DE2415125A1 - DYES FOR PHOTOGRAPHIC PURPOSES, THAT RELEASE A DIFFUSIONABLE COLOR, AND THEREFORE EXECUTED PHOTOGRAPHIC PROCESS - Google Patents

Description

DlPL.-CHEM. DR. VOLKER VOSSIUS ⁸ SS '"' **

PATENT ADVERTISER I ¹ SON? :: 47 40 75

mi UN 1ANWALI l ^^ _{ADDRESS; BnN} ZOLPATENT MUNICH

1HLEX 5-23153 VOPAT D.

uZ: K 739 (Vo / kä)
Case: FP - 1017 - 3

KONISHIROKU PHOTO IND. CO. LTD.,
Tokyo, Japan

¹¹ dyes for photograph! See Zv / corners, which split off a diffusible dye, and thus feasible photo-. graphic process "

Priority: March 28th. 1973, Japan, No. 34 469/73

The invention relates to dyes, the diffusible dyes can split off, as well as a feasible with it. photographic process. In particular, the invention relates Dyes for photographic corners which have the ability to act on exposed photographic recording material with at least one halogen silver emulsion layer with a color developer diffusible dyes split off, as well as a new method of image formation by the dye diffusion transfer method in which this Find dyes use. -

As dyes for photographic Zv / corner which release a diffusion dye, a certain type of so-called DDR ^{n M} -Farbkupplersubstanzen is known. The abbreviation ODR is off

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the first letter of the English name for this type of coupler (Diffusible Dye Releasing Coupler). These DDR couplers are formed when the remainder of a diffusible dye molecule is mixed with the molecule of a dye coupler substance linked via their reactive methylene group, which is linked to the oxidation product of a color developing agent in the known color coupling reaction reacts. Such GDR couplers divide according to the density of what has been developed in their presence Silver image from a diffusible dye. Therefore, they can be used for a photographic process for dye diffusion transfer can be used. Because these DDR couplers are dyes themselves and attached to their active methylene group If a diffusible dye is split off, they can also be used in a conventional photographic negative-positive process use to improve the resulting color image. In this type of application, they are used for color masking.

lim with such DDR couplers on a photographic color recording material To obtain a positive image by dye diffusion transfer, it is necessary, as a photosensitive photographic material containing the coupler to use a material with direct positive emulsions. The complicated production of direct positive emulsions and the high demands on the precise implementation of the Manufacturing processes involve high costs; in addition, such layers are so important to photographic see properties v / ie sensitivity. and resolving power unsatisfactory. Furthermore, it is not possible to do this in the receiving layer resulting negative image, which is related to the

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the positive image arising from the supporting layer, practical to use, because the color image formed in the receiving layer in the inherent color of the coupler substance is of the superimposed on another color image that is developed by reaction between the coupler substance and the oxidized color developer subs dance comes about. This is another disadvantage of the GDR couplers.

If you put the well-known GDR coupler together with one of the usual If you want to use coupler substances as a means of masking, you have to choose a suitable color coupler residue for the molecule of the GDR coupler and for the fixation Proceed carefully with the amount of coupler. The correct selection of a remaining color coupler is necessary for color development the same partial color as comes about with an ordinary color coupler and the color matching in the finished image remains unchanged remain. It has proven extremely difficult in practice to meet these conditions.

The invention is based on the object of finding dyes which are suitable for photographic purposes and which are used in color development split off diffusible dyes and neither when used in a photographic dye diffusion transfer process still have the disadvantages explained above in an ordinary negative-positive color method.

According to the invention, this object is achieved with the aid of dyes solved, which in the development of an exposed, with min-

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-. Ll _m

at least one photographic film provided with a silver halide emulsion layer Recording material in a color developer split off diffusible dye and the general formula (I)

A-D (I)

correspond. In this formula means

A is a remnant of a molecule that develops with the oxidation product the color developer reacts to form a practically colorless compound and

D is a remnant of a molecule, which after cleavage is a diffusible, results in dye containing water-solubilizing groups.

Since the dyes according to the invention split off a diffusible dye during color development and at the same time A colorless compound can be obtained by a dye diffusion transfer process both the image captured from the broadcast material and the image captured in of the originally photosensitive emulsion layer is used for practical purposes.

The dyes according to the invention react during development with the help of part of the molecule A with the oxidation product. a color developing agent (e.g. with the oxidation product, which corresponds to the amount of developed silver in the exposed Emulsion layer arises) with the formation of a colorless compound, while the molecular part D is split off and provides a diffusible dye.

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Molecular part A is preferably a radical with an active methylene group, to which the molecular part D is directly bound. Molecular parts A which are particularly preferred are those within their association have a group adjacent to this active methylene group, which in turn relates to the methylene group has an activating effect.

Preference is given to dyes of the general formula I whose molar part A is either of the general formula (H)

R-CH-

(II) Y

or the general formula (III)

(in)

is equivalent to.

