DE1622271B2 - PHOTOGRAPHIC COLOR REVERSION PROCESS AND RECORDING MATERIAL FOR IMPLEMENTING THESE - Google Patents

Description

in which X denotes an alkyl radical which is optionally replaced by at least one hydroxyl group or at least one carbonyl-containing group is substituted, Z is a hydrogen atom or an alkyl radical, which is optionally substituted by at least one hydroxyl group or carbonyl-containing group is done.

2. The method according to claim 1, characterized in that there is a 4-thiazoline-2-thione used in the 4-position by an alkyl radical having 4 to 5 carbon atoms, each of which carries a hydroxyl group, is substituted.

3. The method according to claim 1, characterized in that there is a 4-thiazoline-2-thione used, which is in the 4-position by a formyl, carboxyl, ethoxycarbonyl, hydroxymethyl or acetoxymethyl radical is substituted.

4. The method according to claim 1, characterized in that there is used as 4-thiazoline-2-thione one of the following compounds is used:

4-thiazoline-4-carboxaldehyde-2-thione,

5-carbethoxy-4-methyl-4-thiazolin-2-thione,

4-carboxy-4-thiazolin-2-thione,

4-carboxy-5-methyl-4-thiazolin-2-thione,

4-carbethoxy-4-thiazolin-2-thione,

4-acetoxymethyl-4-thiazolin-2-thione,

4- (D-arabino-tetraacetoxybutylM-thiazolin-2-thione,

4- (D-gluco-penta-acetoxypentyl) -4-thiazolin-2-thione,

4- (D-gluco-penta-hydroxypentyl) -4-thiazolin-2-thione,

4-hydroxymethyl-4-thiazolin-2-thione,

4-methyl-4-thiazolin-2-thione or

4- (D-arabino-1,2,3,4-tetrahydroxybutyl) -4-

thiazolin-2-thione.

45

55

60

5. The method according to claim 1, characterized in that there is a photographic material used in which the silver halide is at least one of the silver halide-containing Layers composed of a silver halide iodide.

6. The method according to claim 5, characterized in that there is a photographic material used in which the silver halide is at least one of the silver halide-containing Layers consists at least partially of silver bromoiodide.

7. The method according to claim 1, characterized in that that the diffusible 4-thiazolin-2-thione used to form the silver images Developers incorporated.

8. The method according to claim 1, characterized in that the development of the silver images at temperatures of 24 to 82 ⁰ C is carried out.

9. Color photographic recording material for the color reversal process, which at least contains two superimposed hydrophilic, light-sensitive silver halide emulsion layers, characterized in that at least one of the silver halide emulsion layers or one the other colloidal layer is a diffusible 4-thiazolin-2-thione of the general formula

in which X denotes an alkyl radical which is optionally replaced by at least one hydroxyl group or at least one carbonyl-containing group is substituted, Z is a hydrogen atom or an alkyl radical, optionally by at least one hydroxyl group or carbonyl-containing group is substituted, contains.

10. Color photographic recording material according to claim 9, characterized in that there are at least three superimposed photosensitive silver halide emulsion layers, who are sensitized to red, green and blue light.

The present invention relates to a color reversal photographic process using a multilayer photographic Material with several differently sensitized silver halide emulsion layers image-wise exposure developed black and white, exposed a second time or with the help of a nucleating agent Bath is veiled and treated with a color developer at least once. The invention further relates to a photographic recording material for the color reversal process, the at least two superposed hydrophilic light-sensitive silver halide emulsion layers contains.

The dyes used to produce multicolor photographic images are known to provide not always real shades. So absorb z. B. those generated in the context of color photographic processes crimson dyes often have some light blue and red, while the yellow and blue-green In addition to blue or red light, dyes also absorb small amounts of light of other wavelengths. These undesirable absorptions often lead to training in multicolor photography

darker and less saturated colors, d. H. Color falsifications.

It is known that the above-mentioned deficiencies of the dyes can be partially achieved by production can compensate for so-called interimage or interlayer effects. The phenomenon such effects is z. B. in the journal "Journal of the Optical Society of America", Vol. 42 (1952), Pp. 663 to 669, and described in more detail in The SPSE Reporter, November 1960. In The literature references cited also contain information on how such interimage effects arise let measure.

