the white, uncured areas of the original emulsion layer were transferred to the sheet while the developed and hardened surfaces remained on the die

Example 8

A photographic emulsion of the following composition:

Gelatin (f% aqueous solution) 100.0 g

34lberchloride coagulate with 53 % solids

TeUs 15.0 g

Succinimal 21.0 g

Urea 3.0 g

Pyrocatechol 2.0 g

was on a paper covered with a gelatine-baryta layer applied at a sighting knife distance of about 0.15 mm, whereupon the coated material, as described in Example 7!

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ben, exposed and developed by heating for 5 seconds at a temperature of 140 ° C. Subsequently, a Receiving sheet pressed firmly against the surface of the developed stencil. The non-hardened surfaces were exposed Transfer the receipt sheet.

The following example describes a receipt sheet that which contains a developer * which is used to develop an exposed photographic negative can be used, with a transfer and subsequent reduction of the soluble silver halide transferred to the receiving sheet.

Example 9

On a carrier consisting of partially acetylated paper fibers, as described in Example 2, 1.) one of:

50.0 g of a 7 strength polyvinyl alcohol solution, 3.5 g of acetamide and
2.0 grams of tin (II) octoate

existing layer, measured dry, about 0.013 mm thick, as well 2.) after the first layer has dried at 90 ° C one of:

42.0 g acetamide,
7.0 g cellulose acetate,
4.0 g of tetraethylene pentamine and
0.5 g of 1-phenyl-3-pyraeolidone

8 0 9 8 1 1/1 0 U

existing layer with a knife distance of about 0.3 mm applied.

The receiving sheet obtained was pressed with its upper side against the emulsion layer of an exposed silver chloride negative, whereupon the sandwich formed was ^{heated to a temperature of 140 °} C. for 3 minutes. The receiving sheet separated from the negative contained the reverse image of the negative image.

Example 10 A solution consisting of:

SuIf amide 30.0 g

N-oxyethyl-N-ethyl-p-phenylenediamine 8.0 g Ammonium sulfite 2.0 g and

Water 20.0 ml,

which is dispersed in 125 ml of a 7 g solution of ethyl cellulose toluene w «r, was applied to a gelatin-silver halide demulslon layer in this way applied that on about 0.09 square meters of support surface 2 g dry weight were eliminated.

At the same time, a receiving sheet was produced by applying about 1 g of a solution consisting of:

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Polyvinyl alcohol 5 _β 0 g

Ethyl alcohol 75 ml

Water 25 ml

1-naphthol 15.0 g

Ammonium sulfite 2.0 g

was applied.

The material having the silver halide emulsion layer was exposed imagewise and placed with the emulsion side down on the upper side of the paper sheet containing the coupler, whereupon the two were ^{heated together to a temperature of 110 °} C. for 1 second. After separating the sheets, the material having the emulsion layer contained a developed silver negative image, while the paper sheet had a blue-tinted mirror image of the negative.

A fresh receiver sheet was pressed onto the developed negative image and the sandwich was then placed on the for 1 second The specified temperature was heated, so that a blue mirror image was again obtained on the receiving sheet. In the same way were able to produce two more blue images, i.e. a total of 4 prints of the negative original of excellent quality will.

Example 11

A photographic emulsion of the following composition:

Update on page 32. 8098 11 / 10U

Gelatin (7 Z solution) 100.0 g

Silver chloride coagulate with 52 % silver chloride, 47.5 % water and 0.5 % gelatin 6.1 g

Sodium isoacorbate ^ »0g

1-phenyl-3-pyrasolidone 1.0 g

Succinimide 15 * 0 g

was on a barite-coated paper weighing a square meter of about 136 g applied with a knife spacing of about 0.15 mm in such a way that about 2 g, determined dry, were omitted per square meter.

At the same time, a receiving sheet was prepared by applying a transfer method suitable for the silver salt diffusion process Sheets (Apeco copying process) per 0.09 m base area, dry measured about 1 g of one

Sulfamic! 30.0 g,

Ammonium thiosulfate 4.0 g and

Water 10.0 g

containing solution was applied. The coated sheet was then dried.

