CH616248A5 - Photographic product containing a substance forming a magenta dye - Google Patents

Abstract

The product for colour photography comprises at least one layer of silver halide emulsion combined with a substance forming a magenta dye whose mobility is modified by oxidation in an alkaline medium. Use for obtaining a colour image in a dye diffusion/transfer process.

Description

The invention relates to photography, and more particularly to diffusion-transfer photography methods using magenta dye-forming compounds.

Color diffusion-transfer methods generally involve the use of a photosensitive element comprising a support, at least one layer of silver halogen emulsion and a dye-forming substance incorporated therein.

to the emulsion layer or to a layer adjacent to the emulsion layer. The dye image-forming substance can be considered to have the structure Car-COL, where COL denotes a dye or dye precursor radical and Car an associated carrier group or an adjustment group which, depending on the alkaline treatment , strongly modifies the diffusibility at least of the radical COL.

After exposure, the photosensitive element described above is treated with an alkaline treatment solution, which forms an image in the photosensitive element. As mentioned above, the formation of the image is obtained by the carrier group, or adjustment group which, in the presence of the alkaline treatment solution, is responsible for a significant change in the diffusibility, at least of the radical COL.

It is known that an initially mobile dye-forming substance or an initially immobile substance can be used in the treatment solution. After alkaline treatment of a dye-forming substance which is initially immobile, a mobile dye is released according to an image, or else the substance which thus becomes mobile is solubilized according to an image. If the substance is initially mobile, the treatment solution usually insolubilizes the substance in an image and therefore is made immobile.

It is known to use dye image-forming substances in a photosensitive element which, once exposed according to an image, is brought into contact with an alkaline treatment solution, so as to modify, depending on the image, the mobility at least part of the dye-forming substance, that is to say, so as to release a dye, or a dye precursor, and make this compound soluble or insoluble. It is the carrier group or adjustment group particularly used, which determines the change in mobility at least for the dye radical of the substance. In some cases, the solubility of a given compound can be increased by significantly reducing the molecular weight of the compound, as described in U.S. Patent 3,698,897 and Belgian Patent 788,268, as well as in the publication: "Product Licensing Index", Vol. 92, s. 9255 Dec 1971. For example, U.S. Patents 3,227,552 and 3,443,940 and Canadian Patent 602,607 describe such processes, in which a dye-forming compound fractionates and releases a dye. Likewise, US Patents 2,756,142.2 774,668.2 983,606 describe photosensitive elements in which a dye-forming compound is made immobile in an image.

All of these prior processes have their utility; however, it is desired to obtain new compounds which provide dyes having improved characteristics such as improved shade, better diffusibility and better etchability.

The subject of the invention is photosensitive products, in particular for color diffusion transfer photography, using an image-forming compound which provides, in proportion to the conventional alkaline treatment, a magenta dye having a mobility different from that of the compound.

A photographic product according to the invention comprises a support with at least one layer of silver halide emulsion, associated with a substance, forming a magenta dye chosen from the class consisting of compounds which have one of the following formulas:

616,248

6

I.

II,

III.

/ (J-NR) -X- / -Car - q - m where Car represents a carrier radical whose oxidation in alkaline medium, provides a substance which has a mobility different from that of the compound;

m and q are each equal to 0 or 1; if q is equal to 1, X represents a bivalent linking group of formula: -R2-Ln-R2p- where each radical R2 can be identical or different and represents an alkylene radical of 1 to about 8 carbon atoms; a phenylene radical; or a substituted phenylene radical of 6 to about 9 carbon atoms; L represents a bivalent radical chosen from oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl radicals; if q is equal to 0, Car-X can also represent the radicals Car-alkylene-SÓ2, Car-C6H4CH2-S02, Car-pheny-lene-S02, the total number of carbon atoms of X not exceeding 14 ; n is 0 or 1; p is 1 when n is 1 and p is 1 or 0 when n is 0;

R represents a hydrogen atom or an alkyl radical of 1 to 6 carbon atoms; J represents a bivalent sulfonyl or carbonyl radical;

Q represents a hydroxy radical or a radical of formula -NHCOR3 or -NHS02R3 in position 5 or 8 with respect to G, where R3 represents an alkyl radical of 1 to approximately 6 carbon atoms, a substituted alkyl radical of 1 to approximately 6 atoms carbon, a benzyl radical, a phenyl radical, or a substituted phenyl radical of 6 to about 9 carbon atoms;

G represents a hydroxy radical, a salt of this radical, or a hydrolyzable acyloxy group of formula;

O

O

50

55

-OCR4 or -OC OR4

where R4 represents an alkyl radical of 1 to approximately 18 carbon atoms, a phenyl radical, substituted or unsubstituted, of 6 to approximately 18 carbon atoms;

r is 1 or 2;

Z represents a cyano radical, a trifluoromethyl radical, a fluorosulfonyl radical, a carboxy radical, an ester of a carboxylic acid of formula -COOR4, where R4 is as defined above, a nitro radical in position 2 or 3 relative to the azo chain, a fluorine, chlorine or bromine atom, an alkyl-sulfonyl radical or a substituted alkylsulfonyl radical of 1 to about 8 carbon atoms, a phenyl-sulfonyl radical or a substituted phenylsulfonyl radical of 6 to 9 carbon atoms , an alkylcarbonyl radical of 2 to about 7 carbon atoms, a sulfamoyl radical of formula -SO2NR5R6, where R5 represents a hydrogen atom, a substituted or unsubstituted alkyl radical of 1 to about 8 carbon atoms; R6 represents a hydrogen atom, an alkyl radical, substituted or unsubstituted, from 1 to approximately 8 carbon atoms, a benzyl radical, a phenyl radical, substituted or unsubstituted from 6 to approximately 9 carbon atoms, an alkyl-carbonyl radical or a substituted alkylcarbonyl radical of 2 to about 7 carbon atoms, a phenyl-carbonyl radical or a substituted phenylcarbonyl radical of 7 to about 10 carbon atoms, an alkyl-sulfonyl radical or an alkylsulfonyl radical

7

616,248

substituted from 1 to about 6 carbon atoms, a phenyl-sulfonyl radical or a substituted phenylsulfonyl radical from 6 to about 9 carbon atoms; a cyclohexyl radical or a trimethylsilyl radical; R5 and R6, with the nitrogen atom to which they are linked, can represent a morpholino or piperidino radical; a carbamoyl radical of formula -CON (R5) 2 where each R5 can be identical or different and has the meanings described above;

Z1 represents a hydrogen atom or a radical such as z;

R1 represents a hydrogen atom, a substituted or unsubstituted alkyl radical of 1 to about 4 carbon atoms, an alkoxy radical of 1 to about 4 carbon atoms, or a halogen atom;

D represents an electron acceptor group, such as a cyano radical, a sulfo radical, a fluorosulfonyl radical, a halogen atom, an SO 2 -phenyl radical, substituted or unsubstituted, from 6 to approximately 9 carbon atoms; an alkyl-sulfonyl radical or a substituted alkylsulfonyl radical of 1 to about 8 carbon atoms, a phenyl-sulfonyl radical or a substituted phenylsulfonyl radical of 6 to about 9 carbon atoms, an alkyl-sulfinyl radical or an alkylsulfinyl radical or a radical phenyl-sulfinyl substituted from 6 to about 9 carbon atoms, a sulfamoyl radical of formula -SO2NR5R6, a carbamoyl radical of formula -CON (R5) 2 where each R5 and R6 represents a radical as defined above for Z, it being understood that the compound does not contain more than one sulfo radical or more than one carboxy radical.

As mentioned above, the compounds according to the invention contain a carrier group (Car) which, in proportion to, or in inverse proportion to the oxidation in an alkaline medium, provides a substance having a mobility different from that of the starting compound. Depending on the carrier group used, the dye-forming compounds according to the invention can belong to two fundamental classes:

1 °.) - initially stationary compounds, at least part of which is made mobile or diffusible, in proportion to development, or

2 °.) - diffusible or initially mobile compounds which are made immobile in proportion to development.

Carrier groups useful in compounds which form 5 initially stationary dyes, such as those in which the carrier group is responsible, in an alkaline medium, for the separation of a ballast group and a dye group, are described in Canadian patent 602 607 and in United States patent 3,227,552. Among the preferred compounds, initially immobile, mention may be made of those in which the carrier group, in proportion to the oxidation in an alkaline medium, releases a dye having mobility different from that of the starting stationary compound. For example, useful compounds in which the carrier group gives rise to an intramolecular ring closure after oxidation to release a dye, are described in US Patents 3,443,939.3 443,940 and 3,443,941 Initially stationary carrier groups especially useful for forming a diffusible substance in inverse proportion to oxidation, are described in Belgian Patent 810,628. Improved compounds, formers of initially stationary dyes, which give rise to oxido reactions. reduction, then separation in an alkaline medium of the carrier group so as to release a dye, are described in Belgian patent 788 268. The preferred carrier groups are the phenols or the ballasted naphthols of the Belgian patent 788 268. Other groups useful carriers are described in US Patent 3,628,952. In addition, the carrier groups useful for forming initially mobile compounds such as those where the groups Carriers are also used as developers, are described in US Patents 2,543,691, 2,983,606.3 255,001. Carrier groups of this latter class include different radicals from the hydroquinone class.

25

35

Examples of bivalent alkylene linking groups represented by R2 are -CH2-, -C2H4-, -C6H12-, -C3H6-, -C4H8-, etc., as well as branched alkylene radicals, such as

CH,

CH,

CH.

CH,

que-CH2C -CH2-, -CH2-CH-CH2- —CH2-CH-, - (CH2) 6-CH-, etc. I

CHU

"O", "m", "p" mean that the radicals indicated below, can be in ortho, meta, para position, indifferently.

For example, the substituted or unsubstituted phenylene radicals that R2 may represent are the following radicals:

o, m, p-phenylene, o, m, p phenylene substituted by the chloro, methoxy, butoxy, bromo, cyano, nitro, methyl, ethyl, carboxy, sulfo, amino, etc radicals; biva50 radicals

slow containing an oxygen atom or a sulfur atom represented by L, are the oxy (-O-), carboxyl (-00-), carboxamido (-conh-), carbamoyl (-nhco-), sulfonamido (- s02nh-), sulfamoyl (-nhs02-), sulfinyl (-so-), sulfonyl (-s02-). Non-limiting examples of bivalent linking groups represented by X are the following:

-ch2-o-ch2,

.c2h4-c °

conh

~ \ 0) • "C3V

nhco-c.h0-,

H O

och.

so2nh-

R can represent for example, a hydrogen atom, a y——.

methyl, ethyl, isopropyl, pentyl, hexyl, etc. radicals The / \

alkyl radical that R can represent can moreover be su 2 () _O0 © N-CH2- / ()), that is to say, a trial salt-

kills with an alkyl, cyano, hydroxy, methoxy, etc. radical | \ N — s /

Q may for example represent a hydroxy radical, or a \ /

radical of formula: -NHCOR3 or -NHS02R3 where R3 is such that 3 3

previously described, for example, -nhcoch3, kyle or tetraalkyl ammonium (sometimes called salts

—NHCOC2H5, -NHCOC6H13, —NHCOC2H4CN, 25 amines) which does not alter the photographic properties of

-NHCOQHgSO ^ N ^, -NHCOCH2C6H5, compound forming magenta dye or physical processes

-nhcoqh4cooh, -NHS02CH3, -NHS02C6H4CN, ques or chemicals that take place during the development of

-NHS02C6H4C1, -NHS02C2H5, -NHC0C3H6S03H, image. G advantageously represents an acyloxy radical

-NHS02C6H40CH3, etc. hydrolyzable of formula -OC R4 where -OC OR4, where R4 represents

For example, G can represent a hydroxy radical, the salts 30 O O

of this radical, such as an alkali metal salt (for example, jes radica.ux already defined. Non-limiting examples of these

—P Li, 0 ~ K) and the ammonium salts photographically hydrolyzable groups are the following:

inactive, such as-0 © © NH4, -0 © © NH (CH3) 3, -0 © © N (C2H5) 4,

-0®®nh (ch3) 2, -0 ©edi nh (c12h2s) 3, -0e®nh (c2h5) 3, 35 o o c12h25 -o-c-c5hu, -o-c-oc2h5

0

-og-gh3, -oc- / o / ~ c1>

11 ff n / \ 0

0 ~ C12H25 "- ° -C-Gi2H25, -0t-0 ~ (O / ~~ C1" -0-C- GjiH23 "etc

For example Z and Z! may have the radicals-CF3, / \

a cyano radical (-CN-), an ester of a carboxylic acid, such as -S02CH2C6H5, -S02C6H13, -S02- (\ —COOH,

than -cooch3, -COOCnH23, -COOC2H5, -COOC6H5, \ /

-coo -cooc12h25, -coo Cl, -so2c2h4cn, -so2c3h6oh, -so etc. ; a carboxy radical, including the salts of these radicals, such,

as the salts of an alkali metal or the inactive ammonium salts _gQ / (~ \\ OCH etc • -COCH -COC H

photographically (e.g. -COOH, -COO © Li ©, 60 2 \ ^ 'J 3' 3 '3 7'

-COO © K®, -COO © Na®, -COO © NH4®, etc.), a nitro radical N '

(-N02) in position 2 or 3, with respect to the azo group, a —COCH2C6H5, —COCsHn, -SO2NH2, -SO2NHCH3, fluorosulfonyl radical (-SO2F); a halogen atom such as -S02NHC2H5, -S02N (CH3) 2, -S02NHCH2C6H5,

chlorine, fluorine or bromine; and the groups -S02CH3, ^ CH3

-S02C2H5, -S02 ^ yS02NH2, -S02C6H5, -s ° 2N -C3H7, -S02NH- ^ Q ^) - S03H,

9

616,248

-so2nhc2h4cn, -so2nhcoc6h5, -so2nhcoch3, -sonhcoc3h7,

ch3 I

-SOzN -COC6H4CH3, -S02NHC0CH2C6H5j 5

-so2nhc2h4so3h,

ch3

I

-so2n -c3h6-cooh, -so2nhso2ch3)

ch3

l / \

so2n-so2c2h5, -so2nhso2c6h5, -so2n o,

\ - ■ -

-so2, -so2nhso2c2h4cn, -so2nhso2c3h6óh,

-S02NHS02C6H40CH3, etc. ; -CONH2, -CON (C2H5) 2,

-CON -C2Hs, -CONHCHj, -CONHC5Hu, etc.