In the general formulas (II) or (III): Y denotes a hydrogen or halogen atom, an alkyl or aryl group, a heterocyclic radical, the group -OR ^ / R * can be an alkyl or aryl radical, a heterocyclic radical, be an acyl radical or the radical -SO ₂ R ₂ , where R _{2 represents} an alkyl or aryl radical or a heterocyclic radical / or the group -COOR-, (R, - denotes an alkyl radical);

R the group -COR ^ (R ^ can be a hydrogen atom, a hydroxyl group, the group -R _Q , -0R ₀ , ~ N (R _Q ) ₂ , -MI ₂ or -NHR ₀ ), the group -CR, - SOoR, - or -SOR, - (R ₁ - means a water

Il O ^ p ρ P

Il

NH

substance atom, the group -R _Qf -0R _Q or -N (R _Q ) ₂ ), -CN or

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) -, (R- denotes a hydrogen atom or the group R); R denotes an alkyl, aryl or heterocyclic radical or two radicals R together with the nitrogen atom form that they are attached a heterocyclic ring; Z is a group of atoms that together form a carbocyclic or form heterocyclic ring.

Preferred radicals of the general formulas (II) and (III) are Alkyl groups with preferably up to 18 carbon atoms, which are optionally substituted with halogen atoms, hydroxyl or alkoxy groups are;

Alkyl groups in Y can be cycloalkyl groups or aralkyl groups be, where the aryl radical is preferably a phenyl or naphthyl group, which in turn with halogen atoms or Hydroxyl, nitrile, alkyl (e.g. methyl) or alkoxy (e.g. Methoxy) groups can be substituted.

5- or 6-membered radicals can be used as heterocyclic radicals one or more heteroatoms, such as N, O, S or Se, are possible. The heterocyclic radicals can be condensed with benzene or naphthalene. Examples of preferred radicals are benzoxazole, Benzthiazole, pyridine, furan, thiophene, succinimide, pthalimide, hydantoin and urazole groups and their derivatives.

In particular, heterocyclic radicals used for Y are Benzoxazole, benzthiazole, succinimide, phthalimide, hydantoin and urazole groups and their derivatives.

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Heterocyclic groups for R, R ^ or R ₂ are preferably the pyridine, furan and thiophene groups and their derivatives.

1 '1 acyl radicals have the general formula -COR, in which R represents one of the aforementioned alkyl or aryl radicals.

As aliphatic radicals, preference is given to using olefinically unsaturated aliphatic radicals with up to 18 carbon atoms May contain substituents.

As nitrogen-containing heterocyclic radicals consisting of two R groups are formed together with the nitrogen atom, preferably 5- or 6-membered radicals such as the piperidine, Pyrrolidine and morpholine groups.

The carbocyclic or heterocyclic rings which include the atom group Z according to the general formula (III), preferably correspond to the general formula (IV)

0
il

, '* - _N (IV)

A ₁ ^CJl "

in which Z ₁ denotes a group of atoms which are necessary for the construction of a carbocyclic or heterocyclic ring.

The carbocyclic ring can be a saturated or unsaturated 5- to 7-membered ring, such as the cyclopentanone, Cyclohexanone or Cyclohexenoiiring. These carbocyclic rings can contain one or more substituents, such as

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Alkyl, aryl, alkoxy and / or aryloxy groups and / or halogen atoms (these radicals are the same as those above, for example listed); they can also be used in the form of ring systems condensed in the appropriate position. Specific examples are indanone, benzcyclohexenone, and benzcycloheptenone groups.

The heterocyclic rings can have 5- "to 7-membered rings be one or more heteroatoms such as N, O, S or Se; these groups provide their active methylene group upon reaction practically colorless compounds with the oxidation product of a color developing agent. Examples of such heterocyclic Rings are piperidone, lactone, lactam, and hydantoin groups. In addition, these rings can be one or more Contain substituents such as alkyl, aryl and / or aryloxy groups and / or halogen atoms (these substituents are the same as mentioned above).

The molecular residue A can also itself be a water-soluble dye residue of the same kind as the molecular part D, i.e. it can contain the dye residue in the linkage as the group Y contained in the general formula (II). The structure of the molecule then corresponds to a bis structure with one of the named groups as. Intermediate link. If in the remnant of the molecule A is a water-soluble dye residue and apart from the active methylene group, with which the molecular residue D is directly connected, there is still another methylene group, should be with this further methylene group also the further residue of a water-soluble dye can be linked. In other words, the what-

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soluble dye residue in the molecular residue A is easily split off, when the dye takes part in a color development in which the remainder of the molecule is practically colorless Connection forms. The molecular residue Λ can also be equipped with a substituent that gives it diffusion resistance, so that it is neither before nor after development can diffuse.

The molecular residue D according to the general formula (I) is split off from the molecular residue A when a color development takes place; it represents the remainder of a dye with a water-solubilizing substituent. The water-soluble madiende substituent can be the group -SO ₂ H, -SO ₇ M, -COOH or -COOM (M is a cation such as ammonium, sodium or potassium), ie preferably The molecule of the dye corresponding to -D has a group at the end with which it is bonded to part of the molecule A, which allows easy cleavage, for example -0-, -S-, -Hg- , -N = N- or a tertiary nitrogen atom. Examples of dyes, the radicals of which can be used according to the general formula (I), can be found under the azo, azomethine, indoaniline, indophenol and anthraquinone dyes. . The dye residues mentioned. can ·· ..the molecular residue Ά of the ν type ·;, that-a bis-structure is formed from more than 2 of the residues A "?.

. "- '■ - - In this case the

Molecular residue A with an active methylene group on the dye residue be bound.

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The formulas given below are typical examples of compounds according to the general formula (I) which, when developed with a color developer, form a diffusible dye split off and at the same time provide a colorless compound with the oxidized color developer substance.

