BE607420A - - Google Patents

Description

       

   <Desc / Clms Page number 1>
 



  New photographic product and color inversion-transfer process.



   The present invention relates to photography and, more particularly, to a method of forming color images by inversion-transfer, as well as to the products suitable for the implementation of this method.



   A process of this type has been described, for example, in French patent 1,168,292, applied for on December 29, 1956. As indicated in this patent, a photographic product comprising layers of halide emulsion is used. silver and layers containing diffusible "color developers", these color developers, which will be referred to hereinafter as developer dyes, consisting of dyes the molecule of which contains a developing group for the silver halides. products so as to.

   form a latent image in

 <Desc / Clms Page number 2>

 silver halide emulsions and treated with a basic processing liquid which diffuses into the emulsion layers and into the layers containing the developing dyes, these then converting the latent images to silver images.



   Simultaneously, oxidation products of the developing dyes are formed in situ with the silver images, oxidation products which are relatively non-diffusible in the colloid which constitutes the binder of the layers. The fact that the oxidized developer dyes do not diffuse is apparently due, at least in part, to a reduction in the solubility in the basic processing liquid and, perhaps also, to a tanning or hardening action of the oxidized developer on the base. the colloid constituting the binder of the layers, an action having the effect of slowing down the diffusion of the oxidized developing dyes.

   The unoxidized dye developers which remain in the layers in an image dependent topographic distribution are transferred by diffusion onto a receiving material superimposed on the photographic material, to the practically total exclusion of the silver image and the oxidized developing dye. , to form an image of positive dye in the recipient product.



   When using a photographic product containing several layers? of silver halide emulsions, each sensitized to a different spectral region, and that developing dyes whose respective colors are complementary to the sensitivities of the emulsion layers are present in the latter or in layers adjacent to them, the developing dyes are oxidized, upon treatment with the basic processing liquid, and rendered non-diffusible in the developed regions of the emulsion layers, while the? Residual developer dyes from the undeveloped regions, distributed in a positive image of the original, are transferred by diffusion and registration to the receiving product to form a color image.



   It is evident that the success of the. process depends in part on the efficiency of the process by which the dyes develop-

 <Desc / Clms Page number 3>

 Most of the exposed (negative) regions of the emulsion layers become practically non-diffusible during development. Thus if there remains in a negative region exposed to the maximum, that is to say corresponding to the great lights of the subject, a certain quantity of non-oxidized developing dye, the latter is transferred to the subject. the receptor product together with the positive region developing dye, so that the minimum density of the color proof is relatively large.

   Characteristic developer dyes, such as 1,4-bis- [beta-2,5-
 EMI3.1
 dihydroxyphenyl) -ethylaaino7-anthraquinone of formula
 EMI3.2
 are relatively light developers for silver halides, even when used at the high pH value which is necessary for carrying out the process, i.e. at a pH value of about 13, and do not allow the development of a silver halide emulsion quickly enough to take full advantage of the known sensitometric properties of emulsionsf and to provide images of dyes which exhibit the same extreme density range and the same. contrast than those one might expect when using other developers.

   As a result, the color proofs obtained by this process often have an exaggerated minimum density in the regions of the image which correspond to the high lights of the original, poor color saturation, limited contrast, low density. and poor color separation. These effects are partly due to the ineffectiveness of the developer dyes as a developer.

 <Desc / Clms Page number 4>

 silver halide promoters, the lack of discrimination of these developing dyes for the silver halides they must develop, and other factors.



   An improvement has been made by the use of a colorless auxiliary developer, for example, 1-phenyl-3-pyrazolidone, in the treatment liquid, the effect of this developer being an acceleration of the development of the halides. silver and immobilization of the developing dye in the photographic material. However, satisfactory full color proofs are not yet obtained in this manner, particularly because the basic processing liquid which contains the auxiliary developer does not yet allow development to proceed in such a way that the various developer dyes. necessary for a full color system are each immobilized in the desired layer and in the desired time and extent.



   The aforementioned French patent, as well as other patents the references of which are given below, relates to various characteristics of the fundamental process which uses developing dyes for the formation of color images by inversion-transfer and indicates how the process is to be carried out with these developing dyes for obtaining monochrome images and how the same principles are applicable for obtaining polychrome images.

   However, it has been found that while photographic elements containing several layers of differently chromatized silver halide emulsion and adjacent developing dyes and adjacent developing dyes can be used for obtaining full-color subtractive color images. which arise for this application of the process to obtaining polychrome images are very different from those which arise with respect to obtaining monochrome images and that, consequently, the solutions are also very different.

   For example, the development products of one of the emulsions may alter the development of the other emulsions. Diffusion of a developing dye may be hampered or prevented

 <Desc / Clms Page number 5>

 by a developing dye or other substance which is in a layer that must be passed through the first developing dye, the depletion of the processing liquid in the outer layer can alter the development of an inner layer so that one of the emulsion layers may not be developed to the same degree as another emulsion layer, and in particular it may happen that a developing dye is not sufficiently immobilized not to be transferred and do not create parasitic coloring in a dye image of another color.

   In addition, a given developer dye may develop a few silver halide grains in an emulsion layer other than the one on which it is to act, so that the amount of developer dye that remains available for the transfer is insufficient and the corresponding colors are not sufficiently saturated; for example, a magenta developing dye can accidentally develop a few grains of the red sensitive emulsion layer and become immobilized in this layer, which limits the amount of magenta available for red colors which are then lacking. saturation.

   The method according to the invention is such that this action or this reciprocal dependence of the various layers, the various developing dyes and the various other agents which form part of a photographic product with several emulsion layers, is suppressed or compensated, so that polychromatic images of a higher quality are obtained than those obtained until now by the inversion-transfer process.



   It has been found that the quality of color proofs can be considerably improved when certain hydroquinone derivatives are present in one of the layers of the sensitive product containing the developing dyes, because apparently. each of the developing dyes of the various layers is more completely and more uniformly immobilized and the color contamination of the dye images is reduced. Although a noticeable improvement in the quality of the colors is obtained, it appears that the colors

 <Desc / Clms Page number 6>

 The developers have not yet been immobilized in the exposed ranges, at the required speed, to the desired degree and in the appropriate layer.



   It has now been discovered, according to the invention, that the above-mentioned improvements can be obtained with better results due to the use of hydroquinone derivatives in the sensitive product, when the dyes are dispersed. developers in the layers of the sensitive products by means of solvents, such as organic solvents with a high boiling point and, in particular, when the process is carried out in the presence of one or more onium compounds. Likewise, by using solvents, one avoids crystallization of the developing dyes in the hydrophilic colloidal layers, such as gelatin layers and it is necessary to use only a considerably less amount of organic colloid in the developing dye layer. , so that concentrated and very thin layers can be obtained.



  Thus, the developing dyes are quickly immobilized in the thin layers, quickly extracted from the unexposed plaques by the alkaline solution, and transferred to the receiving layers.



  It appears that other methods could be used to incorporate the developer dyes into the layers, for example, by breaking them into fine particles before adding them to the coating solution, or by dissolving them in an alkaline solution or in a solvent. organic miscible with water and precipitating them in an aqueous solution of the colloidal binder of the layer. However, these methods do not give the desired results. When using solvent dispersions of the developer dyes, in the presence of hydroquinones and onium compounds, during the processing of sensitive products the developer dyes are more quickly and more completely immobilized in the exposure ranges. and development, and a considerable reduction in contamination of one color by another is obtained.

   Likewise, there is a much lower tendency of developing dyes to

 <Desc / Clms Page number 7>

 develop silver halides in emulsion layers where they should not be, thereby improving color saturation in prints. However, the desired results are only obtained when the process is carried out in the presence of certain hydroquinone derivatives and / or pyridinium salts and, in particular, when the hydrophilic colloidal binder of the layers of the sensitive product consists mainly of gelatin. Thus, the desired interaction between developing dyes and hydroquinone derivatives or onium compounds occurs best when the developing dyes are dispersed in the layers by means of the organic solvents described in detail below.

   Therefore, it can be hoped that the hydroquinones reduce the minimum density and the contamination of the colors in the prints and that the onium compounds also reduce the minimum density and the contamination of the couplers and, moreover, avoid the loss of saturation.



  In some cases, the maximum density is also increased. Color conta.ni- nation usually appears in proofs as a denaturing of one or more colors by one or more other colors, and it may be bare to one or more dyes. Developers do not immobilize sufficiently and are transferred from the areas where they should have been immobilized.

   The loss of saturation appears as a defect in the color quality of the proofs which is apparently due to the fact that a developing dye has developed grains of silver halides in an emulsion layer on which it should not have This may act, for example, by the fact that the magenta dye has developed red-sensitive silver halide grains and that there is therefore too much magenta dye immobilized, so that the reds thus lack magenta.



   The objects of the invention are therefore in particular - a photographic product comprising, in superposition, several layers of silver halide emulsion of different chromatic sensitivities and, in an adjacent position, dispersions.

 <Desc / Clms Page number 8>

 sions of developing dyes and hydroquinone derivatives, - a process for the treatment of these products, particularly in the presence of certain onium compounds, - sensitive products, treatment compositions and receiving products, particularly suitable for taking of views in a camera, the processing of the images obtained being carried out in the apparatus.



   The characteristics of the present invention will become apparent from the following description of a photographic product comprising several layers of differently chromatized silver halide emulsions (sensitive to different regions of the spectrum), and, in adjacent position, dispersions of developing dyes the color of which can be complementary to the sensitivity of the corresponding emulsion layer and to hydroquinone derivatives, and to a process for forming polychrome images from these products which consists of treating the photographic material exposed by means of a basic processing liquid, the photographic material being in contact with the receiving material,

   especially in the presence of onium compounds and especially quaternary ammonium salts to develop the exposed silver halides of the emulsion layers and thereby render the developing colorances non-diffusible in the regions where development takes place, and to leave the colorants Developers of the undeveloped regions are referred in a distribution corresponding to the positive image, by diffusion and registration, on the receiving medium, where they form a polychrome image of developing dyes.