For example, R1 can represent a hydrogen atom, a radical -CH3, -C ^ Hj, -C3H7, -C4H9, an isopropyl, methoxy, ethoxy, butoxy, isopropoxy, chloro, bromo, fluoro, and substituted alkyl radicals. by a cyano, hydroxy, and methoxy radical, etc.

The electron accepting groups that D can represent are for example: a cyano radical, a sulfo radical, including the salts of these radicals, such as the alkali metal salts, or 3 (1 the photographically inactive ammonium salts ( for example, -S03H, -S03 © Li®, S03 © K®, -S03®Na®, -SO30NH4®, etc.); -S02F, chloro, bromo, fluoro, a radical -S03C6H5,

-s0 (ch2) 3s02nh2, -s0 (ch2) 3s03h, etc., as well as a sulfamoyl or carbamoyl radical described previously for Z such as -s02nh2, -s02nhch3, -s02nhc2h5, -s02n (ch3) 2,

-so2nhch2c6h5,

ch3

-s02n-c3h7, -s02nh "^^^ - s03h,

-so2nhc2h5cn, -so2nhcoc6h5, -so2nhcoch3, '-so2nhcoc3h7,

ch3

I

-so2n-coc6h4ch3, -so2nhcoch2c6h5, -so2nhc2h4so3h,

ch,

-so oh, -so3

35

-so3 OPH-SQ ^,

so2nh2

-so3, -so ■ <3, etc. , -s02ch3,

—SO2C2H5, —so2-

i -so3h, -so2c6h13, -so2c2h4cn,

-so2c6h5, -so2ch2c6h5, -so2- / Q \,

\ l — C.C \ C

-so2n-c3h6-cooh, -so2nhso2ch3,

ch3

I

-S02N-S02C2H5, -S02NHS02C6Hs, etc. ; -CONH2, -CON (C2H5) 2,

ch3

I

-CON -C2H5, -CONHCH3, -CONHC5Hu.

The preferred compounds in accordance with the above formula are those in which Car represents a group which, in proportion to the oxidation in an alkaline medium, releases a dye having a mobility different from that of the compound;

R2 represents an alkylene radical of 1 to about 4 carbon atoms, a phenylene radical substituted or not by a carboxy, chloro, methyl, or methoxy radical;

n is 0;

R represents a hydrogen atom;

J represents a sulfonyl radical;

m is 0 or 1;

Q represents, at position 5 with respect to G, a hydroxy radical, a -nhcor3 or -nhs02r3 radical, where r3 represents an alkyl radical of 1 to approximately 4 carbon atoms; an alkyl radical of 1 to about 4 carbon atoms, substituted by a hydroxy, cyano, sulfamoyl, carboxy or sulfo radical; a benzyl radical, a phenyl radical substituted or not by a carboxy, chloro, methyl, methoxy or sulfamoyl radical;

G represents a hydroxy radical or a hydrolyzable acyloxy radical of formula:

50

O

-ocr4

or

O

-OCR4

55

-so-

02f, -soàrtoh, -so -och3,

-S02 (CH2) 3S02NH2, -S02 (CH2) 3S03H, etc., -SOCH3,

-soqhj, -so- (()) - so3h, -soc6h13, -soc2h4cn,

-soc6h5, -soch2c6h5, -so

-so2f, -soc2h4oh,

where R4 represents an alkyl radical of 1 to about 18 carbon atoms, a substituted or unsubstituted phenyl radical of 6 to about 18 carbon atoms;

r is 1;

Z represents a cyano radical, a trifluoromethyl, fluorosulfonyl, chloro, bromo or nitro radical, in position 2 or 3 relative to the azo chain, an alkylsulfonyl radical of 1 to about 7 carbon atoms, an alkylsulfonyl radical of 1 to about 6 carbon atoms, substituted by a phenyl, cyano, sulfamoyl, carboxy, fluorosulfonyl, or sulfo hydroxy radical; a sulfamoyl radical of formula -SO2NHR6, where R6 represents a hydrogen atom, an alkyl radical of 1 to about 4 carbon atoms, or an alkyl radical of 1 to about 4 carbon atoms substituted by a hydroxy, cyano, sulfamoyl radical , carboxy or sulfo; a benzyl radical, a phenyl radical, substi-

616,248

10

killed or not by a hydroxy, sulfonyl, sulfamoyl, carboxy or sulfo radical;

Z1 represents a hydrogen atom;

R1 represents a hydrogen atom, a methoxy, chloro or fluoro radical;

D represents a chloro, bromo, alkylsulfonyl radical of 1 to about 6 atoms, substituted by a chloro, fluoro, hydroxy, phenyl, cyano, sulfamoyl, carboxy, sulfo, sulfamoyl-phenyl, carboxyphenyl, chlorophenyl, cyanophenyl, methylphenyl, nitrophenyl radical; a phenylsulfonyl radical or a sulfamoyl radical of formula -SO2NR5R6, where R5 represents a hydrogen atom or a methyl radical, R6 represents a hydrogen atom; an alkyl radical of 1 to about 8 carbon atoms; an alkyl radical of 1 to about 6 carbon atoms substituted by a hydroxy, cyano, sulfamoyl, carboxy or sulfo radical; a benzyl, phenyl radical, substituted or not substituted by a hydroxy, sulfamoyl, carboxy or sulfo radical; or, R5 and R6, with the nitrogen atom to which they are linked, represent a morpholino radical.

Very desirable dye imaging compounds are represented by the formula:

Because

2 (1 where D represents the radicals -SO2NHCH3 or -SO2NHC4H9-t;

R1 represents a hydrogen atom or a chloro radical;

Z represents a 5-sulfamoyl radical, when R1 represents a 2-chloro radical; and, when R1 represents a hydrogen atom, Z represents a 4-sulfamoyl, 3-methylsulfonyl, or 3-nitro radical.

The particularly preferred compounds are those corresponding to formulas I, II and III above in which Car represents a radical of formula:

r3o2snh where R1 represents a hydrogen atom, or a chloro radical; 4 (1

R3 represents an alkyl radical of 1 to about 4 carbon atoms;

D represents an alkylsulfonyl radical of 1 to about 5 carbon atoms, a benzylsulfonyl radical, a sulfamoyl radical, of formula -SO2NHR6, where R6 represents an "alkyl radical of 1 to about 8 carbon atoms.

Among these compounds, preference is given to those in which Car is in position 4 with respect to the azo chain, when R1 represents a hydrogen atom and where Car- is in position 5, when R1 represents a chloro radical, R3 representing a methyl radical so and D representing -S02CH2C6H5, -S02NHC4H9-t or

-so2nhch3.

Other preferred dye imaging compounds have the following formula:

iv.

Lease nhso2-

where bail represents an organic ballast group of molecular size and configuration such that they render the compound non-diffusible during development in an alkaline treatment composition and Y represents the carbon atoms necessary to complete a benzene or naphthalene ring, substituted or no. When Y represents the atoms necessary to complete a naphthalene nucleus, the bail radical can be linked to any of the two cyles of this nucleus. Preferred ballast groups are those in which bail represents

O

II

the radicals -CNH- (Ball) 1 or -S02NH- (Ball) 1. Examples of the preferred carrier groups are given by the following formulas:

616,248

16,248

OH

Oh oh

13

616,248

H37C18

nhso -

The nature of the ballast (bail) group in Formula IV for the compounds described above is not critical provided that it confers immobility on the compounds. Typical ballast groups include straight or branched long chain alkyl radicals directly or indirectly linked to the compound, as well as aromatic radicals of the benzene and naphthalene series indirectly linked or attached to the benzene ring, etc. Useful ballast groups generally contain at least 8 carbon atoms; these are in particular substituted or unsubstituted alkyl radicals of 8 to 22 carbon atoms, amide radicals of 8 to 30 carbon atoms, keto radicals of 8 to 30 carbon atoms, etc., and they may even have a structure polymer. Particularly useful compounds are those in which the ballast group is linked to the benzene nucleus by a carbamoyl radical (-NHCO-) or by a sulfamoyl radical (—SOzNH—) in which the nitrogen atom is contiguous to the ballast group.

In addition to the ballast group, the benzene nucleus of the above formula, may contain groups or atoms attached thereto, such as halogen atoms, an alkyl, aryl, alkoxy, aryloxy, nitro radical, amino, alkylamino, arylamino, amido, cyano, alkylmercapto, keto, carboalkoxy, or heterocyclic.

In a preferred embodiment of the invention, Car represents a group which, in proportion to oxidation in an alkaline medium, releases a dye whose mobility is different from that of the dye image-forming compounds.

2. The preferred dyes released from the carrier group in proportion to the oxidation in an alkaline medium can have the following formulas:

v.

n = n vi.

n = n m-x-d-nh

VII.

(z)

_ / 7 \

n = n (/ \

/ (j-nr) -x- / -m q - m

616,248

14

where M represents the radical NH2SO2-, HS02- or an alkyl-NH-lower radical; X, R, J, q, r, m, Q, G, Z, Z1, D and R1 represent the radicals previously described. The preferred released dyes obviously correspond to the dye image-forming compounds described above.

When M represents —SO 2 H, the corresponding dyes can be released by the reactions described in US Patents 3,443,940.3 628,952 and 3,698,897. When M represents a lower alkyl radical -NH (c ' that is to say an alkyl radical of 1 to 4 carbon atoms), the dye represented can be released by the reactions described in Belgian patent 810 678. The dyes released which are particularly preferred are those having the formulas V, VI and VII above, where M represents the radical -SO2NH2. These dyes can be released during the reactions described in Belgian patent 788 268 by the carrier groups described in formula IV.

A suitable method producing a color transfer image using the compounds according to the invention, for example those where Car has the formula IV, comprises the following steps:

1) the photosensitive element described is treated with an alkaline treatment composition in the presence of an agent for developing silver halides so as to develop each layer of exposed silver halide emulsion, which oxidizes the developer which, in turn, gives rise to cross-oxidation with a sulfonamido compound;

2) an image is formed of a released dye diffusible in proportion to the exposure, according to an image, of each layer of emulsion with silver halides as a result of the cleavage of each sulfonamido compound having undergone cross oxidation and;

3) at least part of each of the released diffusible dye images is made to diffuse towards a dye image-receiving layer, so as to obtain an image.

In the process described above, the photosensitive element is treated with an alkaline treatment solution so as to effect or initiate development. A preferred method for applying the treatment composition is to use a frangible capsule containing the treatment composition. Generally, the treatment composition used in the process contains the developing agent, although the composition may be a simple alkaline solution, when incorporating the developing agent into the photosensitive member, in this case the alkaline solution is used to activate the incorporated developing agent.

A composite photographic product, intended to be processed by passing between pressing members comprises:

1) a photosensitive element as described above;

2) a dye image receiving layer and;

3) means for introducing an alkaline treatment composition into the composite photographic product, for example, a frangible capsule which can be arranged so that at the time of treatment a pressure force applied to this capsule by the pressing members , causes the release of its content in the composite photographic product; the composite photographic product further contains a silver halide developing agent.