The material containing the emulsion layer was passed through a negative (white letters on a black background) and then pressed with the emulsion side down onto the top of the receiving sheet. The sandwich formed was then heated from the back of the emulsion-containing material for 30 seconds to a temperature

A η 9 8 1 W 1 0 U

Temperature of 110 ° heated, with a positive image on the receiving sheet entetand. The receiving sheet used contained about 10-20 mg development nuclei per 0.09 n » ^{2 support} surface, for example made of nickel sulfide or zinc sulfide or finely dispersed silver (Carey Lea-Silver) and the like.

Example 12

The developer-containing photographic material of Example 10 was exposed in a Thermofax copier and then pressed against a receiver sheet as described in Example 11, the emulsion side of the photographic material being brought into contact with the developer-containing side of the receiver sheet. The sandwich was then rotated (with a No. k roller setting of the copier) through the heated rollers of the machine, a positive image being obtained on the receiver sheet separated from the sandwich.

Example 13

A-n polyethylene terephthalate support of a thickness of about 0.1 mm, was operated at a coating knife distance of about 0.075 mm a f44l photographic emulsion consisting of:

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37 g of a gelatin silver chloride emulsion, 13 β succinimide and

50 g of a developer dispersion, consisting of

1-phenyl-3-pyraxolidone 120 g

n-butylacetane III 480 ml

Ascorbic acid 40 g Potassium bromide 5 g and Gelatin, 10 % aqueous solution, 1860 g

applied

The photographic material was exposed through a negative of high contrast and then developed on a HeIxtisch at a temperature of 150 ⁰ C.

Example 14 A developer solution was made from:

1-phenyl-5-methyl-3-pyra-olidone 4.0 g

Potassium bromide 0.1 g Formamide 20.0 g and

Acetamide 20.0 g

prepared and dispersed with the help of a colloid mill in 125 g of a 7 % solution of ethyl cellulose in toluene. This dispersion was then applied to the siltorhalide emulsion layers of photographic papers at a flare knife spacing of about 0.15 mm. The silver halide of the layers consisted predominantly of silver chloride or silver bromide.

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The photographic papers coated with the developer dispersion were exposed under a negative and then heated to 80 ^° C. for 3 seconds by means of a heating table. In the process, there was a development towards positive images.

Example 15 One of 30.0 g succinimide, 5 * 0 g ethylenediaminetetraacetic acid

m
reji iron (II) and 40.0 ml of water existing solution was dispersed in 125 g of a 7 solution of ethyl cellulose in toluene, whereupon with the dispersion at a knife distance of about 0.15 mm the emulsion side of predominantly 0 silver chloride as photographic papers containing photosensitive silver halide. These papers were then exposed through a halftone negative image and then ^{heated to I 1} JO ⁰ C for 15 seconds. Good positive prints of the negative were obtained.

Example 16

1 A solution consisting of 40.0 g succinimide, 6.0 g £ -phenyl-5-methyl-3-pyrazolidone, 2.0 g of ascorbic acid and 15.0 ml of water was dissolved in 125 6 of a 7 ί solution of ethyl cellulose in toluene dispersed, whereupon the dispersion is applied to the emulsion layer of a photographic material consisting of a silver halide emulsion layer and a paper support at a Messerabat and was applied from about 0.15 mm. The silver halide

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consisted mainly of silver chloride · The material was dried and exposed under a line negative at a temperature of 24 ° C and a relative humidity of 40 jS. A good quality image was developed by heating for 3 seconds at a temperature of I ¹ JO ^{0 C}

Another part of the material was after it had been previously stored in a desiccator over silica gel at 24 ° C for 6 days, illuminated in a room at 15% relative humidity and a temperature of 21 ⁰ C in the same way and developed.

The sensitometric values obtained for the silver images are compiled in the following Table III.

Table III

veil

Freshly made material developed at 24 ° C and 40 % relative humidity 0.8 0.02

Dried over silica gel in a desiccator and at 2 l | ° C and 15 Jt relative humidity developed material 0.9 0.02

The following example illustrates the use of a barrier layer between the silver halide demulsification layer and the one developer dispersion Containing Layer Described · The barrier layer is designed to increase the migration of the developer as well as the migration

8 0 9 8 ι 1/1 0 U

of any stabilizer compounds used, as well as also the non-aqueous one associated with the developer, etc. Prevent solvent in the emulsion layer during the coating · You must however at the same time opposite the no-aqueous, molten developer (or stabilizer) solution to be permeable during development »