   In the accompanying drawing, given only by way of example, - FIG. 1 comprises a schematic sectional view of the photographic material and of the receptor material superimposed on this photographic material, with the interposition of the treatment liquid, and, in the lower part of the figure, a section of the receptor product after the transfer of the coloring developers ; - Fig. 2 is a schematic sectional view of another embodiment of the photographic element;

 <Desc / Clms Page number 9>

 - Fig. 3 is a schematic representation of setting. implementation of the process.



   As indicated by the upper section of FIG. 1, the photographic product used according to the invention comprises a support 10, layers 11, 12 and 13 containing respectively blue-green, magenta and yellow developing dyes, soluble in basic medium, layers of emulsion with silver halides 14, 15 and 16 respectively sensitive to red, green and blue, intermediate layers 17 and 18 which separate the emulsion layer sensitive to green and the adjacent layer of magenta developing dye. other layers and an overlayer 19 containing a hydroquinone compound.

   The receiving material which comprises a support 20 and a receiving layer 21 (which may contain the onium compound) is placed relative to the photographic material so as to receive the images of dyes which diffuse therein from the photographic material. , a frangible sachet containing the basic treatment liquid 22 with pyridinium salt.

   When the bag 22 opens, for example due to the passage of the assembly between the rollers of the camera, and the contents thereof are spread uniformly over a defined area of the photographic product, the liquid treatment penetrates into layer 19 where it dissolves the hydroquinone compound which is insoluble in water, but soluble and diffusible in a basic medium, and entrains this compound in the subjacent layers to convert there the latent images formed by the silver halides in regions 23, 24 and 25 in silver imaging, while the developer dyes which are in the regions contiguous to regions 23, 24 and 25 are immobilized and rendered non-diffusible.

   The developing dyes located in the layers 11, 12 and 13 and which have not reacted then diffuse in a distribution which corresponds to the positive image and in registration to the receiving layer 21 to form images there. dyes.



   According to the embodiment shown in FIG. 2,

 <Desc / Clms Page number 10>

 developer dyes are incorporated into emulsion layers
31, 32 and 33 differently chromatized and the hydroquinone compound is found in the outer layer 34.



   In Fig. 3, there is shown a light-tight apparatus which is useful for processing a reel of exposed film containing silver halide emulsions and developing dyes, and in which the film is wetted with an alkaline solution. activator and contacted with an etched receiver sheet to transfer multiple images of developer dye onto that sheet.



   The developer dyes are dispersed and emulsified in the layers of the sensitive product using as little solvent as possible, the particular solvent used being selected depending on the process and type of developing dye used. Solvents are generally more soluble in water than developer dyes. The high boiling solvent can be used, alone or in combination with a lower boiling solvent, which can be removed from the dispersion by spraying to leave a low solvent content relative to the developer dye. in the diaper.

   A mixture of high boiling point solvents in which the developers are very soluble can be used to obtain layers containing a low proportion of solvent to the developer dye. Likewise, a mixture of a high-boiling solvent, practically insoluble in water and a more water-soluble solvent can be used to allow washing of the latter solvent from the dispersion. and leaving a low proportion of high boiling solvent relative to the developing dye in the dispersion.



   The developer dyes can be dissolved in the solvent mixture, usually by heating, then added to an aqueous solution of the colloidal binder used, such as gelatin solution, and the mixture passed through a medium.

 <Desc / Clms Page number 11>

 colloid mill an appropriate number of times, after which the dispersion can be coated directly or cooled to gel, cut into noodles, wash, re-melt and coat as part of a color film. The molten developer dye dispersion can also be added to a silver halide emulsion layer prior to coating. Certain combinations of developing dye and solvent are particularly advantageous.

   For example, a dispersion of the dye
 EMI11.1
 yellow developer, namely 1-phenyl-3-1-n-hexylcarboxamido-, 4- para- (2,5-dihydroxyphenethyl) -phenylazo-5-pyrazolone, in a mixture of ditetrahydrofurfuryl adipate and monobenzyl ether ethylene glycol tends to give a polymorphic mixture which crystallizes from gelatin solution and does not readily redissolve on heating. When replacing adipate with diethyl lauramide, a polymorphic mixture does not form and the dispersion is stable.



   The following list of solvents gives examples of high boiling point solvents which are insoluble in water which can be used, lower boiling point solvents useful with the former, and solvents more soluble in water. water also useful with the first ditetranydrofurfurylic phthalate Beta-methoxyethyl phthalate N, N-di-n-butylcarbamate ethyl Guaiacol acetate (ortho-iaethoxyphenyl acetate)

     Tetrahydrofurfuryl pro pionate Triethyl citrate Triethyl acetylcitrate Tricresyl phosphate Tri-para-tertio-butylphenyl phosphate Triethyl phosphate Tri - butyl phosphate Triphenyl phosphate Isoamyl acetate Ditetrahydrofurfurylic succinate Diturfetrahydrofurylic benzoic acid Methylurfetrahydrate diturfetrahydrate diturfetrazoic benzoic acid

 <Desc / Clms Page number 12>

   N-n-amylphthalimide
 EMI12.1
 Ethyl N, N-di-n-butylcarbamate
Diethyl lauramide
Dibutyl lauramide
Lauroyl piperidine
N-n-butyl acetanilide
Tetraethyl phthalamide
N-n-amyl succinimide
4-methyl-2-pentanol
2,4-di-n-amylphenol
Ethylene glycol monobenzyl ether
Methylisobutylcarbinol
Furfuryl alcohol
2- (2-Butoxyethoxy) acetate

  ethyl
Cyclohexanone
The 2-, 3- and 4-methylcyclohexanones areomers are low boiling point solvents particularly useful for dispersing, together with the above high boiling point solvents, developing dyes such as 1,4. -bis- (2,5-di-hydroxyphenylisopropylamino) -anthraquinone, 5,8-bis [beta-hydro-
 EMI12.2
 quinoyl-alpha-methyl) -ethylamino7-quinizarin and 1,4-bis- (2,5- dihydroxyphenyllsopropylamino) -5-hydroxyanthraquinone, and colo- i
 EMI12.3
 Magenta developing agent 4-methoy-2 p- (beta-hydroquinoylethyl) - phenylazo7-1-naphthol. Gelatin solutions containing these dispersions of developing dyes give stable layers after drying.

   in which these compounds do not tend to separate by crystallization.



   The developer dyes for use in the emulsion layers or in adjacent layers are compounds which are simultaneously developers of silver halides and dyes. They are characterized by their property of being practically not diffusible in the colloid layers at neutral pH, but to be so in the presence of basic processing liquids. In the majority of cases, the developing dyes are insoluble in water, which usually necessitates the use of organic solvents to incorporate them into the colloid layers of photographic elements.

   In all other respects, the solubility of

 <Desc / Clms Page number 13>

 developing dyes is not particularly important and, as long as they can be transformed to become non-diffusible in the layers in the presence of the basic processing liquid and where they can themselves diffuse to the recipient product, they are useful. according to the invention.

   These developing dyes are particularly characterized by the fact that they contain a chromophore and at least one group, for example a hydroquinonyl radical, which exhibits developing properties with regard to silver halides and which communicates to the body. The developing dye molecule taken as a whole a developing activity such that, during the development of a silver halide image, the developing dyes are converted by oxidation to less diffusible compounds in the exposed ranges where development takes place with the residual developing dyes, which are in the undeveloped areas, being carried over to the etched receptor layers to form a color image therein.

   Of course, the developer dyes should not have any desensitizing action against the silver halide emulsions.



   Characteristic developing dyes which can be used in the photographic elements according to the invention have the general formula
M - N = N - D where M is an aromatic or heterocyclic ring (or ring system), such as benzene, naphthalene, tetralin, anthracene, anthraquinone, pyrazole, quinoline, etc., this ring which may have substituents, such as hydroxyl, amino, keto, nitro, alkoxy, aryloxy, acyl, alkyllamido, arylamido, alkyl, aryl, carboxamido, sulfonamido, carboxyl or sulfo groups, and D represents a group communicating with the developing dye. developing properties of silver halides, for example a hydroquinonyl radical which may bear amino, alkylamino, alkyl or hydroxyl groups or atoms,

     alkoxyl or halogen.

