DE3725993A1 - LIGHT SENSITIVE COLOR PHOTOGRAPHIC MATERIAL - Google Patents

Abstract

Novel cyan azo dye-formers for use in light-sensitive silver halide photographic layers, are of formula:- (Dye-X)q-Y (I) where q is 1 or 2; X is a chemical bond or linking group; Y is a group which releases "Dye" (counter) corresponding to light-sensitive silver salt having an imagewise latent image and makes a difference in diffusibility between the dye thus released and the compound represented by formula (I); and "Dye" is of formula:- <IMAGE> where one of A and E is a bond to X in formula (I) and the other is H or a specified substituent; B is H or a specified substituent (non-electrophilic); G is OH, OSO2R<21>, OCOR<21> or OP(O)(R<21>)(R<22>) where R<21> and R<22> are defined substituents; and R<1> is H, alkyl or substituted alkyl.

Description

The invention relates to a new, a blue-green azo dye forming connection, it concerns in particular a photosensitive color photographic material containing this contains a blue-green azo dye-forming compound.

A photographic color diffusion transfer process is known in which a compound forming an azo dye is used in the development under basic Conditions forms an azo dye that has a different diffusivity has as the dye-forming compound.

Examples of such a dye-forming compound that releases a cyan dye include those as in US Pat. Nos. 39 42 987, 40 13 635, 42 73 708 and 42 68 625 are described.

The compounds described in these patents however, have been found to have the disadvantage that they are found in the p-position to the azo group contain a nitro group, which is reduced during development, resulting in discoloration leads. It has also been found that azo dyes that contain a nitro group, generally reduced by light so that the authenticity of the image is poor Light is achieved.

Furthermore, there is often a phenomenon in which the development of Silver halide is observed to be inhibited when these dye-forming compounds into the same Layer like a photosensitive silver halide emulsion be incorporated. Probably nitro groups call this Phenomenon.

Examples of a blue-green azo dye-forming compounds which a trifluoromethanesulfonyl group in the  have p-position to the azo group, are in Japanese OPI patent application 66 227/78 (the one used here Abbreviation "OPI" stands for an untested published patent application). However, these connections have the disadvantage that fluorine cannot easily be incorporated and their fluorine-containing compositions cause environmental pollution. In addition, these connections leave a lot to be desired left in terms of sharpness and diffusion of the released Dye. Examples of a purple azo dye forming compounds comprising a diazo component which contains a large number of alkylsulfonyl groups are shown in GB-PS 14 90 248 and in the Japanese OPI patent application 40 402/80. Because these connections, however have a naphthol-2 position which is unsubstituted or contains an introduced electrophilic group is their Color tint in an area that is too short-wave. These connections therefore cannot be considered a cyan dye forming compounds are used.

Compounds forming a cyan dye which are a Nitro group or a trifluoromethanesulfonyl group in the So far, p-position to the azo group are not included known.

Recently, there have been new blue-green azo dye-forming agents Connections made by an azo coupling Diazo component that is free of nitro groups or a tri is fluoromethanesulfonyl group, with 2-acylamino-1-naphthols proposed in U.S. Patent 4,556,632. The described therein compounds forming a dye are admitted as blue-green dyes compared to the known compounds usable, but these compounds have a pale tint and therefore have an inadequate Color rendering ability because these compounds are a cyano group, an alkylsulfonyl group or an arylsulfonyl group in the 2 position (based on the azo group) of the Have phenyl group of the diazo component. Because their color  is pale, they must also be used in excess to an excellent gray balance achieve.

The aim of the present invention is therefore a Find dye-forming compound that contains a dye forms, which has a beautiful blue-green tint. The aim of the invention is also a connection to find a picture with excellent lightfastness delivers. Another object of the invention is in finding a dye-forming compound which does not inhibit the development of the silver halide. The aim of the invention is also a dye to find forming compound that during storage and development is stable.

Another object of the invention is to provide a photosensitive to create color photographic material, which is a teal image with excellent light fastness and forms tint.

These and other objects, features and advantages of the invention go from the detailed description below and from the following examples.

The above objectives are achieved according to the invention with a light-sensitive color photographic material, that is characterized by a carrier with at least a light-sensitive layer of silver salt applied thereon, which is combined with an imaging Compound represented by the general formula

(Dye-X) _q -Y (I)

in which mean:

Dye a cyan dye releasing group or precursor thereof represented by the general formula (II) below; Xa chemical bond or a linking group; A group which releases dye correspondingly or in opposition to the photosensitive silver salt with an imagewise latent image and which ensures that there is a difference in diffusivity between the dye thus released and the compound of the formula (I), with the proviso that that Dye and X in formula (II) are linked by A or E; and q is the integer 1 or 2, with the proviso that when q = 2, the two groups (Dye-X) may be the same or different;

in which mean:

A chemical bond, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group or a group wherein A² and A³ each have the same meaning as A, with the proviso that A² and A³ may be linked together to form a heterocyclic group; R1 is a hydrogen atom or a substituted or unsubstituted alkyl group; The hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted or unsubstituted substituted or unsubstituted arylthio group, an acylamino group, an acyloxy group, a sulfonylamino group, a hydroxyl group, a carboxyl group or a substituted or unsubstituted carbamoyl group; A chemical bond, a hydrogen atom, a substituted or unsubstituted alkyl group, a halogen atom, wherein R⁴ and R⁵ each represent a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, with the proviso that R⁴ and R⁵ can form a 5- or 6-membered ring; and Geine hydroxyl group or a salt thereof or a group which is selected from the groups which consist of groups of general formulas (T), (U) and (V): wherein R²¹ and R²² may be the same or different and each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group or a substituted or unsubstituted amino group, with the proviso that R²¹ and R²² may be linked together to form a 5- or 6-membered group Ring.

Preferred examples of substituents used can be in the event that the above, by A, B and E further substituted substituents are an alkyl group, an aryl group, a -OR² group, an -SR² group, an -SO₂R² group,

a disubstituted amino group, an acylamino group, a Sulfonylamino group, a halogen atom, a cyano group, a sulfo group, a carboxyl group and an alkyloxycarbonyl group, wherein R² and R³ each represent a group, which is selected from the group consisting of one Hydrogen atom, an alkyl group and an aryl group, the can be substituted.  

The structural feature of the dye content (formula II) of the imaging compound represented by formula (I), is that the dye in the 4-position and in the 5-position to the azo group contains cyano groups (if both 0 positions to the azo group have hydrogen atoms uses the 3-position and the 4-position) and that he has none electrophilic group, e.g. B. a sulfonyl group and Cyano group, in the 2 position of the azo group. By the dye according to the invention has this structure Color tint with a considerable wavelength.

It is known that an azo dye which is an electrophile Group in the resonance positions (the 2 position, the 4 position and the 6-position) incorporated into the azo group, has a tint with a long wavelength.

However, it was not previously known that a structure in of the two positions, i.e. H. the 4 position and the 5 position (or the 3-position and the 4-position) to the azo group substituted by an electrophilic group (a cyano group) are a dye with a tint with a longer wavelength than a dye in which two or more resonance positions (the 2 position, the 4 position and the 6-position) to the azo group by an electrophile Group are substituted. It was previously known that the The wavelength of the color tint of the dye is longer the more electrons the substituent in the 2-position to the azo group delivers.

The result is that the 2-position of the azo group is not electrophilic Group and that the two positions, d. H. the 4-position and the 5-position (or the 3-position and the 4-position) to the azo group by an electrophile Cyanogrupe should be substituted is a new one and for fact surprising to those skilled in the art Literature has not previously been described and also not by she was suggested.  

It has also been found that the compound of the invention of formula (I) excellent fastness to light as a blue-green azo dye, as in Japanese OPI patent applications 93 434/85 and 245 156/86 and in the U.S. Patent 4,556,632.

The invention is described below with reference to the Imaging compound of formula (I) used in the present invention explained in more detail.

The connecting group represented by Z is an -NR⁶- group (wherein R⁶ represents a hydrogen atom, an alkyl group or a substituted alkyl group), an -SO₂ group, a -CO group, an alkylene group, a substituted alkylene group, a phenylene group, a substituted phenylene group, a naphthylene group, an -O group, an -SO group or a group formed by combining two or more of these groups. Preferred connecting groups are represented by -NR⁶-SO₂-, -NR⁶-CO- or -R⁷- (L) _k - (R⁸) _l -, wherein R⁷ and R⁸ each represent an alkylene group, a substituted alkylene group, a phenylene group, a substituted one Phenylene group, a naphthylene group or a substituted naphthylene group, L -O-, -CO-, -SO-, -SO₂-, -SO₂NH-, -NHSO₂-, -CONH- or -NHCO-, k is the number 0 or 1 and l the number 1 if k = 1, or the number 1 or 0 if k = 0.

Other preferred examples of the connecting groups include a group formed by combining -NR⁶-SO₂- or -NR⁶CO- with -R⁷- (L) _k - (R⁸) _l -.

Preferred examples of the group represented by R⁶ include a hydrogen atom, a C _1-4 lower alkyl group (the term "C _1-4 " as used herein means that the group thus designated contains 1 to 4 carbon atoms) and a C _1-4 -substituted alkyl group (the substituents are a hydrogen atom, a hydroxyl group, an alkoxy group, a cyano group and the like). A hydrogen atom is particularly preferred among these groups. Preferred examples of the group represented by R⁷ or R⁸ include a C _1-6 alkylene group, a C _1-8 substituted alkylene group (the substituents are an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a cyano group and the like.) , a phenylene group (including an o-, m- and p-phenylene group), a C _6-10 substituted phenylene group (the substituents are an alkyl group, an alkoxy group, a substituted alkoxy group, a halogen atom, a substituted alkyl group, a hydroxyl group, a Carboxyl group, a sulfamoyl group, a substituted sulfamoyl group, an alkylsulfonylamino group, a sulfamide group, a substituted sulfamide group, a disubstituted amino group and the like), a naphthylene group and a C _10-14 substituted naphthylene group (the same substituents used for the substituted phenylene group can be used as a substituent for the naphthylene group).

When E and X are connected, A is preferred for a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.

A preferred example of the alkyl group represented by A is a straight chain or branched C _1-8 alkyl group. Specific examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, a t-butyl group, an n-butyl group, a 2-ethylhexyl group, a 2,2-dimethylpropyl group and a sec-butyl group. A preferred example of the cycloalkyl group represented by A is a 5- or 6-membered C _5-8 cycloalkyl group. Specific examples of such a cycloalkyl group include a cyclopentyl group and a cyclohexyl group.

Preferred examples of the substituents for the substituted alkyl or cycloalkyl group include a halogen atom such as. B. Cl and Br, an -OR² group (wherein R² is as defined above and thus represents a substituted or unsubstituted C _1-8 alkyl group such as a methyl group, an ethyl group, a methoxyethyl group, an ethoxymethyl group, a Trichloromethyl group, a cyanomethyl group, a methanesulfonylaminomethyl group and a sulfamoxymethyl group, and a substituted or unsubstituted C _6-10 aryl group, such as a phenyl group, a tolyl group, a methoxyphenyl group, a chlorophenyl group, a cyanophenyl group and a methanesulfonyl group, cyanogyl group,

(wherein R² represents a hydrogen atom, a C _1-4 alkyl group or a C _6-10 aryl group and R³ represents a hydrogen atom, a C _1-4 alkyl group or a C _6-10 aryl group), an -SO₂R² group ( wherein R² preferably represents a C _1-8 alkyl group or a C _6-10 aryl group, a carboxy group, a sulfo group, an acylamino group (preferably one having 2 to 8 carbon atoms) and a sulfonylamino group (preferably one having 1 to 8 carbon atoms) ).

A preferred example of the aryl group represented by A is a C _6-10 aryl group. Specific examples of such an aryl group include a phenyl group and a naphthyl group. Preferred examples of the substituents for the substituted aryl group include a substituted or unsubstituted alkyl group, preferably one having 1 to 8 carbon atoms, an -OR² group (wherein R² is preferably a C _1-8 alkyl group or a substituted alkyl group (preferred examples for the substituents include a C _1-5 alkoxy group, a halogen atom (Cl, Br and the like) and a cyano group), a halogen atom, an acylamino group (preferably one having 2 to 8 carbon atoms), a sulfonylamino group (preferably one) having 1 to 8 carbon atoms), a cyano group, an -SO₂R² group (wherein R² is preferably a C _1-8 alkyl group), a hydroxyl group, a

(wherein R² and / or R³ preferably represents a hydrogen atom or a C _1-8 alkyl group), one

(wherein R² and / or R³ preferably represents a hydrogen atom or a C _1-8 alkyl group), a carboxy group, a sulfo group, an alkylcarbonyl group (preferably one having 1 to 8 carbon atoms) and a 2-substituted C _2-8 amino group .

Preferred examples of the one represented by A. heterocyclic radical include 5- or 6-membered heterocyclic Compounds that have an oxygen atom, a nitrogen atom or contain a sulfur atom as heteroatoms. Specific examples of such heterocyclic groups include a pyridyl group, a furyl group, a thienyl group, a pyrrole group and an indolyl group. These heterocyclic radicals can contain substituents, such as them above as examples of the substituents for the substituted ones Aryl group have been specified.

In the group represented by A.

A² and / or A³ preferably represent a hydrogen atom, a C _1-8 alkyl group or a C _6-10 aryl group. A² and A³ both particularly preferably represent an alkyl group. The ring formed by connecting A² and A³ is preferably a 6-membered ring. For specific examples of the

belong to a diethylamino group, an anilino group, a piperidino group and one Morpholino group.

When X and E are connected, are among the Substituents represented by A are particularly preferred an ethyl group, an isopropyl group, a t-butyl group, a cyclohexyl group, a 3-heptyl group, a methoxyethyl group, a phenyl group, a p-methylsulfonylphenyl group, a p-methylsulfonylaminophenyl group and one p-sulfamoylphenyl group.