The principle of the inter-image effect, which increases the color saturation, can be seen from the following illustrate a hypothetical example in more detail:

In a photographic recording material consisting of two light-sensitive silver halide emulsion layers one layer is sensitive to red light and designed to produce a blue-green dye, while the second Layer is sensitive to blue light and intended to produce a yellow dye. One sample of this recording material becomes gradually with red light and a second sample gradually exposed to red plus blue light, the amount of red light being the same in both cases, so one can speak of improved interimage effects if the amount of blue-green Dye that was created during exposure to the red light alone is less than that produced by the exposure was made with red plus blue light. This also applies to other dye images, z. B. red, green, blue, purple and yellow.

The object of the invention is to reduce undesired absorption of dye images by producing them to reduce or correct further improved interimage effects and thereby dye images in to produce richer and stronger color tones. In particular, the color saturation should be increased by increasing Inter-image effects are caused, on the one hand, the density of a given color gamut, which is caused by neutral exposure was generated, and on the other hand the density of this color gamut with a Do not reduce exposure to monochromatic light.

The object is achieved with a photographic color reversal process in which a multilayer Photographic material having several differently sensitized silver halide emulsion layers developed black and white after imagewise exposure, exposed a second time or with the aid of a nucleating bath and then treated at least once with a color developer is, which is characterized in that the black and white development in the presence of a diffusible 4-thiazolin-2-thione of the general formula

> = s

-N

Z is a hydrogen atom or an alkyl radical, optionally substituted by at least one hydroxyl group or carbonyl-containing group is substituted. The invention was based on the knowledge that you can achieve such, the color saturation increasing interframe effects by that carries out the development of the silver images in the presence of a 4-thiazoline-2-thione.

According to an advantageous embodiment of the invention, the diffusible 4-thiazoline-2-thione is of the general formula given in that used to perform the color reversal process contain color photographic recording material.

The object is accordingly also achieved with a color photographic recording material for the color reversal process, the at least two superimposed hydrophilic photosensitive Contains silver halide emulsion layers and which is characterized in that at least one of the Silver halide emulsion layers or another colloidal layer a diffusible 4-thiazoline-2-thione the given general formula contains.

Particularly good interimage effects are obtained when at least one silver halide emulsion layer of the recording material contains a silver halide iodide as silver halide.

4-Thiazoline-2-thiones, which have an alkyl substituent with 4 to 5 carbon atoms in the 4-position, are particularly suitable each carbon atom has a hydroxyl group. To carry out Also suitable for the process of the invention are disulfides which produce 4-thiazoline-2-thiones can be split, e.g. B. Bis [5,4- (1,2-D-gluco) -thiazolyl] disulfide, which is used in the later referred to as compound 13 in the following examples. The disulfides themselves are obviously suitable not to produce improved interimage effects, but act after cleavage just like the 4-thiazoline-2-thione.

Typical 4-thiazoline-2-thiones suitable according to the invention are compounds of the general formula in which X denotes a methyl or ethyl radical or a hydroxymethyl, / S-hydroxyethyl, gluco or Arabino radical or an alkyl radical with at least one carbonyl-containing group (= C = O), e.g. B. a formyl, Carboxyl, alkoxycarbonyl, e.g. B. ethoxycarbonyl or an alkoxyalkyl, e.g. B. an acetoxymethyl radical, Z is one of the radicals indicated for X or, preferably, a hydrogen atom.

The 4-thiazoline-2-thiones used in the process of the invention can usually be added to the enolize corresponding mercaptans. The enolization can take place at any suitable point in time, z. B. when the 4-thiazoline-2-thiones contain a hydrophilic, photosensitive silver halide Colloid layer can be added.