 <Desc / Clms Page number 14>

 



   A very useful class of developer dyes, described in Australian Patent 220,279, filed Jan. 31, 1957, and German Patent 1,036,640, filed Feb. 12, 1957 correspond to general formulas.
 EMI14.1
 where p = 1 or 2, R is an alkylene group containing one to five carbon atoms, Ar an aryl group from the benzene or naphthalene series, Z a lower alkyl group, such as methyl or ethyl, or an atom halogen, such as chlorine, Z 'a lower alkoxyl group, such as methoxy or ethoxy, a halogen atom or a lower alkyl group, m = 0.1 or 2, Y is a 2,5- or 2,3- or 3,4-dihydroxyphenyl which may bear alkyl groups or hydrogen atoms, Q the remainder of a coupler, such as a coupler of phenolic or haphtholic groups,

   Open chain reactive 5-pyrazolone or methylene containing the group -CO-CH2-CO. Examples
 EMI14.2
 are 4 p- (2 ', 5'-dihydroxyphenyl) -phenyl.z> -5-acetamido-1-naphthol, 4-Cp- (2', 5'-dihydroxyphenethyl) -phenylazo7-5-bcnzamido- 1 -r.aphthol, 1-phenyl- (3-methyl-4 - /. "" p- (2 ', 5'-dihydroxyphenethyl) - phenylazo7-5-pyrazolone, 2-L p- (2', 5 '-dihydroxyphenethyl) -phenyl- aio2-4-acetamido-1-naphthol, the 2 L p- (2', 5'-âihydroxyphenethyl) - phenylazo7-A-amino-1-naphthol, the 2 L p- (2 ' , 5'-dihydroxyphenethyl) - phenylazQ7-4-methoxy-1-naphthol (magenta developer dye), 2 L P - (', 5'-dihydroxyyphenethyl) -phenylaz-4-ethoxy-1-raphtol, 2-Z P- (2'j 5'-dihydroxyphenethyl) -phenylazo / -4-n-propoxy-1-naphthol (compound II), 1-phenyl-3 Nr¯.-butylcarboxamido-4 p- (2 ', 5' - dihydroxyphenethyl) -phenylazo7-5-pyrazolone,

   1-phenyl-3-Nn-heaylcarbozamido-t Cp- (2 ', 5'-dihydroayphenethyl) -phenylaz> -5-pyrazolohe (compound III), 1-peryl-3-carbethoxy-4 CP- (Z' , 5'- dihydroxyphenethyl) -phenylazo7-5-pyrazolone, 2- ± -p- (2 $, 5y- dih; droayphenethyl) -phenylaz-4-isopropo-1-raphtol, 1-phenyl- 3-N- cyc3ohexylcarbox.amido-4 - (z ', 5'-dydroxyphenethyl) -

 <Desc / Clms Page number 15>

 
 EMI15.1
 ph er.yl = -5-pyrazolone, 1-phenyl-3-pheryl-4 fp- (', 5' -c ihyd roxy - phenethyl) -phenylaz-5-pYz'azolone, 2 - (.'- Lp- (2f ', 5t-ci'ydroxy-périé thyl) -phenyla zo7-alpha-naphthylazo) -4-methoxy-1-nlphtol, 1- phenyl-3-amino-4- (4' ¯ / j> - (2n, 5n-dihydroxyphenethyl) -phenylazo7-2, 5 '- diethoxyphenylazo) -5-pyrazolone, l-acetoxy-2- / ¯p- (beta-hydro- cuinonylethyl) -phenylazo7-4 - methoxynaphthalene, 4-isobutoxy-2- L p- (beta-hydroquinonylethyl) -phenylazo7-l-naphthol,

   1-acetoxy-2- /. p- (b & ta-hydroquinonylëthyl) -phenylazo7-4-propoxy-naphthalene, 2''Z. p- (25,5 - dihydroxy-4.1-methylphenethyl) -phc-'nylF.ZO7-4-propoxi-1- naphthol, 1-phenyl-3 N- (bta-ethylhex5rl) -carboxamid> -4-p - (beta'-hydrocuinonylethyl) -phenylazo7-5-pyrazolone, 1-phenyl-3- (Nn-heptyl) -carboxamido-4 - p- (beta-hydroquinonylethyl) -phenylazQ7- 5-pyrazolone, the lactone of 1 - (o-carboxyphenyl) -3-pheryl-4- ± -p- (2-, 5- trifluoroacetoxy-bt-phenrlethyl) -phenyldz-5-hyc'ro:,; pyrG: .ole or te 1- (o -car-boxyphen; 1) -3-N-pher.ylcarboxaido-4-L p- (beta, '- hYdro-uinonylethyl) -phenylazQ7-5-hydroxypyrazole.



   Another class of developing dyes, described in the aforementioned French patent 1,168,292 corresponds to the general formula
 EMI15.2
 
 EMI15.3
 o to A represents an anthraquinone ring, An organic radical with a developing function and containing an aryl ring, such as benzene or naphthalene, bearing at least two substituents chosen from hydroxyl, amino and amino groups substituted such that the compound can develop the halides exposed silver, Q is a hydrogen atom or an alkyl group or, when the substituents on the aryl ring of D are hydroxyl groups, an aliphatic (eg, acetyl) or aromatic (eg, benzoyl) acyl group, Z a divalent organic radical containing at least one methylene group (-CH2 -), m an integer,

  positive less than 5 and each Y a halogen or hydrogen atom or an amino, alkyl, aryl, nitro, alkyllamino, arylamino, aryloxy, alkoxy ,.

 <Desc / Clms Page number 16>

 hydroxyl, sulfonamido, carboxamido, carboxy, sulfo, Q - N - D or Q - N - Z - D.

   Examples of such developer dyes are
 EMI16.1
 1,4-bi s- (2 ', 5' -dihYdro = yani7.3.no) -, anthraquinone, 1,5-bis- (z ', 5'-dihYdroxyanilino) -., 8-.d3 .lydroxyanthraquinone, 1,4-bis- '- (3', 4'-dihydrorphenyl) -ethylamino7-anthraquinone, 1,4-bis-ffita.- (2 ', 5' -dihydroxyphéDy'l) -1sopropylam1n. 2l-anthraqu1none (blue-green developer dye) of the formula
 EMI16.2
 
 EMI16.3
 1,4-bis tG- (c ', 5'-dihydroxyphenyl) -ethylamin-anthraquinone, 1-chloro-4-L.bêta- (2', 5'-dihydroxyphenyl) -ethylamin-anthraquinone., N-monobenzoyl-1,4-bis-Zbêta- (3% 4'-dihydroxyphenyl) -ethyl-amino7-anthraquinone, 1-monobenzoyl-1,4-bis ta- (2 ', 5'-dihy-droxyphenyl ) -ethylaaino7-anthraqiilnone, 5,8-dihydroxy-1,4-bis- Lbeta-hydroquinonylalpha-methyl) -ethylaminQ7-anthraquinone (compound I), 1,4-bis (beta-hydroquinoryl-alpha-ethyl )

  -ethylamin, ç, 7- anthraquinone, 5-hydroxy-1,4-bis (bta-hydroquinonyl-alpha-methYl) -ethylamino7-anthraquinone, 1- (beta-hydroxy-alpha-ethyl-ethylamino) -4- (beta-hydroquinonyl-alpha-methylethylamino) -anthraquinone and 1- (butanol-2> -amlno) -5> 8-dlhydroxy-4-hydroquinonyl-isopropylamino-anthraquinone.



   In the above formulas, the term “bivalent organic radical Z” is understood to mean an organic radical whose two free valences are not satisfied by the same atom. By way of examples of such radicals, there may be mentioned alkylene radicals such
 EMI16.4
 that -CH2-, -CH2-CH2- '-cHZ-βH-CH3' as well as divalent radicals such as -CH2-Ph- (Ph being a benzene ring). Furthermore, it

 <Desc / Clms Page number 17>

 it is understood that Z can be saturated, unsaturated as -CH2-CH = CH-CH2- or substituted, as in the chloroalkylene or hydroxyalkylene radicals. When Z is an alkylene group, the best results are obtained with a lower alkylene group, i.e. containing less than six carbon atoms, and especially with an ethylene group (-CH2-CH2-).

   However, alkylene groups containing a greater number of carbon atoms can be used, provided that the corresponding developing dye can dissolve in the liquid treatment composition described herein and its oxidation product is not. diffusible in the developed emulsion layer.



   The acylation of the amino nitrogen atoms that are part of the chromophore has the effect of shifting the absorption band of the compound in the visible towards the larger frequencies (shorter wavelengths). This is how the acylation of an atom
 EMI17.1
 of 1,4-bis-rbeta-(2 ', 51-dihydroxydiphenyl) -ethyl-amino [-anthraquinone (blue-green) amino nitrogen causes this compound to turn magenta and acylation of the two atoms of amino nitrogen turns it yellow-orange. Likewise, acylation of the hydroxyl groups of the above classes of developer dyes can be expected to change the color of the developer dyes.

   The developer dyes may therefore undergo a structural and / or color change during development, for example by hydrolysis, so that the carried over dye may be of a different color from that of the developer dye initially present in the photographic material.



   Other developing dyes are described in Belgian patent 554,935, applied for February 12, 1957, British 804,971, 804,973, 804,974 and 804,975, all four filed on March 9, 1955, and French patent 1,168,292 cited above.



   The following developing dyes are also useful for the implementation of the photographic products and of the process according to the invention: - cyanide developing dyes, such as

 <Desc / Clms Page number 18>

 
 EMI18.1
 2-hydroquinone-amino-4- (p-pherylazo) -anilino-b-bydroxy -.- triazine (Canadian patent 579,038, applied for March 28, 1955), - anthraquinone developing dyes, such as
 EMI18.2
 that 1,4-bls- (2 ', 5'-dihydroanilino) -anthra.qu1none and 1,4-diam.no-N- (beta-2', 5'-dihydroz, yphen, yl-alpha- meth, yl-ethyl) -2, 3 ¯ anthraquinone-dicarboximide, - amino-substituted anthraquinone developing dyes, as prepared by reaction of the sodium salt of
 EMI18.3
 l-amino-4- (p-aminoanilino) acid

  -anthraquinone-2-sulfoniçue on chloroacetamido-hydroquinone monobenzoate, - developing dyes obtained by reaction of
 EMI18.4
 1-phenyl-3-aino-4-phenylazo-5-pyrazolone or l, 4-bis- (beta-aminoethylamino) -anthraquinone on lactone or acid chloride of homogentisic acid or on gentisic acid acid chloride, for example 1-phenyl-3- (2 ', 5'-dihydroxyphenylacetamid) -4-phenylazo-5-pyrazolone (Canadian patent 577,021, filed October 17, 1955) , - naphthamide developing dyes, such as
 EMI18.5
 1- (25-dimethoxyphenylazo) -2-hydroxy-N- (2 ', 5-dihydroxyphenyl -3-naphthamide (French patent 1.