Preferred examples of the group represented by R¹ include a hydrogen atom, a lower C _1-4 alkyl group and a substituted C _1-4 alkyl group (examples of the substituents include a halogen atom, a hydroxyl group, an alkoxy group and cyano group). A hydrogen atom is particularly preferred among these groups.

B preferably represents a hydrogen atom, a substituted one or unsubstituted alkylthio group, a substituted one or unsubstituted arylthio group, a substituted one or unsubstituted alkyloxy group, a substituted one or unsubstituted aryloxy group or an acylamino group.

Preferred examples of that represented by B. Halogen atoms include F, Cl and Br.  

Preferred examples of the alkyl group represented by B include a lower C _1-4 alkyl group, such as. B. a methyl group, an ethyl group and an isopropyl group, and a substituted lower alkyl group (preferred examples of the substituents include a halogen atom such as Cl and Br, an -OR² group, wherein R² preferably represents a C _{1- 6} -alkyl group, a cyano group, an -SO₂R² group, wherein R² preferably denotes a C _1-6 alkyl group, an acylamino group, preferably one having 2 to 6 carbon atoms, a C _1-6 sulfonylamino group, a

wherein R² and / or R³ preferably represents a hydrogen atom, a C _1-6 alkyl group or a C _6-10 aryl group and one

wherein R² and / or R³ preferably represent a hydrogen atom, a C _1-6 alkyl group or a C _6-10 aryl group.

Preferred examples of the aryl group represented by B. include a phenyl group and a naphthyl group, which can be substituted.

Preferred examples of the substituents for these aryl groups include a substituted or unsubstituted C _1-6 alkyl group (those which can be used as those mentioned for the above substituted lower alkyl group), an -OR² group, wherein R² is preferred represents a substituted or unsubstituted C _1-6 alkyl group (examples of the substituents for the substituted alkyl group include a C _1-4 alkoxy group, a halogen atom such as Cl and Br, a cyano group, an -SO₂R² group , wherein R² represents a C _1-4 alkyl group, and a 2-substituted C _2-6 amino group), an acylamino group, preferably one having 2 to 4 carbon atoms, a sulfonylamino group, preferably one having 1 to 4 carbon atoms, one Cyano group, a -SO₂R² group, wherein R² represents a C _1-4 alkyl group, a

wherein R² and / or R³ preferably represent a hydrogen atom or a C _1-4 alkyl group, a

wherein R² and / or R³ preferably represent a hydrogen atom and a C _1-4 alkyl group, a 2-substituted amino group, preferably one which is substituted by a C _1-4 alkyl group, a carboxy group, a sulfo group and an alkyloxycarbonyl group, preferably one with 1 to 4 carbon atoms.

Preferred examples of the one represented by B. heterocyclic radical include 5- or 6-membered heterocyclic Groups that have an oxygen atom, a nitrogen atom or contain a sulfur atom as heteroatoms. To specific examples of the heterocyclic groups include a pyridyl group, a furyl group, a thienyl group, a pyrrole group and an indolyl group. These heterocyclic radicals can contain substituents, such as they have been given above for the substituted aryl group are.

The alkoxy or aryloxy group and the alkylthio or arylthio group, represented by B are preferred represented by the following formulas (P) and (Q):  

-OR¹³ (P)

-SR¹⁴ (Q)

Preferred examples of those represented by R¹³ and R¹⁴ Group include those as referenced above to the group represented by B for the substituted one or unsubstituted alkyl group and the substituted one or unsubstituted aryl group.

The substituted or unsubstituted one represented by B. Amino group is represented by the formula

wherein R¹⁵ and / or R¹⁶ represent a hydrogen atom, a substituted or unsubstituted C _1-4 alkyl group or a substituted or unsubstituted C _6-10 aryl group, with the proviso that R¹⁵ and R¹⁶ can be linked together to form a ring. Preferred examples of the substituents for the substituted alkyl group include a halogen atom such as. B. Cl and Br, a cyano group and a C _1-4 alkoxy group. Preferred examples of the substituents for the substituted aryl group include a halogen atom such as. B. Cl and Br, a cyano group, a C _1-4 alkoxy group, a -SO₂R⁴ group, wherein R⁴ represents a C _1-4 alkyl group and a 2-substituted C _2-6 amino group. Preferred examples of these substituted or unsubstituted amino groups include a methylamino group, a dimethylamino group, an anilino group and a morpholino group.

The substituted or unsubstituted one represented by B. Carbamoyl group is represented by the formula  

wherein R¹⁷ and / or R¹⁸ preferably represent a hydrogen atom, a C _1-6 alkyl group or a C _6-10 aryl group. Specific examples of these carbamoyl groups include an ethylcarbamoyl group, a dimethylcarbamoyl group and an anilinocarbamoyl group.

The acylamino group represented by B preferably has 2 to 10 carbon atoms. Specific examples of these acylamino groups include an acetylamino group, a propionylamino group, an isobutylylamino group and a benzoylamino group. The acyloxy group represented by B preferably has 2 to 6 carbon atoms. Specific examples of such an acyloxy group include an acetyloxy group and a propionyloxy group. The sulfonylamino group represented by B preferably contains a C _1-6 alkyl group or a C _6-10 aryl group. Specific examples of such a sulfonylamino group include a methanesulfonylamino group, an ethanesulfonylamino group and a benzenesulfonylamino group.

Particularly preferred among the substituents represented by B. are a hydrogen atom, a halogen atom, such as. B. F, Cl and Br, a methylthio group, a methoxyethoxy group and an acetylamino group.

When A and X are connected, E is preferred for -NHCO-R⁴ or -NHSO₂R⁴, where R⁴ is a hydrogen atom, a substituted or unsubstituted alkyl group or represents a substituted or unsubstituted aryl group.

The alkyl group represented by E preferably has 1 to 8 carbon atoms. Specific examples of such an alkyl group include a methyl group, an ethyl group and an isopropyl group. Preferred examples of the substituents for the substituted alkyl group include a halogen atom such as. B. Cl and Br, a cyano group, a C _1-5 alkoxy group, a sulfonylamino group, an acylamino group, a carbamoyl group, a sulfamoyl group, a -SO₂R² group, wherein R² represents a C _1-8 alkyl group and a 2-substituted C _2-6 amino group.

Preferred examples of the halogen atom represented by E. belong to Cl and Br.

In the group -OR⁴ represented by E, R⁴ preferably represents a substituted or unsubstituted C _1-8 alkyl group or a substituted or unsubstituted C _6-10 aryl group. As the substituent for the substituted alkyl group, there can be used those as mentioned above in relation to the above-mentioned substituted alkyl group. Preferred examples of the substituents for the substituted aryl group include a C _1-8 alkyl group, a halogen atom such as. B. Cl and Br, a cyano group, a substituted or unsubstituted C _1-5 alkoxy group, a sulfonylamino group, an acylamino group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, an -SO₂R² group, wherein R² is a C _{1 -8} alkyl group and a 2-substituted C _2-6 amino group.

In the group represented by E.

R⁴ and / or R⁵ preferably represent a hydrogen atom, a substituted or unsubstituted C _1-8 alkyl group or a substituted or unsubstituted C _6-10 aryl group. As the substituent for the substituted alkyl group, there can preferably be used those as mentioned above in relation to the above-mentioned substituted alkyl group. As the substituent for the substituted aryl group, there can preferably be used those as indicated above with reference to the substituted aryl group represented by -OR⁴.

In the group represented by E.

R⁴ and / or R⁵ preferably represent a hydrogen atom, a substituted or unsubstituted C _1-8 alkyl group or a substituted or unsubstituted C _6-10 aryl group. As the substituent for the substituted alkyl group, there can be preferably used those as mentioned above with reference to the substituted alkyl group. As the substituent for the substituted aryl group, there can preferably be used those as indicated above with reference to the substituted aryl group represented by -OR⁴.

Correspondingly, in the represented by E group

R⁴ and / or R⁵ preferably represents a hydrogen atom, a substituted or unsubstituted C _1-8 alkyl group or a substituted or unsubstituted C _6-10 aryl group. As the substituent for the substituted alkyl group, there can be preferably used those as mentioned above with respect to the substituted alkyl group. As the substituent for the substituted aryl group, there can be preferably used those as mentioned above in relation to the substituted aryl group.

Correspondingly, in the represented by E group

R⁴ and / or R⁵ preferably represents a hydrogen atom, a substituted or unsubstituted C _1-8 alkyl group or a substituted or unsubstituted C _6-10 aryl group. As the substituent for the substituted alkyl group, there can be preferably used those as mentioned above with reference to the substituted alkyl group. As the substituent for the substituted aryl group, there can preferably be used those as mentioned above with reference to the substituted aryl group represented by -OR⁴.

If the group associated with X is A, are below the substituents represented by E are particularly preferred a -NHCOCH₃ group, a -NHSO₂CH₃ group, a -NHCOC₃H₇ group, a -NHSO₂C₂H₅ group,

G represents a hydroxyl group or a salt thereof, such as e.g. B. an alkali metal salt (such as -O⊖Li⊕ and -O⊖K⊕) photographically inert ammonium salt (such as -O⊖NH₄⊕ and -O⊖N (C₂H₅) ₄⊕) or a group that is selected from Groups of formulas (T) to (V):

A preferred example of the alkyl group represented by R²¹ or R²² is a straight chain or branched C _1-18 alkyl group. Specific examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-heptyl group, a 2-ethylhexyl group, an n-dodedyl group, an n-octadecyl group. A preferred example of the cycloalkyl group represented by R²¹ or R²² is a monocyclic or polycyclic 5- or 6-membered cycloalkyl group. Specific examples of such a cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the substituents for the substituted alkyl group or cycloalkyl group include a halogen atom, an alkoxy group, preferably one with 1 to 18 carbon atoms, an aryloxy group, preferably one with 6 to 18 carbon atoms, a cyano group, an alkylthio group, preferably one with 1 to 18 carbon atoms, an arylthio group, preferably one with 6 to 8 carbon atoms, an unsubstituted or disubstituted C _2-18 carbamoyl group, an alkylsulfonyl group, preferably one with 1 to 18 carbon atoms, an arylsulfonyl group, preferably one with 6 to 18 carbon atoms , a disubstituted amino group substituted by an alkyl group, preferably one having 1 to 18 carbon atoms, or an aryl group, preferably one having 6 to 18 carbon atoms, a carboxy group, a sulfo group, an acylamino group, preferably one having 1 to 18 carbon atoms, and a sulfonylamino group.

Examples of the alkenyl group include a vinyl group, an allyl group, a crotyl group and a styryl group.

Examples of the aralkyl group include a benzyl group and a β- phenethyl group.

Such an aralkyl group may contain substituents such as they are given above in relation to the substituted alkyl group have been.

A preferred example of the aryl group is a C _6-18 aryl group. Specific examples of such an aryl group include a phenyl group, a naphthyl group and an anthryl group. Specific examples of substituents permitted in such an aryl group include a substituted or unsubstituted alkyl group, preferably one having 1 to 18 carbon atoms, a substituted or unsubstituted alkoxy group, preferably one having 1 to 18 carbon atoms, a substituted or unsubstituted aryl group , preferably one with 6 to 18 carbon atoms, a halogen atom, an acylamino group, preferably one with 1 to 18 carbon atoms, a sulfonylamino group, a cyano group, a nitro group, an alkylthio group, preferably one with 1 to 18 carbon atoms, an arylthio group, preferably one with 6 to 18 carbon atoms, an alkylsulfonyl group, preferably one with 1 to 18 carbon atoms, an arylsulfonyl group, preferably one with 6 to 18 carbon atoms, a carbamoyl group, a mono- or disubstituted carbamoyl group, preferably one those with 2 to 18 carbon atoms, a mono- or disubstituted sulfamoyl group, preferably one with 1 to 18 carbon atoms, a disubstituted amino group, substituted by an alkyl group, preferably one with 1 to 18 carbon atoms, or an aryl group, preferably one with 6 to 18 carbon atoms, a carboxy group, a sulfo group, an alkoxycarbonyl group, preferably one containing a C _1-18 alkyl portion, and an aryloxy carbonyl group, preferably one containing a C _6-18 aryl portion.

A preferred example of the heterocyclic radical is a 5- or 6-membered heterocyclic group which a Oxygen atom, a nitrogen atom or a sulfur atom contains as a hetero atom. For specific examples of a such heterocyclic groups include a pyridyl group, a furyl group, a thienyl group, a pyrrole group and an indolyl group. Such a heterocyclic residue can Contain substituents as substituted above with respect to the Aryl group have been specified.

Preferred examples of the substituted or unsubstituted Alkyl group, aryloxy group, alkylthio group or Arylthio groups are represented by the following general ones Formulas (W) and (Z)

-OR²³ (W)

SR²⁴ (Z)

Preferred examples of those represented by R²³ or R²⁴ Group includes those as substituted for the above or unsubstituted alkyl group or the substituted one or unsubstituted aryl group with respect to R²¹ and R²² have been specified.

Preferred examples of the substituted amino group include an amino group substituted by a C _1-18 alkyl group or a C _6-18 aryl group.

A particularly preferred example of the invention Compound is the compound in which in the formula (II) R¹ is a hydrogen atom and G is a hydroxyl group. A another preferred example of the compound of the invention is a compound of the formulas below (IA) or (IB):

in which mean:

M is a -SO₂ group or a

X² is a -R⁷- (L) _k - (R⁸) _l group, wherein R⁷, L, k , R⁸ and l are as defined above;
i and j each represent the number 0 or 1; and
A, B and Y are as defined in formulas (I) and (II).

In formulas (IA) and (IB), A is preferably one substituted or unsubstituted alkyl group, a substituted one or unsubstituted cycloalkyl group, a substituted one or unsubstituted aryl group or a substituted one or unsubstituted heterocyclic group; B preferably a hydrogen atom, a halogen atom, a substituted one or unsubstituted alkylthio group, a substituted one or unsubstituted arylthio group, a substituted one or unsubstituted alkyloxy group, a substituted one or unsubstituted aryloxy group or an acylamino group; R⁷ and R⁸ each preferably an alkylene group,  a substituted alkylene group, a phenylene group or a substituted phenylene group; and L preferably one -SO₂NH-, -NHSO₂-, -CONH or -NHCO group.