In a composite photographic product such as that described above, the dye image-receiving layer can be applied to a separate support, capable of being superimposed on the photosensitive element after its exposure. Such image-receiving elements are described, for example, in United States patent 3,362,819. When the means used to discharge the treatment composition is a frangible capsule, it is usually placed between the photosensitive element and the image receiving element, so that a force of

30

35

50

55

60

pressure applied to the frangible capsule by pressing members, such as may be encountered in a camera for “treatment inside the camera”, discharges the contents of the capsule between the element image receptor and the layer of the photosensitive element furthest from the support of this element. After the treatment, the image receiving element is separated from the photosensitive element.

In the composite photographic product described, the dye image-receiving layer can be associated with the photosensitive silver halide emulsion layer so that it is no longer separable therefrom. A useful structure for photosensitive elements with non-separable receiver is described in Belgian patent 757 960. In such an embodiment, the support of the photosensitive element is transparent and is coated with an image-receiving layer, a completely opaque light reflecting layer, or reflecting layer, for example a layer containing TiOz, then the photosensitive layer or layers described above. After exposure of the photosensitive element, the frangible capsule containing an alkaline treatment composition is superimposed on an opaque treatment sheet. The pressing members of the camera bring about the rupture of the frangible capsule and the treatment composition can spread in the photosensitive element, at the moment when the composite photographic product is extracted from the camera. . The processing composition develops each layer of silver halide and the dye images are formed, in proportion to the development, which diffuse towards the image receiving layer to provide an image at the location that is viewed through the lens. transparent support on the opaque reflective layer.

Another structure without separation, comprising the photosensitive element and the image-receiving layer, with which the compounds according to the invention can be used, is described in Belgian patent 757 959. In this embodiment, the support of the the photosensitive element is transparent and is coated with an image-receiving layer, a completely opaque reflecting layer and the photosensitive layers described above. The frangible capsule containing the alkaline treatment composition and an opacifying agent is placed in a position adjacent to the layer furthest from the support and to a transparent complementary sheet. The composite photographic product is placed in the camera, it is exposed through the transparent sheet furthest from the support, then it is passed between the pressing members placed in the camera and it is then extracted from this device. The pressing members cause the frangible capsule to rupture and allow the treatment composition and the opacifying agent to spread over the negative part of the composite photographic product, so as to make it insensitive to light. The treatment composition develops each layer of silver halides and, in proportion to the development, dye images are formed which diffuse towards the image receiving layer. An image is thus obtained which can be seen through the transparent support on the opaque reflecting layer.

Other product structures can be used without separation from the compounds according to the invention; these are described in US Patents 3,415,644, 3,415,645.3,415,646.3,647,437 and 3,635,707.

The composite photographic product according to the invention can be used to obtain positive images of one or more colors. In a three-color system, each emulsion layer is combined with the silver halides constituting the composite photographic product with a dye image-forming compound having a predominant spectral absorption in the visible region of the spectrum to which this emulsion is sensitive. with silver halides, i.e. the blue sensitive silver halide emulsion layer is

15

616,248

associated with a yellow dye imaging compound, the green sensitive silver halide emulsion layer is associated with a magenta dye imaging compound and the sensitive silver halide emulsion layer red is associated with an image-forming compound of blue-green dye. The dye imaging compound associated with each layer of silver halide emulsion may be introduced either into the layer of silver halide emulsion itself or into a layer adjacent to the layer of silver halide emulsion. silver halides. The magenta dye image-forming compound is, of course, a compound according to the invention.

When G is a hydrolysable acyloxy radical, the absorption spectrum of the azo dye has a maximum density shifted towards a lower wavelength. The shifted maximum absorption dyes of this class absorb light outside the range to which the associated silver halide layer is sensitive. The use of certain azo dyes-developers at Max. of offset absorption is described in US Patent 3,307,947. It is advantageous to introduce the dye-forming compounds with offset absorption according to the invention, into the silver halide emulsion layer without reducing significantly the sensitivity of the layer. The acyloxy radical is hydrolyzed by the alkaline treatment composition, which releases a magenta dye of the desired shade. The compound forming the yellow dye image and the blue-green dye image can be chosen from the compounds described in Belgian patent 788 268.

The compounds according to the invention can be used and preferably the compounds which can be separated after oxidation, at a very variable content depending on the particular compound chosen and the desired results. For example, the dye image-forming compounds can be introduced into the layers in the form of a dispersion in a synthetic or natural hydrophilic film-forming polymer, such as gelatin, polyvinyl alcohol, etc., permeable to a treatment composition. alkaline aqueous. Preferably, the amounts of the dye-forming compound and of the polymer are in a ratio of between 0.25 and approximately 4.

The dye-forming compounds according to the invention can also be incorporated into the gelatin by well-known techniques, for example using an organic solvent which is not soluble in water and has a high boiling point, or an organic solvent which is miscible with water and low boiling point. Depending on the carrier group in the dye-forming compounds, different silver halide developing agents can be used. If the carrier group is that of formula IV, any silver halide developer capable of giving cross-oxidation with the dye-forming compounds can be used. The developer can be used in the photosensitive member and activated by the alkaline treatment composition. Specific examples of developing agents which can be used include hydroquinone, aminophenols, for example, N-methylaminophenol, Pheni-done (1-phenyl-3-pyrazolidone) sold by the company Ilford, Ltd . ; Dimezone (1-phenyl-4,4-dimethyl-3-pyrazolidone) sold by the Eastman Kodak Company; 1-phenyl-4-methyl-4-hydroxy-methyl-3-pyrazolidone, N, N-diethyl-j> -phenylenediamine, 3-methyl-N, N-diethyl-g-phenylenedi-amine, 3- methoxy-N, N-diethyl-g-phenylenediamine, etc. The black and white developers listed in this list are preferred because they are less likely to form parasitic colorations in the image receiving product.

According to a preferred embodiment, the silver halide developing agent used is oxidized when, during development, it reduces the silver halide to metallic silver. A cross-oxidation then occurs between the oxidized developer and the sulfonamidophenol or the dye-forming sulfonamidonaphthol. The product of cross-oxidation, through alkaline hydrolysis, releases an image of a diffusible anionic dye which then diffuses to the receiving layer to form a dye image there. The transfer of the diffusible group into the alkaline treatment composition is due either to its own diffusibility or to the fact that it has in its structure one or more solubilizing groups, such as -COOH, -S03H, -S02NR5R6, -OH , etc. (where R5 and R6 have the meanings defined above, one of them at least, representing a hydrogen atom).

When the preferred compounds according to the invention are used, a diffusible dye image is produced in proportion to the development of the silver halide emulsions by a halide developing agent which forms negative or positive-direct silver images in the layers. emulsions. If we use a silver halide emulsion which forms a direct positive silver image, such as a direct positive emulsion with internal image, or a 2 (i solarized emulsion, which we develop in unexposed areas, we obtain a positive image on the dye image receiving layer.

After exposing the composite photographic product, the alkaline treatment composition permeates the various layers to initiate the development in the unexposed areas of the silver halide emulsions. The developing agent present in the composite photographic product develops each layer of silver halide emulsion in the unexposed areas (since a direct positive silver halide emulsion is used), thus causing the oxidation of the developing agent according to an image, corresponding to the unexposed areas of the emulsion layers. By cross-oxidation between the oxidized developing agent and the dye-forming compounds, the oxidized form of these compounds is obtained which then leads, by a reaction catalyzed by a base, to the release of the dyes preformed according to an image consistent with the photographic exposure of each layer of emulsion to silver halides. At least a part of the images of the dyes diffuses towards the image-receiving layer, so as to form a positive image of the original. After being contacted with the alkaline treatment composition, the stabilizing layer of the composite photographic product lowers the pH of the composite photographic product (or the image receptor element) so as to stabilize the image.

5

Useful internal image silver halide emulsions are those which predominantly form latent images in silver halide grains, unlike silver halide emulsions where the i0 latent images form preferably on the surface of the grains. Such internal image emulsions are described in US Patents 2,592,250 and in other publications. Other useful emulsions are described in US Pat. No. 3,761,276. Silver halide emulsions with internal images can be defined by increasing the maximum density obtained when they are develops by so-called "internal" developers instead of developing them with so-called "external" or superficial developers. Useful internal image emulsions are those which satisfy the following test: on ft (apply a layer of a sample of the silver halide emulsion on a transparent support, it is exposed through a sensitometric scale for a time varying from 0.01 s to 1 s, it is developed for 3 min at 20 ° C. in the developer A of formula below; a maximum density must be obtained in f)? at least 5 times higher than the maximum density obtained with a silver halide emulsion similarly exposed and then developed for 4 min at 20 ° C in a developer B ("external" developer) whose formula is given below .

616,248

16

Preferably, with developer A, less is obtained in maximum density 0.5 unit more than with developer B.

Hydroquinone developer

Monomethyl-p-aminophenol sulfate Sodium sulfate dehydrated Potassium bromide Sodium hydroxide Sodium thiosulfate OH2 q.s.p.

developer b P-hydroxyphenylglycine Sodium carbonate OH2 q.s.p.

15 g 15 g 50 g 10 g 25 g 20 g 1 1

10 g 100 g 1 1

10

When treating silver halide emulsions with an internal image, in the presence of veiling agents, or nucleating agents, positive-direct silver images are obtained. In the embodiments of the invention, such emulsions are particularly useful. Suitable veiling agents include hydrazines, described in United States Patent 2,588,982.2,563,785, hydrazides and hydrazones described in United States Patent 3,227,552; the quaternary salts of hydrazone, described in US Patent 3,615,615; hydrazone-containing polymethine dyes described in U.S. Patent 3,718,470, or mixtures of these compounds. The content of fogging agents used can vary widely depending on the desired results. Generally, the level of the leveling agent varies from 0.4 g to about 8 g per mole of silver in the photosensitive layer, or from about 0.1 g to about 2.0 g per liter of developer, if it is introduced into the developer. However, the agents described in U.S. Patents 3,615,615 and 3,718,470 are used in an amount of about 0.5 g to 10 g per mole of silver in the photosensitive layer.

According to a preferred embodiment, the useful solarious emulsions are well-known silver halide emulsions which have been effectively veiled, either chemically, in particular by the use of reducing agents, or by radiation, to the point which corresponds approximately at the maximum density of the inversion curve, as indicated in Mees' Theory of the 45 Photography Process, published by Macmillan Co., New York, New York, 1942, pages 261 -297. Conventional methods for the preparation of solarized emulsions are described in English patent 443,245 in which it is indicated that the emulsions are subjected to Roentgen rays until a marking 50 corresponding to the top of the gradation curve is obtained when it is developed without prior exposure; British Patent 462,730 describes the use of light or chemicals such as silver nitrate to convert conventional silver halide emulsions into solarized positive-direct emulsions 55; US Patent 2,005,837 describes the use of silver nitrate and other compounds associated with heat treatment to accomplish solari-sation. Particularly useful veiled positive-direct emulsions are those described in US Pat.

from America 3 367 778.3 501 305.3 501 306.3 501 307 and combinations of these emulsions can be used.

Other embodiments with the compounds giving rise to the chemical image-forming reactions according to the invention, use the techniques described in the patents of the United States of America 3 227 550, 3 227 551.3 227 552, 3,364,022.

When photosensitive elements are used which contain the compounds according to the invention where Car is a silver halide developing agent, as described for example in US Patent 2,983,606, the composition of Liquid treatment that is applied impregnates the emulsion to provide a dye solution uniformly distributed in the emulsion. While developing the silver halide emulsion exposed in a negative silver image, the oxidation product of the dye-developer is immobilized, or precipitated in situ with the developed silver, which provides an image non-oxidized dye-developer dissolved in the liquid treatment composition. This immobilization seems to come at least in part from the change in solubility of the developer dye after oxidation. At least part of this distribution is transferred according to the image of the non-oxidized dye-developer to an image-receiving layer applied in superposition, to provide a transfer image.

The negative silver halide emulsions used in certain embodiments of the invention, as above, may include the silver halides such as, for example, silver chloride, silver bromide, chlo silver bromide, silver bromoiodide, silver chlorobro-meodide, and mixtures of these halides. The emulsions can be coarse or fine grain emulsions which can be prepared by any of the known methods, for example, single jet emulsions such as those described in Trivelli and Smith, in "The Photograph Journal ”, Vol. LXXIX, May, 1939 (pp. 330-338), double-jet emulsions such as Lippmann emulsions, ammoniacal emulsions, emulsions matured with thiocyanates or thioethers, such as those described in United States patents d America 2,222,264, 3,320,069.3,574,628. The emulsions can be regular, mono-dispersed grains such as those described by Klein and Moisar, in J. Phot. Sci., Vol. 12, No. 5, Sept./Oct., 1964 (pp. 242-251).

According to another embodiment, the image inversion methods described in English patent 904 364, page 19, lines 1 to 41 are used. In this method, the dye-forming compounds according to the invention are combined with germs of physical development, in a layer of germs adjacent to the negative photosensitive silver halide emulsion layer. The composite photographic product contains a silver halide solvent preferably introduced into a frangible capsule with the alkaline treatment composition.

