DE2249857C3 - Process for the color reversal development of photographic recording materials which contain at least one halogen silver emulsion layer - Google Patents

Description

A) the imagewise exposed recording material treated with a developer solution which

a) at least one color developer substance in a concentration of at least 0.02 mol / liter,

b) at least one black and white developer substance with a poiarographic Half-wave potential, measured at a pH value of 10.0, from -10 to -187 millivolts and

c) contains at least 0.10 mol / liter of a water-soluble color coupling inhibitor, which prevents the formation of dye during development by either using the color developing agent in a form that cannot be oxidized by the latent image or its oxidation product in a form that cannot be coupled Form binds and thus blocks the coupling reaction, the molar ratio of color coupling inhibitor to color developer substance is at least 0.97: 1,

B) the recording material then by a second exposure or by chemical means Makes fog nucleation developable at the locations which cannot be developed initially, and

C) the recording material treated in this way, without the developer solution used beforehand from the developed layer (s) in an aqueous alkaline solution odei bathes in water, which neutralizes the effect of the color coupling inhibitor, the coupling reaction between the color developer substance remaining in the layer or layers and the color coupler present at the same time is set in motion and a positive colored image is generated.

2. The method according to claim 1, characterized in that that a recording material is used which already contains color couplers.

3. The method according to claim 1, characterized in that that at least a part of the color coupler is supplied via one of the baths.

4. Process according to Claims 1 to 3, characterized in that the second exposure during the treatment of the developed recording material with an aqueous alkaline Solution or water takes place.

5. The method according to claims 1 to 3, characterized in that the chemical fog nucleation and the elimination of the color coupling inhibitory effect together by a single one Bad is effected.

6. Process according to Claims 1 to 5, characterized in that the recording material is used treated after the second exposure or fog nucleation with an aqueous solution which dissolves the color coupling inhibitor.

7. Process according to claims 1 to 6, characterized in that there is a developer solution used with a pH of 8.5-14.

8. The method according to claims 1 to 7, characterized in that one additional stop, Bleach, fix, bleach-fix, washing, stabilizer and / or hardening baths are used.

The invention relates to a process for color reversal development of photographic recording materials, which contain at least one halogen silver emulsion layer.

The development of color reversal films is usually carried out in several baths in which they treated one after the other. The first bath contains e.g. B. a black and white developer substance that the Silver halide of the latent image is reduced to silver, creating a black negative silver image. The film is then post-exposed with the undeveloped remaining silver halide, and in the fogging nuclei are generated in undeveloped areas of the film. Then this remaining Silver halide color developed in a color developing bath. A color developer substance reduces the silver halide of the haze areas to silver and is itself oxidized in the process. The oxidation product the ParbentWicklersubstanz reacts in turn with one or more color couplers distributed in different emulsion layers to form dyes. Finally, the black image silver from the first and second development is bleached. Through The bleaching process turns the image silver present in the layers into a soluble silver compound transferred and then dissolved out in the fixer. A colored positive image is obtained. To the mutual pollution of the various

avoiding commercial baths is usually switched on Wash baths between the individual treatment stages. Furthermore, one usually uses a so-called stop bath, to stop the black and white development immediately after the film has been processed in the To prevent black and white developer bath.

The known color reversal development processes thus require numerous steps and various ones Treatment baths. It should be taken into account that the shelf life of the solutions once prepared is very high is low. In addition, good photographic color reproductions can only be achieved if the processing steps carefully coordinated. Another disadvantage is that the for Processing of an exposed photographic recording material requires a substantial amount of time Is a cost factor, is extraordinarily long.

The object of the invention is to provide a rapid method for color reversal development of photographic To create recording materials which contain at least one halogen silver emulsion layer which no second development is carried out in a special color developing bath.

The task is solved using a procedure Reversal processing of photographic Iiaif & icing materials comprising at least one shark emulsion layer contained, and is thus ^^^ puizeichnet that one

S 4as imagewise exposed recording material ^ treated with a developer solution that

SS ₆₅ . a) at least one color developer substance in "^ ¹ : ■ a concentration of at least 0.02 mol / liter,

b) at least one black and white developer with a polarographic Halb-C Step potential from -10 to -187 millivolts, 'measured at a pH of 10.0, and

■■ ;. c) at least 0.10 mol / liter of a water-soluble ¹ borrowed color coupling inhibitor contains

prevents the formation of dye during development by either the Color developing agent in a form which cannot be oxidized by the latent image or whose oxidation product binds in a form that cannot be coupled, and so binds the coupling reaction blocked, the molar ratio of color coupling inhibitor to color developing agent is at least 0.97: 1,

B) the recording material then by a second exposure or by chemical means Makes fog nucleation developable at the locations which cannot be developed initially, and

C) the recording material without previously developing the used developer solution (s) Remove layers in an aqueous alkaline solution or in water, thereby bathing the effect of the color coupling inhibitor abolished, the coupling reaction between in the remaining color developer substance (s) and what is present at the same time Color coupler is set in motion and a positive color image is generated.