Typical 4-thiazoline-2-thiones which can be used according to the invention are z. B .:

4-thiazoline-4-curboxaldehyde-2-thione
CHO

in which X denotes an alkyl radical which is optionally replaced by at least one hydroxyl group or at least a carbonyl-containing group is substituted,

2. S-carbethoxy ^ -methyM-thiazoline ^ -thione

CH,

NH

3. 4-Carboxy-4-thiazolin-2-thione

HOOC

-NH

L,

4. 4-Carboxy-5-methyl-4-thiazolin-2-thione

HOOC

NNH

5. 4-Carbethoxy-4-thiazolin-2-thione C ₂ H ₅ OOC

6. 4-Acetoxymethyl-4-thiazolin-2-thione O

Il

CH ₃ COH ₂ C

-NH

L,

8. 4- (D-Gluco-penta-acetoxypentyl) -4-thiazolin-2-thione

-N

> = S

H ₃ COCOC H

CH ₃ CO ₂ CH

HCOCOCH ₃ HCOCOCH ₃ CH ₂ OCOCHj

9. 4- (D-Gliico-penta-hydroxypentyI) -4-thiazolin-2-thione

25 / \

COH H

HIGH ₃ o HCOH

HCOH

i CH ₂ OH

³⁵ 10. 4-Hydroxymethyl-4-thiazolin-2-thione H

-N

> = S

HOH ₇ C

45 11. 4-Methyl-4-thiazolin-2-thione

H \

-S

> = S

CH,

7. 4- (D-Arabino-tetraacetoxybutyl) -4-thiazoline-12. 4- (D-Arabino-1,2,3,4-tetrahydroxybutyl) -4-thia-2-thione 55 zolin-2-thione

CH ₃ CO ₂ CH H

H-COCOCH ₃ H-COCOCH, CH ₂ OCOCH,

-N

> = S

HOC-H H HCOH HCOH

CH ₂ OH

As is known, there are several of the connection 12 Isomers, each of which can be used individually or in the form of mixtures.

The term "diffusible" means that the connections through hydrophilic colloid layers of a photographic material are able to migrate. This means that the substituents of 5-thiazoline-4-thiones must neither inhibit nor prevent diffusion. It is believed that the 4-Thiazolin-2-thione are bound to the silver halide crystals and thereby prevented from passing through freely diffuse the colloid layers of the photographic material. However, the silver halide will too If a silver image develops, the 4-thiazoline-2-thiones are quite obviously released and diffuse imagewise into the photographic material, presumably inhibiting development.

It is necessary that the diffusible 4-thiazoline-2-thione are present during the development of the silver image of the photographic material.

Advantageously, the compounds of one or more of the hydrophilic colloid layers, z. B. incorporated into the photosensitive silver halide emulsion layers. The photographic However, material can also be treated accordingly after the layers have been applied, e.g. B. with an aqueous solution containing the diffusible compounds.

Should the 4-thiazoline-2-thiones be used in the photographic Recording material are accommodated, so they can be in one or more layers of the same be accommodated. The compounds can be used in all colloid layers of a recording material or any or all of the light-sensitive silver halide emulsion layers. That Incorporation of the compounds into one of the upper layers of the photographic material, e.g. Am the gelatin coating or the topmost photosensitive layer has proven to be particularly advantageous.

In general, it is advantageous to apply the compounds at a point in time prior to treatment of the material to introduce into this with a developer solution. However, the 4-thiazoline-2-thiones can also be the To be set developer solution, the development of the silver image in the exposed photographic Material is used. With the connections 1 and 12 z. B. good results also achieved when they are added to the black and white developing solution. With the connections 10 and 11 give the best results when incorporated into the photographic material before treatment with the developer solution.

The 4-thiazoline-2-thiones used according to the invention can, depending on the one used in the individual case photosensitive silver halide emulsion, the concentration of silver halide in the emulsion layers and the concentration of that to be formed Dye can be applied in various concentrations. Be useful when using the compounds in photographic materials, e.g. In the silver halide emulsion layers, 5.0 to 500 mg of compound per mole of silver and preferably 100 to 200 mg per mole of silver are used. Will the compounds in the form of a solution, e.g. B. a black and white developer solution, are used expediently concentrations of about 0.1 mg to 1.0 g per liter of solution and preferably 1.0 mg up to 50 mg per liter of solution used.