(2)

CE - / Λ- COCH ~ S- / V ^ - ^GH - ^C * ^CH 3

O = C H

\ s

S 0, Ka

SO ₃ Ka

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OH

'3 ^ Θ

p7 ίV

- 11

COCH ₂ -S

COOHu

NHCO

KHCO-,

NlICOC - CO

• SO Na 3

COOK

COOK

N-N

N-N

CONH

NHCOCH ₂ Ch ₂ COOH

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(6)

CH

K = II - CH

C = N

SO

C-Ii-

CfJl

S »C - N

I ^ CH- - S

N-C

^ W

K-N- (

Ii-V V-N

CLL

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. O

Il

CH -0-C
25th

CH-S-

NH ₂ O

KaO S 5

-COKH- / ^ -KH

(ΙΟ) ieo-C ^ H f ^

- s - C

N - K

-Ii - H

Ii = K-CH-O-COOH

I Il

O = CK

COOH

(11)

COCH -

NO,

N ί

I Ί

N = N "OH NlISO,

ι— κ = Κ '

SO ₇ Ka

'SO Na ■ 5

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N-N

S-C

C = O

- CH -C-

I l

O = C-N

= K

0 = 0 N

• \ /

SC ^ Well

SOMa

With the exception of compounds (5) and (10), all of the compounds listed above as examples have decomposition points above 270.degree. The decomposition point of compound (5) is 210 ⁰ C and the compound (10) 193-197 ° C. Table I shows the intrinsic color of all the compounds mentioned.

Table I.

Connection no. colour yellow purple blue green yellow blue green yellow yellow purple blue 1 yellow 2 Red 3 yellow. 4th 5 6th 7th 9 (10 (11 2

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The dyes of the structural formulas given above When developing with a color developer, they each provide a diffusible dye and, at the same time, a practical one colorless connection. If you use them in a dye diffusion transfer process, then they can be The dye images created by the transfer material, as well as those on the originally light-sensitive photographie Practically using recorded images. If the dyes according to the invention are used With a mask process, there is no need to fear any disruptive impairment of the resulting images. There too the image that appears at the imagewise exposed areas of the photographic Recording material remains when the diffusible dye has been split off during development istp can be used in practice, the Use dyes to carry out a novel photographic process. If you have these dyes for example, incorporated into a negative working silver halide emulsion layer of a photographic material with their help on the originally photosensitive recording material generate a positive image directly. Therefore, one of the usual ones can be used to directly produce a positive image Use negative-working halogen silver emulsion layers for the recording material. This will make the manufacturing process when using the dyes according to the invention for a light-sensitive photographic recording material much easier than using the usual direct positive emulsion layers have to work.

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The dyes according to the invention which split off diffusible dyes have a number of advantages and are of great use in photographic technology.

In addition, some of the dyes according to the invention provide e.g., those represented by formulas (2), (5), (7), (9), (10), (11) and (12) when developed in a color developer, a dye that also has a particularly beneficial effect on the developed silver image. The presence of one of these dyes improves the sharpness of the images and the quality of the reproduction of details. Hence can one when using · a combination of two different . Coupler substances during development, namely a conventional color coupler and a certain dye according to the invention (the one split off from this dye during development diffusible dye must have the ability to the development process of the silver in the just described Way to influence favorably) some photographic quality characteristics as or even further as in the case of development in the presence of three different types of coupler, namely one of the usual couplers, one DDR coupler and a DIR coupler. (The abbreviation DIR is from the first letters of the English name for these compounds, namely Development Inhibitor Releasing Coupler, formed and denotes a color coupler which, when developed, is proportional to the amount of image silver developed Development-inhibiting substance splits off). In the above explanations, the term "common color coupler" means one practically colorless color coupler substance, which when developing a

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colored picture supplies. With the help of two color coupler substances, one of which is a dye according to the invention, - Improvements can therefore be achieved much more easily than with the three different types used so far Coupler substances. If you use one according to the invention Dye that splits off a diffusible dye in relatively high concentrations, then one can determine the amount of the used Significantly reduce the dye. This means that ■ even a small amount of such a dye is sufficient to achieve a sufficient masking ring effect. Another advantage is that you have one specific to one Easily determine the appropriate combination of a dye according to the invention and one of the customary color coupler substances because the compound that is formed during the coupling reaction with the oxidized color developing agent itself is colorless.

For the production of direct positive images in a light-sensitive photographic material and also for use in dye diffusion transfer processes Of the dyes according to the invention, those of particular value are those in which those which are split off are diffusible Dyes have little or no influence on the development of the silver. This is for example with the dyes the case represented by the formulas (1), (3), (4), (6) and (8).

Typical examples of photographic processes in which the dyes according to the invention are used are given in detail ₇

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- 18 described below.

In a dye diffusion transfer process, generally with a combination of a transfer material receiving the final color image and one with at least a photosensitive halogen silver emulsion layer provided recording material worked. The light sensitive Recording material has at least one light-sensitive layer on a layer support; this consists of gelatin and halogen silver. The transfer material has at least one layer that receives the diffusion image. If a dye according to the invention has been incorporated into the photosensitive layer of the recording material, the splits off a diffusible dye during development, and the recording material comes into contact after exposure is subjected to color development with a transfer material, then that diffuses according to the developed Amount of silver split off diffusible dye at the silver-containing image areas in the layer of the transfer material and there generates an image in which the dye density occurring at the individual locations is that in the recording material corresponds to a reduced amount of silver at the corresponding point. The colored image on the transfer layer is preserved by separating the transfer material from the recording material after color development has ended. On the recording material what then remains is an image whose tone scale is reversed compared to the image on the transfer material. The remaining image cannot be used without further ado because it is still overlaid by the developed silver.