Example 17

A piece of exposed photographic paper, its silver halide emulsion layer containing predominantly silver chloride as the photosensitive silver halide, was converted to a temperature Developer solution heated to 60 ° C, consisting of:

1-phenyl-S-methyl-S-pyrazolidone 6.0 g

Ascorbic acid 2.0 g

Acetamide 38.0 g

Water, 10.0 ml

immersed, during which development of the exposed paper occurred

Another piece of the same photographic paper was coated with a methylene chloride solution of ethyl cellulose phthalate in such a way that 0.3 g of the film former (dry weight) accounted for about 0.09 square meters of support surface. The ethyl cellulose phthalate contained 21% phthaloyl and 42 % ethoxyl groups. The coated photographic paper was exposed to light and immersed in the warm developer solution for 2 minutes, but this time no development occurred.

809811 / 10U

If the solution was increased from 60 ° C to about 93 ° C, there was no change a · It proves this that the ethyl cellulose phtha-:

i lat barrier layer under the specified conditions for the

Acetanld-water solution is impermeable. :

The barrier layer having exposed photogra- \ phisehe paper, but was only 5 seconds into a \

Temperature of about 96 ⁰ C heated, ie melted, water- '

i free developer solution, consisting of: |

1-phenyl-S-raethyl-S-pyrazolidone 6.0 g;

Ascorbic acid 2.0 g: Acetamide 33, Og j

immersed, development of the exposed photographic \

■ I see paper, which proves that the barrier layer is permeable to ■ the developers dissolved in the molten (anhydrous) acetamide »

Example 18 |

———————. j

In this example, the simultaneous development and stabilization described is t of a photographic image. |

On a, predominantly silver chloride as silver halide, in the \ Photographic paper having an emulsion layer were

1st. Red light applied one after the other:

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-ige
1.) a 5 l / ethyl cellulose phthalate solution in methylene chloride (the ethyl cellulose phthalate had the same composition as that described in Example 17) in an amount corresponding to 0.4 g dry weight per approximately 0.09 m²;

2.) one in 125 g of a 7% ethylcellulose-toluene solution dispersed developer solution, consisting of:

1-phenyl-3-pyrazolidone 6.0 g

1-ascorbic acid 2.0 g

Potash iodide 0.5 g Succinimld 30.0 g

Water 40.0 ml,

in a 2 g dry weight per approximately 0.09 square meters of the first layer appropriate amount as well

3.) a 7 ί ethylcellulose-toluene solution dispersed in 125 g Stabilizer solution, consisting of:

Diethylaminoethane thiol hydrochloride 8.0 g Succinimide 30.0 g

Water 40.0 ml

in a 2 g dry weight per about 0.09 of the second layer corresponding amount *

The ftt coated photographic paper was then left for 15 seconds long exposed in a copy box with a 10 watt incandescent lamp through a line negative and then for 30 seconds

8 0 9 8 1 1/10 U

- 4ο «.

heated at a temperature of 150 ⁰ C on a heating surface. After 3 seconds the developed image appeared, which, fully developed, could then be exposed for 24 hours with a 10 watt fluorescent lamp (distance between lamp and image, 15 * 2 cm) without the image being destroyed or the Veil level increased.

Example 19

This example describes the use of practically only non-aqueous solvents for developers according to the invention containing developer solutions on a developing belt.

A solution consisting of:

1-phenyl-3-pyrazolidone 6.0 g

1-ascorbic acid 2.0 g

Acetamide 38.0 g

Water 10.0 ml

was in a colloid mill in 125 g of a 7 JC solution of Xthylcelkilose dlsperglert in toluene, whereupon the dispersion in such a way was applied to a light, gelatin-coated paper backing that 3g accounted for about 0.09 square meters of support surface.

The developing belt obtained was then used to create strips of photographic paper which had previously been processed by a negative image.