According to an advantageous embodiment of the invention, the 4-thiazoline-2-thiones are common with compounds incorporated in a latent image-containing silver halide emulsion layer Ability to develop silver image. For this purpose particularly suitable developer compounds are z. B. polyhydroxybenzenes, N-monoalkylaminophenols and mixtures thereof. Typical suitable polyhydroxybenzenes are z. B. hydroquinone, catechol and pyrogallol. Typical suitable N-substituted aminophenols are z. B. N-methylaminophenols and N-ethylaminophenols. Preferred developer compounds that allow rapid processing of photographic Cause images are z. B. hydroquinone and ρ - N - methylaminophenol. Developer connections, the improved inter-image effects used in a particularly advantageous manner together with those used according to the invention causing compounds can be used, for. B. in U.S. Patents 3,146,102 and 29 83 606 described.

Color reversal photographic processes modified by the use of 4-thiazoline-2-thiones can be, are z. B. from US-PS 3227 550, 32 27 551, 32 27 552, 32 27 554 and 32 43 294 known.

The method of the invention is expedient at

Room temperatures, e.g. B. at about 20 to about 24 ° C, carried out, but optionally also at higher temperatures, for. B. at temperatures of 24 to about 82 ° C or above.

In color reversal processes according to the invention, the dye images can be produced according to one of the two classic methods Methods are generated. In one method, color couplers are applied before the exposure of the Recording material introduced into the emulsion layers or layers adjacent thereto. the Color couplers can be used in a suitable medium, such as. In U.S. Patents 2,322,027 and 2,3 04,940 is described, are dispersed.

Typical suitable color couplers and photographic materials prepared using the same for the color reversal process are e.g. From US-PS 28 01 171,24 74 293,2521 908 and 28 57 057 known. Such photographic recording materials can e.g. B. by procedure as described in US Pat. No. 3,046,129, columns 23 and 24 will. The couplers can e.g. B. from phenolic, heterocyclic, open-chain ketomethylene and 5- pyrazolone compounds exist.

According to the second classic method, the color couplers are incorporated into the recording material with the developer brought in. Thus, the couplers described above can e.g. B. a color developing solution be incorporated as they are z. B. in U.S. Patent 2,252,718 is described.

Suitable developers for carrying out the two methods are known. Are particularly suitable

z. B. Phenylenediamines and their substituted derivatives, as z. B. in US-PS 25 48 574, 25 52 240, 25 52 241, 25 52 242 and 25 66 271. The method of the invention can also be used in the framework be performed by color diffusion transfer processes such as those described in e.g. B. in US-PS 29 83 606, 3146 102, 32 27 551, 32 27 554, 32 43 294, 32 27 550 and 32 27 552 can be described.

Particularly advantageous results are then achieved

509 585/323

hold if at least one emulsion layer contains a silver halide iodide, e.g. B. silver chloride iodide or preferably contains silver bromide iodide or silver bromide chloride iodide. The silver halide expediently contains iodide 1 to 10 mole percent and preferably 4 to 8 mole percent iodide.

Two types of photographic recording materials are used in the following examples. The recording material designated as type 1 was obtained by coating a transparent Polyethylene terephthalate support with the hydrophilic colloid layers described below produced, the coating sequence given below, starting with the carrier, adhered to became:

Type
Layer A - antihalation layer

A dispersion of gray colloidal silver in gelatin was applied to the layer support in such a way that 4.9 g of gelatin and 0.247 g of gray colloidal silver accounted for ^{a support area of 1 m 2.}

1. (2 ', 4', 6 '- Trichlorophenyl) - 3 - [3 "- (2"', 4 '"- di - tert-amylphenoxyacetamido) - benzamido] - 5 - pyrazolone and in coupler no. 8 l- (2 ', 4', 6'-trichlorophenyl - 3 - [3 "- (2" ', 4' "- di - tert - amylphenoxyacetamidobenzamido] - 4 - (p - methoxyphenylazo) - 5 - pyrazolone.

Layer F - yellow filter layer

A layer of gelatin with Carey Lea colloidal silver was applied so that per square meter Support surface 0.97 g gelatin and 0.1075 g silver were omitted.

Layer B - intermediate layer

On top of the antihalation layer was a gelatin interlayer in a thickness corresponding to 1.24 g Gelatine applied per square meter of support surface.