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However, if you remove the developed silver and the remaining silver salts with the help of a bleaching bath and a fixing bath or a combined bleach-fix bath, then in the The recording material reveals a color image that can be used well, its tonal value gradation compared to the color image on the transfer material appears reversed. After this procedure, a positive result is obtained on the original recording material Image and a negative on the transfer material Picture, provided that the -used silver halide emulsion a negative emulsion v / ar. In contrast, it is considered photosensitive If the recording material uses a direct positive emulsion layer, a positive and on is created on the transfer material a negative image on the photosensitive recording material. This procedure is so beneficial because it works for everyone its embodiments always a negative and a positive image is obtained at the same time. It is also an advantage here that you can optionally use a negative emulsion which is easy to manufacture. The advantage of this method is that In addition to the color image actually intended, you always get a second image (e.g. a color image on the light-sensitive photographic recording material in the case v / o the color image on the transfer material is actually intended Image), which can be used to make further copies. The procedure is therefore for a way of working in which it it is important to obtain numerous copies with the help of a recording, just as useful as for a way of working where a recording only needs to provide one image.

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The dyes according to the invention have the ability to impart the properties of a direct positive-working recording material to a light-sensitive photographic recording material. V, ^r enri for example, a dye of the invention the Halogensilberem.ulsionssch.icht is incorporated in a negative working recording material and this material is treated after the exposure with a color developer, a bleach bath and a fixing bath or a combined bleach-fixing bath is all the silver and Halogen silver in solution, and at the end you get a colored positive image. The manufacture and processing of photographic light-sensitive material of this type is extremely simple.

The dyes according to the invention are also suitable for the properties of a photosensitive halogen silver emulsion layer of a negative working recording material, e.g. when adding it to a direct positive emulsion. In any case, in all cases where dyes according to the invention can be a negative, a positive or a direct positive emulsion can be incorporated to achieve excellent photographic properties.

The amount of the dyes according to the invention is 0.07 to 0.7 mol per 1 mol of silver halide in a halide silver emulsion, preferably 0.1 to 0.4 mol if this emulsion is to be used to produce a colored image. The additional amount is the the amount required by a common coupler is practically the same. Should the dye according to the invention serve to improve the properties

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a common coupler or any other photographic To improve the property, for example to produce a color mask, the amount added is per 1 mol Silver halide 0.01 to 0.1 mol, preferably 0.03 to 0.07 mol.

With the help of each of the working methods explained, one can see on a multilayer, preferably three-layer photograph Recording material, its photosensitive layers for one wavelength range each, excluding the other two are sensitized and each contain a compound according to the invention that is complementary to the sensitization area, Generate multicolor images.

The photographic light-sensitive material used in the described method consists of one. Layer support, one or more light-sensitive layers, a protective layer and optionally an undercoat layer and one or more intermediate layers. The transfer material used to record the diffusion image consists of a Layer support, an image-receiving layer, a protective layer, optionally an intermediate layer and one PH control layer. In certain dye diffusion transfer processes it is preferable to work with a recording material which consists of two or more layers of which at least one is clearly translucent, between which light-sensitive emulsion layers and one to accommodate the The diffusion image serving transfer layer are arranged, whereby between the light-sensitive layers and the over-

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. - 22 -

support layer is a layer, which may also be cannot be transparent. One of the aforementioned photosensitive Layers can be a multiple layer of two or more. Individual layers can be formed, all of which are in the same wavelength range be exposed. In the case of the above-mentioned multilayer material, sub-layers with mutually different Spectral sensitivity used.

The binder for the described layers is generally Gelatin, but other colloidal substances such as albumin, cellulose derivatives and synthetic resins can also be used such as polyvinyl compounds such as polyvinyl alcohol alone or in conjunction with gelatin. Acetyl cellulose with 19 to 26 percent by weight of acetyl groups and a water-soluble one can also be used Ethanolamine cellulose acetate along with the foregoing Use connections.

As the support used paper, glass, cellulose acetate, cellulose nitrate, POL3 ^r ester ₅ polycarbonates, polyamides, polystyrene or polyolefins.

The photosensitive layers generally contain silver halides such as silver chloride, silver iodide, silver bromide iodide, Silver chloride bromide or silver chloride iodobromide. These silver halides may be neutral, ammonia, or acidic depending on the type of photosensitive desired Materials are made. In this case, batch processes with simultaneous entry of the halide and Silver solution or with inverse enema can be used. Will

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If a mixed silver halide is used, the mixing ratio may be zv / isehen the halogen ions in a proportionate wide range. For example, silver chloride makes up the major part in those types of emulsions that are relatively low sensitivity are particularly fine-grained. In contrast, the silver chloride content is relatively high in the case of emulsion types small. In the case of direct positive emulsions, which are based either on the utilization of the Herschel effect or the solarization effect latent obscuration must be carried out by optical or chemical methods.