The various layers of silver halide emulsions of a composite product for color photography can be placed in the conventional order, that is to say from the exposed face, a layer of silver halide emulsion sensitive to blue, then a silver halide emulsion layer sensitive to green and finally a silver halide emulsion layer sensitive to red. If desired, a layer of yellow dye, or a layer of yellow colloidal silver can be placed between the layer of silver halide emulsion sensitive to blue and the layer of emulsion silver halide sensitive to green , in order to absorb or filter the blue radiation transmitted through the blue-sensitive layer. If desired, the layers of selectively sensitized silver halide emulsions may be arranged in a different order, i.e., from the exposed side, the blue sensitive layer may be applied. , then the layer sensitive to red and finally the layer sensitive to green.

The frangible capsule used can be in accordance with those described in the patents of the United States of America 2,543,181,

2,643,886.2 653,732.2 724,051.3 056,492.3 056,491 and

3,152,515. In general, such frangible capsules consist of a rectangular sheet of a substance impermeable to fluids and to air, folded longitudinally on itself so as to form two walls which are sealed one by one. the other

17

16,248

along their longitudinal edge and their lateral edges to form a cavity in which the treatment composition is enclosed.

In a composite photographic product, each layer of silver halide emulsion containing a dye image-forming substance, or associated with a dye image-forming substance, present in an adjacent layer, can be separated from the others layers of silver halide emulsions of the imaging element by substances such as gelatin, calcium alginate, or by any substance described in the United States patent 3,384,483, by polymeric substances such as the polyvinylamides described in United States patent 3,421,892, or by any substance described in French patent 2,028,236, or in the patents of 15 states - United States of America 2 992 104.3 043 692.3 044 873, 3 061 428, 3 069 263, 3 069 264, 3 121 011 and 3 427 158.

In general, unless otherwise indicated, the layers of silver halide emulsions used comprise photosensitive silver halides dispersed in gelatin 20 and have a thickness of 0.6 (i to 6 (x; dye imaging compounds in a polymeric binder permeable to aqueous alkaline solutions, such as gelatin, as a separate layer having a thickness of 1 to 7 µm; polymeric interlayers permeable to alkaline solutions , for example, gelatin layers, have a thickness of about 1 to 5 (i. Naturally, these thicknesses are approximate and can be varied according to the desired product.

Any substance can be used as the image-receiving layer used in the invention, provided that the desired etching, i.e., fixing of the dye images, is obtained. The particular substance chosen will obviously depend on the dye to be etched. If acidic dyes are to be etched, the image-receiving layer may contain basic polymeric mordants such as polymers of aminoguanidine derivatives of vinyl methyl ketone, such as those described in United States Patent 2,882,156 and the basic polymeric mordants described in the patents of the United States of America 3,625,694 and 3,709,690, as well as in 4 “the patent applications filed in the United States of America, respectively on September 26, 1973 and November 5, 1973 under numbers 400 778 and 412 992.

The preferred mordants are cationic mordants, in particular polymers comprising quaternary nitrogen atoms and having at least 2 aromatic rings for each quaternary nitrogen atom in the cationic polymer (that is to say, having at least minus two aromatic rings for each positively charged nitrogen atom); such polymeric compounds are practically free from carboxy groups. The useful mordants of this class consist of units of the following formula, copolymerized with units derived from at least one other ethylenically unsaturated monomer:

may represent a divalent alkylene radical of 1 to approximately 6 carbon atoms, a divalent arylene radical, a divalent aralkylene radical, a divalent arylene-alkylene radical, such as:

OOO

/ v II II II

- / Q V-R12-; -C-OR12-, - OC- R12-, or-C-NH-R12-,

where R12 represents an alkylene radical, or R8 forms with Q a radical

—CH-

R8

R7

(q)

Rii_N © —R9

r ©

55

60

10

wherein R7 and R8 each represent a hydrogen atom, or a ts lower alkyl radical of 1 to about 6 carbon atoms and R8 may further represent a radical containing at least one aromatic ring (for example phenyl, naphthyl, tolyl); Q

N — R12; R9, R10 and R11 can represent an O

alkyl radical,

aralkyl or aryl, or else R9, R10 and the nitrogen atom to which they are attached can represent with Q the atoms and bonds necessary to form a heterocycle containing a quaternary nitrogen atom, and X © represents an atom or a monovalent negative salt-forming radical, in ionic relationship with the positive salt-forming radical; the said polymer has practically no carboxy group and the positive salt-forming radical of this polymer comprises at least two aryl radicals for each quaternary nitrogen atom in the polymer. According to a preferred embodiment, Q represents a phenylene radical, substituted or not and R9, R10 and Ru, represent identical or different alkyl radicals whose total number of carbon atoms is greater than 12. These preferred cationic polymer mordants are described in more detail in the aforementioned United States patent 3,709,690 and in French patent application 7,431,745, filed September 20, 1974.

Other useful mordants include 4-vinyl-pyridine polymers, the polymers described in U.S. Patent 2,484,430, cetyltrimethylammonium bromide, etc. Other effective etching compositions are described in U.S. Patents 3,271,148 and 3,271,147.

Generally good results are obtained when the image-receiving layer, preferably permeable to an alkaline solution, is transparent and has a thickness of from 5 to about 6.25 µm. Naturally, this thickness can be modified according to the desired result. The image receiving layer may also contain ultraviolet absorbing substances, to protect the etched dye images from discoloration due to ultraviolet light; this image-receiving layer may also contain optical brightening agents such as stilbenes, coumarins, triazines, oxazoles, dye stabilizers such as chromanols, alkylphenols, etc.

The use of an acidifying or stabilizing layer in the dye image receiving element of a composite photographic product usually increases the stability of the transfer image. In general, the stabilizing layer lowers the pH of the layer containing the image from an initial value equal to approximately 13 or 14, to a final value equal to at least 11 and, preferably between 4 and 8, in a very short time after imbibition. For example, use may be made of the polymeric acids described in U.S. Patent 3,362,819, or solid acids, or metal salts, for example zinc acetate, zinc sulfate, acetate magnesium, etc., described in U.S. Patent 2,584,030; these compounds give good results. Such stabilizing layers lower the pH of the composite photographic product after development so as to

616,248

18

terminate development and significantly reduce the transfer of additional dye, thereby stabilizing the dye image.

According to one embodiment, an inert retarding layer, or spacer layer, placed on the stabilizing layer can be used; the role of this retarding layer is to control the decrease in pH, proportional to the speed at which the alkaline substance diffuses through the inert retarding layer. For example, the retarding layers are layers of gelatin, polyvinyl alcohol, or any substance described in US Patent 3,455,686. The retarding layer can be effective in avoiding differences reaction rates within a large temperature range, for example, it prevents the premature decrease in pH when imbibing is carried out at a temperature above room temperature, for example at 35-37 , 8 ° C. The retarding layer generally has a thickness of approximately 2.5 n to approximately 3.5 μ. Particularly good results are obtained when the retarder layer comprises a hydrolyzable polymer, or a mixture of polymers which are slowly hydrolyzed by the treatment composition. For example, such polymers include polyvinyl acetate, cellulose esters, etc.

The alkaline treatment composition used is a conventional aqueous solution of an alkaline substance, for example sodium hydroxide, sodium carbonate, or an amine such as diethylamine; it preferably has a pH greater than 11 and preferably contains a developing agent as described above. The solution also preferably contains a viscosity-increasing compound, such as a high molecular polymer, for example a water-soluble ether inert to alkaline solutions, such as hydroxyethylcellulose, or the alkali salts of carboxymethylcellulose. , such as the sodium salt of carboxymethylcellulose. Preferably the viscosity increasing compound is used in a content of between about 1% and about 5% by weight of the treatment composition, which gives a viscosity of from about 100 mPl to about 200,000 mPl. According to one embodiment, an opacifying agent can be added to the treatment composition, for example titanium dioxide (TiOz), carbon black, 4 "dyes indicating pH, etc.

While the alkaline treatment composition can be used in a frangible capsule, as described above, to facilitate its introduction into the photographic product, other methods can also be used; for example, 45 the treatment solution can be injected by means similar to hypodermic syringes, attached to the camera, or to the charger.

The light-reflecting layer, permeable to alkaline solutions and opaque used in certain embodiments of the composite photographic product, generally comprises an opacifying agent dispersed in a binder having the desired properties. The white light-reflecting layers are particularly suitable since they provide pleasant backgrounds on which the dye image 55 can be examined and also have the opaque properties desired for the reflection of the incident radiation. Suitable opacifiers include titanium dioxide, barium sulfate, zinc oxide, barium stearate, flake silver, silicates, alumina, zirconium oxide, acetylm zirconium acetate, zirconium and sodium sulfate, kaolin, mica and mixtures of these compounds at levels varying according to the degree of opacity desired. The opacifiers can be dispersed in any binder such as a polymer matrix permeable to alkaline solutions, for example gelatin, polyvinyl alcohol, etc. If desired, optical brightening agents such as stilbenes, coumarins, triazines and oxazoles can be added to the light reflecting layer. When it is desired to increase the opacity of the reflecting layers, it is possible to add opacifying agents of black color, for example carbon black, dyes nigrosine, etc., or else these agents can be applied in a separate layer adjacent to the reflective layer.

The supports of the photosensitive elements can be made of any substance provided that it does not adversely affect the photographic properties of the composite photographic product and that it provides a support of stable dimensions. Typical flexible substances include cellulose nitrate, cellulose acetate, polyvinyl acetal, polystyrene, polyethylene terephthalate, polycarbonate, poly-a-olefins, such as polyethylenes, polypropylenes, resinous substances and related compounds. The support can have a thickness of about 50 µm to about 225 µm.

The silver halide emulsions used according to the invention are well known and described in Product Licensing Index, Vol. 92, December 1971, publication 9232, page 107, in paragraph 1, entitled "Typical emulsions"; they can be sensitized chemically and spectrally as described in this last publication, page 107, in paragraph III, entitled “Chemical Sensitization” and pages 108 and 109, in paragraph XV, entitled “Spectral sensitization”; these emulsions can * be protected from the veil and stabilized against loss of sensitivity during storage, using substances described in the publication cited above on page 107, in paragraph V, entitled: "Antifoggants and Stabilizers"; the emulsions may contain development modifiers, tanning agents, coating aids, described on pages 107-108, in paragraph IV, entitled: "Development modifiers"; in paragraph VII, entitled: "Hardeners" and in paragraph XII entitled: "Coating aids"; the photosensitive layers and the other layers of the photosensitive element may contain plasticizers, binders and filter dyes, as described on page 108, in paragraph XI entitled: "Plasticizers and lubricants" and in paragraph VIII entitled: "Vehicles" and page 109, in paragraph XVI entitled: “Absorbing andfilter dyes”; these photosensitive layers and the other layers may contain adjuvants incorporated by the methods described on page 109, in paragraph XVII, entitled: "Methods of addition". These layers can be applied using the different techniques described on page 109, in paragraph XVIII entitled: "Coating procedures".

It will be noted that after the transfer, there remains in the photosensitive element a dye image in addition to the developed silver. In this element, a dye image consisting of the residual non-diffusible compound can be obtained, if the residual silver and silver halide are removed by a well-known conventional method, for example, bleaching followed by fixing, or whitening-fixing, etc. If desired, the dye image can also diffuse outside the element in these baths, rather than in the image receiving element. If, in such a photosensitive element, a negative silver halide emulsion is used, it is possible in this way to produce a positive dye image such as a transparent color photograph, or a color motion picture film. If, in such a photosensitive element, a direct positive silver halide emulsion is used, a negative color image is then produced.

When the desired dye image is retained in the composite photographic product, the dye image-forming compounds are preferably compounds whose absorption peak is offset (G then represents a hydrolysable acyloxy radical) and they are incorporated in the silver halide emulsion layer.

The following examples illustrate the invention. The structures of all the compounds are confirmed by means of their spectrum of

19

616,248

nuclear magnetic resonance and their infrared spectrum and, in some cases, by elemental analysis. The notation t-C5Hu is the abbreviation for t-pentyl.

4-amino-N- [4- (2,4-di-p-pentylphen-oxy) butyl] -l-hydroxy-2-naphthamide can be prepared as follows: l-hydroxy- is reacted by coupling N- [4- (2,4-di-t-pentylphenoxy) -butyl] -2-naphthamide (described in US Patent 2,474,293), with diazotized p-anisidine for example:

CH30_ ^ N.pCl 0

Then, the azo radical of the compound thus prepared is reduced by sodium dithionite (Na2S204) which gives the corresponding amine (likewise, see US Patent 3,458,314, column 10).

