DE1155333B - Photographic material for the production of multicolor images by a diffusion transfer process employing dye developing agents and carrying out the process - Google Patents

Description

The invention relates to color photography, and is particularly concerned with certain improvements a diffusion transfer method using dye developing agents for manufacture of positive, multicolored images of the in a number of patents and for example in the UK 804,971.

In this process, a photographic material which has silver halide emulsion layers on a support and layers with diffusible dye developer substances (these are dyes, able to develop silver halide) contains, exposed and with an alkaline developer mixture treated. This removes the latent images in the emulsion layers from the dye developing agents developed into silver images, while the oxidation products of the dye-developing substances formed at the same place as the silver images during the development reaction made or set essentially non-diffusible in the colloidal binder of the layers and those in the layers residual, non-oxidized dye developer substances remaining in imagewise distribution essentially with the exclusion of the silver image and the oxidized dye developer on a dem photographic material superimposed image receiving material can be transferred to a positive Provide color image.

When a photographic material is used, the differently sensitized emulsion layers contains, and if subtractively colored dye developing agents in or adjacent to the corresponding emulsion layers are present, the dye-developing substances become during treatment oxidized with the developer liquid and set in the developed areas of the layers and the residual dye developer images remaining in the positive areas in register by diffusion or with correct contours to form a multicolored reproduction on the image receiving material transfer.

When the dye developer images are transferred from a photographic material to the image receiving material that for a certain period of time under unfavorable temperature and humidity conditions has been aged, the color images may sometimes have a lower density, as desired and as judged by the amount of dye developing agent available for transfer could expect.

It is known from a number of publications, oxy- or aminotriaza-, -tetraza- and -pentazaindenes Photographic material

for the production of multicolored pictures for a dye developing agent

using diffusion transfer processes and implementation of the procedure

Applicant:

Eastman Kodak Company,
Rochester, NY (V. St. A.)

Representative:

Dr.-Ing. W. Wolff and H. Bartels, patent attorneys,
Stuttgart N, Lange Strasse 51

Claimed priority:
V. St. v. America, March 27, 1961 (No. 98 292)

Richard William Becker, Rochester, N.Y. (V. St. A.) has been named as the inventor

To add halogen silver emulsions as stabilizers and / or antifoggants. With color photographic Multi-layer material used for the color diffusion transfer process is determined, there has hitherto been no need to add such azaindenes to the individual color-sensitive emulsion layers as well because fogging is not such a problem in the color diffusion transfer method as in black and white photography. For this reason there is also no color photography Multilayer material known with a content of triaza, tetraza or pentazaindenes.

In contrast, the invention is based on the object in a photographic material Making multicolored images by a diffusion transfer process overcome the shortcomings of the known Eliminate materials and, moreover, create a photographic material that can be used for manufacture of dye developer images with improved density is suitable. In addition, the reduction in density should of color images is also reduced when using aged imaging material will.

309 690/228

3 4

According to the invention, this object is thereby achieved. In typical processes, the light-sensitive

solves that at least one emulsion layer contains an oxy- lent material arranged one on top of the other gelatin emulsions or Aminotriazainden, Oxy- or Aminotetrazainden sionsschichten opposite the red, green and or oxy- or aminopentazaindene. blue part of the spectrum are sensitive, and

The inventive design of the photo 5 contains at least one emulsion, preferably in graphic material will have a significantly increased all emulsions, one of the aforementioned azaindic image density obtain. In the Ma connections according to the invention. Next is under each emulterial If a dye developer sub-sion layer is expediently a light-insensitive layer, which is a punch, d. H. a compound that contains both a dye subtractively colored dye developer substance (blue-green is also a silver halide developing agent subordinate to green, magenta or yellow dye developer or adjacent to the silver halide punch), wherein gelatin interlayers the arranged each emulsion layer. The improved middle emulsion layer and its underlying Image density results from each dye developer-dye developer layer from the others Substance in its original, unoxidized emulsion layers and dye-developing agent form. This substance diffuses image-wise on 15 separate layers and one below in detail the receiving layer of the image-receiving material, the hydroquinone derivative described preferably in without other reactants or any of the layers being present. the reaction products of the process hindered to the one support and thereon a receiving layer

will. (which may contain the onium salt) containing

To solve the problem of density reductions of 20 take material is put in such a position, Color images when using aged image - that there are dye images produced by diffusion from the To dissolve recording material, many compounds were transferred to photosensitive material checked but found no success taking a breakable container with the became. Surprisingly, it has been found that alkaline developer fluid served between the two Triaza, Tetraza and 25 mentioned above find. If the container is broken, such as through Pentazaindenes, which in black and white photography carry out the arrangement between rollers in Can be used as an anti-fogging agent, this density- a camera, so that the contents of the container Reduction in color diffusion transfer method- uniformly over a predetermined area of the light can prevent. This property of the Triaza, distributed sensitive material, penetrates the Lö-Tetraza- and pentazaindenes, however, is not a general solution to the emulsion layers, with the consequence that Property of all known antifoggants, such as the latent images in the silver halide to silver developed according to the embodiment and the dye developer substances in show similar attempts. the development areas or

In the following description, characters are made non-diffusing. Not in Resistant, light-sensitive materials are provided, such as dye-developing agents that have undergone reaction developer solutions and variations of the layers also diffuse image-wise and pass winding, which result in the most useful color images, just or with the correct contour on the receiving layer as well as recording materials which are suitable for forming and forming dye images thereon. Diffusion-transferred dye images thereon in a modified photographic material

to record. Furthermore, especially for 40, the dye developing agents can be added to the the dye developer images matched camera and differently sensitized, the azaindene compound developer kits to be discribed. fertilizer-containing emulsion layers incorporated

In a typical process for manufacture, and the hydroquinone derivative can be in one the dye developer image becomes a photosensitive layer which is furthest away from the support, Lich material that several different light 45 be present. This material can be alike sensitive, d. H. opposite different areas are used to make the dye developer images verdes Provide spectrum sensitive silver halide emulsion of better density.

layers and adjacent dye developer sub- What the known (mentioned above), the dye stamps, the diffusion transmitter used with respect to the sensitivity of the developing substances Emulsion layer subtractively colored 50 concerns casting processes, it was found to be partial can, as well as preferably adjacent hydration, due to the ineffectiveness of the dye quinone derivatives having a colored image counter-developing agent as a silver developing agent stood exposed and developed by being with a lack of discernment alkaline developer solution, such as one of the dye developing agents for that silver such, the oxyethyl cellulose halide as a thickening agent, which they should develop and from others keeps, in contact with the receiving layer of the image, in the case of a photosensitive material that receiving material and preferably in the presence of a plurality of differently sensitized emulsions Onium compounds, especially a quaternary layer and neighboring dye developers Salt is moistened to halide the exposed silver substances for subtractive color reproduction Developing 60 in the emulsion layers has to do with the development products of an emulsion and thereby the dye developing agents tend to develop the other emulsions the areas of development to determine what effect. The diffusion of a colored die Dye developing substances in the non-developing substance developing substance from a lower layer Wrapped areas by diffusion imagewise and influenced, for example prevented, are by a Correctly fitting or with the correct contour on the receptor dye developer substance or by another layer can be transferred to a material in an upper or overlying layer multicolored dye developer image from improved layer. A possibly occurring To yield density. Exhaustion of the developer solution by an external

Layer affect the development of a lower layer, and there can be a layer not in that Develop scope like another layer. In particular, a dye developing agent cannot be so sufficient can be determined to prevent them from being transferred to a color image of a different color becomes and the latter is contaminated. Also, a certain dye developing agent can contain some silver halide grains a wrong emulsion layer with the result that an insufficient Amount of that dye developing agent available for transfer and the appropriate Colors are not saturated. Thus, a purple dye developing agent can make some of the red-sensitive ones Silver halide grains develop and become fixed in the process, thereby reducing the amount of material used to produce them of the available purple dye is diminished and the red colors are unsaturated appear. When the below-described hydroquinone derivatives and the azaindenes in the photosensitive Material are present, these adverse effects are less noticeable.

