DE1282455B - Dye developer diffusion process and image receiving layer for carrying out the process - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number:
File number:
Registration date:
Display day:

G03c

German KL: 57 b -5/54

P 12 82 455.4-51 (E 21549)

August 18, 1961

November 7, 1968

The invention relates to a dye developer diffusion process, in which a recording material with differently sensitized silver halide emulsion layers and dye developers imagewise exposed, developed with an alkaline solution and at the same time for diffusion the non-oxidized dye developer is brought into contact with an image-receiving layer, and an image receiving layer for carrying out the method.

It is known to use dye developer diffusion processes to produce multicolor images (British Patent 804,971). In the known process, photographic recording materials, the one or more silver halide emulsion layers and a corresponding one Have a number of layers containing diffusible dye developers, d. H. Compounds that represent the chromophoric system of a dye and the developing principle of a Containing silver halide developing compound, exposed, whereupon the latent image obtained with the help an alkaline solution is developed. When exposed to the alkaline solution, the dye developers become oxidized in the same place as the silver images. These are oxidation products relatively non-diffusible and therefore remain in the recording material, while those in the layers unoxidized dye developer remaining in imagewise distribution due to diffusion an image receiving material superimposed on the photosensitive recording material is transferred, whereby a positive color image is obtained.

The quality of the color images obtained depends essentially on the extent to which the dye developers are fixed in the exposed (negative) image parts of the emulsion layers during the development reaction. If non-oxidized dye developers remain in the fully exposed, negative image parts, which correspond to the high or sharp lights of the recorded object, they are transferred to the image-receiving layer together with the unreacted dye developer substances in the positive areas. Color copies are produced with high color haze densities (D _mi ,, values).

The disadvantage of the known color developer diffusion processes is that the results obtained with them color images have an undesirably high fog density, a low color saturation, a too low Contrast and insufficient maximum color density.

Dye developer diffusion process as well
Image receiving layer for carrying out the
Procedure

Applicant:

Eastman Kodak Company, Rochester, N.Y.

(V. St. A.)

Representative:

Dr.-Ing. W. Wolff, H. Bartels,

Dipl.-Chem. Dr. J. Brandes

and Dr.-Ing. M. Held, patent attorneys,

8000 Munich 22, Thierschstr. 8th

Named as inventor:

Walter John Weyerts,

Kenneth Clayton Kennard,

John Hamilton Van Camfien, '

Wilho Mathias Salminen, Rochester, N. Y.

(V. St. A.)

Claimed priority:

V. St. v. America December 2, 1960
(73 390),

dated August 22, 1960
(50 932, 50 962, 50 963,
51135, 51136)

These effects are due in part to the insufficient effectiveness of the dye developers, such as des 1,4-bis [/ <- (2,5-dioxyphenyl) -älhylamino] -anthraquinone, for the development of silver halide, as well as the lack of "discernment" of the dye developers for the silver halide they should develop and other factors.

Compared to the only monochromatic color images delivering process occur in the production of multicolored images in which recording materials are used which contain a large number of differently sensitized silver halide emulsion layers and dye developers for the subtractive Color reproduction contain special problems. For example, the development products of an emulsion layer tend to undergo development to effect another emulsion layer. Furthermore, the diffusion of a dye can occur

so-called 630/936

3 4

A further subject matter of the invention is based on a different dye developer or a different one of an image-receiving layer for carrying out the connection in an overlying layer. Also, if necessary, it can be characterized in that it affects the development of a lower layer, which may diffuse in alkaline solution, when the developer solution is exhausted due to diffusible development interrupters and an outer layer. Furthermore, a dye det. contains cash, heterocyclic ammonium salt,
Winders are not sufficiently fixed, so that under "development interrupters" are in the rough transfer to a color image of another menu of the invention such compounds are not understood and thus color contamination is not able to be prevented in alkaline solution. Also, a dye from a receiving layer on an adjacent or winder may develop some silver halide grains from a "wrong" adjacent developing silver halide emulsion layer, causing the genide emulsion layer to diffuse, causing an insufficient amount of that dye to develop and develop of the non-exposure winder is available for the transfer and the 15 th silver halide is interrupted, in the counter-received color images are not saturated. In addition to "antifoggants" which, for example, can only be a magenta dye developer capable of restricting the development of silver halide grains some red-sensitive silver halide grains.