Layer C - Cyan Dye Forming Layer

A gelatin silver bromide iodide emulsion which is a dispersion of a mixture of cyan dyes forming couplers, e.g. B. Couplers Nos. 1 to 6 described in US Pat. No. 2,801,171, column 2 in a common solvent, e.g. B. tri-okresyl phosphate, contained was applied in an amount that per square meter of support area 1.18 g of gelatin, 0.7 g of silver and 0.54 g of cyan dye-coupler mixture accounted for. A red sensitization (600 to 700 πΐμ) became through the addition of spectral sensitizing Dyes causes.

The cyan coupler no. 5 known from the above-mentioned US Pat. No. 28 01 171 is it is z. B. to 6 - {{[a- {4- [a- (2,4-Di-tert.-amylphenoxy) butyramido) phenoxy} - acetamido}} - 2,4 - dichloro-3-methylphenol.

Layer D - intermediate layer

A gelatin layer of 0.645 g gelatin / m ² was applied.

Layer E - Magenta dye-forming layer

A silver bromoiodide gelatin emulsion opposed with a spectral sensitizing dye green light (500 to 600 ηΐμ) has been sensitized and some of them are dispersed in tri-o-cresyl phosphate Pyrazolone couplers, e.g. B. in U.S. Patent 28 01 171, column 2, described Coupler No. 7, along with another pyrazolone coupler, e.g. B. that in said patent Coupler No. 8 described above was applied so that per square meter of support area 1.77 g gelatin, 1.02 g silver and 0.7 g coupler mixture were omitted.

The magenta coupler no. 7 known from the USA patent is z. B. to Layer G - yellow dye forming layer

A gelatin silver bromoiodide emulsion (blue sensitized), the yellow image forming coupler, e.g. B. one of the U.S. Patent 28 75 057 described Coupler Nos. I to V dispersed in dibutyl phthalate was contained in such Concentration applied so that per square meter of support surface 1.24 g of gelatin, 0.75 g of silver and 0.54 g Color couplers were omitted.

Coupler No. III described in U.S. Pat. No. 2,875,057 cited above is z. B. 3-Benzoylacetamino-4-methoxy- (2 ', 4'-di-tert-amylphenoxy) -acetanilide.

Layer H - top layer

A gelatin layer of 0.97 g gelatin per square meter was applied.

In the following examples, the type I photographic material described was im Developed within a color reversal process as follows:

First, the exposed film was placed in an aqueous developing solution for 10 minutes as follows Composition developed:

Sodium hexametaphosphate 2.0 g

N-methyl-p-aminophenol sulfate 6.0 g

Sodium sulfite, anhydrous 50.0 g

Hydroquinone 6.0 g

Sodium carbonate monohydrate 35.0 g

Potassium bromide 2.0 g

Sodium thiocyanate 1.5 g

0.5% solution of 6-nitrobenzene

imidazole nitrate 12.0 ml

0.1% solution of potassium iodide .. 10.0 ml

Made up to 1.0 1 with water

The photographic material was then washed vigorously with water for 1 minute and 3 minutes long bathed in a hardening bath of the following composition:

Potassium chrome alum crystals 30.0 g

Made up to 1.0 1 with water

Then the photographic material was washed extensively with water for 3 minutes and Bathed for 30 seconds in a solution of the following composition:

Sodium borohydride 0.25 g

Sodium hydroxide 4.0 g

Made up to 1.0 l with water

11 12

The photographic material was then sensitive to silver halide emulsion layers C, Developed for 15 minutes in a color developer solution containing E and G 200 mg of compound 12 per mole of silver of the following composition: halide. Samples of the materials were made

a uniform sensitometric exposure with

Benzyl alcohol 6.0 ml 5 exposed to red light. Other samples became neutral

Sodium hexametaphosphate 2.0 g exposed (red plus green plus blue light). Thieves-

Sodium sulfite, anhydrous 5.0 g exposure with red light was equally strong in all cases.