809811 / 10U

-Hl-

The photographic paper contained predominantly silver chloride as silver halide in the emulsion layer and was pressed onto the developing belt in such a way that the emulsion side was in contact with the upper side of the developing belt. The sandwich formed from individual strips of paper and the band was 2 to 3 seconds long each heated on a base of 100 ⁰ C, separated again and then the sandwich and could be developed with the same stucco band 7 other exposed paper strip. All the images developed on the strip were of excellent quality / ·

Example 20

One from:

Amber acid almond 15 * 0 g Urea 15.0 g Thiourea 10.0 g

Water 40.0 ml

existing stabilizer solution was in 125 g of a 7 J solution of ethyl cellulose dispersed in toluene, whereupon the dispersion so applied to a photographic copy paper with silver chloride-silver citrate in the emulsion layer that was down to about 0.09 Φ ». Carrier area 2 g (dry weight) accounted for. The photographic paper containing the stabilizer layer was then exposed through a line negative x through a 45 second exposure to a nitrophot lamp was made

80 981 1 / 10U

a reversal image of excellent quality is obtained on the paper. This image was then stabilized by holding it for 30 seconds was heated for a long time on a heating surface of 118 ° C. Sausage

further de the, as described, stabilized DiId / 5 minutes long exposure to the light of the nitrophot lamp did not result in any Destruction of the image observed.

Another sample of the same copy paper was coated with a ethyl cellulose phthalate barrier layer as in Example described, coated in such a way that on about 0.09 square meters of carrier area about 0.2 g (dry weight accounted for over this layer the stabilizer dispersion was then applied, whereupon the material was copied in the same way and then stabilized became. With the photographic paprfler containing the barrier layer between the emulsion and the stabilizer dispersion became copy-out images with excellent stabilization as well obtained with a lighter background than with the paper without a barrier layer «

Example 21 A solution consisting of: Urea 27.1 g Oil nitrate 6.3 g

1-phenyl-3-pyrazolidone 6.0 g

Ascorbic acid 2.0 g Potassium bromide 0.1 g

Water 25.0 ml

809811/1014

U72882

-H ₃ -

was in 125 g of a 7 ϊ solution of ethyl cellulose in toluene dispersed, whereupon the dispersion is so predominantly over a Silver bromide as a photosensitive silver halide-containing photographic emulsion layer of a photographic Paper was applied to about 0.09 Φ carrier area 1.5 g (dry weight accounted for. The coated Paper was then exposed through a line negative in a copy box with a 10 watt incandescent lamp, which was then exposed photographic paper was heated for 3 seconds on a hot table at 105 ° C. A beautiful black image was obtained.

In this example, the non-aqueous solvent consists of the eutectic of urea and lithium nitrate in the specified one Weight ratio, i.e. one component of the solvent is an ionized salt.

Incidentally, it is also possible to use a purely inorganic Components built up non-aqueous solvent system in which all components are ionized, in which Salt mixtures with sufficiently low eutectic temperatures are selected / which is particularly useful for the Development running redox reactions has a beneficial effect.

As already mentioned, the development process can be done according to Invention can also be practiced with color coupler-containing photographic materials. For example, this can be

80981 1 / 10U

Film material with a p-phenylenediamine-type developer When the exposed material is heated, the developer reduces the silver halide in the image areas and the oxidized developer forms a dye image with the coupler present there.

Example 22

A solution consisting of:

Ethyl carbamate 18.0 g

Urea 12.0 g

1-phenyl-3-pyrazolidone 6.0 g Ascorbic acid 2.0 g

Water 10.0 ml

In 125 g of a 7 ϊ solution of ethyl cellulose in toluene dispersed, whereupon the dispersion then predominantly Silver chloride was coated as a photosensitive silver halide emulsion layer of a photographic paper was maintained, with a knife distance of about 0.15 mm became. The coated paper was then exposed through a line negative and finally exposed by heating to 107 ° C in 1 developed into an image of excellent quality in up to 2 seconds.

Example 23:

A solution of 25 * 0 g of Succinlmld, 5.0 g of urea and 25 ml of water was dispersed in 125 β 3 »5% ethyl cellulose, whereupon the

809811 / 10U

dispersion coated on a support, and then containing a 4-Phenylbrenzkatechin silver chloride emulsion of the type described in US Patent 2,716,059 wherein a knife distance of approximately 0 _t was overlaid 15 mm. After the material had dried, it was exposed for 5 seconds through a line negative with a nitrophot lamp placed at a distance of 62 cm and then developed by heating it at 140 ° C. for 5 seconds. An excellent black and white positive image was obtained. The developed material was then immersed in water, whereupon the moist template was pressed against an absorbent sheet and the entire gelatin layer was transferred to the receiving sheet. The uncured areas were then removed by washing.