Means to increase the overall sensitivity are active gelatine, rock sensitizers such as allyl thiocarbamide, Thiourea or cysteine, selenium sensitizers, reducing sensitizers such as tin (II) salts and polyamines, noble metal sensitizers, like the gold sensitizers, e.g. potassium gold (I) chloride, potassium gold (III) ~ rhodanide, potassium tetrachloroaurate (IIl) - or 2-gold (II) sulfobenzothiazolium chloromethylate or a water-soluble salt of ruthenium, palladium, platinum, Rhodium or iridium, e.g. ammonium chloropalladate (II), Potassium chloroplatinate (II) or sodium chloropalladate (left). Some these sensitivity increasing compounds act depending on Concentration may prevent haze. These sensitizers can be used alone or in combination with each other and sensitize the silver halide chemically, oZ.B. the Korabination- a gold sensitizer with a sulfur sensitizer or the combination of a gold sensitizer with a selenium sensitizer.

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The silver halide can be in a desired spectral range be optically sensitized; cyanine dyes such as zero methine, monomethine, diraethine and trlmethine dyes are used for this purpose either alone or in combination with each other.

Depending on the kind and intended use of the photographic material, its halogenated silver emulsion layers may be used in addition to one or more of the dyes according to the invention, depending on their intended use, a magenta coupler, e.g. 5-pyrazolone, a yellow coupler with an active methylene group contain between two carbonyl groups or a blue coupler of the phenol or naphthol coupler type. Couplers are used, which participate in the coupling reaction with two or four equivalents in the conversion.

The light-sensitive layers, the auxiliary layers such as intermediate layers, Protective layers or undercoating layers, furthermore the transfer layers can all contain a wide variety of known photographic additives Compounds included individually or in combination. Examples of this are stabilizers, e.g. mercury compounds, Triazoles, azaindenes, zinc and cadmium salts, sensitizers such as quaternary ammonium salts and polyethylene glycols, compounds to improve certain layer properties, e.g. glycerine, Dihydroxyalkanes, esters of ethylene diglycolic acid and aqueous Emulsions of polymers, compounds for hardening the layers, such as formaldehyde, halogen-substituted aliphatic carboxylic acids, Chloride disulfonates, bisaziridines and ethyleneimines, casting aids, such as saponin, lauryl or oleyl ethers from poly

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ethylene glycols, organic high or low boiling solvents, such as dibutyl phthalate, tricresyl phosphate, acetone, methanol, Ethanol and ethylene glycol monoethyl ether, antistatic Compounds, deformation preventing substances, ultraviolet absorbing Fabrics, optical brighteners, excessive slip restricting agents, matting agents and agents against reflection and diffusion halo.

A dye according to the invention with a detachable dye residue, which is used together with the listed components of the layer, splits off a diffusible dye when the light-sensitive photographic recording material is developed with a color developer. Examples of color developer substances are developer substances from the class of primary aromatic amines, in particular phenylenediamine and its derivatives, such as N, N-diethyl-p-phenylenediamine, 2-amino-5- (N-ethyl-N-ß- methylsulfonylamidoethyl) aminotoluene, 2-amino ~ 5- (N-ethyl-N-ß-hydroxyethyl) -aminotoluene and N-ethyl-N-co-sulfobutyl-p-phenylenediamine. These color developing agents are used alone or in combination with one another or optionally in combination with a black and white developing agent, for example hydroquinone. These developer substances are generally used in the presence of an alkaline compound, v / ie sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfate and sodium sulfite. The various compounds, which are generally contained together in a single color developer solution, can also be brought into action separately from one another in certain embodiments. You can either use the developer

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substance or the remaining components of a color developer incorporated into either the light-sensitive material or the image-receiving transfer material. To the For example, the color developing agent can be contained in the transfer material which receives the diffusion image; in this case, the color development is carried out by treatment with a alkaline solution.

During color development, the color developing agent is oxidized due to the development nuclei on the halogen silver triggered; the oxidation product reacts with the molecular part A of the dye according to the invention, at the same time a colorless connection is created.

The fixing bath, bleaching bath, 'Bleach-Fix _f etc. which serve to remove developed silver and unreacted silver halide .Can in combination with still other baths are used, such as stop baths, V /' aschlösungen and stabilizing solutions, means for fixing are solvents for Silver halides such as sodium or ammonium thiosulfate; Agents for bleaching the silver can be alkali metal ferricyariide salts, sodium or ammonium salts of iron (II) ethylenediaminetetraacetate.

As described above, the dyes according to the invention are which are capable of splitting off a diffusible dye, characterized in that they are developed during development provide a colorless compound and a diffusible dye with a color developer. Therefore, the invention Dyes far more advantageous and better usable

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- 27 bar as the well-known GDR coupler.

The examples illustrate the invention.

example 1 Preparation of the dye of the formula (1)

41 g of p-dodecyl-a- (paminophenylthio) acetophenone were added to 300 ml of 10 percent hydrochloric acid dissolved and diazotized with 7.5 g of sodium nitrite while cooling. After decomposing excess nitrous acid with sulfamic acid, the resulting diazonium salt solution was cooled in 1 liter of 10 percent sodium hydroxide solution added dropwise, the 25 g of 3-methyl-5-pyrazolon-1- (p-sulfophenyl) contained and adjusted to pH 7 to 8 -was. After the addition is complete the resulting crystals were filtered off and off 1.8 liters of 70 percent aqueous ethanol recrystallized. Yield 70 percent.