The magenta dye used for the interruption of the development amount of the development interrupters used to produce the red color image 20 are therefore not available is reduced with the known antifoggants, such as e.g. B. and the red colors appear unsaturated. 6-nitro benzimidazole, not the Z described delay reduction> _ma .r losses of the color images exposed silver halide, but can also have other root cause. The development of exposed silver halide also in other photographic processes will lead to confusion. The development of the silver halide emulsion used in the development of the invention in the diffusion process strives to develop only the exposure interrupters interrupting the development of the third portions of the emulsion. If both exposed and unexposed silver, however, no appropriate precautions are taken. The complete interruption of the design, so the development also proceeds in the non-winding, especially in the unexposed exposed areas, which leads to the formation of an area, which leads to a larger amount of color "development fog". In order to suppress this veil of substance developers for the transfer to the image, so-called receiving layers are usually available. In this way anti-fogging agent is used, which increases the maximum density of the emulsions,
or added to the developer solutions or both 35 The complete interruption of the development can be. In the case of direct-positive color images, in order to avoid loss of color density, it is important to use dye developers, because the unexposed silver halide fusion process causes the development to form under the strongly alkaline conditions of the development fog in the unexposed areas, so that the developer solution is slightly reduced thereby specifying the dye developing agents, the 40 color developing agents should be specified in the unexposed area. It is therefore less rich to be set and can no longer be transferred to the dye developer for diffusion onto the image-image-receiving layer,
receptive layer available, and the resulting Ver-images, which act as development interrupters, do not have the desired density. Bonds are either mercaptoazoles, which are the object of the invention, a dye-developing alkaline solution are diffusible, or azoles, denote diffusion processes, which are produced in alkaline solution with formation of alkaline solution diffusible mercaptoazoles with improved quality in the development of direct-positive images and in which the influences occurring in the known multi-hydrolyze or iodides, which occur in alkaline solution dye systems, as well as compounds from which individual dye developers and other substances 50 iodides are made free in alkaline solution, are reduced or compensated for are diffusible in alkaline solution,
The image-receiving layers, the development reduction in the color quality and the formation of an interrupter can result from linear poly-development fog in the unexposed beamines; Proteins, e.g. B. gelatin; Polyvinylpyrrolicides avoided or kept to a minimum, poly- (4-vinylpyridine); Polyvinyl acetate; Poly is set. vinyl alcohol, cellulose acetate, polyvinyl salicylal; The subject of the invention is based on a partially hydrolyzed polyvinyl acetate, methyl cellulose, dye developer diffusion process, in which a regenerated cellulose, carboxymethyl cellulose and recording material with different sensitivities are available.

developer exposed imagewise, with an alkaline The light-sensitive recording material can

Solution developed and at the same time for diffusion of the possibly with the image receiving material

non-oxidized dye developer with an image-common whole, the support

The receiving layer is brought into contact with it, is such that it is sensitive to light

and is characterized in that an image layer can be stripped off. Between the

receiving layer with a hi alkaline solution image receiving layer and the other layers

If a diffusible development disruptor is used, a special stripping layer may also be present

will. · - be to facilitate separation.

The invention achieves that the maximum density of the color copies is increased without the color fog density is increased significantly, and that color staining and a reduction the color quality can be avoided or reduced to a minimum.

While when using common anti-fogging agents, such as B. benzotriazole and 6-nitrobenzimidazole, in the alkaline developer solution a loss of color density due to the formation of a haze cannot be avoided, because even in the presence of these compounds there is a not insignificant loss of density accompanied overall fog occurs, the dye developer images show a vastly increased maximum density when developing 'the exposed emulsion layers are interrupted according to the invention by means of the development interrupters mentioned when the negative is practically finished developing.

The latent images of the emulsion layers can be developed quickly, and so can the development The interrupting effect is delayed until the development of the exposed parts of the image is practical is finished. In this way, the development of the unexposed parts of the image and another Development of the exposed parts of the image prevented.

Suitable color developing agents for practicing the method of the invention are those known and usual.

According to one embodiment of the invention, an iodide, an in alkaline solution an iodide-producing compound, a mercaptoazole or an alkaline solution a mercaptoazole-yielding azole is used.

Iodide-releasing development disruptors suitable for carrying out the process of the invention, which, apart from z. B. potassium iodide, are e.g. B. Benzothiazolium methoiodide and bis- (2-amino-5-iodopyridine hydroiodide / mercury iodide.

Azole series interrupters suitable for carrying out the process of the invention are, for example: l-phenyl-5-mercapto-l, 2,3,4-tetrazole; 5-myristoylthio-1 -phenyl-1,2,3,4-tetrazole; 5 - ^ - acetylethylthio-1-phenyl-1,2,3,4-tetrazole; 2-mercapto-5-phenyl-1,3,4-oxadiazole; 2 - mercaptonaphth - (1,2) - oxazole; 2-mercaptobenzoxazole; 2-mercaptobenzothiazole and 2- (2'-dicarbethoxy) ethyl mercaptobenzoxazole.

According to a further embodiment of the invention, an alkaline solution is provided with an antifoggant used.

According to a further embodiment of the invention, the diffusion is preferred in the presence of a carried out onium compound contained in the alkaline solution. This onium compound should be colorless. You can z. B. from a ternary sulfonium compound, a quaternary phosphonium compound or a quaternary ammonium compound.

The beneficial effect of the onium compounds is apparently based on the fact that they react with the dye developers to form salts and that the salt formation has a beneficial influence on the solubility and diffusivity of the Dye developer exercises. Presumably, the onium compounds temporarily delay migration the dye developer, so that the original diffusion rates of the dye developer be reduced, but larger amounts of dye developer from less exposed Parts of the image are transferred.