Example 1

Preparation of compound n ° 1 releasing a dye by redox.

c0nh (ch2> 40

* ■ * 5 * 11-

mso2 "/ OY '(OV

so2nhc (ch3) 2ch2c (ch3) 3

OH

CH3S02NH.

- <o>

A solution of a diazonium salt is prepared by bubbling hydrochloric gas into a solution of 12.9 g of 4-p-aminophenylsulfonamido-N - [(2,4-di-t-pentylphenoxy) butyl] -l- hydroxy-2-naphthamide, in 130 ml of absolute ethanol. After cooling to a temperature below -15 ° C, 2.7 g of isopentyl nitrite are added and the mixture is stirred for 35 min.

On the other hand, 8.6 g of 5-methanesulfonamido-1-hydroxy-2-t-octylsulfonamide are dissolved in a mixture of 30 ml of Pyridine and 200 ml of absolute ethanol, then cooled to the temperature of -10 ° C under nitrogen atmosphere. In 20 min, the above diazonium salt solution is added, under a nitrogen atmosphere and while cooling, and the mixture is stirred for 2 h at a temperature of -10 ° C .; then the solution is allowed to warm to room temperature overnight. Filtered to separate the pasty precipitate obtained. It is crystallized from 75 ml of tetrahydrofuran and precipitated by pouring it slowly into 800 ml of hexane, 12.8 g of dye-forming compound are obtained (yield 58%).

Thin layer chromatography indicates a weak trace of impurity. The compound has a maximum absorption (Xmax) at 565 nm in dimethylacetamide.

Preparation of intermediates a) 5-methanesulfonamido-1-hydroxy-2-t-octylsulfonamide is prepared by hydrolyzing 4.3 g of 5-bis (methanesul-fonyl) amino-1-hydroxy-2-t-octylsulfonamide for 3 hours at room temperature in 10 ml of a 45/100 aqueous solution of potassium hydroxide in 90 ml of ethanol. The mixture is acidified with concentrated hydrochloric acid. Diluted with water and 3.14 g of a crystalline product are obtained, the melting point of which is 168-169 ° C.

b) 5-bis (methanesulfonyl) amino-1-hydroxy-2-t-octylsulfonamide is obtained by heating at reflux for 18 h, 24.6 g of 5-bis (methanesulfonyl) amino-1-methanesulfonyl-4 chloride „Oxy-2-naphthalenesulfonyl with 19.6 g of t-octylamine-

(1,1,3,3-tetramethylbutylamine) and 1.29 g of diisopropylethylamine in 700 ml of anhydrous dioxane. The dioxane solution is treated with activated carbon, filtered and poured into three liters of water. The mixture is heated to coagulate the product and by filtration, a gray solid product is separated, washed with water and dried. The crude product is purified by dissolving it in acetone; it is filtered, it is precipitated in a mixture of ether and hexane and 13.9 g of a product are obtained (yield 55%) with a melting point of 212-213 ° C.

50 c) 5-bis (methanesulfonyl) amino-1-methanesulfonyloxy-2-naphthalenesulfonyl chloride is prepared from 7.1 g of the corresponding sodium 2-sulfonate, pasted with 15 ml of N-methylpyrrolidinone, then with stirring , this mixture is added to 50 ml of phosphoryl chloride cooled in an ice-water bath 55, under a nitrogen atmosphere. The mixture thus cooled is stirred for 20 min, then for 10 min at room temperature. The paste obtained is poured into 1.51 ice-cold water, by filtration, a solid is separated and washed with dilute hydrochloric acid. The wet solid is dissolved in 400 ml of 6 () tetrahydrofuran treated with active carbon in the presence of anhydrous magnesium sulfate to dry it, then filtered. The volume of the filtrate is concentrated to 25 ml in a rotary evaporator, then it is diluted with hexane, which causes the precipitation of 5.4 g of sulfonyl chloride (melting point 65 242 ° C, with decomposition) .

d) 5-bis (methanesulfonyl) amino-1-methane-sulfonyloxy-2-naphthalene sulfonate sodium is prepared by dissolving 40 g of the internal salt of 5-amino-1-hydroxy-2-naphthalene acid

616,248

20

sulfonic acid in 100 ml of water and adjusting the pH to 7.5 with a sodium hydroxide solution. 80 g of methanesulfonyl chloride are added dropwise over 4 hours. The mixture is maintained at the temperature of 35-45 ° C and at a pH of 6.5 to 7.5 by cooling it and carrying out periodic additions of a sodium hydroxide solution. After having stirred for 1 h at room temperature (the pH being approximately 7), the precipitate is filtered and dehydrated as much as possible. This precipitate is dissolved in 200 ml of methanol, filtered, washed with ether and dried. 78.5 g of compound are obtained.

e) the internal salt of 5-amino-1-hydroxy-naphthalene-2-sulfonic acid is obtained by sulfonation in 100 g of sulfuric acid at a temperature below 30 ° C., of 50 g of 5-amino- purified l-naphthol. The mixture is stirred for 1 h at room temperature, then poured into about 500 g of ice.

The crude product is separated by filtration; to purify the product, it is first dissolved in a dilute sodium hydroxide solution, precipitated with acetic acid, then it is soaked in 21 of water containing 100 ml of acetic acid and we cool. 48 g of compound are obtained (yield 70%).

The products obtained at each stage of the synthesis described above are identified and / or their purity is verified by chroma-in tography in a thin layer, by spectrography or by nuclear magnetic resonance in dimethylsulfoxide-d6.

is Example 2

Preparation of the dye-forming compound n ° 2:

0.94 g of 5-acetamido-1-hydroxynaphthalene-2-sulfonamide is dissolved in 9 ml of pyridine and diluted with 120 ml of a 20/100 solution of propionic acid in acetic acid. To this solution maintained at a temperature of 10 ° C., there is added dropwise a cooled solution of 2.09 g of 4- (4-amino-benzenesulfonamido) -N- [4- (2,4-di-t- pentylphenoxy) butyl] -1-hydroxy-2-naphthamide in 15 ml of tetrahydrofuran, previously diazotized with 0.4 ml of isopentyl nitrite for 30 min under a nitrogen atmosphere. The mixture is cooled overnight, filtered and diluted with 300 ml of water. The precipitate is filtered and dried. 2.42 g of crude compound are dissolved in 30 ml of acetic acid at a temperature of 25 ° C. Leaving to stand, a precipitate is obtained and 1.28 g of pure compound are thus collected (yield 42%) (Xmax) at 557 nm).

Preparation of intermediates a) 5-acetamido-1-hydroxynaphthalene-2-sul-fonamide is prepared by dissolving 10.8 g of 5-acetamido-1-acetoxynaphthalene-2-sulfonyl chloride in 10 ml of dry chloroform; heated for 2 h 30 in a water bath with 25.0 g of anhydrous sodium carbonate. A solid brown-yellow product is obtained which is dissolved by heating it with 50 ml of water in a water bath for 4 h. Acidified with hydrochloric acid to a pH equal to 5, which precipitates the sulfonamido compound. It is filtered and dried. 5.61 g of compound are obtained (yield 63%).

b) 5-acetamido-1-acetoxynaphta-lene-2-sulfonyl chloride is prepared by pouring dropwise into a suspension of anhydrous sodium 5-acetamido-1-acetoxynaphthalene-2-sulfonate in 100 ml of phosphoryl chloride with 5.5 ml of dry dimethylformamide, under a nitrogen atmosphere. The reaction mixture is stirred for 1 h, then poured onto 600 ml of crushed ice. The crude product is filtered and immediately dissolved in 500 ml of chloroform. The solution is treated with activated charcoal, then dried over anhydrous magnesium sulfate. 10.8 g of a yellow resinous compound are obtained (yield 44%) which has a single spot per chroma-50 tography in a thin layer.

c) sodium 5-acetamido-1-acetoxy-2-naphthalenesul-fonate is prepared by acetylation of 30 g of 5-amino-1-hydroxynaphthalene-2-sulfonic acid (example 1) with 50 ml of acetic anhydride in 25 ml of pyridine; the mixture 55 is heated in a water bath for 1 h 30 min. After cooling, the viscous solution is extracted twice with 600 ml of benzene in total, then the solution is treated with 500 ml of a saturated aqueous solution of sodium chloride. Filtered to separate the amber product which precipitated, washed with a saturated 6H solution of sodium chloride, then dried. 59 g of compound are obtained, containing a few traces of sodium chloride.

Example 3

Preparation of the compound releasing a dye No. 3: The following reaction is represented by the diagram below: Preparation of compound B (intermediate coupler): 5-methanesulfonamido-2-benzyl-sulfonyl-1-naphthol

21

616,248

0s02ch3

0s02ch3

n (S02ch3) 2

0s02ch3

so2ch20 '

* DMF = dimethylformamide

0 = c6h5

nhs02ch3 compound B

Preparation of the intermediate diazonium salt (zene sulfonamido compound) -l-hydroxy-N- [4- (2,4-di-tert-pentylphen-D), by diazotization of compound C: 4- (4-chloro-3- aminoben- oxy) -butyl] -2-naphthamide -

conh (ch „).

2 A

, 0-Y / Vt-C5Hn t_C5Hll

1

Cl

NO,

s02c1

5 11

616,248

22

Diazotation Cl

S02NH - ^

-oh conh (ch) a0

^ "ll

Preparation of the compound rf 3, releasing a dye by redox.

OH

DMF

D8 + D NaOAc

->

c0nh (ch2) a0 - ^

t "C5Hll t-C5HU

SO2CH20

CH3S02NH

Compound 3

Preparation of intermediates Preparation of compound A

When heated to a temperature of 70 ° C., a solution consisting of 98.4 g (0.20 mole) of 1-methane sulfonyloxy-5- [N, N-di (methane-sulfon-yl) chloride is vigorously stirred amino] -2-naphthalenesulfonyl, 126 g (1.00 mole) of sodium sulfite and 400 ml of water. The very thick solution is stirred for 5 h at a temperature of 55-60 ° C., then overnight at a temperature of 25 ° C. The product is filtered and the filter cake is washed with 100 ml of cold water , then with isopropanol. Obtained 101 g of a white powder which is sodium l-methanesulfonyloxy-5- [N, N-di (methanesulfonylamino] -2-naphthalenesulfinate in the very pure state. This substance is used without further purification.

Preparation of compound B

(5-methanesulfonamido-2-benzylsulfonyl-1-naphthol) The mixture consisting of 140 g (0.29 mole) of compound A and 49.5 g (0.29 mole) are stirred while heating in a water bath. ) benzyl bromide and 300 ml of anhydrous DMF. A black solution is formed which is evaporated in a rotary evaporator under reduced pressure, in order to remove most of the solvent and the residue is heated with one liter of IN NaOH while stirring for 1 h in a water bath. The mixture is poured into 2 liters of a water-ice mixture containing sufficient acetic acid to neutralize the excess of NaOH and filtered. 50 The crude coupler is crystallized twice from boiling acetic acid by treating with activated carbon "Darco" sold by the company Atlas Powder Co. and filtering while hot. A white compound is obtained which is the coupler in the pure state (yield 75%) as demonstrated by the NMR, infrared and chromo-55 thin layer spectra.

Preparation of compound C

A solution of 100 g (0.39 mole) of 4-chloro-3-benzenesulfonyl chloride in 400 ml of p-dioxane is added to a solution of 190 g (0.39 mole) of 1-hydroxy-4- amino-N- [4- (2,4-di-t-pentylphenoxy) -butyl -] - 2-naphthamide in 600 ml of p-dioxane and 40.7 g (0.39 mole) of 2,6-lutidine previously cooled to 5 ° C. The reaction mixture is stirred for 3 h under an argon atmosphere at a temperature of 10 ° C. and is poured into (5 in 31% of 10% hydrochloric acid. The gummy solid product which becomes solidifies is separated by stirring; this solid is filtered and dried in air, which gives 280 g of 4- (4-chloro-3-nitrobenzenesulfonamido) -l-hydroxy-N- [4- ( 2,4-

23

616,248

di-tert-pentylphenoxy) -butyl] -2-naphthamide. After recrystallization from 71 of toluene, 232 g of pure substance are obtained, the melting point of which is 221-223 ° C.

3.0 g of 5% sulfur-containing platinum catalyst on carbon are mixed with a solution of 120 g (0.169 mol) of 4- (4-chloro-3-nitrobenzenesulfonamido) -l-hydroxy-N- [4- ( 2,4-di-tert-pentylphenoxy) -butyl] -2-naphthamide in 1.51 metha-nol, then to make the reduction, one operates in a rocking autoclave under a hydrogen pressure of 3445 k Pa at 85 ° C; the reduction lasts 1 hour 30 minutes. The reaction mixture is filtered and the filtrate is evaporated. The residue is dissolved in 600 ml of boiling acetic acid, discolored carbon is added, filtered hot and left to stand to initiate crystallization. The crystalline product is filtered at 25 ° C and recrystallized from acetic acid. 106 g of compound C are obtained: 4- (4-chloro-3-amino-benzenesulfonamido) -l-hydroxy-N- [4- (2,4-di-tert-pentylphenoxy) -butyl] -2-naphthamide, whose melting point is 180-182 ° C (compound C).