Example2 Preparation of the dye of the formula (3)

78 g of n-dodecylsulfamido-a- (p-aminophenylthio) acetophenone were dissolved in 800 ml of pyridine. This solution was at 10 to 20 ⁰ C in the course of 20 minutes with 119 g of 3-A ^l - ( ^z * "~ N-ethyl-N- ^ω · sulfoäthylaminophenylimino) -1'-naphtho-quino-2 ¹ -carbamidq / -phthalic anhydride The mixture was then heated to 50 to 60 ° C. until the end of the reaction. The reaction mixture was then poured into water and salted out with sodium sulfate. The resulting precipitate was filtered off and recrystallized from methanol. Yield 65 percent.

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■ - 28 -

Example 3

Preparation of the dye of the formula (12) 93 g of Ι-ίρ-Ζ ^ -Ο-ρ- "sulfophenyl-3-methyl-5-pyrazolyl) -azc7-phenyl} -5-tetrazolylsulfenyl chloride were dissolved in 500 ml of anhydrous chloroform and 7.2 g of cyclopentanone were added. The mixture was stirred for 24 hours. The chloroform and excess cyclopentanone were then distilled off under reduced pressure. The yellow caramel-like mass obtained was dissolved in 0.1 μm sodium hydroxide solution. The homogeneous solution obtained was adjusted to pH -Value from 5 to 7 and salted out with sodium chloride, a yellow crystal mass was obtained. The crystal mass was filtered off and recrystallized from acetonitrile. The compound "was obtained in yellow platelets. .

Example 4

For the manufacture of a direct positive imaging photographic Color recording material were on a cellulose triacetate pad the following three casting solutions applied and dried:

(1) 8.0 g of the dye of the formula (5) were dissolved in 30 ml of 1 n sodium hydroxide solution and the solution was made up to 100 ml with water. This solution became 1 kg of a red-sensitive silver bromide emulsion added, which contained 70 g of silver bromide; then was with aqueous citric acid solution on a Adjusted pH value of 6.7.

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(2) A solution prepared in (1) with 8.0 g of a dye of the formula (8) became 1 kg of a green-sensitive silver bromide emulsion added, which contained 70 g of silver bromide; then the pH was adjusted to 6.7.

(3) One prepared according to (1) with 8.0 g of the dye of the formula (1) Solution became 1 kg of a blue-sensitive silver bromide emulsion added, which contained 70 g of silver bromide; then the pH was adjusted to 6.7.

The three different light-sensitive layers were back exposed a wedge with blue, green and red light and developed for 10 minutes at 20 ⁰ C in the following developer solution: N-ethyl-N-hydroxjiithyl-p-phenylenediamine 2.5 g Katriumsulfit (anhydrous) 2 , 0 g

Hydroxylamine hydrochloride 1> 0 g

Sodium carbonate (honohydrate) 82.0 g

Potassium bromide 2.0 g

Water made up to 1 liter

After the development, the removal of the silver, the fixing, Washing and drying carried out in the usual way.

The sample exposed to blue light showed a sharp blue positive image, the sample exposed to green light a sharp green one Positive image and the one exposed with red light a sharp red positive image.

409841/0813

As stated, you can according to the invention using a conventional negative emulsion with halogen silver directly come to a colored positive image. That means with others Words that a direct positive working photographic recording material can be produced in a simple manner, and it will be understood that the dyes according to the invention are of great benefit for the production of direct positive layers of these Have kind.

Example 5

1 g of the dye of the formula (i) was dissolved in a mixture of 1.5 ml of dimethylformamide and 7.5 ml of triethylamine. This solution was mixed with 20 ml of a 5 percent aqueous gelatin solution. After the solution had been homogenized, it was adjusted to a pH of 6.7 with aqueous citric acid solution. In a mixture of 10 ml of dibutyl phthalate and 30 ml of ethyl acetate, 7.0 g of the purple coupler 1- (2,4,6-trichlorophenyl) -3 -? 3 ~ Z ^C '~ * (2,4-di-tert. - aray! phenoxyacetamide) _ / ~ benzamidqj- -5-pyrazolone dissolved. This solution was added to a mixture of 30 ml of 5 percent aqueous gelatin solution and 10 ml of 5 percent solution of alkanol B (a sodium alkylnaphthalenesulfonate) and the resulting mixture was emulsified. The previously prepared emulsion with the dye of the formula (1) and the emulsion containing the magenta coupler were added simultaneously to 1 kg of a green-sensitive bromiodide silver emulsion. The mixture obtained was applied to a cellulose triacetate base and dried.

409841/0813

A sample of this film material v; urde behind Einein wedge to white light exposed and escape disgusted 10 minutes at 24 ⁰ C in the following developer:
Sodium sulfite (anhydrous) 2.0 g

N ~ ethyl-N-ß-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.0 g

Sodium carbonate (monohydrate) 50.0 g

Potassium bromide - 0.9 β

Sodium hydroxide ■ · 4.0 g

Sodium hexametaphosphate -. 0.5 ε

Benzyl alcohol 4.0 ml

Water made up to 1 liter. Bleaching and fixing were done as usual.

The finished test strip showed an all-over exposure Surface uniform blue filter density, from which it can be seen that the dye of the formula (1) according to the invention as an agent for Masking for the. Purple coupler can be used.

Examples

This example shows that in an ordinary Haze induction occurring in color couplers is reduced, v; erin a dye according to the invention is used as a masking agent. It is also shown that the application of such a Dye to improve image sharpness and the finest Causes details of the image.