The use of onium compounds in photographic technology is known per se. For example, in the USA. - Patent 2,648,604 the use of non-surface-active quaternary ammonium compounds as development accelerators and in the USA patents 2 271622, 2 271623 and 2 275 727 the use of quaternary ammonium, quaternary Phosphonium and tertiary sulfonium compounds as sensitizers for silver halide emulsions described. In the known method, the silver density is in the negative as a result Presence of the onium compounds increased. However, the enlargement occurs in the exposed Surfaces of the negative, and it is due to the property of the onium compounds, a To sensitize emulsion or to speed up the development.

In the method of the invention, on the other hand, there is an increase in density in the positive one Image, being primarily the result of increased transfer of the dye developer from the unexposed image parts of the recording material. The fact that the onium compounds would cooperate with the dye developers in such a way that they would transfer the Enlarge the dye developer from the unexposed areas of the recording material not to be expected from the previously known use of such compounds.

Particularly advantageous results are obtained when using quaternary ammonium compounds obtain.

Leave suitable quaternary ammonium compounds for carrying out the process of the invention For example, they can be represented by the following formulas:

-N ⁺ -
R.

"Ζ-χ

N ⁺

N ⁺

where R is an organic radical, Y is an anion, ζ. B. [OH], Br, Cl ",

CH ₃ - / V-SO ₃ -

and Z is equal to the atoms necessary to complete a heterocyclic ring.

Examples of suitable salts of the formulas (1), (2) and (3) are:

Tetraethylammonium bromide,

N-ethylpyridinium bromide,

N, N-diethylpiperidinium bromide,

Ethylene-bis-pyridinium bromide,

1 -ethylpyridinium bromide,

1-phenethyl-3-picolinium bromide,

Tetraalkylammonium salts,

Cetyltrimethylammonium bromide,

Polyalkylene oxide bis quaternary ammonium salts, like for example

Polyethylene oxide-bis-pyridinium perchlorate,

S-methyl ^ -äthylisoquinolinium bromide,

3-methylisoquinium methyl p-toluenesulfonate,

l-EthyW-methyM-phenäthylbenzimidazolium bromide,

5,6-dichloro-1-ethyl-2-methyl-3- (3-sulfobutyl) benzimidazolium betaine and

Pyridinium salts.

Ternary sulfonium and quaternary phosphonium compounds suitable for practicing the process of the invention can be expressed by the following formulas:

Forming diffusible methylene bases can be represented by the following general formula:

R - N (--CH-CH) ₁₁ = C-CH ₂ R '(6)

(R) ₃ SX

(R) ₁ PX

(5) ίο Here, D means the formation of a heterocyclic Ringes required non-metallic atoms, the ring being one or more reactive ones - Contains CHoR 'groups or methyl groups and wherein the remaining nuclear hydrogen atoms may optionally be substituted, d. H. which, for example, lead to the formation of a quaternary ammonium salt, which differs from pyridine, quinoline, benzoquinoline, benzoxazole, benzselenazole, thiazole, Benzthiazole, naphthothiazole, benzimidazole, isoquinoline, etc., required atoms; R. an optionally substituted alkyl, aryl or aralkyl radical of the benzene series, preferably with alkyl radicals from 1 to 4 carbon atoms; R 'is a hydrogen atom or one of the above represented by R designated residues; X is a hydroxyl ion or an acid anion, such as, for example, a Br-, CH3SO.4 or

SO ₃ "ion

where R is an organic radical, ζ. Β. an alkyl, aralkyl or aryl radical, and X is one Anion, ζ. B. OH, Br, Cl or toluenesulfonate ion. is.

Examples of suitable tertiary sulfonium and quaternary phosphonium compounds are:

Lauryl dimethyl sulfonium p-toluenesulfonate,
Nonylditnethylsulfonium-p-toluenesulfonat,
Octyldimethylsulfonium-p-toluenesulfonate,
Butyldimethylsulfonium bromide,
Triethylsulfonium bromide,
Tetraethylphosphonium bromide.
Trimethylsulfonium p-toluenesulfonate.
Dodecyldimethylsulfonium p-toluenesulfonate,
Decyldimethylsulfonium p-toluenesulfonate and
Ethylene-bis-oxymethyltriethylphosphonium bromide.

The onium compounds can be used as a hydroxide or as a salt. Will the onium compounds used as a salt, the anion can be any acid anion. Particularly good results are obtained when the onium compounds are used as bromides.

According to a further embodiment of the invention, the onium compound is a heterocyclic Ammonium compound which can form a methylene base diffusible in alkaline solution, preferably a pyridinium salt is used.

Particularly suitable heterocyclic quaternary ammonium compounds for carrying out the process of the invention, those in alkaline solution and /; = 0 or 1.

These quaternary ammonium compounds can be used alone or together with other onium compounds be used.