The invention is based on the surprising finding that this problem can be solved if the color developing agent with the black and white developing agent combined in a single solution.

The halogen silver emulsion layer of the recording material contains e.g. B. gelatin as a colloid.

In the process of the invention, the color couplers can be used in at least one emulsion layer from the start of the recording material, or the recording material contains spectrally sensitized Silver halide and therefore requires the supply of at least a portion of the color coupler via one of the baths.

The black and white and then color development likely goes like this:

When treating imagewise exposed recording material with the developer solution the silver halide in the area of the latent image becomes metallic due to the black and white developer substance Silver reduced, creating a negative silver image. Because of the simultaneous presence of the water-soluble color coupling inhibitor, there is no color formation. All color developing agents, which reduced the silver halide and was itself oxidized, reacts with the color coupling inhibitor, z. B. a sulfite, to a stable, non-couplable compound, e.g. a monosulfonate. In this way, color formation is prevented during the initial black and white development of the latent image. As soon as the black and white initial development of the latent image has ended., d. H. essentially no reducible silver halide in the latent image area is more available, the recording material is removed from the developer solution and ίο "disguises" it as usual with reverse procedures, e.g. B. by diffuse exposure or with the help of known chemical fogging agents such as hydrazine, potassium borohydride or amine boranes. At this time the recording material is still soaked in the developer solution. Subsequently treated one the recording material with the aqueous alkaline solution or water to the inhibiting The effect of the color coupler inhibitor in the absorbed developer solution is canceled, so that in the areas of the recording material that was obscured after the initial black and white development, a color image is created by the absorbed developer solution in the presence of color couplers. The emerging The color image is a positive, which is initially created during the entire treatment Silver is covered; it emerges in pure form if the silver is used in a known manner, e.g. B. by treatment removed from the layer with a flexible bath.

Preferably, the chemical nucleation and the elimination of the color coupling inhibitor effect are brought about together by a single bath. The inhibiting effect of the color coupling inhibitor can be, for. B. cancel by treating the recording material with compounds which weaken or suppress the ability of the inhibitor to react with the oxidized form of the color developer substance. When using a MiI-fits as a color coupling inhibitor, the recording material is treated e.g. B. with a solution of a sulfite reactant to neutralize the sulfite in the sucked developer solution. The inhibitory effect of the color coupling inhibitor is preferably reduced by washing the recording material after the veil nucleation with an aqueous solution which dissolves the color coupling inhibitor. When using sulfites, aqueous solutions with a pH of about 7 to 13, preferably above 10, are suitable for this purpose. Such solutions preferably contain a basic compound, e.g. B. sodium hydroxide, sodium carbonate or sodium phosphate dodecahydrate to make the solution alkaline, as well as photographic additives such as sodium sulfite, fogging agents, surface-active compounds and color couplers (especially if a coupling-free recording material is to be developed into a color image). If sulfites from color coupling inhibitors are used, the washing conditions are preferably chosen so that aUes SuM °, ..?. «""C" t "/ 4MHpi-1nsiinß is removed

rungsoeaendungcn vu ^ ug ^ v, ^,

6o is removed from the absorbed developer solution and color development can take place. Consists z. B. the inhibiting effect in the fact that an amine salt is formed, the pH of the wash bath must be high enough for the salt to convert into the free amine will lead. Although the solution preferably contains the above additives, the simple one also gives Soaking the fogged recording material gives satisfactory results.

The color coupling inhibitors used according to the invention act ζ. B. by selective reaction with the oxidized form of the color developing agent, to because these are no longer suitable for dye formation through coupling reactions. The inhibiting But effect can also be achieved by the oxidation of the color developer substance from Prevents this by reducing the oxidation reacting amino groups of the color developer substance blocked, so with a Ent- ι ο Winding solution works in which the amino groups of the color developer substance in the form of their quaternary Salts are present, and e.g. B. can have the following groups:

[NH ₂ CH ₃ ] ¹ SBr- [NH (CH ₃ ), p OH

'5

Developer solutions in which such salts are present have a lower pH than the commonly used black and white and Color developer solutions. The lower pH value lowers the reducing capacity of the at the same time Black and white developer. However, this loss of reducing power can be avoided compensate by using black and white developing agents that work even at low pH have a sufficiently high reducing power, such as. B. 2,4-diaminophenol dihydrochloride that even sufficiently developed at pH values below 7. The respective bath conditions and parameters the developer solution depend to a certain extent on the means by which the dye is formed is inhibited during negative development.

Should the color formation inhibitor with the oxidized form of the color developing agent become a colorless one or removable compound react, the following properties of the developer solution are preferred:

A) The pH of the solution is around 8.5 to 14, in particular around 10.0 to 11.0;

B) the solution contains the color coupling inhibitor in an amount that causes color formation of the exposed Recording material in the developer solution largely prevented.