Trisodium phosphate 40.0 g The exposed samples were then after

Potassium bromide 0.25 g method I worked up. The blue-green dye seal

0.1% solution of potassium iodide. . 10.0 ml 10 th from the exposure to red light and neutral sodium hydroxide 6.5 g of light were plotted as curves. The sub color developer ¹ ) 11.33 g differed in the slope of the two curves

Ethylenediamine sulfate 7.8 g with an optical density of 0.6 and measured as

Citrazinic acid 1.5 g I log £. The improved intermediate image

Made up to 1.01 with water. 15 effects on the cyan dye were made

,. _Λ . _V7 .. ,, »,,,, r -j ··,. ,,, ■ by increasing the value Λ log E as the difference

¹ 4-Amino-N-athy -N- (rf-methansu fonamidoathy) -m-tolui- .... _, ⁶ .. _c , _rr ^& , _ ...,

din-sesquisuifat-monohydrate from blue-green dye formed from the Rotbüdung

compared to blue-green dye from the neutral

The photographic material was then determined to be 5 minutes exposure. The greater the difference in the

thoroughly watered for a long time and then 20 | for 5 minutes log £ value, the greater the improved

long in a clarifying and fixing bath of the following inter-image effects. The results obtained are

brought composition: in the following Table I reproduced.

Sodium thiosulfate 150.0 g τ h 11 T

Sodium bisulfite 20.0 g

Made up to 1.0 1 ^{25 with water}

The photographic material was then 8 Mi- ** »» ^ Additions ™ SS »

utes long in a bleach bath for the following additions _per mole of silver effects

composition treated: for all cyan dye

-I ₀ emulsion Δ log E at

Potassium dichromate 5.0 g layer density 0.6

Potassium ferricyanide 70.0 g

Potassium bromide 20.0 g

Made up to 1.01 comparative sample with water - +0.26

c ur m · u Jj u. u- u -κ * .. ■, Compound 12 200mg +0.68 Finally, photographic material 35 became

watered again for 1 minute and for 4 minutes
brought into the clarifying and fixing bath described.

It was then watered again for 8 minutes and Example 2 Treated for 1 minute in a stabilizing bath of the following composition: 40

Various photographic ma-

Formaldehyde (37 percent by weight) 7.0 ml ^ts f ^ ^of type I produced, one of which as a

Dispersing ^{agent 1} ) 05g was also used. The photographic material

Topped up with water äui '.'. '.'. '.'. '.'. '.'. U) 1 alien of the invention differ from the

45 of the same material only then that the blue sensitive

') For example Triton X-ioo, i. H. an alkylaryl polyether alcohol layer G contained a 4-thiazoline-2-thione. Different

hol (Octylphenoxypolyäthoxyäthanol). These sections of all samples were taken individually

color sensitometry with red, green or blue light

In the following examples the one described is exposed. Unexposed sections of the photographic

Working method referred to as method I. The Tem- 50 see materials then became an equivalent

The temperature of the treatment baths was 23.9 ° C. exposed to the sensitometric neutral exposure

The material type II used in the examples consisted of red-plus green-plus blue light. The amount

corresponded to Type I with the exception that it was neutral exposure to red, green and blue light

contained no dye formers. The photographic was the same as the single color light exposure

Type II materials became 55 after exposure to red, green and blue light. All samples

driving developed as it z. B. in the USA. Patents were then developed according to Method I. It

Scripture 22 52 718, p. 2, column 2, line 48 to p. 3, were for the blue-green, purple-red or.

Column 1, line 5 is described. These working yellow dyes both from the separately

wise, in the following examples as method II, red, green or blue exposure is also carried out

designated. 60 of the neutral exposure applied density curves. the

Curves from the single exposure were related to

_R · ·,. I log E with the curves from the neutral exposure

^sp ' ^e ''density 0.6 compared. The achieved according to the invention

improved interframe effects resulting from a

Two photographic materials of the 65 increased I log £ value of the test samples were used

Type I produced, one of which as a comparative comparison to the comparative samples, are from

material served. The other material was the same as that summarized in Table II below

Comparative material except that it can be seen in all three light results.