The process of the invention can be used for making lithographic printing plates by the diffualon transfer process or the Colloid transfer methods can be used. By the way, you can those produced by the development process of the present invention Images are further treated by known methods in such a way that they become oleophile.

Are photographic images after the diffusion transfer process produced, it is expedient to use a toner which is present during the transfer of the dissolved silver halide to the receiving sheet is housed in the material. Such toners can

80981 1 / 10U

ηβη can also be used when the diffusion transmission method using the non-aqueous solvents described for the developers and those with silver halides soluble complex-forming compounds is carried out.

In the preparation of the described silver halide emulsions, of course, just as in their subsequent handling in the undeveloped or non-stabilized state the usual safety lighting conditions were observed during development while the emulsions used specifically in office copiers are often used for at least a short time Room light can be managed.

Under "room temperature" is here to be understood to 27 ⁰ C, a temperature of about 21 °.

As has also been found, the non-aqueous substances described are also suitable for stabilizers such as those used to exposed and developed silver halide emulsions to effectively protect against the damaging effects of light in the photographic material concerned or in a special sheet used for stabilization, the desired stabilization by simply Heat the photographic material, optionally together with the "stabilizing sheet, to a temperature above

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- H 7 -

the melting point of the non-aqueous solvent can be brought about.

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Claims (27)