Y stands for a group that Dye releases accordingly or corresponding to the photosensitive silver salt with a pictorial latent image and that creates a difference in terms of diffusivity between the so released dye and the compound of formula (I). Various examples of such a group are on the Field of light sensitive photographic materials already known and for example in US-PS 45 56 632 and the like.

The present invention is described below with reference explained in more detail on Y, but without being limited thereto.

In one embodiment of the present invention, Y selected so that the compound of the formula (I) a non-diffusible imaging compound which forms a diffusible dye, which at oxidation during the development of self-splitting subject to.

Useful examples of Y of this type of compound Formula (I) includes an N-substituted sulfamoyl group. Specific examples of Y include a group of formula

wherein β represents a non-metal atomic group necessary to form a benzene ring to which carbon or hetero rings may be condensed to form a naphthalene ring, a quinoline ring, a 5,6,7,8-tetrahydronaphthalene ring, a chroman ring or the like.

In the formula (YI), α represents a group of the formula -OG¹¹ or -NHG¹², wherein G¹¹ is a hydrogen atom or a group which is hydrolyzed to form a hydroxyl group, and G¹² is a hydrogen atom, a C _1-22 alkyl group or a group which makes the -NHG¹² group hydrolyzable. Ball stands for a ballast group and b stands for the number 0, 1 or 2.

Specific examples of this type of Y group are shown in Japanese OPI patent applications 33 826/73 and 50 736/78. Another example of this type von Y group is a group of the general formula

wherein Ball, α and b are as defined in relation to the formula (YI) and β 'represents an atomic group which is required to form a carbon ring, such as. B. a benzene ring to which carbon or heterocyclic rings can be fused to form a naphthalene ring, a quinoline ring, a 5,6,7,8-tetrahydronaphthalene ring, a chroman ring or the like.

Specific examples of this type of Y group are shown in Japanese OPI patent applications 113 624/76, 12 642/81, 16 130/81, 1631/81, 4043/82 and 650/82 and in U.S. Patent 40 53 312 specified.

Another example of this type of Y group is one Group of the general formula

wherein Ball, α and b are as defined in relation to formula (YI) and β ″ represents an atomic group which is necessary for the formation of a heterocyclic ring, such as e.g. B. a pyrazole ring and a pyridine ring to which carbon or heterocyclic rings can be fused. Specific examples of this type of Y group are given in Japanese OPI patent application 104 343/76.

Another preferred example of this type of Y group is a group of the general formula

wherein γ preferably represents a hydrogen atom, a substituted or unsubstituted alkyl, aryl or heterocyclic group or a -CO-G²¹ group, wherein G²¹ represents -OG²², -S-G²² or

(wherein G²² represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group; G²³ has the same meanings as G²² or represents an acyl group derived from an aliphatic or aromatic carbon or sulfonic acid; and G²⁴ represents a hydrogen atom or a substituted or unsubstituted alkyl group); and δ represents an atomic group which is necessary for the formation of a condensed benzene ring.

Specific examples of this type of Y group are shown in Japanese OPI patent applications 104 343/76, 46 730/78, 130 122/79 and 85 055/82.

Another example of this type of Y group that is in the compound of formula (I) according to the invention can be used, is a group of the formula:

wherein ball is as defined in general formula (YI); ε represents an oxygen atom of the = NG³² group, in which G³² represents an amino group which may contain a hydroxyl group or a substituent (examples of the compound of the formula H₂N-G³² include hydroxylamines, hydrazines, semicarbazides and thiosemicarbazides; and β ″ ′ one Represents the atomic group necessary to form a 5-, 6- or 7-membered saturated or unsaturated non-aromatic hydrocarbon ring.

In the formula (YV), G³¹ represents a hydrogen atom or a halogen atom, such as. B. a fluorine atom, a chlorine atom and a bromine atom. Specific examples of this type of Y group are in Japanese OPI patent applications 3 819/78 and 48534/79.

Further examples of this type of the Y group are in the Japanese patent publications 32 129/73 and 39 165/73, in Japanese OPI patent application 64 436/74 and in US-PS 34 43 934 indicated.

Another example of this type of Y group for the Compound of the formula I according to the invention is represented by the formula

wherein A⁴¹ represents an atomic group necessary for the formation of an aromatic ring; Ball means an organic ballast group on the aromatic ring and, if there is more than one ball group, they can be the same or different, and m represents the integer 1 or 2.

In the formula (YVI), X represents a divalent organic group that contains 1 to 8 carbon atoms. The nucleophilic group (Nu) and the electrophilic center (the carbon atom with the * mark) together form a 5- to 12-membered ring. In the general formula (YVI) Nu stands for a nucleophilic group, n stands for the integer 1 or 2 and α is as defined in the formula (YI). Specific examples of this type of Y group are given in Japanese OPI patent application 20 735/82.

In another embodiment of the present invention Y is selected so that the compound of the invention of formula (I) is a non-diffusible imaging Compound is self-cleaving in the presence of a base is subject to the release of a diffusible Dye, however, with an oxide form of a Developer compound releases practically no dye.

An example of the Y group that is used for this type of compound of formula (I) according to the invention is useful, is represented by the formula

in which mean:

α 'an oxidizable nucleophilic group, such as. B. a hydroxyl group, a primary or secondary amino group, a hydroxyamino group, a sulfonamide group or a precursor thereof; α ″ a dialkylamino group or any of the groups as defined for α ′; G⁵¹ is a C _1-3 alkylene group; a is the number 0 or 1; G⁵² is a substituted or unsubstituted C _1-40 alkyl group or a substituted or unsubstituted C _6-40 aryl group; G⁵³a nucleophilic group, such as. B. -CO- and -CS-; and G⁵⁴ is an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom, with the proviso that when G⁵⁴ is a nitrogen atom it may be substituted by a hydrogen atom, a substituted or unsubstituted C _1-10 alkyl group or an aromatic C _{6- 20} -rest.

In the formula (YVII), G⁵⁵, G⁵⁶ and G⁵⁷ each represent a hydrogen atom, a halogen atom, a carbonyl group, a sulfamoyl group, a sulfonamide group or a C _1-40 alkyloxy group or they are defined as G⁵², with the proviso that G⁵⁵ and G⁵⁶ together can form a 5-, 6- or 7-membered ring.

Alternatively, G⁵⁶ stands for

wherein at least one of the residues G⁵², G⁵⁵, G⁵⁶ and G⁵⁷ a ballast group represents. Specific examples of this type of Y group are in Japanese OPI patent application 63 618/76 specified.

Other examples of this type include the Y group Groups of the formula (YVIII) or (YIX):

in which mean:

Nu⁶¹ and Nu⁶², which may be the same or different, each represent a nucleophilic group or a precursor thereof;
Z⁶¹ is a divalent atomic group that is electronegative to the carbon atoms to which R⁶⁴ and R⁶⁵ are attached;
R⁶¹, R⁶² and R⁶³ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an acylamino group, or wherein R⁶¹ and R⁶² can together form a fused ring when R⁶¹ and R⁶² are adjacent to each other on the ring, or wherein R⁶² and R⁶³ together can form a condensed ring with the rest of the molecule; and
R⁶⁴ and R⁶⁵, which may each be the same or different, each represents a hydrogen atom, a hydrocarbon group or a substituted hydrocarbon group, with the proviso that a ballast group (ball) of sufficient size to immobilize the compound in at least one of the substituents R⁶¹, R⁶², R⁶³, R⁶⁴ and R⁶⁵ is present.

Specific examples of this type of Y group are shown in Japanese OPI patent applications 69 033/78 and 130 927/79 described.

Other examples of this type include the Y group a group of the formula

wherein ball and β 'are as defined in formula (YII) and G⁷¹ represents a substituted or unsubstituted alkyl group. Specific examples of this type of the Y group are described in Japanese OPI patent applications 111 628/74 and 4819/77.

According to a further embodiment of the invention, Y chosen so that the compound of the formula (I) a non-diffusible imaging compound is that does not release a dye itself, but only when reacting with a reducing agent a dye releases. In this case it is preferably in combination thus using a compound that has a redox reaction mediates (a so-called electron donor).

An example of this type of Y group is shown through the formula

wherein ball and β 'are as defined in formula (YII) and G⁷¹ represents a substituted or unsubstituted alkyl group. Specific examples of this type of Y group are described in Japanese OPI patent applications 35 533/78 and 11 082/78.

Other examples of this type include the Y group a group of the formula

_'ox and α _"ox represent a group which α respectively in the reduction' and α" where α forms; and wherein α ′, α ″, G⁵¹, G⁵², G⁵³, G⁵⁴, G⁵⁵, G⁵⁶, G⁵⁷ and a are as defined in the formula (YVII).

Specific examples of this type of Y are in Japanese OPI patent application 110 827/78 and in U.S. Patent 43 56 249 and 43 58 525.

Other examples of this type include the Y group Groups of the formulas (YXIIIA) and (YXIIIB):

wherein (Nu _ox ) 1 and (Nu _ox ) 2, which may be the same or different, each represent an oxidized nucleophilic group and the remaining symbols are as defined in formulas (YVIII) and (YIX).

Specific examples of this type of Y group are shown in Japanese OPI patent applications 130 927/79 and 164 342/81.

Other examples of this type include the Y group a group of the formula

where EAG represents a group consisting of a reducing Compound takes up electrons and N and O are nitrogen atoms or mean an oxygen atom. The single bond between N and O is subject to the electron uptake by EAEC of a split.

D¹ and D² each represent a chemical bond or a substituents other than a hydrogen atom. If D¹ or D²

is bound, D¹ or D² stands for a chemical bond. D¹ and D² can also be connected be forming a ring.

In the formula (YXIV), Time stands for a group belonging to the Implementation triggered by the splitting of the nitrogen-oxygen Single bond, releases a dye.

In the formula (YXIV), t stands for the integer 0 or 1.

In the formula (YXIV) the solid line gives a chemical Bond again and at least one of the broken ones Lines are bound to the respective group.

Specific examples of this type of Y are in Japanese Patent application 244 873/85 indicated.

Electron donors in combination with the invention Compound of formula (I) can be used are described in the patents relating to the formulas (YXI), (YXII), (YXIIIA), (YXIIIB) and (YXIV) have been.  

According to a further embodiment of the invention, Y becomes so chosen that the compound of the formula (I) an LDA compound (a linked donor-acceptor compound) is. Such a connection is non-diffusible imaging compound in the presence of a Base undergoes a donor-acceptor reaction Release of a diffusible dye, however in the reaction with an oxide form of a developer compound releases practically no dye.

An example of this type of Y group is shown by the formula (YXV). Specific examples of this type of the Y group are in the Japanese OPI patent application 185 333/84 stated:

wherein n, x, y and z each represent the integer 1 or 2; m is an integer of 1 or more; Don an electron donor or a group containing a precursor portion thereof; L₁ is an organic group that connects NuP to -L₂-El-Q or Don; Nup a precursor to a nucleophilic group; El an electrophilic center; Q is a divalent group; Ball a ballast group; L₂ is a connecting group; M¹ is an arbitrary substituent.

According to a further embodiment of the invention, Y selected so that the compound of the general Formula (I) a non-diffusible compound which is under basic conditions in the unexposed Section decomposes releasing a dye, which, however, releases practically no dye when it  with the oxide form of a reducing agent, as generally in a photographic system used in the exposed portion is subjected to cross-oxidation. An example for Y, for this type of compound of the formula (I) is represented by the formula

in which mean:

D³ and D⁴ each represent a hydrogen atom or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl or heterocyclic group; D⁵a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl, heterocyclic, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfonyl or sulfamoyl group; and D⁶ and D⁷ each represent a hydrogen atom or a substituted or unsubstituted acyl, alkoxycarbonyl or aryloxycarbonyl group; W¹ is an oxygen atom, a sulfur atom or an imino group; (Time) a timer group; and t is the number 0 or 1.

According to the invention are preferred examples of the Group represented by Y is such as represented by the formula (YI), (YII), (YXII) or (YXIV) is displayed.

The ballast group in the formulas (YI) to (YXIII) and (YXV) is an organic ballast group which can make the compound of the formula (I) non-diffusible. Such a ballast group is preferably a hydrophobic C _8-32 group.

Such an organic ballast group is related to the invention Connection directly or through a connecting group, such as B. an imino bond, an ether bond, a thioether bond, a carbonamide bond, a sulfonamide bond, an ureido bond, an ester bond, a carbamoyl bond, its sulfamoyl bond or a combination bound by it.

Specific examples of such a ballast group include an alkyl group such as. B. a dodecyl group and an octadecyl group; an alkenyl group such as e.g. B. a dodecenyl group and an octadecenyl group; an alkoxyalkyl group, such as. B. a 3- (octyloxy) propyl group and a 3- (2-ethylundecyloxy) propyl group as described in Japanese Patent Publication 27,563 / 64; an alkylaryl group, such as. B. a 4-nonylphenyl group and a 2,4-di-tert-butylphenyl group; an alkylaryloxyalkyl group such as e.g. B. a 2,4-di-tert-pentylphenoxymethyl group, an α - (2,4-di-tert-pentylphenoxy) propyl group and a 1- (3-pentadecylphenoxy) ethyl group; an acylamidoalkyl group such as e.g. B. the groups as described in US Pat. Nos. 3,337,344 and 3,418,129, and a 2- (N-butylhexadecanamide) ethyl group; an alkoxyaryl or aryloxyaryl group, such as. B. a 4- (n-octadecyloxy) phenyl group and a 4- (4-n-dodecylphenyloxy) phenyl group; a residue group containing a long chain aliphatic group, such as. B. an alkyl group and an alkenyl group and a water solubilizing group such as. B. a carboxyl group and a sulfo group (e.g. a 1-carboxymethyl-2-nonandecenyl group and a 1-sulfoheptadecyl group); an alkyl group substituted by ester groups (such as a 1-ethoxycarbonylheptadecyl group and a 2- (n-dodecyloxycarbonyl) ethyl group); an alkyl group substituted by aryl groups or heterocyclic groups (such as a 2- [4- (3-methoxycarbonylunicosamido) phenyl] ethyl group and a 2- [4- (2-octadecylsuccinimido) phenyl] ethyl group; and an aryl group substituted with aryloxyalkoxycarbonyl groups (such as a 4- [2- (2,4-di-tert-pentylphenyloxy) -2-methylpropyloxycarbonyl] phenyl group).