Preparation of compound D Diazotation

A solution of 27.2 g (0.040 mole) of 4- (4-chloro-3-amino-benzenesulfonamido) -l-hydroxy-N- [4- (2,4) is prepared at a temperature of 50 ° C. -di-tert-pentylphenoxy) -butyl] -2-naphth-amide in one liter of ethanol, then cooled to 25 ° C. Anhydrous hydrochloric gas is added to the solution subjected to stirring for 30 min at temperature below 30 ° C. The solution is cooled to 0 ° C., then it is treated with 4.8 g (0.041 mol) of amyl nitrite. The diazotization is complete after 30 minutes at 0 ° C.

Coupling

A solution of 13.7 g (0.035 mole) of 5-metha-nesulfonamido-2-benzylsulfonyl-1-naphthol in 25 ml of DMF is treated with 100 g of anhydrous sodium acetate, then the mixture is cooled to 0 ° C. The solution of diazonium salt prepared above is added, in small portions, with vigorous stirring, while the temperature is maintained at 0 ° C. When the addition is complete, 400 g of sodium acetate. The mixture is stirred for 4 h at a temperature of § 5 ° C. The thin layer chromatography indicates that the coupling is complete. The mixture is then put into 41 of a mixture of water and ice containing 100 ml of acetic acid; while stirring, a red powder is made to coagulate which is separated by filtration. Analysis of the raw dye filtered by thin layer chromatography shows that it consists of a single magenta dye-forming compound, with traces of coupler and some other non-polar impurities which probably result from the partial decomposition of the salt of diazonium during its preparation and / or during coupling. To completely remove the impurities, 32 g of the crude compound are crystallized from a solution prepared by boiling this compound with 1.91 isopropanol and adding the minimum of 2-methoxymethanol to maintain the compounds in solution during boiling 15.5 g of pure dye are obtained The filtrate 5 provides an additional 2.6 g of compound in pure form A total of 18.1 g of compound is obtained (yield 48%).

Example 4 Preparation of Compound No. 4

'■ Vil conh (ch2) 4

w C5Hu so2nhc (ch3) 3

-n = n

- (O / -0H

ch3s02nh

This compound is prepared in an identical manner to that described in Example 1 and in Example 3 and good yields are obtained.

Example 5

Preparation of an offset absorption compound n ° 4.

Compound 4 is esterified with benzoyl chloride in anhydrous acetone using an equivalent of pyridine to consume hydrochloric acid. This compound is similar to compound No. 4, except that the hydroxy radical in the para position relative to the point of attachment of the azo chain of the naphthalene nucleus is replaced by a radical -OCOC6H5.

Example 6

Table I provides examples of the compounds releasing a dye by redox, in particular those whose preparation is described in Examples 1 to 4. The characteristics of these compounds are given in Table II. Table III gives additional examples of dye-releasing compounds, as well as the specifications for these compounds.

In general, the dyes and the compounds releasing a dye by redox according to the invention are prepared by well known methods; the starting compounds are either known or prepared by well known methods. The diazotization and coupling reactions used to prepare the dye-releasing compounds are done as described by Fierz-David and Blangley, "Processes of Pye, 5 Chemistry", translated from the 5th edition "Austrian" by PW Vittum, NY, Publication Interscience, Inc., 1949.

In Tables II and III are collected the data concerning the absorption, the diffusion and the stability in the light of the released dyes corresponding to the compounds releasing a f, d dye by redox listed in Tables I and III.

The tests relating to the light stability and the determination of the spectra are carried out on a sample of colored film consisting of a polyester support with a layer containing 65 a mixture of gelatin and of a copolymer of styrene and chloride of N- vinyl-benzyl-N, N, N-trihexylammonium, at a rate of 22 ml per dm2 of each constituent, except for the compounds 6, 20, 23 and 24 for which

616,248

24

samples with a layer of a copolymer of styrene and benzyl-N, N-dimethyl-N- (3-maleimidopropyl) -ammonium chloride at a rate of 22 mg / dm2, mixed with an equal amount of gelatin, applied to a cellulose acetate support.

The dyes are first dissolved in 0.1 N sodium hydroxide (sometimes only a few drops of dimethylform-amide are sometimes required). A sample of uncolored mordant is immersed in a dye solution until it is absorbed by the mordant providing an approximate density of 1.5 to 2.0. The sample is then placed in a Harleco standardized aqueous buffer solution, the pH of which is indicated in the table, the equilibrium is left to settle for 1 min and dried. Harleco buffer solution contains:

- at pH 4: 0.05 M of potassium acid phthalate,

- at pH 5: 0.05 M of potassium acid phthalate and 0.0226 M of soda,

- at pH 7: 0.0667 M of monopotassium phosphate and 0.0389 M of sodium hydroxide.

A - Spectrophotometric test -

The spectrum of dyes released when absorbed by the mordant on a transparent sheet is determined using a spec trophotometer. The maximum wavelength Çk max) and the bandwidth in nm for a density equal to half that corresponding to the X max of the absorption curve for each dye are indicated in the table. This bandwidth at mid-height with the X max determines the shade; the higher the gloss and the purity of the dye, the more the band width at mid-height.

B - Light stability test -

The light stability is determined by irradiation of a colored film sample according to one of the following two methods:

1 °) exposure to light simulating average insolation facing North (WITHOUT), test for 7 days: Xenon arc lamp of 6000 W and of high intensity (ANSI PH 1.42 - 1969 standards), illumination of the 'sample 5380 lux at 21 ° C, relative humidity 45%.

2) exposure to a 6000 W Xenon arc lamp of high intensity for two days. The sample receives 5000 lux through a Wratten 2B ultraviolet filter at an approximate temperature of 38 ° C and at low humidity.

Table I

In these two tests, the optical density is measured at the maximum wavelength before exposure (D0) and after exposure (D). Tables II and III give these values and the percentage reduction obtained.

5

C - Dye transferred to a receiving element—

Emulsion samples containing the dye-forming compounds are veiled by exposing these samples to light, then to treat them, they are applied face to face with samples of receptor element; and between each veiled emulsion and each receiver thus placed face to face, a viscous treatment composition is introduced and each sample is passed with its receiver between a pair of juxtaposed pressure rollers. The thickness of the developer layer of the resulting superimposed product is between 0.075 mm and 0.10 mm. The receiving element has the following structure:

Gelatin (4.3)

Carbon black (27) + gelatin (17)

*> TiO, (25) + gelatin (22)

Mordant * (22) + gelatin (22)

Cellulose acetate support

* Polymer of styrene and N-vinylbenzyl-N, N, N-trihexylammonium chloride.

The treatment composition contains per 11 of solution, 20 g of sodium hydroxide, 0.75 g of 4-hydroxy-methyl-4-methyl-1-phenyl-3-pyrazolidone, 10 g of potassium bromide and 25 g of hydroxyethylcellulose. After applying the composition to the veiled emulsion layer, the dyes are released which diffuse through the layers of carbon black and titanium oxide towards the etching layer. The density of the dyes on the etching layer is read through the support by means of a reflection densitometer, after 30 seconds, 60 seconds and 120 seconds of transfer, at a temperature of 24 ° C. The increase in density as indicated by the values in the table, is a measure of the speed of the release reaction and the diffusion of the dyes. The three values given in the table represent the percentages of the densities read respectively after 30 s, 60 s and 120 s, compared to the maximum density that can possibly be obtained (Dmax). Most of the dyes measured show a diffusion of at least 70% after 60 s and at least 90% after 120 s.

45

25

30

35

s zj

Dye-forming compound no.

Because x m

d q

z1

1

4 * -a -

o

-s02nhc (ch3) 2ch2c (ch3) 3

-nhso2ch3

h

2

4 — a -

o

-so2nh2

-nhcoch3

h

3

5 — a o

-so2ch20

-nhso2ch3

2-c1

4

4 — a o

-so2nh2

-nhso2ch3

h

5

4 — a o

-so2nhch3

-nhso2ch3

h

6

4-a -

o

-so2nhc (ch3) 3

-nhso2ch3

h

25

616,248

Dye-forming compound no.

Because

X m d

q z1

7

4-a o

-s02nh (ch2) 2ch (ch3) 2

-nhso2ch3

h

8

4 — a o

-so, nhch (ch0-c (chu),

-nhso2ch3

h

9

4-a o

-so2nch2ch2och2ch2

-nhso2ch3

h

10

4-a o

-s02nhc (ch3) 3

-nhs02c3h7-n h

11

4-a o

-s02nhc (ch3) 3

-nhs02c4h9-n h

12

4-a o

-s02nhc (ch3) 3

-nhso2t **

h

13

4-a o

-s02nhc (ch3) 2ch2c (ch3) 3

-nhso2t **

h

14

5 — a o

-so2nhch3

-nhso2ch3

2

15

5-a o

-so2nhch2cf3

-nhso2ch3

2-c1

16

5-a o

-s02nh (ch2) 2ch (ch3) 2

-nhso2ch3

2-c1

17

5-a o

-so2nhc (ch3)

-nhso2ch3

2-c1

18

5-a o

-so2nhch2c (ch3) 3

-nhso2ch3

2-c1

19

3-a o

-s02nhc (ch3) 3

-nhso2ch3

4-c1

20

3-a o

-so2nh2

-oh h

21

3-a

- (ch2) 3- 1

-so2nh2

-oh h

22

3-a o

-so2nhch3

-oh h

23

4-a o

-so2nch2ch2och2ch2

-nhcoch3

h

24

4-a o

-s02nhc (ch,) 3

-nhso2ch3

h

25

4-c o

-so2nch2ch2och2ch2

-nhso2ch3

h

26

4-d o

-so2nch2ch2och2ch2

-nhso2ch3

h

27

4-d o

-s02nhc (ch3) 3

-nhso2ch3

h

28

5-a o

-so2ch3

-nhso2ch3

2

29

5-a o

-so2 (ch2) 2ch (ch3) 2

-nhso2ch3

2-c1

30

5-a o

-so2nhch2cooh

-nhso2ch3

2

31

3-a o

-con (ch3) 2

-nhso2ch3

h

A =

DÌO

C0NH (CH2) 4O (O / t "pC5®ii

NHS02-

B =

D =

S02N (ci2H25) 2

NHS02-

? 2B5

1 tRV

C0NHCH2-CH-O— (y—

'"S * !!

*** 11

NHS02t

"" Position at which the Car motif is linked to the azo radical. * T = -m-C6 H4-S02NH2

616,248

26

Table II

Photographic characteristics

Compound

PH

Max

Width of

Image density of

Stability at

trainer

(nm)

strip at mid

dye transfer

the light

dye No.

height

(% of final image)

(nm)

30 s.

60s.

120s.

test

D0

D

Loss

N ° /

in %

PH

1

5

549

96

38

63

86

2/5

1.53

1.28

16

2

7

542

107

41

64

88

-

-

-

3

4

548

103

31

57

82

1/5

1.41

1.34

5

4

4

552

99

43

68

89

2/5

1.84

1.65

10

5

4

546

98

48

75

94

1/4

1.17

1.07

8

6

4

545

103

40

62

85

1/4

2.75

2.59

6

7

4

546

97

43

69

91

2/5

1.74

1.53

12

8

-

-

-

38

62

84

2/5

1.74

1.57

16

9

4

551

97

38

63

86

2/5

2.08

1.07

48

10

5

556

92

41

64

85

2/5

1.16

0.91

22 '

11

5

551

96

34

58

82

2/5

2.13

1.83

14

12

5

557

92

42

68

90

2/5

1.82

0.95

48

13

4

555

97

36

60

84

2/5

1.82

1.64

10

14

5

549

97

48

75

94

2/4

2.08

2.04

2

15

5

544

102

43

71

92

2/5

1.46

1.23

16

16

5

552

99

42

68

89

2/5

1.53

1.39

9

17

4

554

97

44

70

91

2/4

1.84

1.72

7

18

4

551

99

42

68

90

2/5

1.68

1.54

8

19

4

551

94

47

74

94

2/5

1.59

1.42

11

20

5

546

103

43

67

92

1/5

1.33

1.30

2

22

4

544

104

-

-

-

2/5

1.03

0.73

29

23

4

543

106

29

51

75

1/5

1.40

1.18

26

24

4

545

103

40

62

85

1/4

2.75

2.59

6

25

4

551

97

38

63

86

2/5

2.08

1.07

48

26

4

551

97

38

63

86

2/5

2.08

1.07

48

27

4

552

99

43

68

89

2/5

1.84

1.69

10

28

4

540

102

51

79

98

-

-

29

4

546

-

40

66

90

-

-

30

5

552

96

39

63

87

2/5

1.31

1.21

8

31

6

563

89

49

71

92

-

-

27

616,248

ë #

u C ooint Ph «'t H N

2

, <U

D3

CD

/ cd f3

as ed

- SC

"Q.