If the color coupling inhibitor blocks the reactive amino groups of the color developing agent acts, the pH of the developer solution is preferably below 8.5. Particularly preferred is the range below 7.0; in some cases a pH of up to 3.0 is recommended.

Compounds which reduce silver halides to silver are suitable as color developing agents and are thereby oxidized themselves. The oxidized form must still be able to react with a color coupler to react with a dye. Specific examples of such color developing agents are p-phenylenediamines, z. B. 2-methyl-4- [N-ethyl-N - (/ f-methylsulfonamidoethyl) amino] aniline or 4-amino-N-ethyl- f> o N- (/ f-hydroxyälhyl) aniline or salts thereof. Such Color developing agents are e.g. B. from M e e s and James, The Theory of the Photographic Process, 3rd ed., MacMillan, New York (1966), chapter 17. Color developing agents are particularly preferred with a polarographic half-wave potential, measured at a pH value of 11.0, from ciwa - 159 to -305 millivolts.

45 One or more compounds are suitable as black and white developing agents which reduce silver halides to silver, but do not react in oxidized form with a color coupler to form a dye. Specific examples of such black and white developing agents are hydroquinone and 1-phenyl-3-pyrazolidinone, respectively Mixtures of these Other examples of known black and white developer substances are hydroquinones, such as chlorohydroquinone, bromohydroquinone, methylhydroquinone, dichlorohydroquinone, o-methoxyhydroquinone and pyrocatechol, p-aminophenols, such as N-methyl-p-aminophenol sulfate, p-hydroxypheny! Aminophenol and pyrazolidinones, especially 3-pyrazolidinones.

The black and white developer substances used according to the invention preferably have the general formula

Υ - Μ — Χ

in the M an organic ring, e.g. B. benzene or pyrazolidinone, means that only carbon or Contains nitrogen atoms in the ring, Y a hydroxyl group bonded to a carbon atom of the ring and X represents a hydrogen atom, a hydroxyl or amino group or an alkylamino, carboxyalkylamino, Means an alkyl or aryl radical which is bonded to a ring atom of the cycle.

The half-wave potentials (E Λ of the color developer sublances or black and white developer substances used according to the invention are related, according to the laws of thermodynamics, to the speed of the reaction of developers and silver halides. the more positive the oxidation half-wave potential according to the law of Lewis and Ra η da 11; cf. B e η t et al., Chemical Constitution, Elektrochemical, Photographic and Allergenic Properties of p-Amino-N-dialkylanilines, J. Am . Chem. Soc, Vol. 73 (1951), p. 3100; Willis et al., The Relative Importance of Adsorption and Electrode Potential in Determining the Rate of the Induction Process During Photographic Development, II. Hydroquinones, Photographic Science and Engineering, Vol. 14, No. 2 (1970), pp. 149 to 152; Willis et al., The Relative Importance of Adsorption and Electrode Potential in Determining the Rate of the Inducti on Process During Photographic Development, 1. The p-Aminophenols and p-Phenylenediamines, Photographic Science and Engineering, Vol. 14, No. 2 (1970), pp. 141 to 148.

The values of the polarographic half-wave potentials of black-and-white and color developing agents are defined in terms of Lewis' law and R a η d a 11, see G. N. Lewis and N. R a η d a 11, Thermodynamics, McGraw Hill, New York (1923), p. 389. The polarographic half-wave potentials mentioned are oxidation potentials, following the method of Julian and Ruby, The Use of Stationary Platinum Microelectrodein the Determination of HalfWave Potentials, J. Am. Chem. Soc, Vol. 72 (1950), p. 4719 using the hydrogen electrode as the reference electrode and the black and white developer substances at a pH of 10.0, the color developing substances at a pH of 11.0

be measured. The concentration of black and white developing substances in the developer solution used can be very low lie, e.g. B. be up to 0.0045 mol / liter.

The setting of the respective conditions naturally depends on the substances used. There the method according to the invention is essentially based on the idea, the effect of the black and white developer substance on the silver halide of the latent image versus the color developing agent To favor, the developer solution must be formulated with appropriate considerations. When the black and white developing agent has a significantly higher half-wave potential than that Color developing agent, the black and white developing agent has a strong tendency to develop the latent image, so that a relatively weak color coupling inhibitor can be used. this happens either by selecting appropriate compounds or by using low concentrations. However, if there is no significant difference between the half-wave oxidation potential of the two developer substances, so the developer solution must be controlled so that the development by the Black and white developing agent is preferred. This can e.g. B. done by the fact that you have the effect of the color coupling inhibitor reinforced, e.g. B. by selecting suitable compounds or by application high concentrations, and / or that the tendency of the black and white developer substance for education by increasing the concentration. In general, however, they are suitable Connections of each developer category through the half-level potentials within clear limits set. That is, for example, a black and white developing agent with a half-wave potential less than -187 millivolts at pH 10 will not give satisfactory results delivers, even if the reaction mechanism is controlled by other known measures. The The method of the invention can be carried out with essentially any developing agent which lie within the half-wave potential ranges of the individual connections. The half-wave potential therefore characterizes the connection types suitable for the process according to the invention to an outstanding degree.