Table II

additions

concentration
the

additions
per mole
Silver in
the blue sensitivity
lichen
layer

(mg)

llog £ at density 0.6 blue-green purple-red yellow

Comparative sample
Connection 12
Comparative sample
Connection 7
Connection 8
Connection 9

100 mg

400 mg
200 mg
200 mg

+ 0.30 + 0.50 4- 0.22 + 0.33 + 0.48 + 0.44

+ 0.28 + 0.50 + 0.06 + 0.18 + 0.41 + 0.40

+ 0.10 + 0.20 + 0.28 + 0.29 + 0.13 + 0.29

20th

Example 3

additions

Concentration of additives per mole of silver in the blue-sensitive layer

Improved interimage effects for the cyan dye Δ log E at a density of 0.6

Comparative sample - + 0.05

Compound 1 100 mg + 0.23

Compound 1 200 mg + 0.29

Compound 13 50 mg +0.20

Compound 13 100 mg +0.28

determined by measuring the reduction in the cyan dye formation caused by the additional sensitometric blue exposure caused by a brief, uniform red exposure. The degree of the interlayer effect achieved can be expressed as the greatest change in density of the layer in question (hereinafter referred to as I d ) and as the change in the average gradient (γ) of the layer in question in comparison with a comparison material. The higher the average gradient and the greater the value for I d , the greater the improved interlayer effect brought about by the 4-thiazoline-2-thione.

The results obtained are shown in Table IV below.

Table IV

Additional photographic materials as described in Example 2 were prepared. The single ones Materials differed from the reference material only in that they were blue-sensitive Layer G contained various 4-thiazolin-2-thiones. The specimens were the same sensitometric Subjected to red exposure, both with and without additional exposure to blue light, to form an image in the blue sensitive yellow dye forming layer. The examinees were then developed according to Method I. Then cyan dye density curves were obtained from exposure applied with red light and with the corresponding curves from the red plus blue exposure compared. The improved interframe effects obtained in accordance with the present invention were as in the previous ones Examples are determined and are given in the following Table III.

Table III

additions

Concentration average in mg per gradient (; ·)
Mole of silver

Ad

Comparative sample
Connection 12
Connection 12
Connection 11
Connection 11
Connection 10
Connection 10

100 mg
200 mg
100 mg
200 mg
100 mg
200 mg

0.16
0.30
0.24
0.36
0.31
0.40
0.46

+ 0.18 + 0.31 + 0.27 + 0.31 + 0.30 + 0.36 + 0.46

Example 4A (comparative example)

How surprising the technical effect that can be achieved according to the invention is evident from the fact that a Number of compounds which are closely related to the 4-thiazoline-2-thiones used according to the invention which do not produce improved interimage effects. So z. B. no improved interframe effects obtained when following the procedure described in Example 4 using the following Additions is repeated:

45 S-carboxyäthyM-methyl-

thiazolin-2-thione,

2,2'-dithia- [5,4- (1,2-D-trityl-

gluco) thiazole,

2-amino-5-thiazolecarboxylic acid,

Di- (2-amino-4-methylthiazole-

5-yl) sulfide.

The results of the tests carried out with compounds A to D are shown in the table below V summarized.

Connection A ...
Connection B ...

Compound C ..
Compound D ..

55

Table V

Compound 13 consisted of 2,2'-bis- [4-D-ara additives, bino-1,2,3,4-tetrahydroxybutyl) -4-thiazoline] disulfide. When it was added to the emulsion, it was broken down to give the corresponding 4-thiazolin-2-thione.

Example 4

Comparative material Several photographic materials 65,,.

Type I produced and, as described in Example 3, exposed and developed. Connection A In this example the effect of the additives Compound A

Concentrate Through Ad

tration more cut

in mg per gradient (γ)
Mole of silver

- 0.16 +0.18

100 mg 0.10 +0.14

200 mg 0.10 +0.12

continuation

additions

concentration
in mg per
MoI silver

Average
Gradient (; ■)

Connection D
Connection D
Compound C
Compound C

100 mg
200 mg
100 mg
200 mg

Example 5

0.16
0.16
0.16
0.12

+ 0.10 + 0.14 + 0.18 + 0.16

Several Type I photographic materials were prepared and, as described in Example 2, exposed and evaluated sensitometrically. The exposed photographic materials were then developed according to method I, but this time developer A is a 4-thiazoline-2-thione was added. For comparison purposes, comparison samples were developed in developer A, which, however, did not contain 4-thiazolin-2-thione. The concentration of the thiazoline and the results obtained are given in the following table VI:

Table VI

Concentrate additives. I log E at a density of 0.6

tration

Accessories in blue-green purple yellow
Developer A

(Minor)

Comparative - +0.13 +0.03 +0.11

Connection 12 4.2 ■ 10 ~ ⁵ +0.29 +0.06 +0.18

Similar results were obtained when compound 12 was replaced by compound 1 became.