To particularly preferred examples of these organic Ballast groups belong to those who join connecting groups which are represented by the formulas (B₁) to (B₄):

in which mean:

R⁸¹ a C _1-10 , preferably C _1-6 alkylene group, such as. B. a propylene group and a butylene group; R⁸² is a hydrogen atom or a C _1-10 , preferably a C _1-6 alkyl group, such as. B. a tertiary amyl group; n is an integer from 1 to 5, preferably 1 or 2; R⁸³eine C _4-30 , preferably C _10-20 alkyl group, such as. B. a dodecyl group, a tetradecyl group and a hexadecyl group; and R⁸⁴eine C _8-30 -, preferably C _10-20 alkyl group, such as. B. a hexadecyl group and an octadecyl group or a substituted alkyl group having 8 or more carbon atoms (the alkyl group contains 1 or more carbon atoms; examples of the substituents include a carbamoyl group).

Specific examples of the compound of the invention of formula (I) are given below, the invention is but not limited to this. In the below In formulas, Ph stands for a phenyl group.  

wherein

Specific examples for the synthesis of the invention Connection are described in more detail below. All connections of formula (I) can be easily according to the following Syntheses are made.

Synthesis example Synthesis of compound (1)

Compound (1) was synthesized by the following synthetic method produced:  

Method of synthesizing compound (1)

Synthesis of intermediates (c) and (f)

Synthesis of intermediate (a)

A mixture of 209 g of the potassium salt of 5- (3-sulfophenyl sulfonylamino) -1-naphthol, 136 g zinc chloride, 500 ml ethanol and 100 ml of water was stirred to a temperature of 50 ° C heated. A solution in which 39 g of sodium nitrite in 100 ml Water had been dissolved became the solution at a temperature dropped from 50 ° to 60 ° C. After heating for 3 hours at a temperature of 60 ° C the mixture was at room temperature let cool. The resulting reddish brown Crystals were filtered off, washed with ethanol and dried, to obtain intermediate (a).

Synthesis of intermediate (b)

A mixture of 11.6 g of the reddish-brown crystals of the Intermediate (a), 19 g sodium hydrosulfite, 200 ml water and 200 ml of acetonitrile was in a nitrogen atmosphere heated to 60 ° C for 30 minutes with stirring. After cooling to a temperature of 20 ° C 3.3 g of propionyl chloride to the solution at a temperature of 15 ° to 20 ° C added. After stirring for 30 minutes, the solution Continue heating to a temperature of 60 ° C for 30 minutes. 3.3 g of sodium hydrogen carbonate became the solution admitted. 500 ml of a saturated was added to the mixture Saline solution added. The mixture was stirred for 2 hours stirred at a temperature of 10 ° C. The resulting light brown Crystals were filtered off with a saturated Washed and dried brine, whereby the intermediate (b) obtained (yield 7.5 g).

Synthesis of the intermediate (c)

According to the synthetic procedure given below, that too shows the preparation of the intermediate (f), which in the Synthesis of compound (50) described further below  an intermediate (c) was prepared.

Synthesis of the intermediate (c-1)

The intermediate (c-1) was made from 400 g Phthalimide, 2.8 l concentrated sulfuric acid and 474 ml 94% nitric acid according to that in "Organic Synthesis" (Volume II, Page 459). The resulting Crystals were filtered off and washed. The so obtained Crystals were in an undried state as an intermediate (c-1) used in the next procedure.

Synthesis of the intermediate (c-2)

1 liter of concentrated ammonia water was suspended of the intermediate (c-1) in 1 l of acetonitrile with stirring Room temperature added. The reaction mixture was 2 hours long reacted. The resulting crystals were filtered off, washed with water and carefully dried, being the intermediate (c-2) was obtained (yield 341 g (60%) from phthalimide).

Synthesis of the intermediate (c-3)

475 ml of phosphorus oxychloride were added to a suspension of 340 g of the intermediate (c-2) in 1 l of N-dimethylformamide Stir added dropwise at a temperature of 10 ° C or below. After the dropping was completed, the mixture was poured into a Temperature of 10 ° C or below for 1 hour and 3 hours long at room temperature. The reaction solution was under Stir poured into 6 liters of ice water. After the mixture 1 hour had been stirred at 10 ° C or below for a long time the resulting crystals are filtered off, washed with water and dried to obtain intermediate (c-3) (Yield 264 g (94%)).  

Synthesis of the intermediate (c-4)

A suspension of 300 g reduced iron, 1 l isopropanol, 10 g of ammonium chloride and 200 ml of water were added with stirring Heated to reflux. 260 g of intermediate product were added to the suspension (c-3) added in portions. After the addition is complete the reaction mixture was allowed to react for 1 hour. The reaction solution was supplied by Celite (trade name of the company Johns Manville Sales Corp.) filtered hot and with 1 liter of isopropyl alcohol washed. The filtrate was poured into 6 l with stirring Poured water at 60 ° C. After stirring for 30 minutes, the Cooled mixture to a temperature of 10 ° C or below. The mixture was further stirred for an additional hour. The resulting crystals were filtered off and washed with water. After thorough drying, the crystals were out 500 ml of ethyl acetate recrystallized, giving the intermediate (c-4) obtained (yield 113 g (53%)).

Synthesis of the intermediate (c)

A diazonium salt of the intermediate (c) (= 3,4-dicyanoaniline) was prepared from intermediate (c-4) according to the following described method.

3.2 g of sodium nitrite became 21.3 ml of concentrated sulfuric acid added with stirring and cooling with ice. The Reaction mixture was at a temperature for 30 minutes of 70 ° C reacted. The reaction solution was ice chilled. 30 ml of acetic acid and 13 ml of propionic acid were added added to the reaction solution, while the internal temperature at 10 ° C or below. 5.5 g of the intermediate product were obtained (c-4) in portions to the reaction solution in the form admitted that the internal temperature does not exceed 5 ° C was kept. The reaction solution was for 3 hours allowed to react at a temperature of 5 ° C or below. To the reaction solution was added 1 g of sulfamic acid to to decompose the excess sulfurous acid to form a diazo solution of the intermediate (c).  

Synthesis of intermediate (d)

A solution of 20.8 g of intermediate (b) and 142 ml Methylcellosolve in 142 ml of water was cooled with ice touched. The diazo solution of the intermediate (c) above was added portionwise to the solution which the intermediate (b) contained, added in the form that the internal temperature was kept at 5 ° C or below. After this the reaction solution at a temperature of 5 ° C or below Had been reacted for 1 hour, the Reaction solution added to 1 l of saturated saline. The The reaction mixture was brought to a temperature of 1 hour Heated from 40 ° to 50 ° C. The resulting crystals were filtered off and washed with saturated saline. After this The crystals were thoroughly dried as an intermediate (d) used for the next process (yield 25.3 g)

Synthesis of the intermediate (s)

25 ml of phosphotoxychloride became a suspension with stirring, containing 25 g of the intermediate (d), 12 ml of N, N- Dimethylacetamide and 125 ml acetonitrile, added dropwise. After this the reaction is carried out at a temperature of 60 ° C for 3 hours The reaction solution was left with ice cooled to room temperature. The reaction solution was in Poured 1000 ml of ice water. The reaction solution was 1 hour long at a temperature of 10 ° C or below. The resulting crystals were filtered off with water washed and air dried, leaving the intermediate (e) obtained (yield 16 g).

Synthesis of compound (1)

A suspension containing 22.4 g of 2-amino-4-hexadecyloxy-5-t-octyllphenol-p-toluenesulfonate, 112 ml of N, N-dimethylacetamide and 13.8 ml of α- picoline was stirred with a nitrogen stream at a Maintained temperature of 5 ° C or below. 20 g of the intermediate (e) was added in portions to the suspension. The suspension was heated to a temperature of 70 ° C for 1 hour and then stirred for 2 hours. 160 ml of acetone and 146 ml of methanol were added to the reaction solution. Then 100 ml of water was added dropwise to the reaction solution at a temperature of 50 ° to 60 ° C. After cooling with water, an oily material separated out 1 hour later.

The reaction solution was stirred for an additional 2 hours. As a result, crystallization occurred. The resulting Crystals were filtered off and washed thoroughly with 200 ml of methanol washed. The crystals thus obtained were mixed Solvent from 30 ml acetonitrile, 150 ml ethanol and 50 ml of hot chloroform. The solution was through a Filtered filter paper. The filtrate was brought to room temperature cooled down. 30 ml of acetic acid were added to the filtrate with stirring poured. After the lapse of 3 hours, the resulting ones Filtered crystals, washed with 100 ml of acetonitrile and from a mixed solvent of 400 ml Recrystallized ethanol, 100 ml acetonitrile and 500 ml n-hexane, to obtain the compound (1) (yield 15 g (45%), mp 216 ° -217 ° C,

Synthesis example 2 Synthesis of compound (50)

Compound (50) was prepared as described below Process prepared in which the intermediate (l) and Intermediate (p) were prepared and then reacted with each other were used to form compound (50). For the production of intermediate (p) intermediate (f) was used. Intermediate (f) was obtained from intermediate (c-5) prepared from intermediate (c-4), the manufacture of which has been described above.  

Method of synthesizing compound (50)

Synthesis of the intermediate (c-5)

10 ml of bromine became a suspension of 28 g of the intermediate (c-4) in 300 ml of acetic acid with stirring at one Dropped temperature of 10 ° C or below. The reaction mixture was reacted at this temperature for 1 hour calmly. 300 ml of water was added to the reaction mixture. The resulting crystals were filtered off and washed with water. After drying thoroughly the crystals recrystallized from 100 ml of ethyl acetate, wherein the intermediate (c-5) was obtained (yield 11 g (50%)).

Synthesis of the intermediate (f)

Intermediate (k) (a diazonium salt of 2-bromo-4,5- dicyanoaniline) was prepared from the intermediate (c-5), obtained above using the following described procedure.

9 g of sodium nitrite became 60 ml of concentrated sulfuric acid added while stirring with cooling with ice. The reaction solution was then at a temperature of 70 ° C for 30 minutes reacted calmly. The reaction solution was then cooled with ice. 84 ml of acetic acid and 36 ml of propionic acid were added added to the reaction solution while the internal temperature at 10 ° C or below. There were 24.2 g of the intermediate (c-5) in portions to the reaction solution in the form admitted that the internal temperature does not exceed 5 ° C was kept. The reaction solution was at a temperature of 5 ° C or below reacted for 3 hours. 1 g of sulfamic acid was added to the reaction solution to decompose the excess sulfurous acid, whereby one received a diazo solution of the intermediate (f).

Intermediate Synthesis ()

A solution of 45 g of intermediate (b) and 410 ml of methyl cellosolve in 410 ml of water were cooled with ice  touched. The diazo solution of the intermediate (f) was added in portions to the solution of the intermediate (b) in the form admitted that the internal temperature was not kept above 5 ° C has been. After reacting for 1 hour at one temperature of 5 ° C or below, the reaction solution became 3 l more saturated Saline solution added. The reaction solution was 1 hour heated to a temperature of 40 ° to 50 ° C for a long time. The resulting crystals were filtered off and saturated with a Washed saline. After drying thoroughly, to obtain the intermediate (), the crystals used for the next procedure (yield 100 g).

Synthesis of the intermediate (p)

100 ml of phosphorus oxychloride were stirred with a suspension, containing 100 g of the intermediate (), 40 ml of N, N- Dimethylacetamide and 500 ml of acetonitrile were added dropwise. After this the reaction is carried out at a temperature of 60 ° C for 3 hours was left, the reaction solution was washed with water cooled to room temperature. The reaction solution was then poured into 2 liters of ice water. The reaction solution was 1 hour long at a temperature of 10 ° C or below. The resulting crystals were filtered off with Washed water and air dried, taking the Intermediate (p) was obtained (yield 28 g).

Synthesis of the intermediate (h) (Synthesis of 4-chloro-3-nitro-N-methyl-N-octadecylbenzenesulfonamide)

100 g of 4-chloro-3-nitrobenzenesulfonyl chloride were dissolved in 300 ml Chloroform dissolved. The solution was brought to a temperature of Cooled to 0 ° C. There was a solution of 84.3 g of methyl octadecylamine added dropwise to the solution in chloroform. It became 39.5 g Triethylamine added dropwise to the mixture while at a Temperature was kept from 0 ° to 10 ° C. After completing the  The reaction solution was added dropwise for 1 hour calmly. The chloroform was removed from the reaction solution. 500 ml of methanol was added to the reaction solution. The mixture was heated so that the reaction solution was dissolved in methanol. The solution was allowed to cool whereby crystallization occurred. The resulting crystals were filtered off under reduced pressure and dried, to obtain intermediate (h) (yield 109 g (71.2%), mp 86-87 ° C).

Synthesis of intermediate (i) Synthesis of 5-t-butyl-2- (4-N-methyl-N-octadecylsulfamoyl-2-nitrophenyl) -3-isooxa-zolon

600 g of 4-chloro-3-nitro-N-methyl-N-octadecylbenzenesulfonamide, 202 g of 5-t-butyl-3-hydroxyisoxazole (see page 75 of Japanese Patent Application No. 244 873/85), 200 g potassium carbonate and 1.8 liters of dimethyl sulfoxide were mixed together. The reaction mixture was at a temperature of 65 ° C reacted. The reaction solution was in ice water poured. The resulting crystals were reduced Filtered off pressure, washed with water and dried, to obtain intermediate (i) (yield 709 g (98.0%), mp 68-69 ° C).