It has already been mentioned that onium compounds are preferred in the formation of dye developer images be used. These materials are especially used with the azaindenes the listed adverse properties of the original process, such as paint contamination, to mitigate. It can be assumed that the onium compounds with salt formation with the Dye developing agents react and that the reduced by their use Color contamination, reduced color waste, and reduced minimum density achieved improvements at least in part on the effect of such salt formation on solubility and diffusivity the dye developer substances are due. It is evident that the Onium compounds actually temporarily delay the change in the color developer substances, so that the original diffusion rates of the dye developer substances are reduced, however, taking more of the dye developing agents from less exposed areas Increase in density. The beneficial effects of the hydroquinone derivatives include one that the color contamination of the dye developer images is reduced, obviously, because they provide a more complete and uniform fixation of the dye developing agents in the Effect development areas.

The "color contamination" usually manifests itself in the copies as the degradation of one or more colors by one or more other colors and may indicate the failure of one or more dye developing agents be due to be sufficiently determined to prevent them from being affected by Areas where they should be specified. The "drop in color" manifests itself as a reduction in the Color quality of the copies and is obviously due to a dye developing agent, the silver halide grains developed in the wrong emulsion layer; for example, the purple dye developing agent develops some red sensitive silver halide grains, causing more of the Purple dye developing agent is set than should be set, and the red colors therefore lack of purple dye, d. H. are less saturated.

Exemplary oxy- and aminotriazaindenes, oxy- and aminotetrazaindenes and oxy- and aminopentazaindenes, which are useful in the emulsions in amounts of about 1 to 12 g per mole of silver halide are as follows:

2,4-Dioxy-6-methyl-1,3a, 7-triazaindene, 2,5-dimethyl-7-oxy-1,4,7a-triazaindene, 5-Amino-7-oxy-2-methyl-1,4,7a-triazaindene, 5-carboxy-4-oxy-1, 3,3a, 7-tetrazaindene, 1,2-bis (4-oxy-6-methyl-1,3,3a, 7-tetrazainden-5-yl) ethane,

l, 2,3,4-tetrakis- (4-oxy-6-methyl-1,3,3a, 7-tetrazainden-2-yl) butane,

2-Amino-5-carboxy-4-oxy-l, 3,3a, 7-tetrazaindene, 4-oxy-6-methyl-l, 3,3a, 7-tetrazaindene, 4-oxy-2-beta-oxyethyl-6-methyl-1,3,3a, 7-tetrazaindene,

5-carbethoxy-4-oxy-l, 3,3a, 7-tetrazaindene, 7-oxy-l, 2,3,4,6-pentazaindene, 2,4-Dioxy-5-methyl-1,3a, 7-triazaindene, 4-oxy-2-gamma-oxypropyl-6-methyl-1,3,3a, 7-tetrazainden,

4-oxy-2- (4-pyridyl) -5-methyl-1,3,3a, 7-tetrazaindene,

4-oxy-6-methyl-1,2,3,3a, 7-pentazaindene,

azainden.

Other useful azaindenes are in the following U.S. Patents: 2,735,769 dated February 21, 1956, 2,743,181 of April 24, 1956, 2,835,581 of May 20, 1958, 2,756 147 of July 24, 1956, 2,743 180 of April 24, 1956, 2,716,062 of August 23, 1955, 2,772,164 of November 27, 1956, 2,713,541 of July 16, 1955, 2,852,375 of September 16, 1958, 2 743 180-1 of April 24, 1956, 2 566 658-9 of September 4, 1951, 2 444 605-7 of July 6, 1948, 2 449 225-6 of September 4, 1951 September 14, 1948, disclosed and in the "Journal for Scientific Photographic", 47, pp. 2 to 28 (1952), described.

Onium compounds have been used in photographic art for some time. For example is in U.S. Patent 2,648,604 the use of non-surface-active, quaternary Ammonium compounds as development accelerators and is in the USA. Patents 2,271,622, 2,271,623 and 2,275,727 the use of quaternary ammonium, quaternary phosphonium and tertiary sulfonium compounds as sensitizers for silver halide emulsions. Notwithstanding the fact that such onium compounds are already used as development accelerators and have been used as sensitizers, the results are obtained by using onium compounds in combination with the dye developing agents in the diffusion transfer process of the present invention are noteworthy. In the USA patents cited above disclosed method, the silver density due to the use of the onium compounds in Enlarged negative; however, the increase in density in such processes occurs in the exposed Surfaces of the negative and is due to the above-mentioned suitability of the onium compounds, to sensitize an emulsion or to speed up the development. If in the invention

Process in the presence of the onium and azaindene compounds an increase in density is obtained, it occurs in the positive image and is primarily the result of increased transfer of dye developer from the unexposed Areas of the negative. The fact that the onium and the azaind compounds work together and the transfer of such dye developing agents from the unexposed areas

maintenance of the relevant heterocyclic ring are necessary. Examples of compounds of the general formulas (1), (2) and (3) are: tetraethylammonium bromide, N-ethylpyridinium bromide, Ν, Ν-diethylpiperidinium bromide, ethylenebispyridinium bromide, l-ethylpyridinium bromide, tetraethylammonium bromide, 1-phenicolethylammonium-3-phenolethylbromide, 1-phenicolethylammonium-alkyl , Cetyltrimethylammonium bromide polyalkylene oxide bisquaternary ammonium salts, e.g. B. polyethylene oxide

Enlargement of the negative was in no way made of bis-pyridinium perchlorate, the above mentioned heteroder known use of such compounds as cyclic, quaternary ammonium salts, the methyl sensitizers and to derive or expect development accelerators.