The onium compounds are advantageously either in the developer solution and / or the image receiving layer is used. But they can also be used in the photosensitive recording material be accommodated. In the presence of a hydroquinone derivative, this has an obvious effect together with the quaternary ammonium compound. Effects are achieved which become clear differ from those effects with a hydroquinone derivative or a quaternary ammonium compound be obtained alone. The color images obtained in this way show a noticeably lower color Color pollution as well as improved color saturation, density and contrast.

Pyridinium salts have proven to be particularly advantageous ammonium compounds of the formula (6) given with 1 to 3 active methyl groups (—CHoR ”groups) in the 2-, 4- and / or 6-position of the pyridinium nucleus, where R 'z. B. an alkyl group with 1 to 4 carbon atoms or a substituted one Alkyl group having 1 to 4 carbon atoms, such as an oxyalkyl group. The positions 3 and 5 of the pyridinium nucleus can optionally be substituted.

Typical suitable salts of the formula (6) are, for example:

1 -Benzyl-2-picolinium bromide. -

1- (3-bromopropyl) -2-picolinium-p-toluenesulfonate. 1-phenethyl ^ picolinium bromide.

l -; - phenylpropyl-2-picolinium bromide. 2,4-dimethyl-1-phenethylpyridinium bromide. 2,6-dimethyl-1-phenethylpyridini umbromide.

5-ethyl-2-methyl-1-pheneth} 'pyridinium bromide, 2-ethyl-1-phenethylpyridinium bromide,

l- [3- (N-pyridinium bromide) propyl] -

2-picoliniiim-p-toluene sulfonate,
Anhydro-lH-sulfobutyl ^ -picolinium hydroxide, l - (/ i ~ naphthoylniethyl) -2-picolinium bromide,
! - (// - Phenylcarbamoyloxyäthyl) -

2-picoliniunibromide,
1 - methyl-2-picolinium-p-toluene-sulfonate,
lP] ethyl-2,4,6-trimethylpyridinium bromide,
l-phenethyl-4-n-propylpyridinium bromide,
4-y-oxypropyl-1-phenethylpyridinium bromide

and
ln-heptyl - ^ - picolinium bromide.

A number of pyridinium salts of formula (6) form methylene bases which are in alkaline solution are not sufficiently diffusible. These are not suitable for the method of the invention.

According to a further embodiment of the invention, a recording material with a colorless, water-insoluble, in alkaline solution diffusible Hydroquinonderival used.

Hydroquinone derivatives suitable for carrying out the process of the invention are practically colorless and insoluble in water, but soluble in alkaline solution and through organic colloid layers, such as for example gelatin layers, diffusible. Examples are:

Phenylhydroquinone.

2'-oxyphenylhydroquinone,

Phenoxyhydroquinone,

4'-methylphenylhydroquinone,

1,4-dioxynaphthalene,

2- (4-aminophenethyl) -5 ~ bromohydroquinone,

2- (4-aminophenyl) -5-methylhydroquinone,

4'-aminophenethylhydroquinone,

2,5-dimethoxyhydroquinone,

2,5-dibutoxyhydroquinone,

m-xylohydroquinone,

Bromohydroquinone,

3,6-dichlorohydroquinone,

2-dimethylaminomethyltolohydroquinone,

2-cyclohexylhydroquinone,

Sec.Butylhydroquinone.

2.5-dichlorohydroquinone,

2,5-diisopropylhydroquinone,

2.5-diiodohydroquinone.

3-chlorotoluhydroquinone,

Tetrachlorohydroquinone.

2,5-diphenylhydroquinone,

2,5-diresorcylhydroquinone,

2,5-dioctylhydroquinone and

Dodecyl hydroquinone.

The hydroquinone derivative can be in one of the layers of the recording material or in the image-receiving layer be accommodated. The addition of the hydroquinone derivatives to the developer liquid is less desirable because the hydroquinone derivatives are unstable and easy to move in such solutions oxidize.

The hydroquinone derivatives become the emulsion layers. Top layers and intermediate layers forming hydrophilic organic colloidal binders, preferably in the form of dispersions added.

The hydroquinone derivatives can be used in the recording material in an amount of 10 to 100 mg or more per 0.0929 m ^{2 of} substrate area. It may be desirable to prepare a complex compound of the hydroquinone derivative in a known manner by reaction with sulfur dioxide and to incorporate this complex into the top layer or coating layer, an outer emulsion layer or another layer of the photosensitive recording material. These complexes are usually more soluble and more stable than the hydroquinone derivatives themselves.

In an advantageous embodiment of the method of the invention, a photosensitive, photographic recording material consisting of several differently sensitized, d. H. light-sensitive to different areas of the spectrum, especially red-, green- and blue light-sensitive silver halide emulsion layers is constructed and the dye developer, »which is related to the sensitivity of the corresponding Emulsion layer are preferably subtractively colored, as well as hydroquinone derivatives Contains, exposed and in contact with the image receiving layer of the image receiving material, which the Development interruptor contains, with an alkaline, preferably an antifoggant containing Solution moistened. The diffusion transfer is preferably carried out in the presence of a onium compound diffusible through the layers in alkaline solution.