Synthesis of the intermediate (j) Synthesis of 5-t-butyl-4-chloromethyl-2- (4-N-methyl-N-octadecylsulfamoyl-2-nitrop-henyl) -3-isooxazolone

650 g of intermediate (i) (isooxazolone), 200 g of zinc chloride, 200 g of paraformaldehyde and 3 l of acetic acid were mixed together mixed. The reaction mixture was then under Heated to reflux while introducing hydrogen chloride gas For 10 hours. After cooling, the reaction solution poured into water. The resulting crystals were filtered off and from a mixture of acetonitrile and methanol (1: 4) recrystallized, whereby the intermediate (j) was obtained (Yield 579 g (82.4%), mp 55 ° -56 ° C).  

Synthesis of the intermediate (k) (Synthesis of 5-t-butyl-4- (4-acetylaminophenoxymethyl) -2- (4-N-methyl-N- octadecylsulfamoyl-2-nitrophenyl) -3-isooxazolone

134 g of intermediate (j) (chloromethylisooxazole), 34 g Potassium carbonate, 2 g sodium iodide, 32 g 4-acetylaminophenol and 800 ml of acetone were mixed together. The reaction mixture under reflux with vigorous stirring for 7 hours heated. After the reaction was over, the Cooled reaction solution. After the resulting inorganic Filtered out substances under reduced pressure the solvent was removed under reduced pressure away. Methanol was added to the residue so that crystallization occurred, giving the intermediate (h) obtained (yield 127.1 g (80.8%)).

Synthesis of the intermediate (l) (Synthesis of 5-t-butyl-4- (4-aminophenoxymethyl) -2- (4-N-methyl-N- octadecylsulfamoyl-2-nitrophenyl) -3-isooxazolone

500 g of the intermediate (k) (acetylaminophenoxymethylisooxazole) were added to 2 liters of ethanol. The mixture became 1 l of 6N hydrochloric acid was added. The reaction mixture was heated under reduced pressure for 8 hours. To the reaction solution was cooled with sodium hydrogen carbonate neutralized. The reaction solution was washed with ethyl acetate extracted. The organic layer was concentrated and out crystallized from a mixture of methanol and acetonitrile (10: 1), to obtain the intermediate (l) (yield 445 g (94.2%), mp 71 ° -72 ° C).

Synthesis of compound (50)

21 g of the intermediate (I) (amino compound) were in 120 ml of dimethylacetamide dissolved. 2.8 g of pyridine were added to the solution admitted. 20 g of intermediate (p) were added to the mixture admitted. The reaction mixture was then for 2 hours  allowed to react at room temperature. In portions as methanol was added to the reaction solution. crystallization occurred on. This process was repeated. The desired Compound was in a dimethylacetamide / methanol mixture recrystallized, whereby the compound (50) was obtained (Yield 28.0 g (69.7%), m.p. 10 73228 00070 552 001000280000000200012000285917311700040 0002003725993 00004 731098 ° -112 ° C,

The amount of the imaging compound of the invention (Dye-forming compound) of formula (I), which in the photosensitive silver salt layer according to the invention used can be within a wide range usually it is used in an amount of about 0.01 to about 4 mol per mol of silver used. Preferably, the invention imaging compound in an amount of 0.05 used up to 2 moles per mole of silver.

According to the invention, at least one photosensitive silver salt layer combined with the imaging compound. This means that the imaging compound of the photosensitive Silver salt layer and / or one to the photosensitive Silver salt layer adjacent hydrophilic Layer is added.

Incorporation of the above imaging compound of formula (I) and of hydrophobic additives, for example the imaging accelerators described below in the layers of the photosensitive element, according to any suitable procedure, such as is described in US Pat. No. 2,322,027. In this case can be a high-boiling organic solvent, as described in Japanese OPI patent applications 83154/84, 178 451/84, 178 452/84, 178 453/84, 178 455/84 and 178 457/84 in combination with a low-boiling organic Solvent with a boiling point of 50 ° to 160 ° C be used.  

The amount of this high-boiling organic solvent, that is used is usually 10 g or less, preferably 5 g or less per g of dye-forming ones Connection.

Alternatively, a dispersing process in which a polymer is used as in the Japanese patent publication 39853/76 and in Japanese OPI patent application 599 423/76 described, used.

If the compound is practically insoluble in water, it can they are finely dispersed in a binder.

If a hydrophobic material in a hydrophilic colloid can be dispersed, various surfactants be used. For example, the surface active Agents as described in the Japanese OPI patent application 157 636/84 are used.

The dye-forming compound of the invention Formula (I) can be used in a photosensitive element for the Color diffusion transfer method used with the a treatment or developer solution at room temperature is developed, it can also be used in a heat-developable photosensitive element used by heating can be developed.

The silver halide used in the above photosensitive Element can be used can be silver chloride, Silver bromide, silver chloride bromide, silver chloride iodide or Silver chloride iodide bromide.

In particular, any suitable silver halide emulsion, as described in US Pat. No. 4,500,626, in Research Disclosure, No. 17029 (June 1978, pages 9 to 10) and in Japanese OPI patent application 107 240/86 is used.  

In the silver halide emulsion used according to the invention can be of the latent surface image type act with a latent image mainly on the Surface of the particle is formed or it can be such deal with the latent interior image, in which a latent Image is mainly formed inside the particle. Alternatively, the silver halide emulsion can be a so-called core Envelope emulsion in which the inner portion and the Surface section of the particles show different phases. In addition, a direct reverse emulsion, which is a Combination of an emulsion of the latent interior type, a nucleating agent and / or a light fogging agent contains.

The silver halide emulsion can be used in an unripened state usually, however, it will be used before subjected to chemical sensitization. The emulsion for the light-sensitive material of the usual type a known sulfur sensitization process, reduction sensitization process and precious metal sensitization process be subjected individually or in combination. These chemical sensitization procedures can be carried out in the presence a nitrogen-containing heterocyclic compound, as in Japanese OPI patent applications 126 526/83 and 215 644/83.

The coating amount of the photosensitive silver halide is 1 mg to 10 g / m², based on silver.

The silver halide used in the present invention can be one spectral sensitization with a methine dye or Like. Be subjected. Examples of such Dye include a cyanine dye, a merocyanine dye, a compound cyanine dye, a compound Merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye and a hemioxanol dye.  

Specific examples of these dyes include Sensitizing dyes as used in Japanese OPI Patent applications 180 550/84 and 140 335/85 and in Research Disclosure, No. 17029 (June 1978, pages 12 to 13) and heat-decolorizing sensitizing dyes, as described in Japanese OPI patent applications 111 239/85 and 32446/87.

Can in the light-sensitive material of the invention a yellow and a purple image forming connections with group Y, i.e. H. with the substrate with the same function like that of the compound of formula (I), or one known compound forming a cyan dye in Combination with the compound of formula (I) can be used.

As a suitable dye-forming compound, in combination used with the compound of formula (I) according to the invention can be used, a coupler can be used with a Developer connection can react. In the process in which this coupler is used, the oxidation reduction Reaction of a silver salt with a developer compound an oxide form of the developer compound, which then with the coupler reacts to form a dye. A such a method is described in the literature. This Coupler can be a four-equivalent coupler or a two- Be an equivalent coupler. A two-equivalent coupler that contains non-diffusible groups as elimination groups, of the reaction with the oxidized form of a Developer compound releases a diffusible dye, is preferred. Specific examples of such a developer compound and for such a coupler are in "The Theory of the Photographic Process" (T. H. James, 4th edition, pages 291 to 334 and 354 to 361), and in Japanese OPI patent applications 123 533/83, 149 046/83, 149 047/83, 111 148/84, 124 399/84, 174 835/84, 231 539/84, 231 540/84, 2950/85, 14242/85, 23474/85 and 66249/85.  

Other examples of a suitable dye-forming Compound in combination with the invention a dye-forming compound of formula (I) used can include a dye-silver compound that by combining an organic silver salt with a Dye is obtained. Specific examples of one Dye-silver compound are in research Dischlosure No. 16966 (May 1978, pages 54 to 58).

Another example of a suitable dye forming compound, which in combination with the inventive a dye-forming compound of the formula (I) can be used is an azo dye for use in heat-developable silver dye bleach. Specific Examples of such an azo dye and one Bleaching processes are described in US Pat. No. 4,235,957 and in Research Dischlosure No. 14433 (April 1976, pages 30 to 32). As a dye-donor material according to the invention Leuco dyes are also used, as described in the US Pat 39 85 565 and 40 22 617 are described.

Another example of a suitable dye-forming one Compound in combination with the invention a dye-forming compound (I) can be used can is a connection that releases or diffuses a diffusible dye. This guy a connection can be represented by the general formula

in which mean:

Dye 'a dye of the formula (II), a known dye group, a dye group whose tint is temporarily shifted into a short-wave range, or a dye precursor; X'a chemical bond or a linking group; Y'a group which produces a different diffusivity between the compounds represented by (Dye'-X'-) _n -Y 'corresponding to or in correspondence with a photosensitive silver salt with an imagewise latent image or Dye' with a difference in relation on the diffusivity between the thus released Dye 'and (Dye'-X) _n -Y'; and n is the integer 1 or 2, with the proviso that if n = 2, two (Dye'-X ') groups can be the same or different and that Dye' and X 'are not necessarily replaced by A or E in of formula (II) are interconnected.

Specific examples of the dye-forming Compound of formula (LI) used in the invention can include a color developer compound that linking a hydroquinone developer compound with a dye component, such as in U.S. Patent Nos. 31 34 764, 33 62 819, 35 97 200, 35 44 545 and 34 82 972. It can also be a dye forming compound, that of an intramolecular nucleophilic Substitution reaction is subject to release diffusible dye, as in the Japanese OPI Patent application 63618/76 described can be used. A a dye-forming compound that an intramolecular Rearrangement reaction is subject to release diffusible dye, is in Japanese OPI Patent application 111 628/74 described. In these systems a diffusible dye is released or dispersed in the undeveloped section while in the developed section is neither released nor dispersed becomes.

Another proposed system uses a dye releasing compound in the form of an oxide that is not  is able to release it with a reducing agent or brought together its predecessor. Such a dye releasing compound is caused by the reducing agent reduced that unoxidized after development has remained, releasing a diffusible Dye. Specific examples of a dye forming compounds used in such a system are in Japanese OPI patent applications 110 827/78, 130 927/79, 164 342/81 and 35533/78.

Examples of dye-forming compounds which has a diffusible dye in the developed section release include a dye forming Compound that releases a diffusible dye when implementing with a coupler that the diffusible Contains dye as an elimination group with an oxidized form of a developer compound, such as in GB-PS 13 30 524 and 34 43 940 and in Japanese Patent publication 39165/73.

Systems using color developer compounds often suffer from serious contamination problems of the image through the products of oxidation decomposition the developer connection. To solve this problem, has already been a dye releasing compound suggested that does not require a developer connection and itself has a reducing ability. The typical examples for such a dye releasing compound a dye-forming compound, as in the US-PS 39 28 312, 40 53 428, 43 36 322, 37 25 062, 37 28 113, 34 43 939 and 45 00 626, in Japanese OPI Patent applications 65839/84, 69839/84, 3819/78, 104 343/76, 116 537/83 and 179 840/82 and in Research Disclosure No. 17465 are described.

If the photosensitive color photographic of the invention Material is applied to the system that is generating  of an image by diffusion transfer of a dye are a photosensitive member and an image receiving member or a dye fixing element essential. Typical shapes for such a structure are divided into large groups in a form in which the photosensitive element and the dye mixer element separated on two supports in the form one layer are applied, and a shape in which the two Elements on the same support in the form of a layer are upset.

The relationship between the photosensitive member and the Dye fixing element, between the photosensitive element and the support and between the photosensitive member and the white reflective layer, as in the Japanese OPI Patent application 147 244/86 and described in US-PS 45 00 626, can be applied to the present invention.

A typical form of film unit in which the photosensitive Element and the image receiving element or the dye fixing element are provided on the same carrier a shape in which a photosensitive element and a Image receiving element laminated onto a transparent support are, so that it is not necessary, the photosensitive Element of the image receiving element after the completion of the image transmission deduct. In particular, the image receiving element comprises at least one mordant layer (mordant layer), and a preferred embodiment of the photosensitive Elements comprises a combination of a blue sensitive Emulsion layer, a green-sensitive emulsion layer and a red sensitive emulsion layer; a combination from a green-sensitive emulsion layer, a red-sensitive one Emulsion layer and one for infrared radiation sensitive emulsion layer; or a combination of a blue-sensitive emulsion layer, a red-sensitive one Emulsion layer and one for infrared radiation sensitive emulsion layer, each a combination from a compound forming a yellow dye, one  a purple dye-forming compound and one contains a cyan dye-forming compound (the as used herein, expression "sensitive to infrared radiation Emulsion layer "stands for an emulsion layer with a Sensitivity to light with a wavelength of 700 nm or more, especially 740 nm or more). Each of these photosensitive Emulsion layers can optionally be in two or more Layers. A white light reflective Layer containing a solid pigment such as e.g. B. titanium oxide contains is between the mordant layer (mordant layer) and the photosensitive layer or the layer which some Contains dye-forming compound, arranged so that the Viewing the transmission image through the transparent support can be. A light shielding layer can be between the white reflective layer and the light sensitive Layer should be provided so that the development in Light can be done. It can also have a peel layer if necessary be provided in a suitable position, so that the photosensitive element completely or partially can be deducted from the image receiving element. Such Embodiment is in Japanese OPI patent application 67840/81 and in Canadian Patent 674 082.