   168.292 cited above), - disazole developing dyes, such as
 EMI18.6
 2 L p- (1-hydrory -3, b-disulfo-8-amino-2-naphthylazo) -3,3'-dimethoxy-bis-phenylazQ! -Hydroquinone and 2- (2 ', 5'- acid dimethoxy-4 'p- (2 ", 5" -dihydroxyphenethyl) -phenylazo7-phenylazo) -1,8-dihydroxy-naphthalene-3,6-disulfonic, - arylazonaphtholic developing dyes, such as
 EMI18.7
 as 1-aznino-4-phêrylazo-2-naphthol, - anthrapyridonic developing dyes, such as 1-acetyl-3-bta- (2 ', 5'-dihydrox, yphenyl) -ethyl-6-beta ( 2 ', 5' - dihYdroxyphenyl) -éttlaminoanthrapyr1done, - thiohydroquinolia developing dyes, such as ï-peryl-3-methyl-4 L p- (2 ', 5'-dihydroxyphézylthioethyl) - phenylazo7-5-pyrazolone (patent Belgian 568.344, requested on 5 June 1958),

   

 <Desc / Clms Page number 19>

 - ortho-coupled developer dyes with limited sensitivity to pH variations, such as 2- (p-
 EMI19.1
 / 2 ", 5" -dihydroxydiphenyi7-phenylazo) -4 - methoxy-1-naphthol and 1-phenyl-3-methyl-4 L, p- (Ydroquinolylsulfonoy) -phenylaz-5-pyrazolone, - dyes Oxalyl ester developers, such as 1-phenyl-3-amino-4-p- (z ', 5'-bis-é t:; lox..lß lo:; y-picnc tliyl) - phenylaz> -5- pyrazolone Leuco-compounds, such as 1-pheiiyl-3-methyl-4- (2 -methyl-4'-diethylaaino) -anilino-5-pyrazolone, which have no filtering action on the subjacent emulsion layers, which are immobilized in the developed regions, which diffuse towards the receptor product in the undeveloped areas and which oxidize there forming color images.



   The developer dyes are present in one or more of the silver halide emulsion layers or, preferably, in a hydrophilic organic colloid layer immediately adjacent to an emulsion layer, particularly under an emulsion layer. Particularly satisfactory results are obtained when the developing dyes are present in the layer immediately below the emulsion layer, the spectral sensitivity of which is complementary to the color of the developing dyes, as shown in FIG. 1. It is less advantageous to place the developer dye in a layer above the corresponding emulsion layer.

   The condition of contiguity of the developing dye and the silver halides can be satisfied by a "packet" system in which the developing dye is incorporated into a matrix embedding a particle or globule containing grains of the halides of the dye. 'silver.



   In multi-layered photographic elements of the type shown in FIG. 1, the order of superposition of the various layers of differently chromatized silver halide emulsions on the support may be different, i.e. reversed so that the blue sensitive layer is closest of

 <Desc / Clms Page number 20>

 support and the farthest red-sensitive layer. In such layering arrangements, it is necessary to adjust the sensitivities of the emulsions so as to prevent the recording of the blue image component in the emulsions essentially intended to record the red and the green: for this, an emulsion can be used. silver bromide for the blue sensitive emulsion and silver chloride emulsions for the other emulsion layers.

   In these embodiments, it may be desirable to use the leuco compounds already indicated in place of one or more developer dyes which, since they may absorb somewhat in the blue, would tend to have undesirable filtering action on the blue sensitive emulsion layer located closest to the support.



   It is believed that the onium compounds react with the developing dyes to form salts and that the improvements obtained particularly in density and high lumens are due at least in part to the effect of the formation of these salts. salts on the solubility and diffusibility of developing dyes. It is evident that the onium compounds temporarily retard the diffusion of the developing dyes, so that the initial diffusion rates of the developing dyes are reduced, and yet more of the developing dyes diffuse less exposed areas to increase density.



   It should be noted that when the developing dyes are dispersed in the colloidal layers as described above, the developing dyes are so dispersed that an electron microscope magnification of the order of 20,000 is required to view. the individual blood cells containing the developing dyes.



   Onium compounds have been used for some time in photography. For example, quaternary ammonium compounds without surface activity have been used as development accelerators. French patents 949,227, 949,228 and

 <Desc / Clms Page number 21>

   949,229, all filed on August 11, 1945, describe the use of quaternary ammonium compounds, quaternary phosphonium compounds and tertiary sulfonium compounds as sensitizers of silver halide emulsions. Notwithstanding these known facts it should be noted the reported results obtained when using onium compounds in conjunction with developer dyes in reverse transfer processes.

   In the processes described in the French patents indicated in this paragraph, the use of onium compounds has the effect of increasing the silver density of the negative; however, this increase in density, in these methods, occurs within the exposed negative ranges and can be attributed to the above stated ability of the onium compounds to sensitize an emulsion or to accelerate development.



  On the contrary, in the processes to which the present invention pertains, when there is an increase in density, this takes place in the positive image and is mainly due to the fact that a greater amount of developing dye has been. transferred from unexposed regions of the negative. The fact that the onium compounds cooperate with the developing dyes so as to intensify the transfer of the latter from the unexposed areas of the negative cannot be deduced from the previous use which has been made of these compounds as sensitizers or as development accelerators.

   In addition, the improvements obtained in carrying out the inversion-transfer processes to which the invention relates are not necessarily linked to an increase in surface activity due to the presence of the onium compounds, since the compounds onium which generally result in the greatest increase in density cannot generally be considered to have surface activity. It is believed that the increase in density is at least partially due. the ability of onium compounds to increase the solubility of developing dyes.



   The fact that onium compounds also have the effect,

 <Desc / Clms Page number 22>

 especially in the presence of hydroquinone compounds, preventing the transfer of oxidized developing dyes from the exposed regions and thus improving the regions of the image which correspond to the bright lights is also unexpected. This latter improvement is believed to be due to the ability of onium compounds to control, especially within the exposed ranges, the diffusivity of these developing dyes.



   Particularly advantageous results are obtained when using quaternary ammonium compounds. It is known that quaternary ammonium compounds are organic compounds which contain a pentavalent nitrogen atom. In general, they can be considered to derive from ammonium compounds in which the four valences generally satisfied by hydrogen atoms are satisfied by organic radicals. In general, organic radicals are linked directly to pentavalent nitrogen through a carbon-nitrogen or double bond.

   In this specification, the term quaternary ammonium covers compounds where pentavalent nitrogen is one of the nuclear atoms of a heterocyclic ring, as well as compounds where the four valences are satisfied by separate organic radicals, such as example, as is the case for tetraalkylated quaternary ammonium compounds. Examples of quaternary ammonium compounds are those compounds which can be represented by the following formulas
 EMI22.1
 

 <Desc / Clms Page number 23>

 where R represents an organic radical, Y ur. anion, for example a hydroxyl or toluenesulphonate group, a bromine, chlorine atom, etc. and Z the atoms necessary to complete a heterocyclic ring.

   Specific examples of compounds corresponding to formulas I, II and III are tetraethylammonium bromide,
 EMI23.1
 N-ethylpyridinium bromide, N, N-dietiylpiperidinium bromide, ethylene-bis-piperidinium bromide, 1-ethylpyridinium bromide, 1-phenethyl-3-picolinium bromide, tetra- alkylammonium, cetyltrimethylammonium bromide, polyalkylene oxides with two quaternary ammonium salt functions, such as polyethylene oxide bis-pyridinitun-perchlorate, the mentioned heterocyclic quaternary ammonium salts which form ethine bases such as 3-methyl-2-ethylisoquino- bromide
 EMI23.2
 linium,

   3-ethylisoquiaoliniu.¯n methyl-para-toluenesulfonate, 1-ethyl-2-methyl-3-pnenethylbenzi: nidazoliuai bromide, 5,6-dich.loro-1-ét.yl-2- betalne methyl-3- (3-sulfobutyl) -benzimidazoli.im and the pyridinium salts indicated below.



   The tertiary sulfonium and quaternary phosphonium compounds can be represented respectively by the formulas (IV) (R) 3 S + X- (V) (R) 4 p + X- where R represents an organic radical, for example an alkyl or aralkyl group , aryl, etc., and X an anion such as a hydroxyl or toluenesulfonate group, a bromine or chlorine atom, etc.

   Examples of tertiary sulfonium and quaternary phosphonium compounds are lauryldimethylsulfonium p-toluenesulfonate, nonyldimethylsulfonium p-toluenesulfonate and octyldimethylsulfonium p-toluenesulfonate, butyldimethylsulfonium bromide, butyldimethylsulfonium bromide, triphethylsulfonium bromide , dimethylsulfonium para-toluenesulfonate, dodecyldimethylsulfonium para-toluenesulfonate, dodecyldimethylsulfonium para-toluenesulfonate,
 EMI23.3
 decyldimethylsulfonium and ethylene-bis-oxymethyltriethyl phosphonium bromide.

 <Desc / Clms Page number 24>

 



   The oniua compounds can be used in the form of hydroxides or in the form of salts. When used in the form of salts, the anion can be derived from any acid. However, when the anion is an iodide anion, appropriate precautions must be taken, since this anion has harmful effects on the emulsion. Particularly satisfactory results are obtained when the onium compounds are used in the bromide state.