The fact that the onium compounds, especially

form lenbases, including 3-methyl-2-ethylisoquinolinium bromide, 3-methylisoquinolinium methyl p-toluenesulfonate, 1 - ethyl - 2 - methyl - 3-phenethyl-

especially in the presence of hydroquinone derivatives, 15 benzimidazolium bromide, 5,6 - dichloro - 1 - ethylauch are so effective that they transfer the 2 - methyl - 3 - (3 - sulfobutyl) - benzididazolium betaine oxidized dye developing agents from the pyridinium salts specified below, Prevent exposed areas and in this way the ternary suI-

Improving the high or pointed lights was like fonium and quaternary phosphonium compounds if unexpected. This improvement in terms of 20 have the following general formula: high or pointed lights is likely due to the (R) ₃ S ⁺ X "(4)

Ability of the onium compounds. _and especially in the exposed areas, the diffusivity of such dye developer substances

25th

(R) ₄ P ⁺ X- (5)

Here, R in each case denotes an organic radical, e.g. B. an alkyl, aralkyl, aryl, etc. radical, and X is an anion, such as. B. an OBT, Br ~, CT,

too active.

Particularly useful results are achieved through
Use of quaternary ammonium compounds obtained. As is known, quaternary ammonium compounds are organic compounds that
contain a "pentavalent" nitrogen atom. They become 30, etc. Examples of useful ternary sulfonium in general as derivatives of ammonium and quaternary phosphonium compounds may be considered to have four hydrogen atoms
are replaced by organic residues. In general

are the organic residues directly attached to the pentavalent

led: Lauryldimethylsulfonium - ρ - toluenesulfonate, Nonyldimethylsulfonium - ρ - toluenesulfonate, octyldimethylsulfonium - ρ - toluenesulfonate, butyldimethyl-

Nitrogen atom by means of a single or double sulfonium bromide, triethylsulfonium bromide, tetra-carbon-nitrogen bond bound. The Aus äthylphosphoniumbromid, Trimethylsulfonium - p-to-

As used herein, "quaternary ammonium compound" is intended to include compounds in which the pentavalent nitrogen atom forms one of the nucleus atoms of a heterocyclic ring, as does verbromide.

bonds, the four valences of which to separate, organic The onium compounds

niche residues are linked, z. B. tetraalkylquaternary ammonium compounds. As examples of quaternaries

luenesulfonate, dodecyldimethylsulfonium - ρ - toluenesulfonate, Decyldimethylsulfonium - ρ - toluene sulfonate and ethylene - bis - oxymethyltriethylphosphonium-

Ammonium compounds may be mentioned by the following formulas:

R -N ⁺ -R

Y ~

N +

Y ~

(2)

can be called hydroxide

or used as salt. When the onium compounds are used as a salt, the anion fol- can be any acid anion. It should be noted, however, that if I ^{- is used} as the anion, the iodine can have adverse effects on the emulsion and therefore appropriate precautions should be taken. Particularly favorable results have been obtained when the onium compounds were used as the bromide.

The particularly effective heterocyclic, quaternary ammonium compounds that are found in alkaline Solution to form diffusible methylene bases have the following general formula:

U)

55

R _N (= CH— CK) _n = C— CH ₂ R '(6)

X ~

Y ~ (3) 60 Herein D means non-metallic atoms which

are necessary to complete the heterocyclic nucleus of the quaternary ammonium compound, where R is an organic radical, Y is an anion, the former having one or more reactive z. B. OH ~, Br ~, Cr, capable methyl groups, ie (- CH ₂ R '-) groups

,, 65 contains and where the remaining nuclear hydrogen atoms

CH ₃ - -f ^S \ —SO ₃ "can be substituted or unsubstituted, such as

^ = / for example in quaternary ammonium salts, the

etc., and Z denotes the atoms that make up the pyridine, quinoline, benzoquinoline, benz-

derive oxazole, benzoselenazole, thiazole, benzothiazole, naphthothiazole, benzimidazole, isoquinoline, etc .; R is an alkyl, aryl or aralkyl radical of the benzene series or a substituted alkyl, aryl or aralkyl radical of the benzene series with preferably alkyl radicals of 1 to 4 carbon atoms; R 'is a hydrogen atom or one of the radicals identified above with R and X is a hydroxyl ion or an acid anion, e.g. B. a Bf, CH ₃ SOr or

10

CH,

and is H = O or 1. One or more of these quaternaries Ammonium compounds can be used alone or in combination with the onium compounds of the general formulas (1), (2), (3), (4) and (5) can be used and are advantageously used in either the developing solution, the recording material, or both, and less desirable in that photosensitive material by itself, to the quality of the copy after a previously not fully understood Improve Mechanism. If the hydroquinone derivatives are also present, they work with the quaternary ammonium compounds together in such a way that a considerably improved effect is achieved which is markedly different from the effect obtained by using the hydroquinone derivative or the quaternary compound alone is obtained. The color copies thus obtained show a noticeable one less color contamination and improved color saturation, density and contrast.

The onium compounds can be used in varying amounts depending on the individually selected connection. When using the same in the alkaline developer solution useful results obtained with about 0.2 to 15% onium compound. In some cases it will get the best result with 0.2 to 3% of the onium compound. Similarly, the amount of in the light-sensitive material or the onium compound used in the recording sheet with the in onium compound chosen in each individual case.

The quaternary ammonium compounds comprising a preferred embodiment of the invention are pyridinium salts which form diffusible methylene bases and which have the above formula (6), the pyridinium nucleus being separated from one to three active methyl groups (—CH ₂ R ”groups) in 2-, 4 - and / or 6-position is substituted, e.g. B. by a lower alkyl group or a substituted, lower alkyl group, such as. B. an oxyalkyl or an oxyethyl group, the alkyl groups in question are responsible for the formation of the methylene base. Positions 3 and 5 of the pyridinium nucleus can be substituted or unsubstituted, for example by halogen, lower alkyl and lower haloalkyl groups, such as by chlorine, methyl, ethyl, propyl or chloroethyl groups.

Characteristic salts of the formula (6) given above are as follows:

l- (3-bromopropyl) -2-picolmium-p-toluenesulfonate, l-phenethyl-2-picolinium bromide, l-gamma-phenylpropyl-2-picolinium bromide, 2,4-methyl-1-phenethylpyridinium bromide, 2,6-dimethyl-1-phenethylpyridinium bromide,

S-ethyl ^ -methyl-1-phenethylpyridinium bromide,

2-ethyl-1-phenethylpyridinium bromide, 1- [3- (N-pyridinium bromide) propyl] -2-picolinium p-toluenesulfonate =

-CH ₃ > N ⁺ C ₃ H ₆ - ν ' Bf ^

pts

Anhydro-1 - (4-sulfobutyl) -2-picolinium hydroxide =

-CH,

N '+

OH"

C ₄ H ₈ SO ^
1- (beta-naphthoylmethyl) -2-picolinium bromide

CH ₃

CH.OC-V Y ^

Br "

l-beta-Phenylcarbamyloxyäthyl ^ -picoUniumbromid =

~ - CHs

N +

C ₂ H ₄ OCONHC ₆ H ₅ J

l-benzyl-2-picolinium bromide =

N +
CH ₂ C ₆ H ₅

Br ~ l-Methyl-2-picolinium-pts,
l-phenethyl ~ 2,4,6-trimethylpyridinium bromide, l-phenethyl-4-n-propylpyridinium bromide, 4-gamma-oxypropyl-1-phenethylpyridinium bromide and
ln-heptyl-2-picolinium bromide.