Known developing agents and their half-wave potentials are compiled in the table below.

Half-wave polarographic oxidation potentials of some color developing agents

pH

9.2

11.0

CH ₂ CH ₃

-279.5 -266.0 -222.0 Ν, Ν-diethyl-p-phenylenediamine

CH, CH,

CH ₃

- N (C ₂ H

₅ J ₂

-321.5 -229.0 -190.0 2-amino-5-diethylaminotoluene

(CD-2)

CH ₂ CH ₂ SO ₃ CH ₃

-269.5 -247.0 -190.0 4-Amino ^ N-ethyl-N ^ -methan-

sulfonarnidoethyl) -Tn-toluidine

(CD-3)

CH ₂ CH ₂ OH

188.0 4-Amino ^ 2-methyl-N-ethyl- N- (ji-hydroxyethyl) -ämHn

(CD-4)

609620/241

Half-wave polarographic oxidation potentials of some black and white developing agents

pH

8.0

9.0

10.7

11.0

12.5

HO

CH ₃

OH

OH

-256.0 -181.0 -152.0

-181.0 -126.0 -29.0

-206.0 -166.0 -129.0

Chlorohydroquinone

Melhylhydroquinone

Hydroquinone

SO ₃ H
HO- ^ V-OH

-215.0

-141.0 phenidone

-246.0 -188.0 (just usable) hydroquinone-

monosulfonate

^HO N = / ° ~ ^C - ^NHNH 2 (not usable) -191.5

The table shows that the black and white developing agents are more reactive than the color developing agents if one takes the oxidation i <half-wave potentials as a measure of the reactivity. The more positive the potential at a certain pH value, the more reactive TS the respective developer. As expected, the half-wave potential changes with the pH value, with the reactivity of each developer increasing with increasing pH value. The less reactive black and white developers phenidone and hydroquinone monosulfonate are particularly noteworthy as they are not sufficiently reactive to intercept the silver halide before the color developer present produces a color image. Black and white developing agents that are more reactive than phenidone and hydroquinone monosulfonate therefore give excellent positive images < ₀ in the method of the invention

When using about 40 to 95 mole percent Color developer, based on the total number of moles the black and white and color developing agents you get good results. Furthermore, the inven-

S ^ ⁸ ₁ ffm ^a - ^ßVe i: ^We " ^dete development solvent at least 1 mol ^ ter color developer substance and the highest amount required for saturation. Especially

5 ^ KfR f ^the _u ^Verw . ^endu "S ν» "about 0.06 b 3.10 UoMUXa color remover.

The water-soluble color coupling inhibitor used according to the invention is preferably used to react

T> T α ^{he Wa} ^ ^{nd at} l ^schwa ^ white development sntstehenden oxidized form of the color developer Mbshuiz capable of being a stable Reaktionspro-ΐV? S ^ i used is preferably sulfites, L h sulfite or bisulfite compounds, the η when releasing water sulfite form. Specific examples of ler-like compounds smd ammonium sulfite and - 151.5 hydroquinone-

monocarboxylic acid hydrazide

Alkali metal sulfites such as sodium sulfile. Potassium sulfite, especially sodium sulfite. The developer solution used according to the invention contains the "color coupling inhibitor" in an amount which largely prevents dye formation in the silver halide layer of the recording material after exposure in the developer solution. The developer solution contains the color coupling inhibitor, for example sulfide in a concentration of 0.10 mol / liter. Is particularly preferred the range from about 0.10 to 0.48 mol / liter, in order to accelerate color development, a molar ratio of sulphite to ^WIC i ^{Cr S content of} at least 0.97: 1 ^{is preferably used: £ 7 9 i S} i ^{evor zu} S ^l is a molar ratio of 1.46 ms / 8: 1 we, tere Examples of suitable color domes, with the oxidation product of:. ER- rsubstanz reactive compound, ^Asc sorbic acid, Citracinsäure and 4-HymJn ° "· also suitable? is hydroquinone monocarboxylic acid hydrazide.

"A ™, ~ ^s .e" ^{is used in the} process according to the invention as developer solution, the --ler substance a primary aromatic

^ black and white developer substance Hydro- ¹ UJO up to 0.48 mol / liter of the color cap

Flir Λ » v! ^r ^ t ^{or preferably contains a sulfite} .