   Particularly effective heterocyclic quaternary ammonium compounds which form the diffusible methylene bases in basic solution correspond to the general formula
 EMI24.1
 where D represents the non-metallic atoms which complete the heterocyclic ring of the quaternary ammonium compound containing one or more reactive groups -CH2R 'attached at one or more positions of the ring, the other positions of the ring bearing or not , such as a nucleus of the series of pyridine, quinoline, benzoquinoline, benzoxazole, benzoslénazole, thiazole, benzothiazole, naphthothiazole, benzimidazole, isoquinoline, etc. , n being zero or 1, h an alkyl group,

   substituted or unsubstituted aryl or aralkyl, from the benzene series, the alkyl groups preferably being lower alkyl groups (one to four carbon atoms), R 'a hydrogen atom or one of the groups represented by R and X the OH ion or an acid anion, such as Br, CH3SO4- or CHE - # - SO3-. One or more of these quaternary ammonium compounds can be used, alone or in combination with onium compounds of formulas I, II, III, IV and V and, advantageously, they are incorporated into the treatment liquid, the receiving product or. to both, or less .advantageously to the photographic product, their presence improving the quality of the print by a process little known.

   When hydroquinone compounds are also present, a reciprocal action occurs.

 <Desc / Clms Page number 25>

 resulting in a much better result than when only the hydroquinone compound or the quaternary compound is present. The color proofs obtained show much less color contamination, as well as better color saturation, density and contrast.



   The amount of onium compound which can be used varies depending on the nature thereof. When incorporated into the treatment liquid, useful results are obtained when it is in the proportion between 2/1000 and 150/1000. In some cases, a proportion between 2/1000 and 30/1000 is preferable. Likewise, when it is incorporated into the photographic material or the receiving material, the amount of onium compound to be used varies depending on the nature of this compound.



   According to a particular embodiment of the invention, the quaternary ammonium compounds used are pyridinium salts which form diffusible methylene bases and which have formula (VI), the pyridinium nucleus carrying in at least one positions 2, 4 and 6 one to three reactive methyl groups -CH2R ', such as a lower alkyl group (methyl, ethyl, propyl) optionally substituted, for example by a hydroxyl group (hydroxyethyl, etc.), which methyl groups reagent act as precursors of methylene bases. Positions 3 and 5 may or may not bear substituents, such as halogen atoms or lower alkyl or haloalkyl groups, for example chlorine atoms or methyl, ethyl, propyl or chloroethyl groups.



  Typical salts of formula (VI) are as follows.
 EMI25.1
 1-Benzyl-2-picolinium bromide 1- (3-bromopropyh) -2-picolinium p-toluenesulfonate
 EMI25.2
 1-Phenethyl-2-picolinium bromide 1-ganma-phenylpropyl-X-picollnlum bromide 2, t-dimtbyl.-1-phenethylpyridinium bromide 2,6-dimethyl-1-phenethylpyridinium bromide 5-ethyl-2 bromide -methyl-1-piienethylpyridiiaium 2-ethyl-2-phenethylpyridinitim bromide 1- / 3- (N-bromopyridinlum) -propyl7-2- picolinium p-toluenesulfonate

 <Desc / Clms Page number 26>

 
 EMI26.1
 Anhydro- (4-sulfobutyl) -2-picolinium hydroxide
 EMI26.2
 
 EMI26.3
 :

  % C'tÎ2iûï W üüi ddsalpha-picoline-beta-naphthoyl
 EMI26.4
 
 EMI26.5
 1-beta-phenylcarbamoyloxyethyl-2-picolinium bromide
 EMI26.6
 l-methyl-2-picolinium p-toluenesulfonate
 EMI26.7
 1-Phenethyl-2,4,6-trimethylpyridinimn bromide 1-Phenetr1-4-n-propylpyridiniUfu bromide 4-gamma-hydroxypropyl-1-phenethylpyridinium bromide 1-n-heptyl-2-picolinium bromide
A certain number of pyridinium salts of the general formula indicated above do not form methylene bases

 <Desc / Clms Page number 27>

 sufficiently diffusible in a basic medium to be of some use in the process according to the invention.

   These are, for example,
 EMI27.1
 ln.-Decyl-2-picolinium, 1,2-dibenzylpyridinium, 6-amino-1-phenethyl-2-picolinium, 2-amino-1-phenethyl-4-picolinium, 2-benzyl bromides -1-phenethylpyridinium and 4-benzyl-1-phenethyl-pyridinium.



   The bromides of 1-phenethylpyridinium, 1-ethylpyridinium, and 1-phenethyl-3-picolinium and 1- n-nonylpyridinium p-toluenesulfonate, which do not form methylene bases in a basic medium, are also less useful.



   The hydroquinones which have the required properties and which can be incorporated according to the process of the invention should be practically colorless and practically insoluble in water, but soluble and diffusible in a basic medium in colloid layers such as gelatin. . Examples of such compounds are given below.



   Phenylhydroquinone
 EMI27.2
 2'-hydroxyphenyihydroquinone Phenoxyhydroquinone 4'-methylperylhydroquinone 1,4-dihydroxynaphthalene 2- (4-a-minophenethyl) -5-bromohydroquinone 2- (4-aminophenethyl) -5-methylhydroquinone 4'-aminophenethylhydroquinone
 EMI27.3
 z, 5-dimethoxyhydroquinone 2,5-dibutoxyhydroquinone m-xylohydroquinone bromohydroquinone 3,6-dichlorohydroquinone 2-dimethylaminomethyltoluhydroquinone 2-cyclohexylhydroquinone sec.

   butylhyroquinone 2,5-dichlorohydroquinone
 EMI27.4
 2,5-düsopropylhydroquinone 2,5-diiodohydroquinone 3-chlorotoluhydroquinone Tetrachlorohydroquinone 2,5-diphenylhydroquinone 2,5-dresorcylhydroquinone

 <Desc / Clms Page number 28>

 
2,5-dioctylhydroquinone
Dodecylhydroquinone
Useful hydroquinone compounds are particularly distinguished from developer dyes which contain a hydroquinonyl group in that they are substantially colorless and therefore do not color the test.



   Thus, the process of the invention is carried out with silver halide emulsion layers and the developing dyes in the presence of quaternary ammonium salts and hydroquinone derivatives. In other words, the onium compound can be present in the alkaline treatment liquid and / or in the receiving sheet, but less advantageously in the sensitive product and the hydroquinone derivative can be present in one of the layers of the sensitive product such as an overcoat, an emulsion layer, a developer dye layer, an intermediate layer or in the receiver sheet. For some purposes, the hydroquinone derivatives may be present in the processing liquid.

   However, according to the invention it is much less advantageous to be so, since the hydroquinone derivatives are unstable in such solutions and readily undergo oxidation therein which is accompanied by unfavorable doloration. tests.



   The hydroquinone compounds used, as described above, are preferably incorporated in the emulsion layers, in the overcoat, in the intermediate layers or in other layers, as a dispersion in the mixture. hydrophilic organic colloidal binder of the layer. The hydroquinone derivatives can also be dissolved in alkaline solutions and precipitated in aqueous gelatin solutions, increasing the acidity of the solution.



  However, this procedure is less advantageous because of the instability of the compounds in alkaline solution.
 EMI28.1
 .. <. * .. '.' ,: -, .. hydroquinone derivatives in a solvent, such as a lower alcohol, and precipitating it in the aqueous gelatin solutions for coating on the sensitive product. They can also be added to gelatin solutions which are then passed through a grinder.

 <Desc / Clms Page number 29>

 beads to reduce the size of the crystals.

   However, the hydroquinone derivatives are preferably dissolved in a crystalloldal solvent which is permeable to alkaline processing solutions and has a boiling point above about 175 ° C., such as dibutyl phthalate and added to a solution. aqueous gelatin which is then passed through a colloid mill until the desired degree of subdivision is reached. An auxiliary organic solvent can also be used, such as a solvent having a solubility in water greater than that of the crystalline solvent and which is at least equal to about two parts per hundred parts of water.



  Thus, the auxiliary organic solvent can be washed away from a gelatin gelatin dispersion in the presence of the other solvent.



  The auxiliary solvent may be a solvent having a boiling point at least about 25 ° C lower than that of the crystalloldal solvent, so that it can be removed by volatilization during drying. one layer, to leave the hydroquinone derivative dispersed only in the crystalline solvent. As a result, the hydroquinone derivatives are rapidly and uniformly dissolved in the alkaline treatment composition and thus incorporated throughout the sensitive product to produce a more uniform development than when the hydroquinone derivatives are incorporated into the products. by any other means.



   The hydroquinone derivatives can be used in one or more layers of the sensitive product and in amounts on the order of 107 to 1070 mg or more per square meter. However, the amount used depends in part on the amount of silver halide, the layer in which it is incorporated, the amount of developing dye and the amount of pyridinium salt in the sensitive product or in the solution. treatment of the receiving product. In some cases, it may be desirable to train. a complex of hydroquinone derivatives by reacting with sulfur dioxide in a known manner and incorporating the complex in the overcoat, in the outer emulsion layer or in another layer of the sensitive product.

   These hydroquinone complexes and

 <Desc / Clms Page number 30>

 Sulfur dioxide tend to be more stable than the hydroquinone derivatives themselves.



   It is possible, to a certain extent, to modify the nature of the hydrophilic organic colloid constituting the binder of the emulsion layers, the overlays, the layers of developer dye and the intermediate layers; can be, for example, gelatin, gelatin compounds such as esters of dibasic acids, polyvinyl alcohol and cellulose aceto-monophthalate or mixtures thereof. However, the best and most consistent results, and therefore the best quality prints, are obtained when gelatin is used as a binder for all layers of the photographic material.

   In fact, when using gelatin intermediate layers, as shown in Fig. 1, their thickness must be at least equal to about three-quarters of the thickness of the layer of yellow developer dye and they must contain an amount of gelatin at least about twice the amount of gelatin in that same layer, so preventing the diffusion of the developing dye and the developing products from layer to layer. Other hydrophilic organic colloids give poorer results in the layers. For example, when some of the layers contain gelatin as a binder and intermediate layers of polyvinyl alcohol or cellulose acetomophthalate are used, the layers tend to separate, especially when dry.