In order to make a comparison with the photosensitive used in Example 5 To be able to carry out material, the procedure was as follows:

409841/0813

In a mixture of 10 ml of dibutyl phthalate and 30 ml of ethyl acetate were solved:

1,2g 1- (2,4,6-trichlorophenyl) -3-i3-Za- (2,4-di-tert-amylphenoxyacetamido) benzamide) ^ / -4- (4-methoxyphenylazo) -5-pyrazolone and 7.0 g of 1- (2,4,6-trichlorophenyl) -3-13-Z- (2,4-di-tert-amy! Phenoxyacetamide ^ benzamide / f-5-pyrazolone.

The resulting solution was in a colloid mill with 15 ml emulsified with a 5 percent solution of alkanol B. The resulting Emulsion was added to 1 kg of a green-sensitive silver bromide emulsion. The mixture was placed on a cellulose triacetate pad applied and dried. A sample of this material and a sample of that prepared according to Example 5 The material was exposed to white light behind a wedge and in the developer specified in Example 5 at 24 ° C. for 10 minutes developed. Bleaching and fixing were carried out as usual.

The results showed that the haze value for the material according to Example 6 was 0.25, while for the material according to Example 6, the haze value was 0.25 Example 5 the haze value was 0.40. This proves that the inventive Dye works excellently as a masking agent. In addition, that prepared according to Example 6 showed Material a better reproduction of fine picture details and a better sharpness.

Example 7

The materials for a color diffusion transfer process were manufactured as follows:

1.) Red-sensitive layer: In a mixture of 2 ml of dimethylformamide and 1.0 ml of triethylamine were 2 g of the dye

409841/0813

Formula (3) solved; this solution became 20 ml of a 5pro: · .entigen Gelatin solution added. After thorough mixing, the solution was made up with a 20 percent solution of citric acid adjusted to a pH value of 6.5. The resulting solution became 100 g of a red sensitive one Bromoiodosilver emulsion was added, the mixture on a cellulose triacetate support applied and the layer dried

2 net. The area concentration contributes 15 rag of silver per 100 cr.

2.) Interlayer: A 10 percent solution of photographic gelatin with a Layer thickness of (dry) 2 µm applied and dried,

3.) Green-sensitive layer: One as in 1.) using The solution prepared by 2 g of the dye of the formula (2) was added to 100 g of a green-sensitive silver bromide emulsion. This mixture was applied over the second layer with a surface concentration of (converted) 15 mg silver per 100 cm applied and the layer dried.

4) Intermediate layer: \\ ^r Ie at 2) was above the green-sensitive layer, a gelatin layer of (dry) 2 to applied.

5.) Blue-sensitive layer: a solution of 2 g of the dye of formula (1) was prepared as described under 1.) and added to 100 g of a blue-sensitive silver bromide emulsion. This mixture was applied to the fourth layer with a surface concentration of (converted) 20 mg of silver per

409841/0813

100 cm applied and dried.

6.) Top layer (protective layer): A 10 percent solution of photographic gelatin was mixed with 1 mg of mucochloric acid per 100 ml added and applied to the fifth layer with a thickness of (dry) 2 μm and dried. The multilayer photosensitive material produced in this way was behind a wedge with 3 filter strips in the Colors blue, green and red exposed.

The transfer material intended to receive the colored diffusion image was produced by applying a gelatin solution containing 2 percent by weight trimethyllaurylammonium chloride to a transparent cellulose triacetate support. A solution of the following composition was used for development:
Sodium sulfite (anhydrous)
Potassium bromide
Sodium carbonate anhydrous

4-Amino-N-ethyl-N-ß-hydroxyethylaniline hydrochloride

10 percent solution of sodium hydroxide made up to water

This solution was introduced between the layers of the two superimposed materials. After 3 minutes standing at 22 ⁰ G under slight pressure to remove the developing solution and the transfer of the dye image by vigorous was ex-.quetschen effected with a squeegee. This resulted in

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2 G 1 G 40 G 10 G 22nd ml 1 Liter.

'- 35 -

the sheet for taking up the diffusing dyes is negative Image of the colored stripes in the colors yellow, purple and blue-green. After treating the multilayer photosensitive material with the usual solutions for removing silver and fixing it showed up on the originally photosensitive Get a positive image of colored wedge strips in shades of blue, green and red. This easy way to get material one has both the negative and the positive image.

409841/0813

Claims (1)