The alkaline solution used to develop the exposed material should be strongly alkaline be to increase the developer activity of the dye developer as much as possible.

The development of the photosensitive recording material, i. H. treatment with a alkaline activator solution, can be done in a camera if using destructible containers Developing solution as shown in Fig. 1 was used will. In such a case it can be advantageous to use an alkaline developer solution use a thickener such as carboxymethyl cellulose or oxyethyl cellulose high viscosity. The developer solution can be applied to the exposed recording material but can also be applied by spraying, dipping, coating by means of rollers, etc. The alkaline developer solution can optionally also be replaced by water or an aqueous solution a pH of 7.5 or less if the image receiving material used is alkali or contains a substance from which alkali is released.

Several successively exposed areas of a strip of a recording material can with the same alkaline developer solution and the dye developer images in one Transfer operation to a strip of the image receiving material be transmitted.

In the accompanying drawing, FIG. the implementation of the dye developer diffusion process according to the invention in the scheme.
According to FIG. 1, step 1, a photosensitive recording material consisting of a layer support 10, layers 11, 12 and 13, the subtractively colored alkali-soluble blue-green, magenta-red or. Contain yellow dye developers, light-sensitive

809 630 / ""

Lichen silver halide emulsion layers 14, 15 and 16 which oppose red, green and blue light, respectively are sensitive, and intermediate layers 17 and 18, which are the green sensitive emulsion and its adjacent subtractively colored purple color developing layer from the other layers and one Separate hydroquinone compound-containing cover layer 19 is used. The image receiving material consists of a substrate 20 and an image receiving layer 21 which are a development stop and which may contain an onium salt.

The image receiving material is with respect to the photosensitive recording material in a . placed in such a position that it picks up color images by diffusion from the photosensitive Recording material are transferred. Between the photosensitive recording material and the image receiving material is a destructible container 22 with alkaline developing solution, which are a quaternary ammonium salt and a silver halide solvent, and preferably contains an antifoggant. When the container 22 is destroyed, for example by passing through the Arranged by the rollers of a camera, the contents of the container are distributed evenly over a certain area of the light-sensitive ■ recording material. The solution penetrates the Layer 19, dissolves the practically water-insoluble, alkali-soluble and diffusible hydroquinone derivative and transports it to the underlying layers, where the latent silver halide images of the surfaces 23, 24 and 25 developed to silver and the dye developers in those adjacent to areas 23, 24 and 25 Areas can be specified. The unreacted dye developers of the layers 11, 12 and 13 then diffuse image-wise and with the correct contours into the image-receiving layer 21 and form the color images here.

F i g. 2 of the drawing shows a photosensitive recording material in which the Dye developers are located in the differently sensitized emulsion layers 31, 32 and 33 and in which a hydroquinone derivative is contained in the layer 34 furthest from the substrate 30 away.

It may optionally be advantageous in the context of the method of the invention to use a silver halide solvent to use, as opposed to using these silver halide solvents in the known silver halide diffusion processes, the amounts used here are very small are so that during the transfer of the dye developer images practically no silver halide is transferred to the image-receiving layer. At the In the method of the invention, the presence of the silver halide solvent appears to increase the activator properties to change in such a way that a catalytic reduction of the latent image centers of the exposed areas of the negative element occurs. The activator solutions that have a certain dissolving effect Effect on the silver halide tend to have, in particular, in the absence of the Onium compounds to cause more efficient development of exposed silver halide grains. Also, the desired results are not obtained when using the silver halide solvent alone, d. H. in the presence of either the onium compound or the hydroquinone derivative, is used. Beneficial results are obtained when using the alkaline developer solution about 0.5 to 2 weight percent silver halide solvent can be added.

As the silver halide solvent, the usual known compounds are used, such as. B. sodium, potassium and ammonium thiosulfate as well as sodium, potassium and ammonium rhodanide.

In the presence of a silver halide solvent and a hydroquinone derivative, a considerable reduction in color contamination and the color fog density (Dm-in) of the color images is achieved. In the presence of a silver halide solvent and an onium compound, a similar reduction in color contamination and color fog density is achieved, as is a marked improvement in color saturation. Particularly advantageous results are obtained when a silver halide solvent, a hydroquinone derivative and an onium compound are present. In addition, a considerable improvement in the sensitivity of the photosensitive recording material is achieved here.

B e i s ρ i el 1

First, a recording material of the structure shown in Fig. 1 was prepared in which a layer support 10 has been coated with the following hardened gelatin layers: An aqueous gelatin solution and a solution of the cyan color developer 5,8-dihydroxy-1,4-bis - [(^ - hydroxychinonyla - methyl) - äthylaminoanthraquinone] in a mixture of N-n-butylacetanilide, 4-methylcyclohexanone and a wetting agent (sodium alkylnaphthalene sulfonate) were repeated together in one Grind the colloid mill. The dispersion obtained was applied to the support and under Volatilization of the 4-methylcyclohexanone dried (layer 11).