A number of pyridinium salts of the general formula given above form methylene bases, which are not sufficiently diffusible in alkaline solution, so that they are suitable for the inventive Procedures cannot be used in practice; these are, for example, the following:

l-n-decyl-2-picolinium brornide, 1,2-dibenzylpyridinium bromide, ö-amino-1-phenethyl ^ -picolinium bromide, 2-amino-1-phenethyl-4-picolinium bromide, 2-benzyl-1-phenethylpyridinium bromide, 4-benzyl-1-phenethylpyridinium bromide.

309 690/228

The following compounds that do not form methylene bases in alkaline solution are also less useful:

1-phenethylpyridinium bromide,

1-ethylpyridinium bromide,

l-phenethyl-3-picolinium bromide

and

1-n-Nonylpyridinium-p-toluene sulfonate.

The hydroquinones that have the required properties are essentially colorless and essentially insoluble in water as well as in alkaline Solution soluble and diffusible through gelatin layers. Examples of this are the following:

Phenylhydroquinone,

2'-oxyphenylhydroquinone,

Phenoxyhydroquinone,

4'-methylphenylhydroquinone,

1,4-dioxynaphthalene,

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

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

4'-aminophenethylhydroquinone,

2,5-dimethoxyhydroquinone,

2,5-dibutoxyhydroquinone,

m-xylohydroquinone,

Bromohydroquinone,

3,6-dichlorohydroquinone,

2-dimethylaminomethyltoluhydroquinone,

2-cyclohexylhydroquinone,

Sec-butylhydroquinone,

2,5-dichlorohydroquinone,

2,5-diisopropylhydroquinone,

2,5-diisopropylhydroquinone,

2,5-diiodohydroquinone,

3-chlorotoluhydroquinone,

Tetrachlorohydroquinone,

2,5-diphenylhydroquinone,

2, 5-diresorcylhydroquinone,

2,5-dioctyl hydroquinone

and

Dodecyl hydroquinone.

The hydroquinone derivatives which can be used according to the invention differ from the dye developer substances, which contain the hydroquinone radicals listed below, in particular in that they are essentially colorless and therefore do not stain the copies.

The inventive method is therefore carried out so that the silver halide emulsions and the dye developing agent preferably with both the quaternary ammonium salts and the Hydroquinone derivatives are in contact, d. i.e., the quaternary salt can be in either the alkaline Developer liquid, or in the receiving sheet, or both, and less desirably in the photosensitive one Material be present, and the hydroquinone derivative can be in any of the layers of the photosensitive material such as a coating layer, emulsion layer, dye developer layer, an intermediate layer or also be present in the receiving sheet. So can the Receiving layer of the receiving sheet of a mordant for the dye developing agent, as below listed, i.e. for example consist of poly (4-vinylpyridine) and can additionally contain at least one of the contain the above hydroquinone derivatives. Similarly, the receiving layer of the receiving sheet can have the combination a mordant for the dye developing agent, at least one of the hydroquinone derivatives and at least one of the onium compounds, in particular the heterocyclic methylene base-forming compounds contain quaternary ammonium compounds. The hydroquinone derivatives can be used for some purposes be present in the developer liquid containing the oxyethylcellulose, but is in

ίο of this invention the use in the developer liquid much less desirable because the hydroquinone derivatives are unstable in such liquids and easily oxidize, accompanied by discoloration of copies if not in the absence kept out of air, or other precautions taken to prevent their oxidation to prevent.

The hydroquinone derivatives used as described are preferably in emulsion layers,

Coating layers, intermediate layers or other layers incorporated as dispersions in the hydrophilic, organic, colloidal binder of the layers. The hydroquinone derivatives can be dissolved in alkaline solution and precipitated in aqueous gelatin solutions by acidifying the solution. However, this is a less desirable method because of the instability of the compounds concerned in alkaline solution. The hydroquinone derivatives can be dissolved in a solvent such as a lower alcohol and precipitated into aqueous gelatin solutions for coating on the photosensitive material. They can be added to gelatin solutions which, in order to reduce the particle size, are ground in the ball mill. However, the hydroquinone derivatives are preferably in an organic, water-insoluble, crystalloidal solvent of low molecular weight, which is permeable to the alkaline developer solution and has a boiling point of about 175 ° C, dissolved (such as in dibutyl phthalate) and an aqueous gelatin solution added, which then is passed through a colloid mill until the desired degree of distribution is achieved. An organic cosolvent can also be used, such as e.g. B. one which has a greater solubility in water than the crystalloidal solvent, namely at least about 2 parts per 100 parts of water. Therefore, the co-organic solvent can be washed out of a quenched gelatin dispersion in the presence of the other solvent. The auxiliary solvent may be one which has a boiling point of at least about 25 ⁰ C lower than the kristalloidale solvent so that it can be removed during the drying of a layer by evaporation, wherein the hydroquinone derivative behind remains dispersed in only the kristalloidalen solvent. As a result, the hydroquinone derivatives are quickly and uniformly dissolved from the alkaline developer mixture and transported through the photosensitive material, thereby causing more uniform development than if the hydroquinone derivatives were otherwise incorporated into the photosensitive material.

The hydroquinone derivatives can be in one or more layers of the light-sensitive material in amounts on the order of about 0.108

up to 1.08 g per square meter or more can be used. However, the amount used depends in part on the amount of silver halide, the layer in which it is contained, the amount of the dye developing agent and the amount of the pyridinium salt in the light-sensitive material or the developing solution. In some cases it may be desirable to perform a complex of the hydroquinone derivative in a known manner Reacting with sulfur dioxide to form and the complex in the coating layer, the outer emulsion or to incorporate another layer of the photosensitive material. These hydroquinone-sulfur dioxide complexes tend to be more stable than the hydroquinone derivatives themselves.

The dye developing agents that are included in the * 5 Emulsion layers or in the layers adjacent to the emulsion layers are used, are compounds of the character of a dye, which at the same time have a silver halide-developing activity own. They are characterized in that they are at a pn around the neutral point in the colloid layers relatively little diffusible, but in the presence of the alkaline developer solutions are diffusible in the photosensitive materials. The dye developing agents are largely insoluble in water per se, which property usually makes it necessary, organic solvents for incorporating the dye developing agents into the organic colloid layers of the to use light-sensitive materials. On the other hand, there is the solubility of the dye developing agents not particularly important if the dye developing agents are only capable of being present of the alkaline developer solution to get set in the layers, and when they are on the Recording material can be transferred, they can be used for the method according to the invention. The used Dye developing agents are particularly characterized in that they are both chromophoric Groups as well as at least one part of the molecule, such as, for example, a hydroquinone radical, contain the has a silver halide developing activity, the latter being the dye developer molecule as a whole gives a silver halide-developing activity, resulting in has that during the development of a silver halide image the dye developing agents in the area of exposure and development are oxidized to less diffusible compounds, and that the remaining dye developing agents in the undeveloped areas are transported imagewise onto pickled receiving layers in order to provide a color image thereon. Of course, the dye developing agents used should not have a desensitizing effect on the silver halide emulsions.