VI ■> *

W ° c in es es

0 \ r-H T-t O H H

CS es 00 oo m tj *

in in ^ es eS eS

0>

Ti

4); <D

2P ^

<«* W

11

us 2

H§l 2 S-

• * h mn ai

S 8- °

o es en O v ©

(at

O in

^ Ih ✓cd p

. 4) 0) u <ri

§1 u

ûû S5 _c '

b-8

ed D hJ "O

sf if s

o <

O rH \ D

Os ON 00

00 H in VO F- VO

CS VO es

Tfr rf

(S (N h-Os On On r * - vd co> n ^ io> n in »n m Tt rf

Ol

NOT

a>

'è

> u gz

II!

g §.§ öl 8

rfr in cn rS

o oP:

33 * r n ci n m tn m

B55. *

5CuÖ

CS CS CS CN

oooo 3 3 3 3

es co in en en en en

5

6

u rr \ 8 ©

»4

(8 O

Example 7

Dyes such as those released during the alkaline treatment are prepared from compounds comprising the Car radical described above and are dissolved in 30 ml of a 0.5 N sodium hydroxide solution containing 30 g per liter of hydroxyethylcellulose. . Each solution is spread between a complementary sheet of cellulose acetate and a receiving element; the alkaline composition has a thickness of 0.1 mm. The receptor element is that described in Example 6. On ft5 determines the spectrum of the dyes when they have been adsorbed by the mordant, as in Example 6. Tables IV, V and VI below give the formula general coloring and the results obtained.

Table IV

Dye r1

z r5

r6

r3

AT. max

Width of

(nm)

tape to

mid-height

(nm)

1

h

4 — s02nh2

h n — C3H7

ch3

545

101

2

h

4 — s02nh2

h

- (ch2) 3-so2nh2

ch3

547

95

3

h

4 — s02nh2

h

-ch2cf3

ch3

541

98

4

h

4 — s02nh2

h

-cyclohexyl ch3

549

95

5

h

4-s02nh2

h c6h5

ch3

546

100

C2H5

6

h

4 — s02nh2

h

1

CH2C H-nC4H9

ch3

544

98

7

H

4 — s02nh2

H

-ch2 - / ^ (^ j \ so2nh2

ch3

547

96

so2nh2

8

H

4-s02nh2

H

ch3

546

90

9

H

4 — s02nh2

= R6

-ch (ch3) 2

ch3

557

96

10

h

4-s02nh2

= R6

—If (CH3) 3

ch3

546

100

Dye r1

r5

11

12

13

14

15

16

17

18

19

20

21

22

h h

h h h h h h h h h

h

4 — s02nh2

4 — s02nc

4-s02n <^

4-s02nh2 4-s02nh2 4 — s02nh2 4 — s02nh2 4 — s02nh2 4 — s02nh2 4 — s02nh2

4 — s02nh

"ch3

ch3

ch,

(ch3) 3cch2 4 — s02nh n-C3H7

ch3 ch3 I I -ch2c h-o-c h-ch2-

-ch2ch2-o-ch2ch2-

-ch2ch2-o-ch2ch2-

= r6

ch3

-ch2ch2ch2ch2ch2-h

= r6

-ch2ch2-o-ch2ch2-

h h

h

23

h

4-s02 | 4h A

h

24

25

26

27

h h h h h2nso2- (ch2) 3 -ch2ch2-o-ch2ch2-4 — s02nh

I

h2ns02- (ch2) 3 -ch2ch2-0-ch2ch2-

4 — s02nh2 4 — s02nh2

h h r6 r3 AT. max Width of

(nm) band to

mid-height (nm)

ch3

548

98

ch3

552

99

ch3

556

102

-ch2ch2oh ch3

548

100

-C6hs ch3

550

97

ch3

550

105

n_cshu ch3

ch2ch2cn ch3

543

100

c6h5

551

98

—Tc4h9

c6h5

553

96

NOT"

—Tc4h9

ch3

548

—Tcjhl

4n9

ch,

—TCiHi

• 4n9

ch,

560

96

ch3 543. 89

c (ch3) 3

c (ch3) 2ch2c (ch3) 3

ch3

b b

553 555

95

96

Dye R1

Z

28

2-Cl

5-S02NH2

29

2-a

5-S02NH2

30

2-Cl

5-S02NH2

31

4-Cl

3-S02NH2

32

4-a

3-S02NH2

33

4-Cl

3-S02NH2

34

4-a

3-S02NH2

35

H

4-CONH2

36

H

2-S02NH2

37

2-OCH2

5-S02NH2

38

H

2-CN

39

H

2 — S02NH2

40

H

3-N02

41

H

3-S02CH3

42

2-Cl

5-C1

43

2-Cl

5-a

44

2-Cl

5-Cl

45

2-Cl

4-a

46

2-Cl

4-Cl

47

2-Cl

4-a

48

• 2-Cl

4-Cl

49

H

3-S02CH3

"\ 2r

R6 R3 X max

(nm)

H

ch3

550

ch3

1

ch-c (ch3) 3

ch3

555

c (ch3) 3

n-C3H7

558

ch3

ch3

536

c (ch3) 2ch2c (ch3) 3

ch3

551

c (ch3) 2ch2c (ch3) 3

at

c (ch3) 2ch2c (ch3) 3

b

c (ch3) 3

ch3

548

c (ch3) 3

ch3

559

c (ch3) 3

ch3

542

h ch3

554

ch3

ch3

c (ch3) 3

b

554

c (ch3) 3

b

547

c (ch3) 3

at

559

c (ch3) 3

b

558

ch3

b

555

c (ch3) 3

b

557

c (ch3) 3

at

555

ch3

at

553

ch3

b

552

t-C8hi7

b

-

Band width at mid-height (nm)

99

97

98 95 95

99 94

100

98

96 90

99

101

101

97

102 100 100

31

616,248

Table V

6

Dye

R1

Z

R5

R6

A. max

Width of

(nm)

tape to

mid-height

(nm)

50

H

3-S02NH2

H

COCHj

546

104

51

H

4 — S02NH2

H

COCHj

551

111

52

4-Cl

3-S02NH2

H

H

547

109

53

3-C1

3-S02NH2

H

H

544

98

54

H

3-S02NH2

H

(CH2) 3S02NH2 552

-

55

H

3-S02NH (CH2) 3S02NH2

H

H

545

Table VI

n = n

Dye

R1

Z

D pH 'A, max

Width of

(nm)

tape to

mid-height

(nm)

56

h

3-s02nh2

-s02nhc0ch3 5

528

103

57

h

4-s02nh2

-s02nhc0ch3 4

541

109

58

H

3-s02nh2

-s02nh2 7

534

100

59

2-och3

5-s02nh2

-s02nh2 7

537

109

60

H

4 — s02nhch3

-so2nh2

538

109

61

H

3-s02ch3

-s02nh2 7

541

106

62

h

4-g *

-s02nh2 7

529

-

63

2-Cl

4-s02nh2

-s02ch3 4

546

113

64

2-Cl

4-s02nh2

-so2ch20 4

561

110

65

h

4-s02nh2

-s02ch3 4

530

114

66

2-Cl

5-s02nh2

-S02CH2-p-C6H4C00H 4

545

-

67

2-Cl

5-s02nh2

-s02ch2ch2s03h 4

540

-

616,248

32

Dye

R1

Z

D

pH

A, max

Width of

(nm)

tape to

mid-height

(nm)

68

2-Cl

5-s02nh2

-so2ch2ch2cooh

4

542

69

H

4-s02nh2

-con (ch3) 2

7

573

96

70

h

4-SOzNH2

-so2nhch2cooh

5

547

96

71

H

3-s02nh2

-soc6h5

5

554

91

72

2-Cl

5-s02nh2

-so3h

7

566

_

73

H

4 — s02nh2

-soc6h5

5

567

99

74

2-Cl

5-s02nh2

-so3c6h5

5

544

100

75

h

4-s02nh2

-so3c6h5

5

537

99

* G = S02 (Œ2) 2C0NH-m-C6H4S02NH2

Example 8

A photosensitive element for color photography, with an inseparable structure, is prepared by applying the following layers in the order indicated on a transparent support of polyethylene terephthalate:

1) an image-receiving layer containing per dm2: 22 mg of a copolymer of styrene and N-vinyl-benzyl-N, N, N-trihexylammonium chloride and 22 mg of gelatin.

2) a reflective layer containing per dm2: 220 mg of titanium dioxide and 22 mg of gelatin.

3) an opaque layer containing per dm2: 27 mg of carbon black and 17 mg of gelatin.

4) a layer containing per dm2: 7.3 mg of gelatin and 0.54 mg of an image-forming compound of blue-green dye, of formula:

(/ \ v_n0

L \ = A 2

OH

5) a layer of silver gelatin-chlorobromide emulsion sensitive to red with internal image, containing per dm2: 11 mg of gelatin, 11 mg of silver, 8 g / mole of 2-sec-octadec acid cylhydroquinone-5-sulfonique and 1.5 g / mol of silver of a nucleating agent, l-acetyl-2- {p- [5-amino-2- (2,4-di-t-pentyl phenoxy ) -benzamido] phenyl} hydrazine.

6) an interlayer containing per dm2: 5.5 mg of gelatin and 11 mg of 2,5-di-sec-dodecyl-hydroquinone.

7) a layer containing per dm2: 11 mg of gelatin and 6.5 g of a compound releasing a magenta dye, compound designated in Table I, under No. 9.

8 °) a layer of emulsion with silver gelatin-chlorobromide sensitive to green with internal image, containing per dm2: 12 mg of gelatin, 11 mg of silver and 16 g / mole of silver of 2-sec acid -octadecylhydroquinone-5-sulfonic and 1.5 g silver per mole of the nucleating agent, l-acetyl-2- [p- [5-amino-2- (2,4-di-t-pentylphenoxy ) benzamido] phenyl] hydrazine.

9 °) an interlayer containing per dm2: 5.5 mg of gelatin and 11 mg of 2,5-di-sec-dodecylhydroquinone.

10 °) a layer containing per dm2: 11 mg of gelatin and 11 mg per dm2 of a yellow dye image-forming compound, of formula:

CONHCHL

33

616,248

11 °) a layer of silver gelatin-chlorobromide emulsion sensitive to blue with internal image containing per dm2: 11 mg of gelatin, 11 mg of silver and 8 g per mole of silver of 2-sec acid -octadecylhydroquinone-5-sulfonic and 1.5 g per mole of silver nucleating agent, l-acetyl-2- [p- [5-amino-2- (2,4-di-t-pentyIphenoxy) benzamido] phenyl] hydrazine.

12 °) an overlay containing 5.4 mg of gelatin per dm2.

The above silver halide emulsions are positive-direct emulsions with high internal sensitivity and low surface sensitivity; they are described in US Patent 3,761,276.

Then, the photosensitive element prepared above is exposed, through a color sensitometric range. The following treatment composition is used in a frangible capsule; this composition is spread between the photosensitive element and an opaque complementary sheet of cellulose acetate by passing the composite photographic product formed from the photosensitive element and the complementary sheet applied against each other, between a pair of rollers side-by-side pressers.

Potassium hydroxide

4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone

5-methylbenzyltriazole t-butylhydroquinone Sodium sulfite (anhydrous)

Carbon black Hydroxyethyl cellulose Distilled water

56g

8 g 2.4 g 0.2 g 2.0 g 40 g

The additional sheet is prepared by applying to a support of polyethylene terephthalate, as described in French patent application 7,306,645:

- a retarder layer in cellulose acetate at a rate of s 33 mg / dm2 and a layer of polyacrylic acid at a rate of 230 mg / dm2.

After 3 h, the following sensitometric results are read on the image-receiving layer of the product:

, 0 Maximum density Minimum density

Red Green Blue I5 2.18 2.18 1.54

Red Green Blue 0.28 0.27 0.24

q.s.p.

25 1000

g ml

The yellow dye imaging compound used in this example is prepared by the following method. 6.4 g (0.016 mole) of l-phenyl-3-methylcarbamyl-4- (p-chlorosul-2o fonylphenylazo) -5-pyrazolone is added to a solution of 7.3 g (0.015 mole) of l-hydroxy- 4-amino-N- [4- (2,4-di-t-amylphenoxy) -butyl] -2-naphthamide in 60 ml of anhydrous pyridine which is cooled to 20 ° C in an ice bath and l 'It is stirred under a nitrogen atmosphere. The mixture is stirred for 2 h at room temperature, then poured into 1 liter of a mixture of water and ice containing 75 ml of hydrochloric acid. A precipitate is collected, dried and recrystallized and 10.4 g of the yellow dye-forming compound are obtained.