  In addition, when gelatin is used for all layers, a more uniform distribution of the basic treatment liquid and hydroquinone compound is obtained in the layers and the developing dyes forming the test are carried over more easily. ment on the receiving product.



   The processing liquid used to initiate the development of the exposed photographic material containing the developing dyes and hydroquinone compounds, and optionally the quaternary ammonium salt, should be strongly basic in order to accelerate the developing activity as much as possible. dye

 <Desc / Clms Page number 31>

 developer. For this, it is advantageous to use, to constitute the activator, alkali metal hydroxides such as sodium hydroxide, or alkali metal salts such as sodium carbonate. However, it is also possible to use quaternary ammonium hydroxides or volatile amines, such as diethylamine, which have the advantage of evaporating and leaving no basic residue on the prints which tends to decompose the image. of dye.



  As already indicated, since the hydroquinone compounds may be unstable in the strongly basic activator, it is preferable not to incorporate them into the treatment liquid although, when pyridinium salts are present, satisfactory results are obtained. in other respects. Best results are obtained when the hydroquinone compound is present in the elbows of the photographic element, so that no silver halide developer is required in the processing liquid. The basic treatment liquid can be replaced with water or with an aqueous solution of pH 7.5 or less, if the adjacent receiver sheet contains an alkali or an alkali releasing compound.

   If water or aqueous solutions become occluded in the photographic material or in the etched receptor material, they can be released by a suitable agent, such as pressure or heat.



   The photographic elements according to the invention are naturally suitable for the exposure customary in cameras.



   In addition, their development or the treatment with the basic liquid which triggers their development can also take place in the camera through the use of frangible caps to contain this liquid, as shown in Fig. .l, or through other devices making it possible to spread this liquid uniformly over the exposed image or over a series of consecutive exposed images, in contact with the receiving product. Therefore, it may be desirable to use a processing liquid which contains, in addition to the strongly basic compound, a thickening agent, such as

 <Desc / Clms Page number 32>

 
 EMI32.1
 as carboxymethylcellulose or hydroxyethylcellulose of high viscosity, in an amount capable of ensuring the desired viscosity.



  Other means, such as fine dispersion spraying, dipping, roll transfer, etc., can be used to apply the treatment liquid to the exposed product and initiate development there *
Thus, a series of consecutive images taken on a strip of the photographic material can be moistened with the processing liquid and the developer dye images can be transferred onto a single strip of the receiving material to obtain several color proofs in a single transfer operation. .



   The alkaline treatment solution can be replaced by water or an aqueous solution of pH 7.5 or less, if the congested receiver sheet contains an alkali or an alkali releasing product. If the water or aqueous solutions are bagged and incorporated into the photosensitive material or the etched receiver sheet, they can be released by any suitable means, such as pressure or heat.



   One method of obtaining color proofs from a web of photographic material containing a series of consecutive views, for example three or four, is to apply a viscous processing liquid contained in a frangible or opening envelope, inside a compartment, such as a magazine secured to the camera, as indicated below, so as to moisten each of the frames with the treatment liquid, almost simultaneously, in contact with a strip of the receiver product and to transfer the corresponding polychrome images thereon to form on a single sheet of receiver product a series of color proofs.



   Another method of obtaining prints from the photographic material carrying a series of consecutive views, for example three or four, is to expose this material in a standard camera, that is. i.e. not suitable

 <Desc / Clms Page number 33>

 to the use of frangine capsules to contain the treatment liquid, and to remove from the device in the dark, by winding on a reel of the usual type with protective backing paper or in a cartridge or charger.

   The exposed photographic material is then introduced into a portable, light-tight box of small dimensions, as shown in FIG. 3, so that there is received the treatment liquid contained, for example, in a single frangible container or in a number of frangible containers equal to the number of views exposed, or applied by a wick, roller or equivalent device , so that each exposed view is moistened * As a result, the photographic material which has several exposed views on a single strip containing differently chromatized emulsion layers and subtractive color-developing dyes contiguous with the silver halides of each emulsion layer is moistened with the basic liquid in the presence of cationic onium salts,

   and in the presence also of hydroquinone compounds, and brought into contact with the receptor product for a time sufficient for the correct development of each image, such that the silver halides of the various exposed patches of each layer d The emulsion is developed, and thus the corresponding developing dyes are immobilized therein, while the developing dyes of the unexposed plaques are transferred to the recipient product to form therein a series of tests consisting of the developing dyes. Fig. 3 is a schematic representation of an apparatus which can be used for this embodiment of the invention.

   The film 40 wound up with the emulsion inward, and having the structure shown in FIG. 1 (upper section), is driven rapidly between rollers 41 and 42 to be wetted with the basic treatment liquid 43 (for example, activator II of the formula given below) contained in the cuvette 44. The film passes then between rollers 45 and 46 which apply it in contact with an etched receiver sheet 47 (for example, the receiver sheet A described

 <Desc / Clms Page number 34>

 below) to constitute the complex product 48 which then leaves the apparatus. When the two products are separated, a series of positive images consisting of developing dyes is obtained on sheet 47, at 50.



   The cameras allowing, in addition to the exposure, the development and the transfer of an image on a receiving product inside the apparatus itself are well known and have been described, for example, in the patent. of the United States of America No. 2,435,717, requested October 6, 1945. Such apparatuses can be used for practicing the invention.



   Receiving products which can be used according to the invention comprise a suitable support, such as a sheet of paper, transparent film or cellulose ester film with white pigmentation, on which an image-receiving layer is applied.



  The latter can be constituted by various substances, such as linear polyamides, proteins (for example gelatin), polyvinylpyrrolidones, poly-4-vinylpyridines, polyvinyl acetate, polyvinyl alcohol, acetate. cellulose, polyvinyl salicylal, partially hydrolyzed polyvinyl acetate, methyl cellulose, regenerated cellulose, carboxymethyl cellulose and hydroxyethyl cellulose.



   As in other processes where the images are formed from dyes, these are somewhat sensitive to the action of heat, light and humidity. It is therefore advantageous to process the tests to remove them as much as possible from this action. For this, solutions of certain compounds can be applied to the tests! improve the image stability of dyes, for example tannic acid solutions, a condensation product of naphthalenesulfonic acid and formaldehyde, and polyvinylpyrrolidone.

   A particularly useful synergistic composition is a solution of polyvinyl alcohol containing a saccharid, such as mannite, levulose, arabinose, maltose, amnose, etc .; neither polyvinyl alcohol alone nor the saccharide alone effectively protects images from developing dyes.

 <Desc / Clms Page number 35>

 



   It may be desirable to incorporate a haze inhibitor into the photographic material, the basic processing liquid or the recipient material or each of these, as well as a development stopper compound to the recipient material. When development arrest compounds are present in the receiving material, and not in the photographic element or in the processing liquid, they cannot work until they have been dissolved by the processing liquid and have reached the photographic product under development. As a result, the latent image can develop very quickly and the development is not significantly inhibited until the exposed areas are substantially fully developed.

   This prevents any development in the unexposed areas and increases the amount of develpppateur dye carried over. Results are further improved when the development inhibitor agent is present in the receptor layer and the indicated quaternary salts are present in the treatment liquid or in the receptor layer or both.



  Suitable growth inhibitors are heterocyclic mercaptans, such as mercaptotetrazoles and mercaptobenzothiazoles, for example 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzolthiazole, etc. Many compounds which are commonly considered to be haze inhibitors for silver halides do not sufficiently inhibit growth in the process according to the invention.



   According to another embodiment of the invention, a small amount of a solvent for silver halides, such as a metal thiosulfate or thiocyanate, is incorporated into the basic treatment liquid or the receiving layer or both. alkaline or ammonium, which increases the general sensitivity of the process.



  The effect of this solvent is most marked when the mentioned hyroquinone compounds and / or the quaternary salts are present.



  Usually, the amount of solvent for the silver halides used is not sufficient to determine the dissolution of an appreciable amount of silver halides in the non-ranges.

 <Desc / Clms Page number 36>

 exposed and undeveloped photographic material and its transfer to the receiving layer.



   The invention extends to photographic elements whose support is adapted to receive the images of developing dyes and is of such a nature that it can be separated from the sensitive layers or is separated from these layers by a layer facilitating the peeling. The basic liquid can be supplied as already indicated or, if the alkali is contained in one of the layers, the liquid can be water.



   Silver halide emulsions which can be used according to the invention include the known silver halides and mixtures thereof, for example silver bromide, silver bromoiodide or silver chlorobromide.



   The following non-limiting examples illustrate the invention.



  EXAMPLE 1. Hydroquinone Derivatives in the Outer Layer.



   A sensitive product is prepared having the structure shown in FIG. 1 (upper diagram) by applying on a substrate film substrate 10 the following gelatin layers, suitably tanned.



   Layer 11.



   Aqueous gelatin solution containing a blue-green developing dye (compound 1) in a mixture of N-n-butylacetanilide, 4-methylcyclohexanone and the dispersing agent Alkanol B.



  The mixture is passed through a colloid mill several times, then this solution is coated and dried to volatilize 4-methyl-cyclohexanone.



   Layers 14. 15 and 16.



   Gelatin silver bromoiodide emulsion layers sensitized to red, green and blue, respectively.



   Layers 17 and 18.



   Gelatin interlayer.



   Layer 12.



  This layer is obtained from a solution

 <Desc / Clms Page number 37>

 aqueous gelatin containing the magenta developing dye (compound II) dissolved in a mixture of cyclohexanone, Nn-butyl-acetanilide and Alkanol B. This solution is passed through a colloid mill several times, coated and dried for volatilize cyclohexanone.



   Layer 13.