Characteristic dye developing agents are described in Australian Patent Specification 220,279, dated December 17, 1958 and in the German patent 036 640 of August 14, 1958, e.g. B .:

4- [p- (2 ', 5'-dioxyphenyl) -phenylazo] -5-acet-

amido-1-naphthol,

4- [p- (2 ', 5'-dioxyphenethyl) phenylazo] -5-benz-

amido-1-naphthol,

l-phenyl-3-methyl-4- [p- (2 ', 5'-dioxyphenethyl) -

phenylazo] -5-pyrazolone,

2- [p- (2 ', 5'-dioxyphenethyl) -phenylazo] -4-acet-

amido-1-naphthol,

2- [p- (2 ', 5'-dioxyphenethyl) phenylazo] -4-amino-1-naphthol,

OH

OH

CH ₂ -CH ₂

-N = N- /

OH

OCH,

(Purple dye developing agent)

= 2- [p- (2 ', 5'-dioxyphenethyl) phenylazo] -

4-methoxy-l-naphthol,

2- [p- (2 ', 5'-dioxyphenethyl) phenylazo] -4-ethoxy-1-naphthol,

2- [p- (2 ', 5'-dioxyphenethyl) phenylazo] -4-n-propoxy-1-naphthol (Connection 2),

-I- CHo-CH

C-NH-C ₄ H ₉

= l-phenyl-3-Nn-butyl-carboxamido-4- [p- (2 ', 5'-dioxyphenethyl) -phenylazo] -5-pyrazolone,
l-phenyl-3-Nn-hexylcarboxamido-4- [p- (2 ', 5'-dioxyphenethyl) phenylazo] -5-pyrazolone (compound 3),

l-phenyl-3-carbethoxy-4- [p- (2 ', 5'-dioxyphenethyl) phenylazo] -5-pyrazolone,
2- [p- (2 ', 5'-dioxyphenethyl) phenylazo] -4-isopropoxy-1-naphthol,

l-phenyl-3-N-cyclohexylcarboxamido-4- [p- (2 ', 5'-dioxyphenethyl) -phenylazo] -5-pyrazolone,

l-phenyl-3-phenyl-4- [p- (2 ', 5'-dioxyphenethyl) -

phenylazo] -5-pyrazolone,

2- (4 '- [p- (2 ", 5" -Dioxyphenethyl) -phenylazo] -

alpha-naphthylazo-4-methoxy-l-naphthol,

l-phenyl-3-amino-4- (4'-tp- (2 ", 5" -dioxyphene-

ethyl) -phenylazo] -2 ', 5'-diethoxyphenylazo-

5-pyrazolone,

1-acetoxy-2- [p- (beta-hydroquinonylethyl) -phenylazo] -4-methoxynaphthalene, 4-isobutoxy-2- [p- (beta-hydroquinonylethyl) phenylazo] -1 -naphthol,

1-acetoxy-2- [p- (beta-hydroquinonylethyl) -phenylazo] -4-propoxynaphthalene, 2- [p- (2 ', 5'-Dioxy-4'-methylphenethyl) -phenylazo] -4-propoxy-1-naphthol,

1-phenyl-3- [N- (beta-ethylhexyl) -carboxamido] -4- [p- (beta'-hydroquinonylethyl) -phenylazo] - 5-pyrazolone,

1 -Pheiiyl-3- (N-n-heptyl) -carboxamido-4- [p- (betahydroquinonylethyl) -phenylazo] -5-pyrazolone, l- (o-Carboxyphenyl) -3-phenyl-4-p - [(2,5-trifluoroacetoxy-beta-phenylethyl-phenylazo] -5-oxypyra- Zollacton,

! - (o-Carboxypheny ^ -S-N-phenylcarboxamido-4- [p- (beta'-hydroquinonylethyl) -phenylazo] - 5-oxypyrazole lactone.

British patents 804,971 and 804, dated November 26, 1958, describe other dye developing agents:

1,4-bis (2 ', 5'-dioxyaniüno) -anthraquinone, l, 5-bis (2 ', 5'-dioxyanilino) -4,8-dioxy-anthraquinone,

l, 4-bis [beta- (3 ', 4'-dioxyphenyl) ethylammo] anthraquinone,

CH ₃ ^OH

CH,

OH

(Blue dye developing agent or cyan dye developing agent) = 1,4-bis [beta- (2 ', 5'-dioxyphenyl) isopropylamino] anthraquinone,

1,4-bis [beta- (2 ', 5'-dioxyphenyl) ethylamino] anthraquinone,

l-chloro-4- [beta- (2 ', 5'-dioxyphenyl) ethylamino] anthraquinone,

N-Benzoyl-1,4-bis- [beta- (3 ', 4'-dioxyphenyl) -ethylamino] -anthraquinone,

N-Benzoyl-1,4-bis [beta- (2 ', 5'-dioxyphenyl) ethylamino] anthraquinone,

5,8-Dioxy-1,4-bis - [(beta-hydroquinonyl-alphamethyl) -äthylamino] -anthracrmion (compound 1), l ^ -Bis-Kbeta-hydroquinonyl-alpha-äthyrj-äthylamino] -anthraquinone,

5-Oxy-1,4-bis - [(beta ~ hydroquinonyl-alphamethyl) -äthylamino] -anthraquinone, l- (beta-Oxy-alpha-ethyl-ethylamino) -4- (betahydroquinonyl-alpha-methylethylamino) -anthra- chinone

and

1- (butanol-2'-amino) -5,8-dioxy-4-hydroquinonylisopropylamino-anthraquinone.

Additional dye developing agents which are useful for the invention are in the Belgian U.S. Patents 554,935 and 568,344, British Patents 804,972, 804,974 and 804,975, the French Patent 1,168,292 and Canadian Patent Nos. 577 021 and 579 038 are disclosed.

Leuco compounds that do not have a filter effect on the underlying emulsion layers that are present in ίο the developed areas are defined, pictorially diffuse from the undeveloped areas onto the receiving layer and become colored therein Images are oxidized can be used similarly, e.g. B. 1-Phenyl-3-methyl-4- (2'-methyl-4'-diethylamino) -anilino-5-pyrazolone.

The dye developing agents are in the light-sensitive materials adjacent to the Silver halide is used in the emulsion layers; that is, they can be in one or more of the emulsion layers or preferably be present in a hydrophilic, organic colloid layer, which is in is in the immediate vicinity and in particular under the relevant silver halide emulsion layer. Particularly favorable results are obtained when the dye developing agents are arranged in such a way that that they are present in the layer immediately below the emulsion layer, their sensitivity the color of the dye developing agents is complementary. It is less desirable that the To arrange dye developing agents in a layer overlying the corresponding silver halide emulsion layer lies. The touch or proximity of the color developing agent with respect to the Silver halide can also be implemented using a mixed "packing system" wherein the dye developing agent may be present in a matrix comprising a silver halide grain containing particles or beads. In multilayer photosensitive materials the order of arrangement of the differently sensitized silver halide emulsion layers the support must be such that the red-sensitive layer is on the support, the blue-sensitive Layer on the outside and the green-sensitive layer in between. Or the arrangement can be reversed so that the blue-sensitive layer is on the support and the red-sensitive layer is on outermost. With such an arrangement of the layers, the sensitivities of the individual Silver halide emulsions be adjusted so that the inclusion of unwanted blue light images in the emulsions that are primarily sensitive to the red and green regions of the spectrum is prevented. For example, a silver bromide emulsion can be used for the blue-sensitive emulsion layer and silver chloride emulsions can be used for the other layers. In cases of this kind, it may be desirable to use the above-mentioned leuco compounds in place of one or more of the To use dye developer substances, as these have a certain absorption in the blue and therefore may tend to have an impermissible filter effect on the blue-sensitive, lower Exercise emulsion layer.