VS

Claims (21)

616,248 1 or v -s02nh- nh-so, nh-so, where B1 represents the rest of the ballasting group. „1 R II. (Z) N = N Car-X-J-NH IIL (Z) R N = M / TJ-NR) -X- / -Car ~ q - m in which; Because represents a carrier radical whose oxidation in alkaline medium leads to a substance whose mobility is different from that of the dye-forming substance; m and q each represent a number equal to 0 or 1; if q is equal to 1, X represents a bivalent linking radical, of formula -Rz-Ln-R2p- where each of the radicals R2, which are identical or different, represents an alkylene radical containing from 1 to 8 carbon atoms, phenylene or substituted phenylene containing from 6 to 9 carbon atoms; L represents a bivalent radical chosen from the class consisting of oxy, carbonyl, carboxamido, carbamoyl, sulfonamido, sulfamoyl, sulfinyl or sulfonyl radicals; if q is equal to 0, Car-X can also represent the radicals Car-alkylene-SO2, Car-C6H4CH2-SO2, Car-phenylene-SOz, the total number of carbon atoms of X not exceeding 14; n is 0 or 1; p is 1 when n is 1 and p is 1 or 0 when n is 0; R represents a hydrogen atom or an alkyl radical containing from 1 to 6 carbon atoms; J represents a bivalent sulfonyl radical or. arbonyl; Q is in position 5 or in position 8 relative to the radical G and it represents a hydroxy radical or a radical of formula -NHCOR3 or -NHS02R3 in which R3 represents an alkyl radical containing from 1 to 6 carbon atoms, a benzyl radical, a phenyl radical or a substituted phenyl radical containing from 6 to 9 carbon atoms; G represents a hydroxy radical or a salified hydroxy radical or a hydrolyzable acyloxy radical which has one of the formulas; 55 o o -OCR4 or -OC OR4, in which R4 represents an alkyl radical containing from 1 to 60 18 carbon atoms, a phenyl or substituted phenyl radical containing from 6 to 18 carbon atoms; r is 1 or 2; Z is chosen from the class consisting of the cyano, trifluoromethyl fluorosulfonyl, carboxy, carboxylic ester radicals of formula -COOR4, R4 having the abovementioned meaning, nitro in position 2 or 3 with respect to the azo, fluoro, chloro or bromo, alkylsulfonyl group or substituted alkyl-sulfonyl containing from 1 to 8 carbon atoms, phenylsulfonyl or phenyl 1. Photographic product comprising a support with the class constituted by the compounds which have one of the least a layer of photosensitive emulsion with halides following formulas: silver associated with a dye-forming substance 2 »Y represents the carbon atoms completing a benzene or naphthalene nucleus. 2. Product according to claim 1, characterized in that it contains a magenta dye-forming substance of formula I, II or III in which R2 represents an alkylene radical containing from 1 to 4 carbon atoms, a phenylene radical or a phenylene radical substituted by a carboxy, chloro, methyl or methoxy group; n is 0; R represents a hydrogen atom; J represents a sulfonyl radical; m is 0 or 1; Q is in position 5 with respect to the radical G and represents a hydroxy radical, -NHS02R3 or NHCOR3 in which R3 represents an alkyl radical containing from 1 to 4 carbon atoms, or such a radical substituted by the cyano, sulfamoyl, carboxy or sulfo; a benzyl radical, a phenyl radical, or a phenyl radical substituted by a carboxy, chloro, methyl, methoxy or sulfamoyl radical; r is 1; Z represents a cyano, trifluoromethyl, fluorosulfonyl, chloro, fluoro, bromo, 2-nitro or 3-nitro radical with respect to the azo group; -SO2-alkyl containing 1 to 7 carbon atoms, -SOs-alkyl containing 1 to 6 carbon atoms and substituted by a hydroxy, phenyl, cyano, sulfamoyl, carboxy, fluorosulfonyl or sulfo radical; a sulfamoyl radical of formula -SO2NHR6 in which R6 represents a hydrogen atom, an alkyl radical containing from 1 to 4 carbon atoms, an alkyl radical containing 1 to 4 carbon atoms and substituted by a hydroxy, cyano, sulfamoyl radical, carboxy or sulfo; a benzyl radical, a phenyl or phenyl radical substituted by a hydroxy, sulfonyl, sulfamoyl, carboxy or sulfo radical; Z1 represents a hydrogen atom, a methoxy radical, a chloro or fluoro radical; D represents a bromo, chloro, SO 2 -alkyl radical containing from 1 to 6 carbon atoms, optionally substituted by a chloro, fluoro, hydroxy, phenyl, cyano, sulfamoyl, carboxy, sulfo, sulfamoylphenyl, carboxyphenyl, chlorophen-s nyl radical, cyanophenyl, methylphenyl, nitrophenyl; a phenylsulfonyl radical or a sulfamoyl radical of formula -SO2NR5R6 where R5 represents a hydrogen atom or a methyl radical and R6 represents a hydrogen atom; an alkyl radical containing from 1 to 8 carbon atoms or an alkyl radical containing from 1 to 6 carbon atoms and substituted by a hydroxy radical, a cyano, sulfamoyl, carboxy or sulfo radical; a benzyl radical, a phenyl radical or a phenyl radical substituted by a hydroxy, sulfamoyl, carboxy or sulfo radical; Rs and R6 can be combined with the nitrogen atom 15 to which they are attached so as to represent a morpholino radical. 2 magenta, characterized in that said substance is chosen from 3. Product according to claim 2, characterized in that the dye-forming substance has the formula: 3 616,248 substituted-sulfonyl containing from 6 to 9 carbon atoms, alkylcarbonyl containing from 2 to 7 carbon atoms, sulf-amoyl of formula -SO2NR5R6 in which R5 represents a hydrogen atom, an alkyl or substituted alkyl radical containing from 1 to 8 carbon atoms; R6 represents a hydrogen atom, an optionally substituted alkyl radical containing from 1 to 8 carbon atoms, a benzyl radical, a phenyl or substituted phenyl radical containing 6 to 9 carbon atoms, an alkylcarbonyl or substituted alkyl-carbonyl radical containing from 2 to 7 carbon atoms, a phenylcarbonyl or substituted phenyl-carbonyl radical containing 7 to 10 carbon atoms, an alkylsulfonyl or substituted alkyl-sulfonyl radical containing from 1 to 6 carbon atoms, a phenylsulfonyl or substituted phenyl radical -sulfonyl containing from 6 to 9 carbon atoms; a cyclohexyl radical; a trimethylsilyl radical; R5 and R6 can represent together, with the nitrogen atom to which they are attached, a morpholino or piperidino radical; a carbamoyl radical of formula -CONR5R5 where the radicals R5, identical or different, are as described above; Z1 represents a hydrogen atom or a radical such asZ; R1 represents a hydrogen atom, an alkyl radical containing from 1 to 4 carbon atoms, an alkoxy radical containing 1 to 4 carbon atoms or a halogen atom; D represents a cyano, sulfo, fluorosulfonyl, halo-geno, -SO3-phenyl or -SO3-substituted phenyl radical containing from 6 to 9 carbon atoms, -SO2-alkyl or -SO2-substituted alkyl containing from 1 to 8 atoms carbon, -SO2-phenyl or -S02-substituted phenyl containing from 6 to 9 carbon atoms, SO-alkyl or substituted SO-alkyl containing from 1 to 8 carbon atoms, SO-phenyl or substituted SO-phenyl containing from 6 to 9 carbon atoms, sulfamoyl of formula -S02NR5R6, carbamoyl of formula -CONR5R5 where R5 and R6 have the meaning previously indicated for Z, with the additional condition that said compound does not contain more than one sulfo radical and more than one carboxy radical. 4 in which: D represents a radical -SO2NHCH3 or -SO2NH-t-C4H9; R1 represents a hydrogen atom or a chlorine atom; Z represents a 5-sulfamoyl radical when R1 is a 2-chloro radical and a 4-sulfamoyl, 3-methylsulfonyl or 3-nitro radical when R1 represents a hydrogen atom. 5 616,248 5. Product according to claim 4, characterized in that in the formula of the compound, R1 represents a hydrogen atom and D a radical -SO2NH-t-C4H9. 60 6. Product according to claim 3, characterized in that in the compound formula, Car is in position 4 relative to the azo group, R1 represents a chlorine atom, R3 represents a methyl radical and D represents an h5 radical - S02CH2C6H5, -S02NH-t-C4H9 or -S02NHCH3. 7. Product according to claim 2, characterized in that the dye-forming substance has the formula: 616,248 8. Product according to claim 1, characterized in that the carrier radical has the formula: Lease nhso2- 9. Product according to claim 8, characterized in that in the formula of the carrier radical Car, Y represents the atoms necessary to complete a naphthalene ring. 25 10. Product according to claim 8, characterized in that the ballasting group comprises a CONH radical or an SO 2 NH radical linking this ballasting group to the rest of the molecule of the dye-forming compound as follows: Oh oh / y ■ conh-b 11. Product according to claim 10, characterized in that the ballasting group fixed in position 2 relative to the group 45 hydroxy, has the formula: Ms "u -C0NH- (CH,), 0 t-csHu 55 12. Product according to claim 1, characterized in that the magenta dye-forming compound is incorporated into a layer adjacent to a layer of silver halide emulsion. 6o 13. Product according to claim 1, characterized in that it comprises a layer of emulsion with silver halides sensitive to red, associated with a substance forming a blue-green dye, a layer of emulsion with halides of silver sensitive to green, associated with a magenta dye-forming substance 65 according to one of claims 1 to 12, and a layer of blue-sensitive silver halide emulsion associated with a yellow dye-forming substance. 14. Product according to claim 13, characterized in that each silver halide emulsion is a direct positive emulsion. 15. Product according to claim 1, characterized in that it is further designed for a treatment involving passage between a pair of juxtaposed pressing members and for this purpose comprises a) a photosensitive element consisting of a support with at at least one layer of silver halide emulsion associated with a magenta dye-forming substance according to claim 1 or 2, b) a dye image-receiving layer, and c) means for introducing an alkaline treatment composition to inside of this product. 15 in which: Bail represents an organic ballasting group whose size and configuration are such that the compound is non-diffusible during development in an alkaline treatment solution; 16. Product according to claim 15, characterized in that the dye image-receiving layer is disposed between the support and the silver halide emulsion layer closest to this support. 17. Product according to claim 15, characterized in that the dye image receiving layer, applied on a separate support is adapted to be applied in superposition on the photosensitive element after the exposure of the latter. 18. Product according to claim 15, characterized in that the means for introducing the treatment composition is a frangible capsule arranged so that, at the time of treatment, a pressure force applied to this capsule by means of the pressing members allows the content of this capsule to be introduced inside the product. 19. Product according to claim 15, characterized in that the image-receiving layer comprises a cationic polymer mordant. 20. Product according to claim 19, characterized in that the cationic mordant is a polymer comprising s units derived from at least one ethylenically unsaturated monomer copolymerized with units of formula: R7 I ch — c R1 (q) I ' R »_N © _R9 I N10 x © in which R7 and R8 each represent a hydrogen atom or a lower alkyl radical, R8 may also represent a group containing at least one aromatic nucleus; Q can represent a divalent alkylene radical, a divalent arylene radical, a divalent aralkylene radical, a divalent arylene alkylene radical, a COOR12, OCOR12, CONHR12 radical, where R12 represents an alkylene radical, or else R8 can represent with Q a radical -R12- 35 where R9, R10, and R11 can represent an alkyl, aral-kyle radical or else R9 and R10 can represent with Q and with the nitrogen atom to which they are linked the atoms and bonds necessary to form a heterocyclic radical with a quaternary nitrogen atom, and X® represents a negative monovalent salt-forming radical or else an atom linked by ionic bond with the positive salt-forming radical, the said polymer being moreover practically free of carboxy group and containing at least in the positive radical two aryl groups for each quaternary nitrogen atom. 20 in which : 40 R1 represents a hydrogen atom or a chlorine atom; R3 represents an alkyl radical containing from 1 to 4 atoms of 45 carbon; D represents an alkylsulfonyl radical containing from 1 to 5 carbon atoms, a benzylsulfonyl radical, a sulfamoyl radical of formula -SO2NHR6 where R6 represents an alkyl radical which contains from 1 to 8 carbon atoms. n / a 4. Product according to claim 3, characterized in that in the compound formula, R1 represents a hydrogen atom, R3 represents a methyl radical, D represents a radical -S02CH2C6H5, -S02NH-t-C4H9 or -S02NHCH3 and Car is in position 4- relative to the azo group. 55 21. Product according to claim 18, characterized in that the frangible capsule is arranged so as to cause the introduction of the treatment composition between the receiving layer and the layer of the photosensitive element furthest from this support.