IuSl Sf? ^{hear the} invention suitable Farbduici Suef ^ ^{1 ϊ} ΙΙΟΓΓη - ^{with de} ™ Oxidationsprodurch r ^ ^arbe "'ersubstanz react ^twick can evaluate: ^{S ei" times Tes} ^ selected

2-MPiS ^ ¹ ^ V ^aqueous Testiösunp. the 0.3g - Hvdrnv ^ ⁴ " ^d ! ^ath >' ^{lami: i} oaniline-hydrochiorid, 0.05g Hydroxy - N - [// - (2 - aceUnnidnnh« iv1) - iithvll-

huh S ^
stop.

yy.
^[(t ' ⁽² " ^a cetamidophenyl) - ethyl] - ^^ ^{d 2} ^ S sodium carbonate entman 0.006 mol of the m investigating dye

clutch inhibitor. The resulting solution is mixed and treated with 2 drops of an aqueous solution containing 75 g of Kaliumhcxacyanofcrrat (111) per Liter contains. If the solution does not change color when the hexacyanofrate solution is added, this is the color coupling inhibitor for the method according to the invention suitable.

For example, those used in the photographic art can be used as competitive or colorless couplers known compounds can be used as color coupling inhibitors. From US-PS 27 42 832 are z. B. numerous competing couplers known that react with oxidized color couplers and therefore for the method according to the invention are suitable.

Color coupling inhibitors, which prevent oxidation of the color developing agent, can be caused by the following test can be selected:

Any compound which, when added to the developer solution, reduces the oxidation potential of the color developing agent reversibly lowered below that of metallic silver, is used as an oxidation inhibitor for the color developing agent suitable. This process can be carried out in a simple manner with known electrochemical Methods are measured. The expression "reversible" is to be understood as the fact that by changing the bath conditions slightly or adding another compound the color developer can be released again from the blocked form.

If necessary, the color developer can be added to the solution of the black and white developer before it is added To block. That is, the color developing agent and the color coupling inhibitor can be used admit as a single compound, e.g. B. as an already inhibited color developer. Specific examples of such formulations are protected amine salts or complexes of the color developing agent.

The developing solution of the invention can contain other photographic additives such as bromides, surface-active agents Contain compounds, color couplers, benzyl alcohol, ethylene glycol or thiocyanates.

After developing the positive colored image, the usual process steps for producing one follow finished image, d. H. after the bath. which cancels the effect of the color coupling inhibitor, one uses an acidic stop bath, then a bleach bath, a fixer bath (or a bleach fixer bath). a washing bath and a stabilizing bath. The stop, bleach, fix and / or bleach-fix baths like this if necessary, hardener is added, or else one uses a pre-hardening bath prior to developing in the developer solution. The said baths are made in a known manner.

It has proven to be advantageous between the treatment in the developer solution and the bath, that cancels the effect of the color coupling inhibitor, interposed a quick wash to to remove the solution adhering to the surface of the recording material and thus contamination to avoid the latter bath. The watering is not so long and thorough, that the color coupling inhibitor effect is reduced, but is carried out in a way that only removes the developer solution adhering to the recording material due to the surface tension will. However, if water is used as a second bath to neutralize the effect of the color coupling inhibitor, so of course there is no need for such a quick wash.

The developing solution used according to the invention is surprisingly stable over a long period of time. For economic reasons, however, it is advantageous to To provide developer kits for the preparation of the developer solution used according to the invention. The developer kits consist of several packages with specific quantities of the individual components the developer solution, d. H.

A) at least one color developer substance in an amount which has a concentration in the developer solution of at least 0.02 moles / liter.

B) at least one black and white developer substance with a polarographic half-wave potential, measured at a pH of 10.0, from -10 to -187 millivolts and

C) a water-soluble color coupling inhibitor in an amount in the developer solution a Concentration of at least 0.10MolLiter and the one molar ratio of color coupling inhibitor to the color developer substance of at least 0.97: 1 and preferably from 1.46 to 7.8: 1 results.

In a set of two packs, e.g. B. the first pack an acidic solid or an acidic aqueous liquid with a sulfite as a color coupling inhibitor, the color developer substance and the black and white developer subscription. while the second pack is a concentrated alkaline liquid or a solid with an alkaline compound such as sodium hydroxide, a Bromide ion-donating compound and the sulfite contains. Contains in a set of three packs z. B. the first pack a concentrated acidic aqueous liquid or an acidic reacting solid with a color developer and a sulfite, the second pack a concentrated acidic aqueous Liquid or an acidic reacting solid with the black and white developer substance and a Sulphite and the third pack a concentrated alkaline aqueous liquid or an alkaline reacting liquid Solid with a base such as sodium hydroxide, a bromide ion donating compound and a Sulfite. For economic reasons, each pack contains the chemicals in as concentrated a manner as possible Shape. Although the packs usually contain solvents, it can be useful in certain circumstances be to prepare aqueous dispersions in order to enable high concentrations of the constituents and di < To facilitate the dissolution of the dispersed constituents during the preparation of the developer solution. Ge if necessary, the components of the developer solution can be used in solid form, preferably as a powder pack. The contents of the individual packs are precisely measured so that the developer solution can be used; by successively dissolving the contents of the pack in water and then diluting can produce to a certain volume. The Em winder sets must therefore be a sufficient amount contain a basic compound, such as sodium hydroxide, to ai the pH of the developer solution 8.5 to 14 set, in addition, the color coupling inhibitor must vorhai in a sufficient amount so that the developed developer solution during the black and white development of the recording