   This layer is obtained from an aqueous gelatin solution containing the yellow developing dye (compound III) dissolved in a mixture of di-tetrahydrofurfuryl adipate, ethylene glycol monobenzyl ether and Alkanol B. mixing it several times in a colloid mill, the dispersion is cooled to gel, washed to remove the ethylene glycol monobenzyl ether, applied to layer 18 and dried.



   Layer 19.



   D-1 dispersion of the hydroquinone derivative.



   Part A.
 EMI37.1
 



  4 '-methylphenyihydroquinone 136 g
Methyl alcohol .......................... 136 ml
Di-n-Butyl phthalate .................... 272 ml
This mixture is heated to 70 ° C. to dissolve it, then it is cooled to 40 ° C.



   Part B.



   10% gelatin solution ................. 1360 ml
Water ........................................ 1360 ml
55% aqueous solution of Alkanol B .......... 136 ml This mixture is heated to 40 ° C.



   Part A is slowly added to part B with mechanical stirring. The resulting solution is then passed five times through a Manton-Gaulin laboratory colloid mill. The colloid mill is then rinsed, the dispersion is adjusted to a weight of 3775 g, it is gelled and it is stored in a refrigerator.



   The coating composition is prepared to form the coating.

 <Desc / Clms Page number 38>

 che 19 by operating as follows:
Part I.



   Dispersion D-l ..................... 3775 g
Water ................................ 2225 ml
This mixture is heated to 40 C.



   Part II.



   10% gelatin solution 3130 g
Water ................................ 12000 ml
Mucochloric acid (2.7% aqueous solution) 515 ml
This mixture is heated to 40 ° C. and the pH is adjusted to 5.5.



   Parts I and II are combined and diluted with water to 22,700 ml. This solution is applied to form the layer 19 of FIG. 1 at a rate of approximately 1280 mg of gelatin per square meter and 428 mg of 4'-methylphenylhydroquinone per square meter, hereinafter designated by the abbreviation HQ.



   Samples of the product obtained (n 71) exhibiting the structure shown in FIG. 1 (upper diagram) and samples of an identified product
 EMI38.1
 that (n 68) but which does not contain 4'-methylphenylhydroquinone in the layer 19, and they are wetted, by activators I, IIQ and IIIQ (as indicated below) by putting them in contact with a receiver sheet A (as also indicated below), which consists of the support 20 and the receiver layer 21 (tests 1 to 6).

   As a result, the silver halides in the exposed areas 23, 24 and 25 of each sample are developed, the developing dyes in the adjacent areas of the underlying layers 11, 12 and 13 are immobilized depending on the development, and that the unreacted dyes diffuse imagewise and register on the receiver sheet to give a colored positive image consisting of images 26, 27 and 28 as shown in the lower diagram of FIG. 1.

   In this process, owing to the presence of picolinium salts and in part of that of 4-methyl-phenylhydroquinone in the film, the dyes

 <Desc / Clms Page number 39>

 Developers of layers 11, 12 and 13 are immobilized in the appropriate amount and in the appropriate layers, so that the color proofs obtained show larger, brighter lights (lower minimum density), that the selection of colors is improved and the loss of saturation is reduced compared to the control film # 68 not containing HQ.



   The results of tests 1 to 6 shown in the following table show the improvement in the minimum density in the neutral scale of the tests as a result of the use of quaternary salts. These tests show that when the product not containing HQ is treated with activators IIQ and IIIQ (tests 2 and 3) the minimum densities in the neutral scale of tests 2 and 3 obtained in red light and in green light are reduced compared to test 1 where the activator does not contain quaternary salt.

   In addition, visual examination of the samples from tests and 3 show that the color contamination is decreased and that the loss of saturation is considerably reduced. From tests 4 to 6 we can see that, while the MQ by itself decreases the minimum density (test 4), on the other hand when the quaternary salt is present (tests 5 and 6), a further decrease is obtained. of minimum density.
 EMI39.1
 



  EXAMPLE 2. Hydrocuinone derivatives in the emulsion layer.



   A film # 69 of identical structure to that of Example 1 was prepared, except that a sufficient amount of dispersion D1 was added to emulsion layer 16 (rather than layer 19) to obtain 480 mg of 4. '-methyl-phenylhydroquinone (HQ) per square meter. This product is treated as in Example 1, using activators I, IIQ and IIIQ with the results indicated in the following table (tests 7, 8 and 9), where it can be seen that results similar to those of Example 1. Further improvements are obtained with regard to color contamination and loss of saturation.

   It should be noted that the combination of hydroquinone derivatives in the product and the quaternary salt used during the process (tests 1 to 9) gives improvements in the quality.

 <Desc / Clms Page number 40>

 considerably better colors than when one of these compounds is used in isolation.
 EMI40.1
 EXAMPLE 3. Solvent for alienide, silver and gyridinirta salt in the activator.



   Films were prepared as in Example 1, except that film no.15 did not contain HQ, film no.18 contained 430 mg of HQ per square meter in layer 19, film no.14 contained 430 mg of HQ per square meter. square meter in layer 18 and that the film 75 contains 430 mg of HQ per square meter in the layer 17. The films are treated with the IVQ and V activators indicated below each containing sodium thiosulfate as a solvent for the halides of silver, the active ingredient IVQ also containing the pyridinium salt.

   As indicated by the results of tests 10 to 17 reported in the following table, improved colors, reduced minimum densities, reduced color contamination and loss of saturation are obtained, regardless of the position of the HQ in the film, and , in particular, when the pyridium salt is present in the activator solutions.



    EXAMPLE 4. Pyridinium salt in the receiver sheet.



   Film # 68 prepared as in Example 1 (without HQ in Layer 19), Film # 69 from Example 2 (HQ in Layer 16) and Film # 71 (HQ in Layer 19) are exposed. , they are wetted with the activator I in contact with the receptor product B indicated below and containing the pyridinium salt, in order to transfer polychrome images to the receptor product. As a result, the color qualities of the prints obtained are much improved over those of similar prints prepared on the receptor product A which does not contain pyridinium salt.

   The density values of tests 18, 19 and 20 show that the HQ in layers 16 and 19 and the pyridinium salt in the receptor product B cause a significant reduction in the minimum densities as well as an improvement in contamination and fading colors.



  .Activator I.



  Aqueous solution containing 3.5% hydroxyethylcellu-

 <Desc / Clms Page number 41>

 High viscosity lose, A, 5% sodium hydroxide, and 2% benzotriazole.



  Activator 110,
Activator 1 plus 2.0% 1-phenethyl-2-picolinium bromide.



  Activator 1110.



   Activator 1 plus 2.0% 1-Benzyl-2-picolinium bromide.



  IVO activator.



   Activator IIIQ plus 1.0% sodium thiosulfate.



  Activator V.



   Activator 1 plus 1% sodium thiosulfate.



  Activator VI.



   Aqueous solution containing 4% carboxymethyl cellulose, 4% sodium hydroxide, 1% sodium thiosulfate, 0.2% 5-
 EMI41.1
 nitrobenzimidazole, 5,1 p hexemethylenetetramine.



  Activator VII.



   Activator VI plus 2% 1-phenethyl-3-picolinium bromide.



  Activator VIII.



   Activator VI plus 2% 1-phenethyl-pyridinium bromide.



  Activator IX.



   2.5% aqueous solution of carboxymethylcellulose, 3.5% sodium hydroxide, 0.2% 6-nitrobenzimidazole, 1% sodium thiosulfate,
 EMI41.2
 0.4% 2,5-bis-ethyleneim.inohydroquinone, 0.6-1-phenyl-3-pyrazolidone and 105 ethylene glycol.



  Activator X.



   Activator IX plus 0.4% cetyltrimethylammonium bromide.



  Activator XI.



   Activator IX plus 0.6% tetradecyldimethylsulfonium para-toluenesulfonate.



  Receiver sheet A.

 <Desc / Clms Page number 42>

 



   Paper support with a gelatin layer containing a mixture of poly-4-vinylpyridine as the binding agent and 1-phenyl-
5-mercaptotetrazole.



  Receiver sheet B.



   A paper support bearing a gelatin layer containing a mixture of poly-4-vinylpyridine, 1-phenyl-5-mercaptotetrazole and 1-phenethyl-2-picolinium bromide.



   Similarly, the other effective hydroquinones can be used in films containing the developing dyes and other effective quaternary salts, preferably in the alkaline processing solution and / or in the receiving layer.



    EXAMPLE 5. -
In the same way as in Example 1, but using the IVQ activator, 53 mg, 107 mg, 214 mg, 430 mg and 1070 mg of HQ are incorporated respectively per square meter in layer 19. It is possible to observe while the improvements are obtained from 53 mg and 107 mg. However, optimum results are obtained. in the range of 214 mg to 1070 mg.



   Similar results are obtained when the same series of concentrations is used in layer 16.



  EXAMPLE 6.-
In the same way as in Example 1, but using the IVQ activator, the following hydroquinones are used in layer 19 Compound n mg / m2
2 4'-chlorophenylhydroquinone 470
3 Phenylhydroquinone 300
4 phenoxyhydroquinone 430
5 2,5-dioctylhydroquinone 535
The improvements obtained are analogous to those of the previous examples where HQ is used. However, it was noted that compounds 2 and 3 give somewhat better results.

 <Desc / Clms Page number 43>

 



    EXAMPLE 7.-
In the same manner as in Example 1, the film is treated with activators VI, VII and VIII with the result that the films treated with activators VII and VIII containing the quaternary compounds have minimum densities lower than. the film treated with activator VI without quaternary salt.



  EXAMPLE 8.-
The films containing the developing dyes of Example 1 are treated with activators IX, X and XI. Films treated with activators X and XI containing quaternary ammonium and sulfonium salts, respectively, have lower minimum densities of yellow, magenta and blue-green than the same films treated with activator IX. in the absence of quaternary salt or sulfonium salt.