The hydrophilic, organic, colloidal binder of the emulsion layers, coating layers, dye developer substance layers and intermediate layers can be varied somewhat. For example, gelatin,

17 18

Gelatin derivatives, such as dibasic acid, allow the taking of images in the usual way use esters of gelatine, polyvinyl alcohol and cellulose. In addition, the development of light acetate hydrogen phthalate or mixtures of the organically sensitive material, d. H. treatment with niche colloid binders can be used. However, an alkaline activator solution to the development the best and most constant results and 5 initiate are also carried out in the camera as a result, copies of the highest quality are obtained when destructible containers with the developer gelatin are made be used as a colloid binder in all layers of solution or other means to of the photosensitive material is used. Tat developer solution uniformly across the image area especially should if gelatin interlayers add one or more consecutively exposed images be used to understand them at least 75% of the measured and in contact with the receiving layer Divide the thickness of the yellow dye developer layer. For this purpose it may be desirable make up and use at least two times the amount of a developing solution other than one Gelatins, as present in that layer, contain strong alkali, a thickening agent such as an undesirable migration of the dyes - carboxymethyl cellulose or oxyethyl cellulose, higher contains winding substances and the development products of 15 viscosity in a suitable amount to coat the layer to prevent shift. Other hydrophilic, desired viscosity to be obtained. Other means can organic colloids give less desirable results- are used for this, such as spraying, nits when used in shifts. Immersion, roller coating, etc. to achieve the For example, if some developer solution is applied to the exposed material, the layers tend to be coated Bring layers of gelatin and the intermediate layers 20 and initiate its development. Polyvinyl alcohol or cellulose acetate hydrogen phthalate.

contain, especially after drying, stains on a strip of the photosensitive solve each other. Also, if gelatin is thru- material, all with the alkaline developer route is used, a more even transport of the solution and moistened the dye developer images alkaline developer solution and the hydroquinone 25 onto a single strip of recording material derivats obtained through the layers and it will be transferred to multiple color copies in one the dyes forming the final copy!: - to provide a single transfer operation, Wrappers more easily on the receiving layer A method of making colored copies of a strip

transfer. of the photosensitive material to obtain the one

The developing solution that is used to make the 30 series of, for example, three or four in a row Development of the exposed material, which contains the color exposures carried out, consists in a Substance developer substances and the hydroquinone viscous developer solution from a destructible vate contains, and to use the quaternary ammonium salt container, which is in a compartmentalized should be strongly alkaline to the room or compartment located, such as a Developer activity of dye developers 35 magazine, which, as described below, with the camera Increase as much as possible, alkali metal hydroxides, forming a common whole. This becomes for example Sodium hydroxide, or alkaline reactant, has an approximate effect on each of the exposed areas Generating salts, such as sodium carbonate, at the same time in contact with a strip of the are advantageously included in the recording material with the developer mixture and activator mixture for the stated purpose used. However, quater- 40 is moistened and that the corresponding multicolor case Ammonium hydroxides, or volatile amines, are transferred to a number of images such as diethylamine, which has the advantage of having color images on a single strip of the recording, to evaporate from the copies and therefore to provide material.

leave no alkali residue on it (the one different means of making copies of

could give reason to provide the dye images to decompose the light-sensitive material, the one set) can also be used. As mentioned earlier, series of image exposures, e.g. B. three or four after which contains hydroquinone derivatives, as they tend to be exposed to each other can, in the strongly alkaline activator unstable in it, the photosensitive material in a usual to be, preferably not in the developer liquid camera, so not necessarily for the incorporated, although if pyridinium salts are present, use will be made with the developer mix, Results are obtained which must be arranged in other filled, fragile containers, Respect. Best results are obtained by exposing multiple image objects and on it when the hydroquinone derivative is in the layers of the exposed material in a suitable manner from the photosensitive materials. Therefore, the camera needs to be taken out, so that obscuring the no silver halide will develop in the developer solution - emulsions are avoided. So can the photosensitive Part of being included. The alkaline borrowed material in an ordinary camera dated Winding solution can be wound onto a spool by water or an aqueous type of roll film Solution of a pH of 7.5 or less that a light entry is excluded, for example if that comes into contact with it- by using an opaque binder Contains an alkali or a material from the envelope, such as black paper, a cassette or Alkali (with water) is set free. If a magazine. The material can then be taken from the Water or aqueous solutions are removed from the photosensitive camera and placed in a suitable, portable, Material or worn in the stained receiving sheet on opaque housing of small dimensions and incorporated, they can be brought through to the viscous developer liquid suitable means, such as by applying 65 to the material, such as from from pressure or heat. a single destructible container or from

The light-sensitive material of the invention is several of the number of light on the strip of light Of course, it is suitable for exposures made in a camera for sensitive material

19 20

corresponding number of destructible containers, It can be used for the method according to the invention or finally, by applying the developer, you may want an antifoggant in the light liquid on the material by means of a wick, sensitive material in the alkaline developer cleaner Roller or a similar application device, solution and / or the receiving material as well as a so that each of the exposed areas is moistened. 5 the development-interrupting link in the This way, the multiple exposures will use recording material. If connections, on a single strip with different light- which interrupt the development, in the recording-sensitive emulsion layers and subtractive material instead of in the light-sensitive material If colored dye developing agents are adjacent to or are present in the liquid, they only become to the silver halide of each emulsion layer is effective when it is removed from the developer liquid Pointing material has been dissolved with the alkaline liquid and up to which the development preferably penetrated in the presence of the onium salts and the effecting photosensitive material Hydroquinone derivatives moistened and with the up are. As a result, the latent image can become very large take shift during a reasonable rapid development, and the interruption of development each image is delayed for sufficient time in winding, i.e. H. the develop contact brought to the effect that the silver lung is only noticeably inhibited when the enthalide In the various exposed areas, the exposed areas essentially develop of each emulsion layer is developed and has thereby become complete, whereby it is achieved that the corresponding dye-developing substances fix the development only in the unexposed areas be placed while the dye developer 20 prevents and the amount of transferred color substances in the unexposed parts of each of the developer substance is enlarged. Another multiple exposed areas on the inclusion improvement is achieved when the development layer with the formation of a number of the color-interrupting compounds in the receiving layer Substance developer substances composed copies is present and if the listed quaternary be transmitted. 25 salts in either the developer solution or the

Photographic cameras of the exposure layer or both are present,

and development of the photosensitive development interrupters according to the invention.