In another form of construction, the peeling is not required is the above photosensitive member applied in the form of a layer on a transparent support. A white reflective layer is on the light sensitive Layer applied. There is also an image receiving layer laminated to the white reflective layer. A form of construction in which an image receiving element, a white reflective element, a decal and a laminated photosensitive element on the same support are so that the photosensitive element is intentional can be deducted from the image receiving element is in the U.S. Patent 37 30 718.  

On the other hand, typical forms of construction, in which a photosensitive member and an image receiving member separately are applied to two supports in the form of layers, largely divided into two forms, d. H. peel-off type and non-peel type. In particular, a preferred one Form of the peel-type film unit at least one Image receiving layer on a surface of a support is provided, and a light reflecting layer on the opposite side of the carrier is provided. The photosensitive element is on a support with a Light shielding layer is provided. The photosensitive Layer side of the carrier and the mordant layer side are not opposite to each other before the exposure ends is. After the exposure is finished (e.g. during development) the photosensitive layer side is turned over and placed on the image receiving layer side. Once that Image transfer on the mordant layer (stain layer) is finished, the photosensitive element is removed from the image receiving element quickly removed.

A preferred form of the non-peel-off film unit comprises at least one a mordant layer (mordant layer) on a transparent support is provided. The light sensitive Element is on a transparent support or on a carrier provided with a light shielding layer. The light-sensitive layer side and the mordant layer side are placed on top of each other so that their front sides face each other opposite.

These shapes can be applied to both the color diffusion transfer process as well as applied to the heat development process will. Especially when these forms first mentioned methods can be applied, these forms of the structure include pressure-breakable containers (treatment or development element), which is an alkaline treatment or developer solution included. Especially in the case a non-peel-off film unit which is a lamination of a  Image receiving element and a photosensitive element on a carrier, this is treatment or Development element preferably between the photosensitive Element and arranged on a cover sheet placed thereon. In the Form of construction in which a photosensitive element and an image receiving element is provided separately on two carriers the treatment or development element is not later than in the development between the photosensitive Element and the image receiving element brought. The treatment or developing element preferably contains a light shielding material (Carbon black, a dye that is the result of a Change in pH value is subject to a change in color and the like) and / or a white pigment (titanium oxide), depending on the shape of the film unit. In the film unit for use in color diffusion transmission method is preferably a neutralization Timer mechanism from a combination of a neutralizing layer and a neutralizing Timer layer preferably in the cover sheet the image receiving member or in the photosensitive member incorporated.

A preferred example of the mordant described in the above Image receiving element or in that described below Dye fixer can be used is a Polymer mordants. The term "polymer mordant" used here stands for a polymer, the tertiary amino groups contains, for a polymer containing nitrogen-containing heterocyclic Contains proportions, a polymer that is quaternary cationic Contains groups thereof or the like.

Specific examples of such a polymer mordant are in Japanese OPI patent application 147 244/86 and in US-PS 45 00 626 described.

When the present invention relates to a heat developable Photosensitive material applied can be an organic Metal salt as an oxidizing agent in combination with a Silver halide can be used. In this case  photosensitive silver halide and the organic metal salt be arranged close to each other.

Among these organic metal salts is particularly preferred an organic silver salt.

Examples of organic compounds used to form of such an organic silver salt oxidizing agent can include compounds such as those found in Japanese OPI patent application 107,240 and in U.S. Patent 4,500,626 are described. To other useful examples of such organic compounds include silver salts of carboxylic acids, which contain alkyl groups, such as. B. silver phenyl propiolate, as in Japanese OPI patent application 113 235/85 and in the US-PS 46 03 103 described, and acetylene silver, as in Japanese OPI patent application 249 044/86. These organic silver salts can be used in combination will.

The organic silver salts can be used in an amount of 0.01 to 10 mol, preferably from 0.01 to 1 mol, per mol of the photosensitive Silver halide can be used. The sum the coating amount of photosensitive silver halide and organic silver salt is preferably 50 mg / m² to 10 g / m², expressed as silver.

Incorporation of the dye-forming agents described above Compounds that can be used in combination with the dye-forming compound of the invention (I) and hydrophobic additives, such as. B. imaging accelerators, as described below into the layers in the photosensitive element can be any Suitable procedures are carried out, such as in the US-PS 23 22 027 is described. This procedure can if desired, a high-boiling organic solvent, as in Japanese OPI patent applications 83154/84, 178 451/84, 178 452/84, 178 453/84, 178 454/84, 178 455/84 and  178 457/84 is described in combination with a low-boiling organic solvents with a boiling point of 50 ° to 160 ° C can be used.

The amount in which this high-boiling solvent is used can be 10 g or less, preferably 5 g or less, per g of dye-forming compound, in combination with the dye-forming compound of the invention (I) to be used.

It can be a dispersing process in which a polymer is used is, as in Japanese Patent Publication 39853/76 and described in Japanese OPI Patent Application 59943/76, be applied.

If a connection is used that is essentially in Water is insoluble, it can be finely dispersed and contain be in a binder rather than as stated above to be processed.

If a hydrophobic material in a hydrophilic colloid can be dispersed, various surfactants be used. For example, such surfactants Agents are used as used in Japanese OPI patent application 157 696/84 are described.

According to the invention, it is preferred that in the photosensitive Element contains a reducing material. To Examples of such a reducing material include compounds which are commonly known as reducing agents, and the above-mentioned dye-forming compounds have a reducing ability. For other useful examples for such a reducing material belong a reducing agent Forerunner who has no ability to reduce himself however, has a reducing ability when using a nucleophilic reagent or heat during development comes into contact.  

Examples of reducing agents used in the invention can include reducing agents such as those found in the US-PS 45 00 626 and 44 83 914 and in the Japanese OPI Patent applications 140 335/85, 128 438/85, 128 436/85, 128 439/85 and 128 437/85. Reducing agent Precursors are used as used in Japanese OPI patent applications 138 736/81 and 40245/82 and in the US-PS 43 30 617 are described.

Combinations of different reducing agents can also be used as described in US Pat. No. 3,039,869.

According to the invention, the amount of reducing agent added is preferably 0.01 to 20 mol, in particular 0.1 to 10 moles per mole of silver.

According to the invention, the photosensitive element can be a compound included, which serves to activate the development and stabilize the picture. Specific examples for such a compound that can be used according to the invention is described in US Pat. No. 4,500,626.

According to the invention, various fog inhibitors or photographic stabilizers are used. For examples for such fog inhibitors or photographic stabilizers include azoles and azaindenes, as in Research Disclosure (December 1978, pages 24 to 25). Carboxylic acids and phosphoric acids containing nitrogen as described in Japanese OPI patent application 168 442/84, Mercapto compounds and metal salts thereof, as in Japanese OPI patent application 11163/84, and Acetylene compounds.

According to the invention, the photosensitive element may be a Tinting agents included. Specific examples of useful ones Tinting agents include compounds such as those found in Japanese OPI patent application 147 244/86 are described.  

To achieve a wide range of colors in the Chromaticity diagram using the subtractive Primary colors, d. H. of yellow, purple and teal, can be a photosensitive element used that at least three silver halide emulsion layers with photosensitivity in different spectral ranges. To Examples of such a photosensitive element include a combination of a blue sensitive layer, one green sensitive layer and a red sensitive layer as well as a combination of a green-sensitive layer, a red sensitive layer and one for infrared radiation sensitive layer. Each of these photosensitive Layers can consist of two or more sub-layers.

The photosensitive element according to the invention can optionally be different Contain additives known as such for heat-developable photosensitive materials or others Layers as light-sensitive layers, such as. Legs Protective layer, an intermediate layer, an antistatic Layer, an antihalation layer (antihalation layer), a peel layer to facilitate peeling the photosensitive Elements from the dye fixing element, and a matting layer. Examples of such additives include plasticizers, matting agents, image sharpness enhancers Dyes, antihalation dyes, surface active Agents, fluorescent whiteners, non-lubricants, Oxidation inhibitors and discoloration inhibitors, as in Research Disclosure (June 1978, pages 9 to 15) and in the Japanese OPI patent application 88256/86.

In particular, the protective layer generally contains an organic one or inorganic matting agent to improve adhesion To prevent (liability). The protective layer can also be a Contain pickling agent or an ultraviolet absorber. The The protective layer and the intermediate layer can each be made of there are two or more layers.  

The intermediate layer can be a reducing agent for prevention discoloration or color staining, an ultraviolet absorber or contain a white pigment such as titanium oxide. To improve sensitivity, such a white Pigment both in an emulsion layer and in the Intermediate layer can be incorporated.

The dye fixing element can optionally be an auxiliary layer, such as. B. a protective layer, a peel layer and an anti-roll Layer. It is particularly preferred to have a protective layer to provide. One or more of these auxiliary layers can be a hydrophilic heat solvent, a plasticizer, a discoloration inhibitor, an ultraviolet absorber Lubricant, a matting agent, a Oxidation inhibitor, a dispersed vinyl compound for Improve dimensional stability, a surface active Agent, a fluorescent brightener, or the like. Especially in the system in which the heat development and dye transfer at the same time in the presence of a minor The dye fixing element contains a lot of water preferably a base and / or a base precursor, as described below to improve the Stability of the photosensitive element. Specific examples for these additives are in the Japanese OPI patent application 88256/86.

According to the invention, the photosensitive element and / or the dye fixing element is an imaging accelerator contain. Such an image generation accelerator is used to the redox reaction of a silver salt oxidant with a Reducing agent, the formation of a dye from a a dye-forming compound or the decomposition of the Dye, the release of a diffusible dye or the migration of a dye from the photosensitive Material layer in the dye fixing layer to accelerate. From a physico-chemical point of view considered these imaging accelerators are classified  into the following categories: a base or a base precursor, a nucleophilic compound, a high-boiling organic Solvent (oil), a heat solvent, a surface active Agent, a connection that is mutually dependent Acts silver or silver ions, or the like. These materials generally have composite functions and thus result in a combination of those described above Acceleration effects. Such imaging accelerators are described in Japanese OPI patent application 93 451/86 described.

Several other methods of generating a Base suggested. Any connections like those in these Methods used are useful as base precursors. Examples of these methods include a method at which is a poorly soluble metal compound with a compound mixed, which can form a complex with the metal ions, which build the metal connection (complex-forming Compound) to form a base and a method such as described in Japanese OPI patent application 132 451/86 which includes electrolysis to form a base.

The former method is particularly effective. For examples for the sparingly soluble metal compound belong carbonates, Hydroxides and oxides of zinc, aluminum, calcium and Barium. Examples of the complex-forming compounds are in "Critical Stability Constants" (edited by A. E. Martell and R. M. Smith, Vol. 4 and Vol. 5, Plenum Press) described in more detail. To specific examples of such complex-forming Compounds include salts of aminocarboxylic acids, Iminodiacetic acids, pyridylcarboxylic acids, aminophosphoric acids, Carboxylic acids, monocarboxylic acids, dicarboxylic acids, tricarboxylic acids and tetracarboxylic acids and compounds, the substituents included, such as B. phosphono-, hydroxy-, oxo-, Ester, amide, alkoxy, mercapto, alkylthio and phosphino groups, Hydroxams, polyacrylates and polyphosphoric acids with  Alkali metals, guanidines, amidines or quaternary ammonium salts.

The poorly soluble metal compound and the complex-forming Compound are preferably separated into the photosensitive Element and incorporated into the dye fixing element.

The photosensitive element and / or the dye fixing element can contain various development stoppers, to get a constant image regardless of any Fluctuations in the development temperature and development time.

The term "development stopper" as used herein stands for a compound that is a base after a suitable one Development quickly neutralized or reacted quickly, so that the base concentration in the film decreases to the development to stop, or a connection that is either on Silver or silver salts acts while inhibiting the Development. Specific examples of such a development stopper include acid precursors that are associated with Heating to release an acid, electrophilic compounds, those with a base that is present at the same time when heated enter into a substitution reaction containing nitrogen heterocyclic compounds, mercapto compounds and precursors of which (such as compounds as described in Japanese OPI patent applications 108 837/85, 192 939/85, 230 133 / 85 and 230 134/85 are described).

Other useful examples of such a development stopping agent include compounds that when heated a Release mercapto compound, e.g. B. Connections, such as they in Japanese OPI patent applications 67 851/86, 147 244/87, 124 941/86, 185 743/86, 182 039/86, 185 744/86, 184 539/86, 188 540/86 and 53 632/86.  

As a binder for the photosensitive element and / or the Dye fixation elements can use hydrophilic binders will. Typical examples of these hydrophilic binders include transparent or translucent hydrophilic Binder. For specific examples of these binders proteins, such as gelatin and gelatin derivatives, include natural ones Substances such as cellulose derivatives, polysaccharides, for example Starch, gum arabic and the like, and synthetic polymeric substances, such as. B. water-soluble polyvinyl compounds, such as polyvinyl pyrrolidone, acrylamide polymers and the like. Other useful examples of suitable binders include a dispersed vinyl compound that is in the form of a Latex is used to improve dimensional stability of a photographic material. These binders can can be used individually or in combination.

According to the invention, the coating amount of the binder is 20 g or less, preferably 10 g or less, especially 7 g or less, per m².

The amount in which the high-boiling organic solvent together with a hydrophobic compound, such as. B. one a dye-forming compound in the binder dispersed is preferably 1 cm³ or less, in particular 0.5 cm³ or less, particularly preferably 0.3 cm³ or less, per g of binder

The the photosensitive element and / or the dye fixing element constructive layer (for example a photographic Emulsion layer and a dye fixing layer) contain an inorganic or organic hardener.