   BOARD.
 EMI43.1
 
<tb> n <SEP> of <SEP> n <SEP> of <SEP> n <SEP> of <SEP> n <SEP> of active- <SEP> Sheet <SEP> Minimum <SEP> density < SEP> on
<tb>
<tb>
<tb> example <SEP> test <SEP> film <SEP> receiver <SEP> receiver <SEP> scale <SEP> of neutral <SEP>
<tb>
<tb>
<tb> Red <SEP> Green <SEP> Blue
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 1 <SEP> 1 <SEP> 68 <SEP> (indicator) <SEP> 1 <SEP> A <SEP> 0.69 <SEP> 1.15 <SEP> 1.72
<tb>
<tb>
<tb>
<tb>
<tb> 1 <SEP> 2 <SEP> "<SEP>" <SEP> IIQ <SEP> A <SEP> 0.45 <SEP> 0.55 <SEP> 1.76
<tb>
<tb>
<tb>
<tb>
<tb> 1 <SEP> 3 <SEP> "<SEP> IIIQ <SEP> A <SEP> 0.53 <SEP> 0.63 <SEP> 2.00
<tb>
<tb>
<tb>
<tb>
<tb> 1 <SEP> 4 <SEP> 71 <SEP> (HQ <SEP> in <SEP> 19) <SEP> 1 <SEP> A <SEP> 0.55 <SEP> 0.69 <SEP> 0 , 95
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 1 <SEP> 5 <SEP> "<SEP>" <SEP> IIQ <SEP> A <SEP> 0.32 <SEP> 0.25 <SEP> 0,

  26
<tb>
<tb>
<tb>
<tb>
<tb> 1 <SEP> 6 <SEP> "<SEP> IIIQ <SEP> A <SEP> 0.31 <SEP> 0.28 <SEP> 0.41
<tb>
<tb>
<tb>
<tb>
<tb> 2 <SEP> 7 <SEP> 69 <SEP> (HQ <SEP> in <SEP> 16) <SEP> I <SEP> A <SEP> 0.48 <SEP> 0.58 <SEP> 0 , 69
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 2 <SEP> 8 <SEP> "<SEP>" <SEP> "<SEP> IIQ <SEP> A <SEP> 0.25 <SEP> 0.27 <SEP> 0.32
<tb>
<tb>
<tb>
<tb>
<tb> 2 <SEP> 9 <SEP> "<SEP>" <SEP> IIIQ <SEP> A <SEP> 0.29 <SEP> 0.29 <SEP> 0.37
<tb>
<tb>
<tb>
<tb>
<tb> 3 <SEP> 10 <SEP> 15 <SEP> (indicator) <SEP> IVQ <SEP> A <SEP> 0.70 <SEP> 0.57 <SEP> 0.96
<tb>
<tb>
<tb>
<tb>
<tb> 3 <SEP> 11 <SEP> "<SEP> V <SEP> A <SEP> 0.72 <SEP> 1.20 <SEP> 1.46
<tb>
<tb>
<tb>
<tb>
<tb> 3 <SEP> 12 <SEP> 18 <SEP> (HQ <SEP> in <SEP> 19) <SEP> V <SEP> A <SEP> 0.27 <SEP> 0.45 <SEP> 0 , 57
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 3 <SEP> 13 <SEP> "<SEP>" <SEP> IVQ <SEP> A <SEP> 0,

  27 <SEP> 0.21 <SEP> 0.25
<tb>
<tb>
<tb>
<tb>
<tb> 3 <SEP> 14 <SEP> 14 <SEP> (HQ <SEP> in <SEP> 18) <SEP> V <SEP> A <SEP> 0.21 <SEP> 0.44 <SEP> 0 , 90
<tb>
<tb>
<tb>
<tb>
<tb> 3 <SEP> 15 <SEP> "<SEP>" <SEP> IVQ <SEP> A <SEP> 0.25 <SEP> 0.20 <SEP> 0.25
<tb>
<tb>
<tb>
<tb>
<tb> 3 <SEP> 16 <SEP> 75 <SEP> (HQ <SEP> in <SEP> 17) <SEP> V <SEP> A <SEP> 0.23 <SEP> 0.76 <SEP> 1 , 29
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 3 <SEP> 17 <SEP> "<SEP> n <SEP> IVQ <SEP> A <SEP> 0.23 <SEP> 0.20 <SEP> 0.26
<tb>
<tb>
<tb>
<tb>
<tb> 4 <SEP> 18 <SEP> 68 <SEP> (indicator) <SEP> I <SEP> B <SEP> 0.53 <SEP> 0.89 <SEP> 2.32
<tb>
<tb>
<tb>
<tb>
<tb> (contains <SEP> Q)
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> 4 <SEP> 19 <SEP> 69 <SEP> (HQ <SEP> in <SEP> 16) <SEP> 1 <SEP> "<SEP> 0.31 <SEP> 0.41 <SEP> 0 , 89
<tb>
<tb>
<tb>
<tb>
<tb> 4 <SEP> 20 <SEP> 71 <SEP> (HQ <SEP> in <SEP> 19)

   <SEP> 1 <SEP> 0, <SEP> 20 <SEP> 0, <SEP> 25 <SEP> 0.53
<tb>
 

 <Desc / Clms Page number 44>

 
The unique results obtained with heterocyclic quaternary ammonium compounds forming methylene bases appear to be due to their reaction with two moles of a quinone (obtained by reduction of a developing dye or other dye derivative. (hydroquinone) to form an adduct of quinone and methylene base and to regenerate a hydroquinone, as reported by James, Snell and Weissberger "Journal of American Chemical Society" 60 2084 (1938).



   In the silver halide emulsion layers and the adjacent layers of the sensitive products according to the invention can advantageously be used emulsion builders described, for example, at the first addition requested on May 5, 1959 and attached to the invention. French patent 1,224,012 applied for September 11, 1956 comprising salts of noble metals, stannous salts, polyamines, optical sensitizers, azaindenes and mercury salts as stabilizers, quaternary ammonium salts and polyethylene glycols as sensitivity enhancing compounds, plasticizers, tanning agents, coating aids and colloidal binders.



   Of course, the invention is not limited to the embodiments described and shown which have been chosen only as examples.


    

Claims (1)

ABSTRACT. The objects of the invention are in particular: 1 - as a new industrial product, a remarkable photographic product in particular by the following characteristics considered separately or in combinations: a) - it comprises (1) a support carrying, in superposition, several layers of silver halide emulsion of different chromatic sensitivities, and (2) a dispersion in an organic solvent of a developing dye adjacent to the silver halides of each emulsion layer, said developing dye. being a compound which is at the same time a developer of halo- <Desc / Clms Page number 45> silver genides and a dye, a substantially colorless hydroquinone insoluble in water, but soluble and diffusible in alkaline solution, being present in a layer on said support; b) the emulsion layers indicated under 1 a) are sensitive, respectively and in the order of enumeration from the support, to red, green and blue; c) according to an embodiment of la), at least one of the developing dyes has been dispersed in a mixture of organic solvents having markedly different boiling points and a significant amount of a low boiling solvent was removed from the dispersion by spraying; d) according to another embodiment of 1 a), at least one of the developing dyes has been dispersed in a mixture of a substantially water-insoluble organic solvent and a water-soluble organic solvent, and a a significant amount of the latter solvent was removed from the dispersion by washing with water; e) the hydroquinone is present in a non-photosensitive layer, applied to the support; f) this hydroquinone is present in an emulsion layer; g) each layer indicated under 1 b) contains gelati-; not as a colloidal binder; h) it comprises a support carrying, in superposition and in the order of enumeration, layers of gelatin-silver halide emulsion sensitive respectively to red, green and blue, and in a position adjacent to the halides of each emulsion layer a dispersed subtractive color developing dye. in gelatin by means of an organic solvent substantially insoluble in water, said developing dye being a compound which is at the same time a developer of silver halides and a dye, a substantially colorless and insoluble hydroquinone in water. water, but soluble and diffusible in alkaline solution, being present in a layer on the support, the layer of emulsion sensitive to water. <Desc / Clms Page number 46> green and the corresponding contiguous developer dye being separated from the blue sensitive emulsion layer and the red sensitive emulsion layer and also from the developing dyes contiguous to these last two layers by means of gelatin interlayers; ; i) according to two embodiments of l h), the hydroquinone is present respectively in a non-photosensitive layer applied to the support or in an emulsion layer; j) according to another embodiment of 1 h), the developer dyes are dispersed in gelatin layers which are placed under the emulsion layers; k) according to an embodiment of la), the dispersion of at least one of the developing dyes has been obtained by dispersing the developing dye in a mixture of organic solvents, having markedly different boiling points, and by removing the lower boiling solvent by vaporization; 1) According to another embodiment of 1a), the dispersion of at least one of the developing dyes obtained by dispersing the developing dye in a mixture of a substantially water-insoluble organic solvent and a more organic solvent. soluble in water and washing off the latter; 2) a color inversion-transfer process, notably remarkable for the following characteristics considered separately or in combination: a) a photographic product is exposed photographically as indicated under 1, the product is applied under pressure in contact with a receiving layer etched with a layer of alkaline solution placed between the emulsion layers and the receiving layer, to develop the silver halides and render the developer dyes non-diffusible in the exposure and development areas, the developer dyes from the unexposed areas are allowed to imageally transfer, by diffusion and registration, onto the layer receiving, and we separate the layer <Desc / Clms Page number 47> receptor to obtain a polychrome image on this layer, which image is constituted by the developing dyes; b) according to one embodiment, a quaternary ammonium salt is also present during the development of the silver halides; c) this quaternary ammonium salt is a heterocyclic quaternary ammonium salt forming a methylene base diffusible in alkaline solution.