Lichen material usable type are for example cyclic mercaptans, such as mercapto

wise in US Pat. No. 2,435,717 betrazoles and mercaptobenzothiazoles, such as 1-phenyl-

wrote. 30 5-mercaptotetrazole, 2-mercaptobenzothiazole, etc.

Such cameras allow a series of connections, usually as anti-fogging Bring exposure of individual image sections of the medium to be mistaken for silver halide light-sensitive material from the emulsion side the development as desired, not to a standstill, as well as the development of an exposed image. In a further modification of the invention Section, by the exposed part of the light 35 a small amount of a solvent for silver-sensitive material with part of the copy halide, such as an alkali or ammo-absorbent Material placed in a superimposed position nium thiosulfate or an alkali or ammonium is rhodanid, while these parts of the film assembly, in the alkaline developer mix or the receiving layer or both are incorporated between a pair of pressure rollers with breaking, an associated container pulled 40 through it, thereby increasing the effective photographic sensitivity, whereby the developer liquid is increased between the process. However that is and in contact with - the light-sensitive material effect of the silver halide solvent then on and the corresponding, fittingly arranged surface most conspicuous, if either the listed hydrodes Copy recording material is distributed. While quinone derivatives or the quaternary salts or both of which the photosensitive material and the 45 are present. Usually the amount of Copy recording material such a combination that the silver halide solvent used does not affect the light-sensitive material and that of the copy contain some noticeable amount of silver halide The receiving material lie one on top of the other so that those from the unexposed and undeveloped areas Liquid has access to both. This overlaid the photosensitive material to loosen and to Position of the photosensitive material and the 50 cause this to be on the receiving layer Copy recording material is retained as long as it is transferred.

until the final color image is printed on the copy. The invention also relates to photosensitive

absorbing material forming dye is deposited, materials, their emulsion layers, adjacent

whereupon the materials separated from one another hydroquinone derivatives and

will. 55 layers with the carrier (the recording material)

The receiving layers on which the dyes form a common whole, e.g. B. on one

Curling substances are transferred image-wise to a carrier that is able to color

To obtain the multicolor images, you can record from fabric developer images, with the carrier

different materials exist, such as is such that it is of the photosensitive

made of linear polyamides, proteins like gelatin, 60 layers can be stripped or separated.

Polyvinylpyrrolidone, poly- (4-vinylpyridine), polyvinyl or there may be a special stripping layer between

alcohol, polyvinyl salicylal and methyl cellulose. the recording layer and the other layers

These recording layers will be provided on a suitable to facilitate separation, Neten carrier, such as paper, with poly- The viscous, alkaline liquid can be such as Ethylene coated paper, a transparent 65 described, fed or, if the alkali Film or a white pigmented cellulose ester in one of the layers can be used as a liquid carrier applied to a transparent or not only an aqueous solution can be supplied, to obtain a transparent image depending on the situation of the case. to set the alkali free.

21 22

The silver halide emulsions of the invention The following mixtures were prepared:

According to photosensitive materials include hydroquinone derivative dispersion D-I

the well-known silver alo shirts and their mixtures,

the example of silver bromide, silver bromide ^iodide "" ■
or silver chlorobromide emulsions. 5 4'-methylphenyl hydroquinone 136 g

The in French patent 1 205 755 methyl alcohol 136 ml

of August 17, 1959, described emulsion additives, heating to 70 ° C,

finally the precious metal salts, stannous salts, poly- to dissolve,

amines, optically sensitizing dyes, mercury then cooled to 4O ⁰ C

silver compounds, the sensitivity increasing io di-n-butyl phthalate 272 ml

quaternary ammonium salts and polyethylene glycols,

Plasticizers, hardeners, coating auxiliaries ^Te " ^B

and colloid binders, can advantageously be added to the 10% gelatin solution 1360 g

Silver halide emulsion layers and in the adjacent water 1360 ml

zenden layers of the light-sensitive 15 heating according to the invention to 40 ° C

sensitive material can be used. Alkanol B

The use of exemplary, inventiveness (5 ° / _o aqueous solution) 136 ml

appropriate, photosensitive materials that the

Azaindene compounds are included in the following Part A was slowly added to Part B, being

characteristic example shown. 20 was stirred mechanically. The solution obtained

was then five times through a Manton-Gaulin laboratory colloid mill given. The colloid sample mill was rinsed out and the dispersion on

Weight of 3775 g brought, quenched and put in

A photosensitive material was prepared and stored in a refrigerator.

A coating mixture provided with an undercoat was prepared as follows

Film carrier provided with suitably hardened gelatin layers:
was coated as follows: Part I.

An aqueous gelatin solution that removes the blue-green.

dye developer substance (compound 1, above) in 30 dispersion LM 3775 g

a mixture of N-n-butyl acetanilide, 4-methyl-water TtL "?

cyclohexanone and dispersant alkanol B dissolved. Warming to 40 ° C

contained, was several times through a colloid mill -p ·> ττ

given, then applied and dried so that

the ^ methylcyclohexanone evaporated. 35 ίΓ ^{/ ο Gelatmelosun} S ³¹ ? 2 £ _nΛ ,

A gelatin - silver bromide iodide emulsion layer, ^water ·· ■ · ;. -JJOOO ml

which was sensitized in the red region of the spectrum, warm to 40 C
and which contained 4 g of 4-oxy-6-methyl- .. adjusting the p _H to 5.5 l, 3.3a, 7-tetrazaindene ^{per mole of silver halide, was adjusted to the blue M} " ^c ^ ^{,. orsa} ^. _T .., ".,

applied green dye developer layer. ₄ o (2 ^'7 Vo ¹ S S ^{6 waßri e} solution) 515 ml

A gelatin interlayer was then applied - part I and II were then combined and with

carried. An aqueous gelatin solution that brought the water to 22.7 liters. This solution was obtained on purple dye developing agent (Compound 2, the blue-sensitive layer, one above) in a mixture of cyclohexanone, Nn-Bu layer containing about 1290 mg of gelatin tylacetanilide and alkanol B dissolved, was 45 and about 430 mg 4'-Methylphenylhydroquinone per passed through a colloid mill several times, then contained square meters.

applied to the intermediate layer and dried, a sample of the freshly coated, with the No. 4894

to evaporate the cyclohexanone. designated film was represented by red, green and

A green-sensitive emulsion, which also exposed 4 g of blue filter under a step wedge and contained 50 of the above azaindene compound per mole of Ag halide contact with the recording sheet described below, was moistened on the purple layer with the following developer solution:
wear.

This was followed by a second intermediate gelatin developer or activator solution

layer. 3 _{) 5} <y _o oxyethyl cellulose (Hercules, type 250),

An aqueous gelatin solution that makes the yellow dye 55 highly viscous,

developing agent (Compound 3, above) in a 4.5 ° / ₀ NaOH,

Mixture of dimetrahydrofurfuryl adipate, 2.0 ⁰ I ₀ benzotriazole,

Ethylene glycol monobenzyl ether and alkanol B dissolved 2 ^ 0% l-phenethyl picolinium bromide.