processing material prevents the formation of dye. When preparing the developer solution, z. B. from the developer kits, one can largely avoid solubility problems of the color developer substance, if you first prepare an aqueous solution of the color developer and then the alkaline admits reacting constituents.

If in the above there is talk of an extensive suppression of the formation of dye, then so What is meant by this is that no colored form of a dye is formed from the recording material can no longer be removed. The formation of leuco compounds or intermediate stages or easily removable, ζ. Β water-soluble dyes, must be in the developer solution used according to the invention not be suppressed.

example 1

Color photographic recording material (silicon halide / gelatine) with red-, green- and blue-sensitive layers in which suitable color couplers have been dispersed by solution dispersion, is indicated in a sensitometer by a gray wedge (wedge with continuous, logarithmic density) exposed and then 3 minutes at 21 ° C and complete darkness in a developer solution of the following composition developed:

Water 800 ml

Sodium hexametaphosphate 2.0 g

2-methyl-4-diethylaminoaniline

(Color developing agent) 12.0 g

Sodium sulfite 50 g

Hydroquinone 6 g

Sodium carbonate anhydrous ... 40 g

Potassium bromide 2.0 g

Water to 1000 ml

The recording material is then absorbed into an aqueous solution with absorbed developer solution brought, which contains 40 g of sodium carbonate / liter, and exposed for 3 minutes, then watered and 2 minutes in a bleach bath

Water 900 ml

Potassium hexacyanoferrate (111) 75 g

Potassium bromide 15g

Glacial acetic acid 10.0 ml

Sodium acetate 5.0 g

Potassium aluminum sulfate 15.0 g

Water on , 1000ml

bleached and then treated for 2 minutes in a customary fixer with the following composition:

Water 500ml

Sodium thiosulphate 240g

Sodium sulfite 15.0 g

: Glacial acetic acid 48.0 ml

Boric acid 75, above

- potassium aluminum sulfate 15.0 g

Water on, 1000ml

After washing and drying, the recording material exhibits positive color formation the following densitometric properties:

/} "" "

D, ""

Blue light (yellow density) 0.58 2.93

Green light (purple 1.62 3.16

density)

Red light (blue-green- 0.92 3.42

density)

Example 2

The procedure of Example 1 is repeated, however, distilled water is used in place of the aqueous sodium carbonate solution. It will achieved similar results.

Example 3

Recording material according to Example 1 is exposed through a gray wedge and then for 5 minutes 21 ° C and complete darkness in a developer solution of the following composition:

Water 800 ml

Sodium hexamelaphosphal 2.0 g

2-methyl-4-diethylaminoaniline ... 12.0 g

Sodium sulfite 50.0 g

Chlorohydroquinone 6.0 g

Sodium carbonate anhydrous ... 40.0 g

Potassium bromide 2.0 g

Water to 1000 ml

When processing the recording material according to Example 1, the following densitometric Get results:

^u '~~ ""

blue light 0.30 3.30 40 green light 0.52 3.10 red light 0.60 3.76

Example 4

Recording material according to Example 1 is exposed through a gray wedge and then exposed for 5 minutes 2PC and total darkness in one developer solution with the following composition:

Water 800 ml

^s ° sodium hexamethaphosphate ..... 2.0 g

2-methyl-4-diethylaminoaniline ... 12.0g

Sodium sulfite 50.0 g

Methyl p-aminophenol sulfate ..... 6.0 g

Sodium carbonate anhydrous ... 40.0 g

Potassium bromide 2.0g

Water to 1000ml

When processing the recording material according to Example 1, the following densitometric results are obtained:

blue light

Green light

red light

0.50 1.20 0.80

3.42 2.92 3.70

15 16

Example 5 p- (N-ethyl-N- / i-hydroxyethyl) -

aminoaniline sulfate,

The procedure of Example 1 is using similar hydroquinone 7.5 g

Recording material exactly repeated, each l-phenyl-3-pyrazolidinone 0.30u

but the developer solution 9.0 g of p-hydroxyphenyl 5 sodium thiocyanate 0.5 g ~

contains glycine instead of hydroquinone. Potassium bromide 2.0 g

obtained the following densitometric results: potassium iodide 0.01 g

Sodium carbonate anhydrous ... 30.0 g

Sodium hydroxide 4.0 g

^D - "· ^D « ° * ίο water to 1000 ml

Blue light 0.30 2.88

Green light 0.86 3.72

Red light 0.70 3.52

Example 6

A silver halide color reversal film, which is similar to the recording material from Example 1, is exposed in a sensitometer through a gray wedge and then developed for 3 minutes at 21 ^° C. and in complete darkness with stirring in a developer solution of the following composition:

Water 800 ml

Sodium hexametaphosphate 2.0 g

p- (N-ethyl-N-fi-hydroxyethyl) aminoaniline (Color developing agent) 18.0 g

Potassium sulfite 48.0 g

Hydroquinone 7.5 g

1-phenyl-3-pyrazolidinone 0.35 g

Potassium bromide 2.0 g

Sodium carbonate anhydrous ... 30.0 g

Sodium hydroxide 4.0 g

Water to 1000ml

The film is then made into a second bath

Water 800 ml

Na ₃ PO ₄ - 12H ₂ O 4.0g

Sodium hydroxide 4.0 g

Water to 1000 ml

brought and exposed for 3 minutes in normal room lighting. Then the film is made according to Example 1 watered, bleached, fixed, watered and dried. There are the following densitometric Get results:

The film is soaked for 2 seconds and then exposed again. Then the movie Treated minutes in a bath containing 4.0 g of trisodium phosphate dodecahydrate and 4.0 g of sodium hydroxide per liter contains. The film is then successively placed in a stop bath for 1 minute, 2.5 minutes Treated in a bleach bath, treated in a fixer bath for 2 minutes, watered 1 minute, 1 minute in one Formaldehyde stabilizer bath treated and ruined dried. The components of the stop, bleach and fix baths are listed below:

Stop bath

Glacial acetic acid 12.0 ml

Sodium acetate 6.3 g

Water to 1000 ml

Bleach bath

Water 800ml

Potassium hexacyanoferrate (111) 112.0 g

Potassium bromide 24.0 g

Disodium hydrogen phosphate .... 12.0 g

Sodium thiocyanate 12.5 g

Sodium dihydrogen phosphate .... 12.5 g

Water to 1000 ml

Fixer

Water 800 ml

Ammonium thiosulphate (60%

aqueous solution) 120.0 g

Sodium metabisulfite 20.0 g

Water to 1000 ml

The following densitometric results are obtained:

D _m " o _max 50 RlmilirHt 0.19
0.11 5.20
3.21 Green light 0.08 3.58 0.35 4, G0 red light Example 8 blue light 0.16 2.24 Green light 0.12 3.50 SS red light

Example 7

A silver halide color reversal film according to Example 6 is exposed to a light object and then developed for 4 minutes at 21 ^° C. and in complete darkness in a developer solution of the following composition:

Water 800ml

Sodium hexametaphosphate 2.0 g

Potassium sulfite 48.0 g

Benzyl alcohol 3.5 g

Ethylene glycol 4.5 g

The procedure of Example 1 is repeated, but only 2 g of hydroquinone instead of 6 g used in the developer solution. The following densilometric results are obtained:

D _ml " 4.70 blue light 0.96 3.36 Green light 0.86 2.22 red light 0.62 609 620/241

'.Example·?

A photographic silver halide black and white Aüfzeichnungsmaterial which contains no color coupler is sitometer Se.-exposed in a by a gray wedge 5 and then developed for 2 minutes at 21 ⁰ C and complete darkness in a developer solution prepared by mixing 300 the solution A ml with solution B was prepared:

Solution a

Water 800 ml

Sodium hexametaphosphate 2.0 g

2-methyl-4-diethylaminoaniline ... 12 g '5

Sodium sulfite 50 g

Hydroquinone 6.0 g

Sodium carbonate anhydrous ... 40.0 g

Potassium bromide 2.0 g

Water to lOOOmi

Solution b

Water 50 ml

Sodium carbonate 2.0 g

N- (1-hydroxy-2-naphthoyl) "
N-hexadecyl-3,5-dicarboxyaniline (cyan coupler) 3.0 g

The recording material is then placed in an aqueous solution containing 40 g of sodium carbonate / Liters, and exposed for 3 minutes with room lighting. Then it is watered according to Example 1, bleached, fixed, watered and dried. It becomes a positive monochromatic color image obtained with the following densitometric properties:

40

red light

0.58

0.72

10

Example .-. _u

Recording material of the type described in Example 1 is exposed through a gray wedge and then developed in the developer solution of Example 1 ^{at 21 ° C. and in complete darkness for 3 minutes.} The recording material is then immersed for 3 minutes in complete darkness in a second aqueous bath which contains 40 g of anhydrous sodium carbonate and 0.05 g of potassium borohydride per Liier. The recording material is then developed for 2 minutes in complete darkness in the fixing solution from Example 1 and then watered, bleached, fixed, watered and finally dried according to Example 1. The recording material has a positive color image with the following densitometric properties:

857

Example 11

A silver halide color reversal film according to Example ό is exposed through a gray wedge and then 4 minutes at 21 "C and in complete darkness developed in a developer solution of the following composition:

Water KOO ml

Sodium hexametaphosphate 2.0 »

p- (N-ethyl-N -,; - hydroxyiithyl | -

aminoaniline sulfate 18.0u

Potassium sulfite 20.0 g

Hydroquinone monocarboxylic acid

hydrazide 11.5g

Potassium bromide 2.0 g

Sodium carbonate anhydrous ... 30.0g

Sodium hydroxide 4.0 g

Water to 1000 ml

The film is then processed further according to Example 6. There are the following densitometric Get results:

Blue light 0.70 2.20

Green light 0.44 4.10

Red light 0.60 4.20

Example 12

A silver halide color reversal film according to Example 6 is exposed through a gray wedge and then developed for 3 minutes at 21 ^° C. and in complete darkness in a developer solution of the following composition:

Water 800 ml

Sodium hexametaphosphate 2.0 g

p-fN-ethyl-N - ^ - hydroxyethyl) -

aminoaniline 18.0 g

Ascorbic acid 44.0 g

Hydroquinone 7.5 g

l'Phenyl-3-pyrazolidinone 0.30u

Potassium bromide 2.0 g

Sodium carbonate anhydrous ... 30.0 g

Sodium hydroxide 4.0 g

Water to 1000 ml

The film is then immersed in a second bath of the following composition and for 3 minutes exposed in room lighting:

Water 800 ml

Sodium phosphate dodecahydrate .. 4.0 g

Sodium hydroxide 4.0 g

Water to 1000 ml

The film is watered, bleached, fixed, watered and finally dried according to Example 1. It will obtain the following densitometric results:

D "". " 0 , ⁶⁵ blue light
Green light
red light /) "" " 2.30
1.46
2.60 blue light
Green light
red light 0.21
0.42
0.78 2.27
3.10
3.38 0.55
0.42
0.52

Example 13

red light

blue light

Green light

The effect of the color coupling inhibitor is explained using an experiment in which by To block the color developer substance and prevent it from oxidizing:

Developer solution

Sodium hexametaphosphate 2.0 g

Amino-5-diethylaminotoluene monohydrochloride 12.0 g

Sodium sulfate 50.0 g

2,4-diaminophenol dihydrochlori J 10.0 g

Potassium bromide 2.0 g

Water to 3000 ml

IO

20th

A cine-positive release film is used, which gives excellent color slides when processed by the reversal process and for commercially available Negative silver halide color materials or silver halide color materials for the reversal process is typical. The color couplers in this recording material are dispersible in synthetic resins ated, although this is not generally required. The structure of the tripack is well known.

A test strip of this recording material is exposed for 1 second in a sensitometer in front of a wedge with logarithmic steps. The test strip is then processed in the developer solution described above at 21 ° C. and in complete darkness for 4 minutes. The test strip is then removed from the developer solution and placed in a bath containing 40.0 g sodium carbonate / liter for 3 minutes and exposed to light in a room. During this time, the color is formed. The test strips are then processed in the usual ferricyanide bleach, wash, stop-fix, wash and stabilizer baths. This creates a positive color formation with the following densitometric properties:

D _mtix 3.20 2.70 2.72

D, _{/ m} 0.32 0.08 0.70

Gamma 4.3 2.6 3.7

If a water bath is used for the second exposure, there is no color formation in the test strip, which indicates that in this case an increase the pH is required to activate the color developer. Although the sulfite concentration in this example is sufficiently high that the inhibiting effect also by reaction with the oxidized Form of the color developer could occur, but it comes because of the pH value of the The bath does not lead to any oxidation of the color developer substance. The sulfite only acts as a stabilizer and prevents in the present case not the coupling of the oxidized color developer substance, since this only occurs when higher pH values arise.

A developer set consisting of two packs for the preparation of a developer solution used according to the invention has z. B. the following composition:

Package A.

Sodium hexametaphosphate 2.0 g

p- (N-Ethyl-N- / i-hydroxyethyl) -

aminoaniline 18.0 g

Potassium sulfite 48.0 g

Hydroquinone 7.5 g

1-phenyl-3-pyrazolidinone 0.30 g

Pack B

Sodium carbonate 30.0 g

Sodium hydroxide 4.0 g

Potassium bromide 2.0 g

For use, the contents of pack A are in 700 ml of water and the contents of pack B in 200 ml Dissolved water. The two solutions are combined to produce the ready-to-use developer solution and dilute it to 1000 ml.

Claims (1)

Patent claims: 1. Process for color reversal development of photographic recording materials which contain at least one halogen silver emulsion layer, characterized in that man