The layer 11 was then sensitized in the red, green and blue regions of the spectrum Gelatin silver bromide iodide emulsion layers 14, 15 and 16 and gelatin interlayers 17 and 16 18 and also the layers 12, 13 and 19 are applied.

Layer 12 was prepared as follows: an aqueous gelatin solution and a magenta color developer ζ - [ρ - (2 ', 5' - dihydroxyphenethyl) phenylazo] - 4 - η - propoxy -1 - containing naphthol Solvent mixture consisting of N-n-butyl acetanilide, cyclohexanone and wetting agent repeatedly ground in a colloid mill. The dispersion obtained was then applied and dried up, whereby the cyclohexanone was volatilized.

Layer 13 was made from an emulsion which was prepared as follows: An aqueous one Gelatin solution and a solution of the yellow color developer 1 - phenyl - 3 - N - η - hexylcarboxamido-4 - [ρ - 2 ', 5' - dihydroxyphenethyl) - phenylazo] - 5 - pyrazolone in a mixture of adipic acid di-tetrahydrofurfuryl ester, ethylene glycol monobenzyl ether and a wetting agent were repeatedly ground together in a colloid mill. The received The dispersion was quenched and washed to remove the ethylene glycol monobenzyl ether. she

13 14

was applied to layer 18 and tetrazole to the activator (experiments 5 and 6) which dries. D ^ ru density not compared with the use To produce the layer 19, a hydroquinone derivative dispersion of the receiving material A was first used in the image of the same development disruptor (experiment 3).
Sets A and B made: '5 Moreover, prevented the use of the same

Development interrupter in the activator (experiment 6)

Approach A ^ j ₆ Development of the outer emulsion layer 16 in

4'-MethyIphenylhydroquinon 136 g such a volume that a high minimum

Methanol 136 ml yellow density (1.23) was obtained in the copy. Development

Di-n-biUylphthalat 272 ml io still held the activator VII neither a development interrupter another antifoggant

The mixture was first to solution (Experiment 2), it was due to a general at 70 "C and then cooled to 40 ⁰ C. Fogging, compared with the use of activator II, which contained an anti-fogging agent (Vera set B _v ' 5 ^sucn 4), a low £> _m «.r density is obtained.

10'Voige gelatin solution 1360 g "The aqueous active ingredients used in the experiments

Water 1360 ml vator baths contained the following ingredients:

Aqueous solution of sodium activator T-

alkylnaphlhalinsulfonat 136 ml AKUvator ι.

20 3.5% highly viscous oxyethyl cellulose,

Approach B was warmed to 4OC. Approach A 4.5% NaOH, 2.0% benzotriazole;

was slowly added to batch B, stirring ... "

became. The resulting solution was then 5 times in rva.or

ground in a laboratory colloid mill. Like activator I + 2.0% 1-phenethyl

Dispersion was made to a weight of 3775 g ^ 5 2-picolinium bromide;

brought, frightened and in a refrigerator ... _mad

kept. Activator 111:

The coating liquid for the preparation of the activator I + 2% 1-benzyl-

Layer 19 was then prepared as follows from the batches C 2-picolinium bromide;

and D manufactured: 30 _{Aküvator IV:}

^{Approach C} as for activator III + 1.0% sodium thiosulfate;

Hydroquinone derivative dispersion .... 3775 e. al * · * \ r

Water 2225 ml activator V:

_ΓΛ . _, ._ "35 like activator II + 0.005% 1-phenyl-

Approach C was heated to 40.degree. 5-mercaptotetrazole;

Approach D activator VI:

10% gelatin solution 3 180 g as activator II + 0.05% 1-phenyl-

Water 12,000 ml of 40 5-mercaptotetrazole;

Mucochloric acid (2.7% ...., _TT

aqueous solution) ... 515 ml activator VII:

3.5% highly viscous oxyethyl cellulose,

Approach D was warmed to 40C. The 4.5% NaOH; 2.0% 1-phenethyl

pH was adjusted to 5.5. 45 2-picolinium bromide;

Approaches I and II were combined and with ... _vm

Water diluted to 22.71. The coating activator obtained viii.

processing liquid was applied as layer 19 such as activator VII + 0.2% nitrobenzimidazole;

borne that about 120 mg gelatin and 40 mg,.

4'-methylphenylhydroquinone on a layer support 50 activator 1λ:

area of 0.0929 m ^{2 was} accounted for. like activator VII + 0.2% benzimidazole;

Samples of the recording material obtained,.

were under a step wedge by red, green activator X.

and blue filters exposed and in contact with those like activator VII + 0.2% imidazole.