Specific examples of such hardeners include those as in Japanese OPI patent applications 147 244/86 and 157 636/84 are described. These hardeners can  can be used individually or in combination. About the hike accelerating a dye can be a hydrophilic Heat solvent that is solid at normal temperature, however melts at elevated temperature, the photosensitive element or be incorporated into the dye fixing element. A such a hydrophilic heat solvent can the photosensitive Element and / or the dye fixing element incorporated will. To the layers to which the hydrophilic heat solvent can be incorporated include an emulsion layer, an intermediate layer, a protective layer and a dye fixing layer. Are particularly preferred among these layers a dye fixing layer and / or the neighboring ones Layers. Examples of suitable hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, Imides, alcohols, oximes and other heterocyclic compounds. A high-boiling can be used to accelerate dye migration organic solvent the light sensitive Element and / or the dye fixing element are incorporated.

As a support for the photosensitive element and / or Dye fixing element a material can be used that the Resists treatment or development temperature. As a such a support material can be commonly used glass, Paper, a polymer film, metal and analog materials are used will. In addition to these materials, those like they as substrates in the Japanese OPI patent application 147 244/86 are used.

The photosensitive element and / or the dye fixing element can be in the form of an element with an electrically conductive Heating element layer as a heating device for heat development or for the diffusion transfer of the dye.

The transparent or translucent heating element that at this structure can be used, according to any  suitable known method produced as a resistance heating element will. Such a resistance heating element can be made of a thin film of a semiconducting inorganic material or from an organic thin film in one Binder dispersed fine particles from an electric contains conductive material. For examples for materials used in this manufacturing process can be ones like those in Japanese OPI patent application 29835/86 are described.

According to the invention, the application of the heat-developable photosensitive layer, the protective layer, the intermediate layer, the undercoat layer, the back layer, the dye fixing layer and other layers by any suitable Procedures are carried out, as is the case, for example, in US Pat 45 00 626 is described.

Examples of light sources used for imagewise exposure to record an image on the photosensitive member Radiation light sources that can be used include such as B. those for visible light. In general, one Light source used as in a usual Color reproduction method is used, such as. B. a tungsten lamp, a mercury lamp, an iodine lamp, a laser light source, a CRT light source, a light emitting diode (LED) and light sources such as those in the Japanese OPI patent application 147 244 86 and described in US-PS 45 00 626 are.

In the imaging process, which includes a heating step, to which the present invention is applied can, the level of heat development and the level of Dye transfer carried out separately or simultaneously will. These stages can be done one after the other whereby the development is followed by the transfer. It can for example the following two imaging processes be applied:

• (1) A photosensitive member is exposed imagewise. After the photosensitive member has been heated, a dye fixing element on the photosensitive Element laid. The photosensitive element is in the required extent heated so that a movable Dye is transferred to the dye fixing element.
• (2) A photosensitive member is exposed imagewise. A dye fixing element is placed on the photosensitive Element laid. The photosensitive element is heated.

These procedures can be performed essentially in the absence of water or in the presence of a small amount of water will.

The heat development can be at a temperature of about 50 ° C up to about 250 ° C, preferably 80 ° C to about 180 ° C, be performed. If heating in the presence of a slight Amount of water is carried out, the upper limit is the heating temperature below the boiling point of the Water. If the transfer stage is performed after the evolution of heat has ended, the heating temperature in the transmission stage in the range of room temperature up to the temperature at which the heat development stage is carried out, in particular in the range from 50 ° C to to a temperature about 10 ° C below the temperature, at which the heat development stage is carried out.

In a preferred imaging method, such as that according to the invention is applied, the heating is carried out after the imagewise exposure or simultaneously with the imagewise exposure in the presence of a small amount Water and a base and / or a base precursor and a diffusible dye, formed in the sections accordingly or corresponding to the silver picture, becomes simultaneous  transferred with the development into the dye fixing layer.

In this process, the formation or release of a diffusible dye progress extremely quickly. This facilitates the migration of the diffusible dye into the dye fixation layer. That way a color image with a high density within a short Period can be achieved.

The amount of water to be used in this system can be so small be at least 0.1 times, preferably 0.1 times or more of the total coating weight of the photosensitive Element and the dye fixing element, related on the weight of the solvent in a volume that is equal to the maximum swollen volume of the coating film (especially less than the value obtained by subtracting the weight of the coating film from the weight of the Solvent in a volume equal to the maximum swollen volume of the coating film is obtained).

Since the film is unstable when swollen, it can be under local discoloration (staining) under certain conditions exhibit. To avoid this problem, it is too amount of water used preferably less than the volume, this is equal to the maximum swollen volume of the coating film of the photosensitive element and dye fixing element. It is particularly preferred 1 to 50 g, especially 2 to 35 g, particularly preferably 3 to 25 g per m² of the total area of the photosensitive element and dye fixing element to use.

The base and / or base precursor contained in this System used can also be the photosensitive element or be incorporated into the dye fixing element. The Base and / or the base precursor can also be in the form of a  aqueous solution can be used.

In the embodiment described above, this includes Imaging system preferably as a base precursor a basic Metal compound which is sparingly soluble in water, and a compound that can undergo a complex formation reaction with the metal ions when they make the metal connection and with water as the medium, so that these two compounds react with each other when heated while increasing the pH of the system. Under the term "imaging system" used here is an area to understand where a Imaging reaction takes place. For specific examples for such a system belong a layer that belongs to both photosensitive element as well as the dye fixing element belongs. If there are two or more layers, each of these layers can be such a system.

The poorly soluble metal compound and the complex-forming Connection must at least be worked into separate layers to prevent them from developing react with each other. For example, in so-called mono sheet, which is a photosensitive element and has a dye fixing element on the same support, the two elements are preferably incorporated into separate layers with one or more in between Layers. A preferred form of such a structure is where the poorly soluble metal compound and complexing Connection can be incorporated in layers that are provided separately on two carriers. For example the poorly soluble metal compound into a photosensitive Element incorporated during the complex-forming connection is incorporated into a dye fixing element which is provided on a carrier by that for the photosensitive element is different. The complex forming Connection can be dissolved in the water that together with it is present. The poorly soluble metal compound  is preferably incorporated in the form of a fine dispersion, which has been produced by the method as described in Japanese OPI patent applications 174 830/81 and 102 733/88 is described. The average size of the fine Particle is preferably 50 µm or less, especially 5 µm or less. The poorly soluble metal compound can be in any of the photosensitive layers, Intermediate layer and protective layer of the photosensitive element be incorporated. Alternatively, the sparingly soluble Metal compound separated in two or more layers be incorporated.

The amount of the poorly soluble metal compound or the complex-forming compound, which in the provided on the carrier Layer to be incorporated depends on the type of Compound, on the particle size of the sparingly soluble metal compound and the rate of reaction of complex formation from. It is preferably in the range of 50% by weight or less, in particular from 0.01 to 40% by weight, based on the Weight of the coating film. If the complex-forming connection is dissolved in water before it is added, is Concentration preferably 0.005 to 5 mol, in particular 0.05 to 2 mol per liter. According to the invention, the molar ratio is between the content of the complex-forming compound in the reaction system and that of the poorly soluble Connection preferably 1/100 to 100, especially 1/10 to 20th

Examples of the process to water the photosensitive Add layer or dye fixing layer are in Japanese OPI patent application 147 244/86.

Examples of heaters for use in the Development stage and / or in the transfer stage a hot plate, an iron and a heating roller, as in the Japanese OPI patent application 147 244/86.  

There can be a layer of an electrically conductive material, such as As graphite, carbon black and metal, on the photosensitive Element and / or provided lying on the fixing element be so that the photosensitive element and / or the Dye fixing element can be heated directly by Passing an electrical current through the electrical conductive layer.

As printing conditions and as a pressure application process for Laminating the photosensitive element onto the Dye fixation elements can be applied as described in Japanese OPI patent application 147 244/86.

The treatment or development of the photographic element can be by any suitable heat generating device be performed. Preferred examples of such a heat generating device include those as in Japanese OPI patent applications 75247/84, 177 547/84, 181 353/84 and 18951/85, and in the Japanese OPI utility model application 2594/87 are.

Experimental example

The blue-green dyes of the formula (I) according to the invention and known blue-green dyes were measured to determine the wavelength of their absorption maximum ( λ _max ). The ( λ _max ) value was obtained after these dyes had been mixed with a quaternary ammonium salt polymer (the polymer was methyl polyacrylate-co-N, N, N-trimethyl-N-vinylbenzylammonium chloride (quantitative ratio of methyl acrylate to vinylbenzene ammonium chloride = 1: 1)) had been stained. The synthesis of these dyes was carried out using a conventional azo coupling method. The dyes of formula (I) and the known cyan dyes used in this experiment are represented by the formula below and the substituents are shown in the table below.

The above results show that the dyes of the invention the absorption maximum in a longer wavelength range than the known dyes.

The invention is illustrated by the following examples, without being limited to it.

Example 1

A benzotriazole silver emulsion was prepared as follows:

28 g of gelatin and 13.2 g of benzotriazole were in 3000 ml of water solved. The solution was stirred while at a Temperature of 40 ° C was maintained. The solution became within a solution of 17 g of silver nitrate in 100 ml of 2 minutes Water added.

The pH of the benzotriazole silver emulsion became more appropriate Set so that deposition took place for removal the excess salts from it. The pH of the emulsion was then adjusted to 6.30, 400 g of a Benzotriazole silver emulsion obtained.

A silver halide emulsion was then prepared as follows:

600 ml of an aqueous solution of sodium chloride and potassium bromide and an aqueous solution of silver nitrate (solution of 0.59 ml of silver nitrate in 600 ml of water) became one aqueous solution of gelatin (solution of 20 g gelatin and 3 g Sodium chloride in 1000 ml of water at a temperature of 75 ° C) at the same time in a constant flow rate added within 40 minutes while the latter was strongly stirred. As a result, a monidisperse was obtained Emulsion of particulate cubic silver chloride bromide (Bromide content 80 mol%) with an average Particle size of 0.35 µm.  

The emulsion was then washed with water and desalted. 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl 1,3,3a, 7-tetrazainden added to the emulsion so that the Emulsion has been chemically sensitized. Received as a result the emulsion in a yield of 600 g.

A gelatin dispersion of a cyan dye Connection was made as follows:

5 g of a comparative compound forming a cyan dye (Comparative compound A) and 5 g of triisononyl phosphate were measured and mixed with 20 ml of ethyl acetate. The mixture was heated to a temperature of 70 ° C, so that a uniform solution was obtained. Then the Solution with 100 g of a 10% solution of lime-treated Gelatin and 60 ml of a 2.5% aqueous solution of Sodium dodecylbenzenesulfonate as a surface active agent mixed with stirring. The mixture was run at 10,000 rpm dispersed for 10 minutes using a homogenizer. The dispersion thus obtained is hereinafter referred to as "dispersion a compound forming a blue-green dye " designated.

A photosensitive coating material was as follows produced:

(a) Benzene triazole silver emulsion 10 g (b) Photosensitive silver chloride bromide emulsion 15 g (c) Dispersion of cyan dye forming compound 25 g (d) 5% aqueous solution of the following compound 5 ml

(e) 10% methanol solution of benzenesulfonamide 5 ml (f) 7% solution of guanidine-p-chlorophenylsulfonylacetate in one
50% aqueous ethanol solution 15 ml

The above components (a) to (f) were mixed together. A thickener and water were added to the mixture added to make up to 100 ml. Then the Solution in the form of a layer on a 180 µm thick polyethylene terephthalate film applied in a wet film thickness of 50 microns.

Then a coating composition for a protective layer manufactured as follows:

(h) 10% gelatin solution 400 mg (i) 7% solution guanidine-p-chlorophenylsulfonylacetate in one
50% aqueous solution of ethanol 240 ml (j) 4% film hardener solution with the structural formula 50 ml CH₂ = CHSO₂CH₂CONH (CH₂) ₂NHCOCH₂SO₂CH = CH₂

The above components (h) to (j) were mixed together. A thickener and water were added to the mixture to make up to 1000 ml. The coating thus produced composition was then applied in the form of a layer on the Surface of the photosensitive coating composition coated film up to a thickness of 30 µm upset.

The photosensitive material thus produced is shown below referred to as "photosensitive material 101".

In the same way as the photosensitive material 101 photosensitive materials 102 to 105 were produced, but this time as a cyan dye forming  Compound the comparative compound (B) or the invention Compounds (5), (19) and (37) instead of the comparative compound (A) were used.

Comparative Compound (A)

Comparative Compound (B)

These photosensitive materials were dried and Illuminated imagewise with light of 5000 lux from a tungsten lamp. These photosensitive materials thus exposed were then evenly heated on a heating block for 20 seconds, which had been heated to a temperature of 150 ° C.

A dye fixative was made as follows:

63 g gelatin and 130 g mordant with the one given below Structural formula were dissolved in 1300 ml of water. The so The coating solution obtained was then in the form of a layer on a paper backing laminated with polyethylene in one Wet film thickness of 45 µm applied. The coating film was then dried.  

Mordants

A solution of 35 g gelatin and 1.05 g 1,2-bis (vinylsulfonylacetamidoethane) in 800 ml of water were in the form of a Layer on top of the coating film in a wet film thickness of 17 µm applied. The coating film was dried to Manufacture of a dye fixative.

The coated side of the dye fixative was Water supplied in an amount of 15 ml per m². That on thus exposed and heated photosensitive material was placed on the dye fixative in such a way that their coated sides faced each other.

The laminate was then placed on a heating block for 6 seconds heated, which had been heated to a temperature of 80 ° C. The dye fixing material was removed from the photosensitive Material peeled off, leaving a teal image on the Fixing material received.

These photosensitive materials were then used of a Macbeth reflection densitometer (RD 519) measured for the density of the blue-green color image. The results are given in Table I below.

The following Table I also shows the results with respect to the wavelength of the absorption maximum ( λ _max ) and the change in the density of the section whose initial density was 1.0 after 2 weeks of exposure to 80,000 lux with xenon light.

Table I

Table I above shows that some are blue-green Dye forming compounds of the present invention high densities and low veils and a picture with a excellent lightfastness.

The compounds (1), (9), (10), (11), (12), (27), (8), (31), (74), (70) and (36) gave similar results.