Example 6

Two Type II photographic materials were prepared. That contained one of these materials 200 mg of compound 12 per mole of silver in each light-sensitive silver halide layer. the Both materials were exposed as described in Example 2 and developed according to Method II. The interimage effects were determined as described in Example 2. The results are shown in Table VII below.

Table VII

40

55

additions

Concentration i log E at density 0.6

tration

per mole blue-green purple-red yellow

silver

Comparative sample - +0.05 +0.02 -0.21

Compound 12 200 mg +0.16 +0.16 +0.15

Corresponding interimage effects were obtained when compound 12 was replaced by compound 8

was replaced or if the two compounds are each dissolved in an aqueous solution and the photographic materials prior to first processing by Method II with this solution treated or when the two compounds are each added to the first developer according to Method II became.

Example 7

This example shows the influence of increased process temperatures.

A type I photographic material without the addition of 4-thiazolin-2-thione and a corresponding one was obtained photographic material containing 200 mg of compound 12 per mole of silver in the blue-sensitive Layer G made. The influence of the addition was as described in Example 4, determined. in the individual were measured:

1. The additional sensitometric blue and green exposure, the reduction in short-term, uniform red exposure induced cyan dye formation;

2. the reduction of the. Caused by an additional sensitometric red and blue exposure

magenta dye formation caused by brief, uniform green exposure and

3. the reduction of the. Caused by an additional sensitometric red and green exposure

yellow dye formation caused by brief, uniform blue exposure.

The evaluation was also carried out as described in Example 4.

After exposure, the samples were placed in a pre-hardener bath of the following at 35 ° C for 2 minutes Composition treated.

link lot until 27.0 ml Octyl alcohol 0.10 ml 1.01 Sodium sulfate 158.0 g 4.80 Sodium bromide 2.0 g Glacial acetic acid 21.7 ml Succinaldehyde (100%) 2.20 g Mixed for 15 minutes NaOH 10.0 g 5 minutes or so long mixed, NaOH is dissolved Formalin (37.5%) Topped up with water pH at 26.7 ° C

Subsequently, the specimens were placed in a neutralization bath at 35 ° C. for 30 seconds as follows Composition bathed:

Compound hydroxylamine sulfate

Sodium bromide
Eiscssiu

lot

25.0 g
(26.3 g M) 2.0 g
10.0 ml
509 585/323

16 continuation 22 271 lot link 6.0 g NaOH 100.0 g Na ₂ SO ₄ 1.01 Topped up with water 5.00 pH at 26.7 ° C on

The test specimens were then developed according to Method I, but the baths were each kept at 51.5 ³ C and the duration of treatment was limited to

Table VIII

a total of 4 minutes was reduced. The results obtained are shown in Table VIII below.

additive

Concentration mg / mol Ag

Cyan dye density γ Ad

Purple dye density
; · Ad

Yellow dye density Ad

Comparative sample
Connection 12

200

0.09 0.15

+ 0.12 + 0.30

The results indicate that when multilayer photographic materials were processed in the presence of 4-thiazoline-2-thiones, 0.23
0.44

at higher

image effects can be obtained.

+ 0.48 0.11 + 0.22 + 0.78 0.17 + 0.36 Deraturei ι improved Between-

Claims (1)

Patent claims: 1. Color reversal photographic process in which a multilayer photographic material with several differently sensitized silver halide emulsion layers after imagewise Exposure developed black and white, exposed a second time or with the help of a nucleating agent Bath is veiled and then treated at least once with a color developer, characterized in that the black-and-white development in the presence of a diffusible 4-thiazolin-2-thione of the general formula