Claims A photographic development process in which an exposed, mounted on a support photographic silver halide emulsion is developed "Wicklerverbindung using an activated by heating Ent, characterized in that the development by heating in the presence of a solid at room temperature but melt below HLO ⁰ C, dissolving Silberhalogenidentwlcklerverblndungen Substance is carried out. 2. A photographic development process according to claim 1, characterized characterized in that the substance dissolving silver halide developer compounds is a crystallizable, monomeric, highly dielectric, polar compound with an electron withdrawing - or -CO group is used. 3 photographic development process according to claims 1 and 2, characterized in that as silver halide developer compounds solvent substance a compound of the following formulas is used I, XCONRR II. YSO ₂ NH ₂
III · R ¹ CH ₂ O 80981 1 / 1OU IV. ZCONRR * · 'or V. ICON W where mean: R is a Vaaaeratoffatom or a CIU or R ^{1 is} a hydrogen atom or a CH, group; R ^N * and Z together represent a radical of the formulas: - (CH ₂ ) _a -CO- or - (CH ₂ ) _b -, wherein a * 2 or 3 and b = Is 3, Ί or 5; X is a hydrogen atom, an alkyl group with 1 to 4 carbon atoms or an R ¹ HH, R "0 ~ or - (CHg) _n CONRR» group, where R and R * ignore the meaning given, n »1, 2 , Is 3 or 4 and R "is an alkyl group with 1 to 4 carbon atoms; Y is an alkyl group with 1 to 4 carbon atoms, an NH ₂ -, R "0- or optionally substituted aryl group, where R" has the meaning given and W which includes the N atom for completion of a heterocyclic ring. BATH ORIGINAL 80981 1 / 10U 4. A photographic development process according to claims 1 to 3 »characterized in that, in the diffusion transfer process, an exposed photographic silver halide emulsion layer is pressed onto a receiving sheet with heating in the presence of a silver halide developer compound and a silver halide solvent, which consists of a support, a layer containing development cores and a layer above this layer arranged receiving layer comprising a solid at room temperature but below I ^{1 0} C IO-melting, Silberhalogenldentwleklerverbindungen solute contains as well as a film-forming colloidal binder. 5 · Photograph! See8 developing method according to claim 4, characterized in that characterized in that the silver halide developing agent is accommodated in the silver halide emulsion layer. 6 · A photographic developing method according to claim 4, characterized characterized in that the silver halide developer compound In the receiving layer is housed. 7- A photographic development process according to claim 4, characterized characterized in that the silver halide solvent is in the receiving tube will be accommodated * 80981 1 / 10U 8. Photographic development process according to claims 1 to 3 »characterized» that in the colloid transfer process an exposed photographic silver halide emulsion layer is pressed in the presence of a tanning developer compound with heating on a receiving sheet, which consists of a support and a receiving layer, consisting of a solid at room temperature, however below I ¹ JO ⁰ C melting substance dissolving silver halide developer compounds and a film-forming colloidal binder in which the substance is dispersed, the layer optionally being separated from the carrier by a veil layer. 9. A photographic development process according to claim 8, characterized characterized in that the tanning developing agent is accommodated in the silver halide coating layer. 10. A photographic development process according to claim 8, characterized characterized in that the tanning developer composition is in the receiving layer of the receipt sheet is accommodated. 11 · Photographic development process according to claims 1 to 3 » characterized in that a silver image is developed in an exposed photographic silver halide emulsion layer Bringing this layer into contact, with heating, with a layer which is preferably dispersed in a binder. 80981 1 / 10U a solid at room temperature, but melting below 140 ° C, Contains a substance which dissolves silver halide developer compounds and a silver halide developer compound. 12. Photographic material for carrying out the process according to Claims 1 to 11, characterized by a carrier and at least one layer (a) applied thereon, which in one Binder dispersed, a solid at room temperature, however Silver halide compound compounds melting below 140 ° C contains solvent * 13 * Photographic material according to claim 12, characterized in that that it contains a compound of the following formulas as a substance which dissolves the silver halide developer compound: I. XCONRR ¹ II. YSO ₂ NH ₂ III. R ¹ CH CH ₂ O IV. ZCONRR "* or V XCON W where mean: a hydrogen atom or a CH - or HOCH ₂ CH ₂ group; a hydrogen atom or a CH, group or 8 0 9 8 1 1/1 0 U ■ R " ¹ and Z together represent a radical of the formulas: - (CH ₂ ) _a -C0- or - (CH ₂ ^ -, in which as 2 or 3 and b = 3, 4 or 5 iet; X is a hydrogen atom, an alkyl group with 1 to 4 C- Atoms or an R ¹ NH, R ^w 0 or - (CHg) _n CONRR 'group, in which R and R * have the meaning given, η = 1, 2, 3 or k and R ″ is an alkyl group with 1 to k represents carbon atoms; Y is an alkyl group with 1 to k carbon atoms, an NH ₃ -, R "0-, or an optionally substituted aryl group, where R * has the meaning given and W including the N atom to complete of a heterocyclic ring. 14 * Photographic material according to claims 12 and 13 »characterized in that that layer (a) additionally contains a developer compound for silver halide. 15 · Photographic material according to claims 12 and 13 »characterized in that that the layer (a) additionally contains a silver halide and a developer compound for the halogen silver. 16. Photographic material according to Claims 12 to 15, characterized in that that the binding agent of the layer (a) consists of gelatin, 80981 1 / 10U fUmforming proteins, cellulose esters, cellulose ethers or Made of vinyl polymers. 17. Photographic material according to claims 12 to 16, characterized characterized in that the layer (a) contains at least 0.1 g of the SiI superhalide developer compounds dissolving substance per millimole contains silver halides to be developed, 18. Photographic material according to claim l6, characterized in that that the binder consists of ethyl cellulose. 19. Photographic material according to claims 12 to 14, and 16 to 18, characterized in that it has at least one light-sensitive silver halide emulsion layer (b), which with the Layer (a) is in contact. 20. A photographic material according to claim 19, characterized in that that the silver halide emulsion layer (b) contains a tanning silver halide developing agent. 21. Photographic material according to claims I9 and 20, characterized in that that layer (a) is a silver halide solvent contains. 22. Photographic material according to claim 21, characterized in that that layer (a) has a silver halide solvent - ¹ O ° 1 f - 1 η 1 /. COPY Thiourea, a thiocyanate, thiosulfate, a a mercapto group containing compound or a polyamine. 23. Photographic material according to claims 12, 13 and 16 to 18, characterized in that a layer (c) containing development cores is arranged between the support and layer (a). 2k, photographic material according to claim 19, characterized in that it contains a tanning and a non-tanning developer compound. 25 Photographic material according to Claim 19, characterized in that that the two developer compounds are accommodated in layer (a). 26. Photographic material according to claims 19 to 22 and 2 * 1 to 25, characterized in that the layer (a) is arranged between the carrier and the layer (b). 27. Photographic material according to Claims 20 to 26, characterized in that that it contains an M-phenyl-pyrocatechol as the tanning silver halide developing agent. COPY