Contained was passed through a colloid mill several times

given, the resulting dispersion quenched, 60 The blue-green, purple and yellow solidify them, and then wash them to remove the dye developer images from the undeveloped ones Ethylene glycol monobenzyl ether to remove, whereupon areas on the white pigmented surface applied to the second intermediate layer and cellulose ester carrier, which is a mixture of poly-dried became. (4-vinylpyridine) mordant and l-phenyl-5-niercapto-

A blue-sensitive silver bromide iodide emulsion containing 65 tetrazole over the existing receiving sheet the amount of azainds given above.

Binding was over the yellow dye- Further samples of film # 4894 were 7 days

developer substance layer applied. stored at 49 ° C and 50% relative humidity

and then exposed and developed as above. As a result, dye developer images with good density were obtained obtain.

A control # 4893 was made on the same Made in the same way as film # 4894, except that the azaindene compound continues from the emulsions.

was left. As with film 4894, this film was also made fresh and after 7 days of heat-moisture pretreatment exposed and developed as above. The following table shows those obtained with Film Nos. 4893, 4894 in each individual case relative densities compiled.

Dense with fresh film blue-green purple yellow

Densities with at 49 ° C and
50% relative humidity

Film stored for 7 days
Blue-Green I Purple Yellow

Movie # 4893

Film No. 4894 (contains the azainden compound)

1.64 1.66

1.70
1.61

1.02
1.68

0.78 1.18

I.
1.65 1.65

It is understood that the azaindene compound-containing film of the present invention, No. 4894, provides cyan, magenta and yellow images as well as after prior temperature and moisture treatment of the original, fresh film show essentially the same densities on exposure, whereas no azaind compound Control film no. 4893 containing cyan, magenta and yellow dye images yields the same as in previous Temperature and moisture treatment have significantly lower densities.

In the manner described in the previous example, two similar photosensitive Materials comprising green sensitive gelatin silver bromide iodide emulsion layers and underlying Dye developing agent layers contained, 4 g of 4-oxy-6-methyl-1,2,3,3a, 7-pentazaindene per Mol of silver halide or 4 g of 2,4-dioxy-6-methyll, 3a, 7-triazaindene per mol of silver halide Emulsions added. After the two materials under the above conditions of heat and After exposure to moisture, color images were made with it. It turned out that this were subjected to a lower loss of density than that from a comparison material which did not contain azaindene compound contained, produced images.

Comparative experiments

Various multilayer photographic films have been made using various antifoggants manufactured. The films were then exposed according to the previous example and ao further treated. The multilayer photographic films had the following based on the support Layers:

1. A gelatin layer with 4877 mg / m ² gelatin,

2. a purple dye developing agent ^{layer containing 828 mg / m 2 of} gelatin and the same amount of the purple dye developing agent given in the above example,

3. a green-sensitive silver bromoiodide emulsion layer with 1162 mg / m ² silver and 860 mg / m ²

Gelatin,

4. a coating layer containing 108 mg / m ^{2 of} 4'-methylphenylhydroquinone and 2688 mg / m ^{2 of} gelatin.

The green-sensitive layer (layer No. 3) were those given in the following table Fogging agent added. The various films were marked on an intensity scale Exposed sensitometer and then processed in the manner described in the example above,

that is, the released dye was image-wise transferred onto the receiving layer. The maximum density (Dmax) of the purple dye was determined in fresh film samples and in film samples after an incubation time of 7 days at 49 ° C.

The relative speeds of the films were also determined. The results obtained are in the compiled in the following table.

sample

Additions in g / Ag MoI

Relative
sensitivity

fresh
sample

Dmax

Sample after
7 day

Incubation
at 49 ° C
(12O ⁰ F)

Δ Dmax

Sample after
7 day

Incubation
at 49 ° C
(120 ⁰ F)

Control sample without stabilizer

Control sample + 4g 2,4-dihydroxy-6-methyll, 3a, 7-triazaindene

Control sample + 4g 4-hydroxy-6-methyll, 3,3a, 7-tetrazaindene

Control sample + 0.13 g ammonium chloropalladate

Control sample + 0.045 g decamethylene bis-benzothiazolium perchlorate ,

Control sample + 0.090 g 5-chlorobenzotriazole

100

100

100

71

50

80

2.18
2.14
2.00
2.30
2.14
2.14

1.80
1.90
1.85
1.95
1.80
1.78

0.38
0.24
0.15
0.35
0.34
0.36

The results obtained show that with samples to which azaindenes were added, a lower Dmax shift occurs during the incubation than with a sample which does not contain any azaindenes. In addition, the film speed is only influenced to a very small extent. If, on the other hand, the azaindenes are replaced by other antifoggants, the film speed decreases quite considerably without the Dmax shift being influenced in the same way as in the case of the addition of the azaindenes. An increase in the amounts of antifoggant used in Examples 4 to 6 leads to an even greater desensitization, ie an even greater reduction in the relative sensitivity.

The other triazaindenes, tetrazaindenes and pentazaindenes can be added to the Emulsion layers are used. In some cases it may be desirable to use different amounts and various types of azaindenes in the related emulsion layers of the multilayer film to use.

When films are coated in the manner described above, the coating uniformity becomes the emulsion layers are greatly improved when using an anionic surfactant such as z. B. an alkylarylsulfonate such as alkanol B (sodium triisopropylnaphthalenesulfonate), the dye developer layers is added and when the silver halide emulsion layers coated thereon a cationic surfactant, such as. B. laurylpyridinium p-toluenesulfonate contain. The unique effectiveness of the azaindenes may also be due to the interaction of the dye-developing agents or other components of the system based on the azaindenes.

Claims (4)

PATENT CLAIMS: 1. Photographic material for the production of multicolor images by a diffusion transfer process using dye developing agents, in which a light-sensitive material, which contains different light-sensitive emulsion layers on a support and adjoining the silver halide of each emulsion layer, a dye developing agent, exposed and in contact with an image receiving material with an alkaline Solution is developed, characterized in that at least one emulsion layer has an oxy- or aminotriazaindene, oxy- or aminotetrazaindene or oxy- or aminopentazaindene. 2. Photographic material according to Claim 1, characterized in that the photosensitive Material on the carrier has a layer which is essentially colorless and water-insoluble and hydroquinone derivative which is soluble and diffusible in alkaline solution. 3. Photographic material according to claim 1 or 2, characterized in that the emulsion layers opposite the red, green and blue In the region of the spectrum that are sensitized, the dye-developing substances are colored subtractively and in a light-insensitive layer which lies under the respective emulsion layer are arranged. 4. Using diffusion transfer method for making multicolor images of the photographic material according to one of Claims 1 to 3, characterized in that that is developed in the presence of a quaternary ammonium compound and that after the Develop a multicolored positive image receiving material from the photosensitive Material is separated. Considered publications:
U.S. Patents Nos. 2,735,769, 2,743,181, 835,581, 2,756,147, 2,743,180, 2,716,062, 2,772,164, 713,541, 2,852,375, 2,566,658, 2,244,605, 2,449 225; "Journal for Scientific Photographic", 1952, pp. 2 to 26. © 309 690/228 9.63