Example 2

A photosensitive color photographic material 201 with a multilayer structure, as shown in Table II below was made. The incorporation of the one yellow dye-forming compounds, a purple one Dye-forming compounds and a cyan Dye forming compounds in the form of dispersions  was carried out using the same procedure as in Example 1 carried out.

Then, a photosensitive material 202 was produced in the same manner as the photosensitive material 201, except that the compound used in the photosensitive material 201 and used as a cyan dye was replaced by the compound (2) of the present invention.
Sixth layer of gelatin 800 mg / m² film hardenerh) 16 mg / m² zinc hydroxide 300 mg / m²

Fifth layer: blue-sensitive emulsion layer
Silver iodide bromide emulsion (iodide content 5 mol%) 400 mg / m² expressed as silver benzotriazole silver emulsion 60 mg / m² expressed as silver film hardener⁵) 16 mg / m² A yellow dye-forming compound (7) 400 mg / m² gelatin 1100 mg / m² high-boiling solvent⁴) 400 mg / m² surfactant²) 100 mg / m²

Fourth layer: intermediate layer
Gelatin 900 mg / m² film hardener⁵) 18 mg / m² zinc hydroxide 300 mg / m²

Third layer: green sensitive emulsion layer
Silver chloride bromide emulsion (bromide content 80 mol%) 300 mg / m² expressed as silver benzotriazole silver emulsion 50 mg / m² expressed as silver film hardener⁵) 18 mg / m² A magenta dye-forming compound 400 mg / m² gelatin 1100 mg / m² high-boiling solvent⁴) 400 mg / m² surface-active Agent²) 100 mg / m²

Second layer: intermediate layer
Gelatin 800 mg / m² film hardener⁵) 16 mg / m² zinc hydroxide 300 mg / m²

First layer: red sensitive emulsion layer
Silver chloride bromide emulsion (bromide content 80 mol%) 300 mg / m² expressed as silver benzotriazole silver emulsion 50 mg / m² expressed as silver sensitizing dye³) 8 × 10 ^-7 mg / m² A blue-green dye-forming compound 300 mg / m² gelatin 820 mg / m²

carrier
1) Polyethylene terephthalate

⁴) (isoC₉H₁₉O) ₃P = O
⁵) 1,2-bis (vinylsulfonylacetamide) ethane

Compound forming a yellow dye

Compound forming a purple dye

Compound forming a cyan dye
Comparative compound (A) of Example 1

The dye fixing material used was that shown in Table III below.
Second layer Coating amount of gelatin 0.7 g / m² 1,2-bis (vinylsulfonylacetamide) ethane 0.06 g / m²

First layer
Gelatin 1.4 g / m² mordant¹) 2.8 g / m² guanidine picrinate 2.6 g / m²

Backing (paper coated with polyethylene)

The light-sensitive color photographic material with the above-mentioned multilayer structure was made with light from 2000 lux from a tungsten lamp through a separating filter (B, G and R) with a continuous density gradation of 1 second long exposure.

The emulsion side of the photosensitive so exposed Material became water in an amount of 15 ml / m² fed. The above dye fixing material was then placed on the photosensitive material in the manner that their coated sides faced each other.

The laminate was heated on a heat roller for 25 seconds heated, the temperature had been set so that the Temperature of the film that had absorbed water at 90 ° C  was held. Then the photosensitive material of deducted from the dye fixative. As a result you got sharp yellow, purple and teal images that the separating filter (B, G and R) corresponded on the dye fixative.

In addition, the photosensitive material after 1 week of storage at a temperature of 40 ° C and a relative humidity of 80% was subjected to the same treatment or development. The results relating to the maximum density (D _max ) and the minimum density (D _min ) of the cyan image are given in Table IV below.

The photosensitive material was also subjected to a decolorization test using xenon light in the same way as in Subject to Example 1. The results are also in the given in Table IV below.

Table IV

Table IV above shows that the inventive a cyan dye-forming compound to the photosensitive Excellent material stability and gave an image with excellent light fastness.  

Example 3

The layer compositions given below were on a transparent polyethylene terephthalate support in succession applied to produce a photosensitive Materials 301:

• (I) dye-receiving layer containing:
  • (a) poly (styrene-co-N-vinylbenzyl-N, N, N-trihexylammonium chloride) (4.0 g / m²); and
  • (b) gelatin (4.0 g / m²)
• (II) White reflective layer containing:
  • (a) Titanium dioxide (22 g / m²); and
  • (b) gelatin (2.2 g / m²)
• (III) Opaque layer containing:
  • (a) carbon black (2.7 g / m²); and
  • (b) gelatin (2.7 g / m²)
• (IV) a cyan dye-providing layer
  • (a) Gelatin dispersion of a cyan dye forming compound of the formula below (0.33 mmol / m²) and Compound C (0.4 mmol / m²); and
  • (b) gelatin (1.1 g / m², gelatin enclosed in (a))
• (V) red-sensitive emulsion layer containing:
  • (a) red-sensitive silver iodide bromide emulsion (0.5 g Ag / m²); and
  • (b) Gelatin (1.1 g / m², including the gelatin in (a))
• (VI) intermediate layer containing:
  • (a) 2,5-di- (t-pentadecyl) hydroquinone (0.82 g Ag / m²);
  • (b) vinyl acetate (0.8 g / m²); and
  • (c) gelatin
• (VII) a magenta dye-providing layer containing:
  • (a) Gelatin dispersion of a magenta dye-forming compound of the formula given below (0.3 mmol / m²) and Compound C (0.4 mmol / m²); and
  • (b) Gelatin (1.1 g / m², including the gelatin in (a))
• (VIII) Green-sensitive layer containing:
  • (a) green sensitive silver iodide bromide emulsion (0.5 mmol / m²); and
  • (b) Gelatin (1.1 g / m², including the gelatin in (a))
• (IX) like (VI)
• (X) a yellow dye-providing layer containing:
  • (a) Gelatin dispersion of a yellow dye-forming compound of the general formula given below (0.5 mmol / m² and Compound C (0.6 mmol / m²)); and
  • (b) Gelatin (1.1 g / m², including the gelatin in (a))
• (XI) Blue-sensitive layer containing:
  • (a) blue sensitive silver iodide bromide emulsion (0.5 g / m²); and
  • (b) Gelatin (1.1 g / m², including the gelatin in (a)
• (XII) protective layer containing:
  • (a) latex of polyethylene acrylate (0.9 g / m²);
  • (b) quinubine (UV absorbent manufactured by Ciba-Geigy Co., Ltd.) (0.5 g / m²);
  • (c) triacryloyl perhydrotriazine as a film hardener (0.026 g / m²); and
  • (d) gelatin (1.3 g / m²)

Compound C

Blue-green dye-forming compound (comparison)

Compound forming a purple dye

Compound forming a yellow dye

A photosensitive material 302 was made the same How the photosensitive material 301 is manufactured, wherein this time, however, that in the photosensitive material 301 used a cyan dye-forming compound was replaced by the compound (50) according to the invention.

The layer compositions given below were on a transparent polyethylene terephthalate film in the specified order applied to produce a Cover film (cover film):

• (I) Acid neutralization layer containing:
  • (a) polyacrylic acid (17 g / m²);
  • (b) N-hydroxysuccinimide benzenesulfonate gelatin (0.06 g / m²); and
  • (c) ethylene glycol (0.5 g / m²)
• (II) timer layer comprising a 2 µm thick coating Cellulose acetate (degree of acetylation 54%)
• (III) timer layer comprising a 4 µm thick coating from a copolymer latex of vinylidene chloride and acrylic acid

There was a treatment or developer solution with the following specified components manufactured:

Potassium hydroxide 48 g 4-hydroxymethyl-4-methyl-1-p-tolyl-3-pyrazolidinone 10 g 5-methylbenzotriazole 2.5 g Sodium sulfite 1.5 g Potassium bromide 1 g Benzyl alcohol 1.5 ml Carboxymethyl cellulose 6.1 g Carbon black 150 g Water spout 1 l

The photosensitive material was passed through a color separation wedge exposed. The cover sheet was so exposed on the photosensitive material placed. The treatment or Developer solution was between the photosensitive material and the cover film in the form of a 80 µm thick film by means of a Pair of parallel rollers evenly distributed. After a Hour, the density of the blue-green part of the image was measured.

In addition, the image stability was measured at a density of 1.0, after the photosensitive material has light from 17,000 lux exposed from a fluorescent lamp (fluorescent tube) had been.

The results are shown in Table V below.

Table V

Table V above shows that the inventive a blue-green dye-forming compound is excellent positive image with excellent light fastness of the dye resulted.

The compounds (42), (49) and (53) according to the invention provide similar results.

The cyan dye-forming dye of the present invention Compounds can be synthesized relatively easily. The inventive, a blue-green dye forming Compounds can also use a cyan dye result in a color tint in a long-wave range. The a cyan dye-forming compounds of the invention can also have a nice color picture with an excellent Lightfastness result. In addition, some blue-green dye-forming compounds of the invention make the light-sensitive color material stable.

While the invention has been described above with reference to specific ones preferred embodiments explained in more detail, it is however, it goes without saying for the skilled person that they care is by no means limited, but that this in multiple Terms can be changed and modified without thereby leaving the scope of the present invention.

Claims (13)

1. Photosensitive color photographic material, characterized by a support and at least one photosensitive silver salt layer applied thereon, which is combined with an image-forming compound of the general formula (Dye-X) _q -Y (I) in which: Dye is a cyan dye group or a precursor thereof general formula (II) given below; Xa chemical bond or a linking group; A group that releases dye correspondingly or in opposition to a photosensitive silver salt with an imagewise latent image and that causes a difference in diffusibility between the dye thus released and the compound of formula (I), with the proviso that Dye and X in formula (II) are linked by A or E; and q is the integer 1 or 2, with the proviso that when q = 2, the two groups (Dye-X) may be the same or different; wherein: A represents a chemical bond, a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group or a group wherein A² and A³ each have the same meaning as A, with the proviso that A² and A³ may be linked together to form a heterocyclic group; R1 is a hydrogen atom or a substituted or unsubstituted alkyl group; The hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted or unsubstituted substituted or unsubstituted arylthio group, an acylamino group, an acyloxy group, a sulfonylamino group, a hydroxyl group, a carboxyl group or a substituted or unsubstituted carbamoyl group; A chemical bond, a hydrogen atom, a substituted or unsubstituted alkyl group, a halogen atom, wherein R⁴ and R⁵ each represent a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, with the proviso that R⁴ and R⁵ can form a 5- or 6-membered ring; and Geine hydroxyl group or a salt thereof or a group selected from the groups consisting of groups represented by the following formulas (T), (U) and (V): wherein R²¹ and R²² may be the same or different and each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group or a substituted or unsubstituted amino group, with the proviso that R²¹ and R²² may be linked together to form a 5- or 6-membered group Ring. 2. Photosensitive color photographic material according to claim 1, characterized in that X represents a connecting group represented by -NR⁶-SO₂-, NR⁶-CO-, -R⁷- (L) _k - (R⁸) _l - or a combination thereof, wherein R⁶ is a hydrogen atom or a substituted or unsubstituted alkyl group, R⁷ and R⁸ each have a substituted or unsubstituted alkylene group, a substituted or unsubstituted phenylene group or a substituted or unsubstituted naphthylene group, L -O-, -CO-, -SO-, -SO₂-, -SO₂NH-, -NHSO₂-, or -NHCO-, k is the number 0 or 1 and then when k = 1, l is the number 1, and then when k = 0, l is the number 1 or 0. 3. Photosensitive color photographic material after Claim 1, characterized in that E and X together are connected and A is a substituted or unsubstituted Alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic Group means.   4. Photosensitive color photographic material after Claim 3, characterized in that E and X together and A is an ethyl group, an isopropyl group, a t-butyl group, a cyclohexyl group, a 3-heptyl group, a methoxyethyl group, a phenyl group, a p- Methylsulfonylphenyl group, a p-methylsulfonylaminophenyl group or a p-sulfomoylphenyl group. 5. Photosensitive color photographic material after one of claims 1 to 4, characterized in that B a hydrogen atom, a substituted or unsubstituted one Alkylthio group, a substituted or unsubstituted Arylthio group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryloxy group or a Means acylamino group. 6. Photosensitive color photographic material after Claim 5, characterized in that B is a hydrogen atom, a halogen atom, a methylthio group, a methoxyethoxy group or an acetylamino group. 7. Photosensitive color photographic material after one of claims 1 to 6, characterized in that A and X are connected to each other and E -NHCO-R⁴ or -NHSO₂R⁴ mean, wherein R⁴ is a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or represents unsubstituted aryl group. 8. Photosensitive color photographic material according to claim 7, characterized in that A and X are connected to each other and E means 9. Photosensitive color photographic material after one of claims 1 to 8, characterized in that R¹ is a hydrogen atom and G is a hydroxyl group. 10. Photosensitive color photographic material according to claim 9, characterized in that dye is represented by the general formula (IA) or (IB): where mean: M -SO₂- or X² -R- (L) _k - (R⁸) _l -, wherein R⁷, L, k , R⁸ and l have the same meanings as in claim 2 and
A, Y and B have the same meanings as in claim 1. 11. Photosensitive color photographic material after Claim 10, characterized in that A is a substituted one or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group or a substituted or  unsubstituted heterocyclic group; B is a hydrogen atom, a halogen atom, a substituted or unsubstituted one Alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryloxy group or an acylamino group; R⁷ and R⁸ each represent an alkylene group, a substituted alkylene group, a phenylene group or a substituted phenylene group; and L -SO₂NH-, -NHSO₂-, -CONH- or -NHCO- mean. 12. Photosensitive color photographic material after one of claims 1 to 11, characterized in that the imaging compound in an amount of about 0.01 up to about 4 moles per mole of silver. 13. Photosensitive color photographic material after Claim 12, characterized in that the imaging Compound in an amount of 0.05 to 2 moles per mole of silver is included.