P__a ten tan s τ- r _ .. JL ₁ C, h ^ g, 1. Dyes, which in the development of an exposed, - with provided at least one halogen emulsion layer photographic recording material in a color developer split off a diffusible dye, thereby characterized in that the dyes of the general formula I A-D (I) correspond, in which A denotes a molecular residue, which during development with the oxidation product of the color developing agent reacts to form a practically colorless compound, and D means a molecular residue which, after cleavage, is a containing diffusible, water-solubilizing groups Dye results. 2. Dyes according to claim 1, characterized in that the molecular residue A has an active methylene group to which the molecular residue D is directly bound, 3. Dyes according to claim 2, characterized in that the molecular residue A within its association adjacent to the active methylene group has an atomic group which corresponds to the Methylene group has an activating effect. 4. Dyes according to claim 3, characterized in that the activating group is a -CO-, -SO ^ -, -SO ₃ H, -CN or a quaternary ammonium group. 409841/0813 5. Dyestuffs according to Claim 1, characterized in that the molecular residue A of the general formula R-CH- corresponds to, in the Y is a hydrogen or halogen atom, an alkyl or aryl group, a heterocyclic radical, the group -Ö'lp in which R _{1 is} an alkyl or aryl radical, a heterocyclic:! ·· Re: -: t, an acyl radical or the Radical -SOpRp and Ii., -, a / ¹ IlIyI- or aryl radical or a heterocyclic Rr-.-.it. represents, or Y denotes the group -COOR, where R, _{shares an AIkyireet dsv S} - and R is the group -COR ^, where R ^ is a hydrogen "·· -torn, a hydroxyl group, a group -R, -OFi, -N (R) p, -NHp or -1-" HR, a group - CR. -SO _{0 is} Rc or -SORn, - ,. ^r obei Rr HO CJ J, j NH is a hydrogen atom, the group -R ₀ * " ⁰ ^ ₀ or - ^ j (R) _o , or R-dia is a group -CN or -N (Rg) ₃ , where Hq is a hydrogen atom or the group E and R denotes an alkyl, aryl or heterocyclic radical, or zv: ei radicals R _Q together with the nitrogen atom to which they are attached form a heterocyclic ring. 6, dyes according to claim 1, characterized in that the molecular residue A of the general formula Z GH » \ I V ^ / corresponds, in which Z represents a group of atons leading to Construction of a carbocyclic or heterocyclic ring . 409841/0813 - 35 are required. 7. Dyes according to claim 1, characterized in that the molecular residue A of the general formula corresponds, in which Z * denotes a group of atoms which are necessary for the construction of a carbocyclic or heterocyclic ring. 8. Dyestuffs according to Claim 1, characterized by one of the following formulas: (.1) c H ⁼ * r - ^CH " ^c - 0 = c SO ₇ Ka. N-N N-N _0H NHCO · .- A098A 1/0813 • COOKa CH -NHSO - 25 ² COCH -S ~ / ~ \ -NHC0 NHCO- CH 0 ₂ - SO ₂ ^ v / Vv— KHCOC ·· CO
H Il COOK COOK N .- N Il N-N 'COHH- "NIICOCH CH COOH -CIL -cn miso, cn .. 409841/0813 N. H ₂ C CH C. ο Il ο CHL, CH ₂ -S - C N - Ii CH. S = C-N CH-S NC I Il - IT KHCO- C = N Λ -Αι -Oil ' com-f \ - Ka N - C-C = O -N CH ₁ OH OH, 409841/0813 NH ₂ ο II -O- C. NaO ^12? -5 ^ CH-S- / - w »ο - σ ^s Il ο ■ ₁ "lip,
12 2 ■ KHCOCK CH ₂ -COKH- / ~ \ - Μϊ ■ - COCK-N-N S "Ο IJ - K r / ^ - CH -Ο- COOH ■ ι it 0 β C 2ί • V 00Η r COCII ~ V KO λ -0iL 409841/0813 N ~ _Ϊ1 -CH-C- CH 9. A method of image formation by the dye diffusion transfer method using a photographic one provided with at least one halogen silver emulsion layer Recording material, characterized in that in one or more of the emulsion layers a dye of the general Formula I. A-D. (D is contained, in which A denotes a molecular residue, which in the development with the oxidation product of a color developer substance reacts to form a practically colorless compound and D denotes a molecular residue which, after splitting off gives a diffusible, water-soluble dyestuff containing capping groups. 409841/0813 10. The method according to claim 9 »characterized in that the molar ratio of halogen silver to the dye of the general Formula (IJ1: 0.07 to 1: 0.7 is. 11. The method according to claim 9, characterized in that the molar ratio of halogen silver to the dye of the general Formula (1) is 1: 0.1 to 1: 0.4. 12. The method according to claim 9 »characterized in that the Molar ratio of halogen silver to the dye of the general formula C1) is 1: 0.01 to 1: 0.1 and that at the same time one other coupler substance is present in the usual amount. 15. The method according to claim 9, characterized in that the molar ratio of halogen silver to the dye of the general Formula (I) is 1: 0.03 to 1: 0.07 and that at the same time one other coupler substance is present in the usual amount. 14. Photographic silver halide emulsion, characterized in that that they are a dye of the general formula I. A-D (I) contains, in which A means a remainder of the molecule in the development reacts with the oxidation product of a color developing agent to form a practically colorless compound and D denotes a molecular residue which, after cleavage, contains a diffusible, water-solubilizing group containing dye results. 409841/0813 15. Photographic silver halide emulsion according to claim 14, characterized in that the molar ratio of silver halide to the dye of the general formula (I) 1: 0.07 to 1: 0.7. 16. A photographic silver halide emulsion according to claim 14, characterized in that the molar ratio of silver halide to the dye of the general formula (I) 1: 0.1 to 1: 0.4. 17. A photographic silver halide emulsion according to claim 14, characterized in that the molar ratio of silver halide to the dye of the general formula (I) 1: 0.01 to 1: 0.1 and that at the same time another coupler substance is present in the usual amount, 18. A photographic silver halide emulsion according to claim 14, characterized in that the molar ratio of silver halide to the dye of the general formula (I) is 1: 0.03 to 1: 0.07 and that at the same time another coupler substance is present in the usual amount. 409841/081 3