Image receiving materials A or C with the active 55

vators II, V, VI and VII (see below) moistened. The image receiving materials used possessed

The image receiving layers were approximately as follows:

2 minutes separated, whereupon the D _min - and D _max - nw « _m « fv, «„ «, _m ♦ -» ia. ■

Values of copies in the usual way using image receiving material A.

of red, green and blue fillers were measured. 6 ° White pigmented cellulose ester substrate

The density values obtained are in the following with a layer containing 300 mg gelatin, 300 mg

Table I compiled under tests 1 to 6. Poly- (4-vinylpyridine) and 15 mg of l-phenyl-5-mer-

A comparison of tests 1 and 2 gives captotetrazole per 0.0929 m ^{2 of substrate surface}

z. B. that in the presence of the developing contained;

Breaker 1-phenyl-5-mercaptotetrazole in the ⁶ S in

Image receiving material a noticeably higher D _m ", - Image receiving material B:

Dfchte was received. The addition of white pigmented cellulose ester substrates also improved

of the development interrupter l-phenyl-5-mercapto- with a layer containing 300 mg gelatin, 300 mg

Poly (4-vinylpyridine), 15 mg of l-phenyl-5-mercaptotetrazole and 100 mg of l-phenethyl-2-picolinium bromide per 0.0929 m ^{2 of} substrate area;

Image receiving material C:

White pigmented cellulose ester support with a layer containing 300 g of gelatin and 300 g of poly (4-vinylpyridine) per 0.0929 m ^{2 of} support area;

Image receiving material D:

White pigmented cellulose ester support with a layer which contained 300 mg * gelatine, 300 mg poly (4-vinylpyridine) and 15 mg 2-mercaptobenzothiazole per 0.0929 m ² support area.

Table I.

Activator Image reception
material Red green Neutral Skaia Red green , 93 blue attempt
No. 0.19 0.20 1.58 1.13 1.55 VII A. 0.21 0.23 blue 1.24 0.94 1.27 1 VII C. 0.19 0.20 0.41 1.97 1.69 1.93 2 II A. 0.17 0.20 0.37 ■ 1.52 1.52 2.07 3 II C. 0.18 0.21 0.25 1.41 1.58 2.13 4th V C. 0.17 0.40 0.24 1.53 2.18 5 VI. C. 0.17 0.20 0.25 1.82 1.83 6th II A. 0.16 0.20 1.23 1.54 1.90 7th VIII A. 0.16 0.21 0.27 1.65 1.95 8th IX A. 0.16 0.21 0.36 1.39 1.83 9 X A. 0.19 0.20 0.41 1.58 1.55 10 VII A. 0.69 1.15 0.51 1.61 2.11 Π I. A. 0.55 0.69 0.41 1.42 1.99 12th I. A. 0.53 0.89 1.72 1.76 2.36 13th I. B. 0.20 0.25 0.95 1.68 2.49 14th I. B. 0.55 0.69 2.32 1.42 1.99 15th I. A. 0.32 0.25 0.53 Ul 2.05 16 II A. 0.20 0.25 0.95 1.68 2.49 17th I. B. 0.19 0.20 0.26 1.58 1.55 18th VII A. 0.21 0.23 0.53 1.24 1.67 1.27 19th VII C. 0.20 0.30 0.41 2.01 1.48 2.20 20th III A. 0.22 0.25 0.37 1.94 1.35 2.14 -21 III D. 0.42 1.40 22nd 0.36 1.15. 1.13 , 91 1.81 [, 97 , 99 , 81 , 79 , 99 , 13 0.94 1.99 1

Experiments 7 through 11 relate to the use of various development interrupters in the activator solution. The results show that when using antifoggants (experiments 7 to 11) more favorable results are obtained than in Experiment 12, in which no antifoggant is in the Activator was present.

In experiments 12 and 14, a negative material was used which had the same structure as the negative materials used in the other experiments, but did not contain 4'-methylphenylhydroquinone in layer 19. The results of Experiments 12 to 15 show that in the presence of 4'-methylphenylhydroquinone a noticeable decrease in the color haze density (D _n H ₁₁ ) is achieved (comparison of Experiments 12 and 13). In addition, the copy of Experiment 13 showed reduced color staining. In the presence of the quaternary salt, reduced color soiling as well as higher color saturation and a reduced fog density were obtained (comparison of experiments 12 and 15). With the simultaneous presence of 4'-methylphenylhydroquinone and quaternary salt, an even greater increase in Dmax and a greater reduction in D _m i, i were obtained (comparison of experiments 13 and 15). The copy of test 15 also showed less color soiling and higher color saturation.

The results of Runs 16-20 show that considerable improvements in D ₁₁ "" and Dmux were obtained when the activator contains an antifoggant and when the image receiving layer contains a development disruptor (comparison of Runs 17-20 with Run 16). The copies of tests 17 to 20 also show a higher color density and less color soiling.

Favorable results were obtained even when the activator did not contain an antifoggant, while the image receiving material has a development stopper and a quaternary compound contained.

Runs 21 and 22 show that, when the development disruptors are used, l-phenyl-5-mercaptotetrazole and 2-mercaptobenzothiazole approximately equally favorable results can be obtained.

Example 2

A recording material as described in Example 1 was produced. Sections of the material were after exposure as described in Example 1, and using the activator IV and image-receiving materials containing poly (4-vinylpyridine) as a mordant, and using image-receiving materials which, in addition to the mordant, those in the following table II listed compounds. The maximum densities of the neutral scale against red, green and blue light were determined. The table shows the changes in the maximum densities (I D _ma x) are given, which were caused by the compounds used.

Table II

attempt
No.

link

Neutral scale blue UA.J +0.10 Red green +0.09 +0.05 +0.07 +0.06 +0.10 +0.08 +0.21 +0.11 +0.03 +0.03 +0.15 +0.15 +0.16 +0.11 +0.05 +0.07 +0.09 +0.07 +0.24 +0.11 +0.04 ' +0.35 +0.12 +0.19 +0.21 +0.32 +0.28 -0.06 + 0.09 +0.18 -0.15 -0.19 -0.08 +0.11 -0.15 -0.07 +0.15 +0.06 +0.03 -0.99 +0.02 +0.06 -0.85 +0.05 +0.03 -1.49 -0.83 -1.19 -1.31

l-phenyl-5-mercaptotetrazole

5-myristoylthio-1-phenyl tetrazole

S-zi-acetylethylthio-1-phenyltetrazole:.

2-mercapto-5-phenyl-1,3,4-oxadiazole

2-mercaptonaphth-1,2-oxazole

2-mercaptobenzoxazole

2- (2'-dicarbethoxy) -ethylmercaptobenzoxazo! ....

Potassium iodide

Benzthiazole methoiodide

Bis (2-amino-5-iodopyridine hydroiodide) mercury iodide

Thiobarbituric acid

Benzothiazole

3-methylbenzothiazole methyl sulfate

Thioacetanilide

7-mercapto-1,3,4,6-tetrazaindene

1 -Methyl-l ^ J ^ -tetrahydro-l ^ S-triazine ^ -thioI l-Cyclohexyl-l ^^. ö-tetrahydro-l ^^ - triazine ^ -thio!

The results obtained from experiments 1 to 10 clearly show the substantial improvement of Dmiij. which is obtained when using development interrupters in the image receiving material. The results of Runs 11 to 17 show that antifoggants either reduce the maximum color density [D _n ,,,,) or only slightly improve it, with other disadvantages. Thus, benzthiazole decreases D _m ,,. R compared to an increased Dm «i value when it is present in the activator (experiments 1, 2 of Table I). Thiobarbituric acid reduces the D _ma ., - value (test 11 of Table II) and additionally causes a yellow discoloration of the copy. Thioacetanilide slightly increases D _mrir , but the copies have an undesirably high color fog density (Dmin). When using the compounds from experiments 15, 16 and 17, very low D _nnx values were obtained.

The quaternary ammonium compounds obtained with heterocyclic methylene bases forming advantageous results are apparently based on their reaction with 2 moles of a quinone (created by the oxidation of a dye or another hydroquinone derivative), whereby an addition product of the quinone in question and the methylene base and a hydroquinone is formed is receded as by James. Sηe 11 and Weißberger (cf. J. of the Am. Chem. Soc., 60, 2084 [1938]) has been shown.

The silver halide emulsion layers and the adjacent layers in the process of The image receiving material used in the invention can be those described in French patent specification 1 205 755 Emulsion additives described, such as. B. noble metal salts, stannous salts, polyamides, optically sensitizing Dyes, mercury and azaind stabilizers, quaternary ammonium salts, polyethylene glycols. Contain plasticizers, hardeners and coating aids.

Claims (7)

Patent claims: 1. Dye developer diffusion process. in which a recording material with different image-wise exposed to sensitized silver halide emulsion layers and dye developer, developed with an alkaline solution and at the same time for the diffusion of the non-oxidized Dye developer is brought into contact with an image receiving layer, characterized in that an image receiving layer used with a development interrupter diffusible in alkaline solution will. 2. The method according to claim 1, characterized in that as a development breaker an iodide, a compound which yields an iodide in alkaline solution, a mercaptoazole or a a mercaptoazole-yielding azole is used in alkaline solution. 3. The method according to claim 1, characterized in that that an alkaline solution is used with an antifoggant. 809 630 936 4. The method according to claim 1, characterized in that the diffusion in the presence an onium compound preferably contained in the alkaline solution is carried out. 5. The method according to claim 4, characterized in that the onium compound is one heterocyclic ammonium compound which is a "methylene base that is diffusible in alkaline solution can form, preferably a pyridinium salt, is used. 6. The method according to claim 1, characterized in that a recording material with a colorless, water-insoluble, in alkaline solution diffusible hydroquinone derivative is used will. 7. image receiving layer for performing the method according to claim 1, characterized in that that they are a diffusible in alkaline solution development disruptor and optionally contains a heterocyclic ammonium salt which is diffusible in alkaline solution. Considered publications:
German Patent Nos. 473,000, 890,755;
U.S. Patent Nos. 2,636,821, 2,725,290;
British Patent No. 804,971;
Journal for Scientific Photographic, 1954, Vol. 49, pp. 1 to 9. 1 sheet of drawings 109 630/934 19. «O Bundeadtucketel Berlin