JPS6257020B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to color light-sensitive materials containing novel dye-releasing compounds. More specifically, the present invention relates to a dye-releasing compound that releases a diffusible yellow dye by a redox reaction following silver halide development, and a color photosensitive material containing the same. Color photosensitive materials using various diffusible dye-releasing compounds (dye-releasing agents) are already known. For example, US Patent No. 3928312, US Patent No. 4076529, US Patent No.
No. 4152153, No. B351673, No. 4135929, No.
No. 4258120, etc. are p-sulfonamide naphthol dye-releasing agents; o-sulfonamide naphthol dye-releasing agents described in U.S. Pat. No. 4,053,312, etc.; U.S. Pat.
O-sulfonamide phenol dye releasing agent described in No. 16131, No. 56-12642, etc.; US patent
Heterocyclic dye-releasing agent described in No. 4179291, No. 4273855, etc.; U.S. Patent No. 4110113, West German application (OLS)
2,534,424; is a typical example of this type of diffusible dye-releasing compound. Color diffusion transfer imaging methods using these are also described in detail in the above patents. Diffusible dye-releasing compounds described in these known materials,
Generally called a dye-releasing redox compound, it is a compound in which a group called a redox core and a dye (including precursor) moiety are bonded. When these and a photosensitive silver halide emulsion are exposed together and then developed, these redox mother nuclei are oxidized depending on the amount of developed silver halide. This oxidant decomposes into a dye moiety with a diffusible sulfonamide group and a non-diffusible quinone or analog by attack with an alkaline treatment solution. It is said that the diffusible dye thus produced is transferred to the image-receiving layer. Examples of dye-releasing redox compounds that release yellow dyes include U.S. Pat.
4156609, Research Disclosure 16475 (1977)
etc. are described. Furthermore, U.S. Patent No. 4245028, Japanese Unexamined Patent Publication No. 53-
No. 149328, No. 55-43585, No. 55-134849, No. 55-134849, No. 55-43585, No. 55-134849, No.
No. 55-138744, No. 56-71072, No. 56-25737, etc., describe improved yellow dye-releasing redox compounds. However, these yellow dye-releasing compounds are the best available at the time the invention was made and are by no means perfect. Therefore, there is a need to further improve various performances (for example, hue, fastness (to light or heat), etc.) that have been considered for some time.
Along with this, subsequent research has made it necessary to add another evaluation item. In other words, when the previously known yellow dye-releasing redox compounds described above are processed at low temperatures, e.g., 15°C or lower, the transfer density (Dmax) is lower than when processed at room temperature (e.g., 20°C). It turned out that there was a problem. For this reason, the difference between Dmax in low-temperature treatment and Dmax in room-temperature treatment has become important as a new evaluation item. The first object of the present invention is to provide a novel yellow dye-releasing compound and a photographic material containing the same. The second object is to provide a dye-releasing redox compound that provides high transfer density when used in diffusion transfer, and a photographic material containing the same. Thirdly, Dmax at low temperature treatment and at room temperature treatment
The object of the present invention is to provide a dye-releasing redox compound with a small difference in Dmax and a photographic material containing the same. Fourth, it is an object of the present invention to provide a dye-releasing redox compound, which is an o-sulfonamidophenol derivative, which exhibits good dye-releasing efficiency, and a photographic material containing the same. The present inventors have proposed the following general formula () or ()
It has been found that the dye-releasing compound represented by the formula satisfies the above objectives well. However, Q is a cyano group, a trifluoromethyl group, or a carbamoyl group represented by -CONY ³ Y ⁴ (where Y ³ represents a hydrogen atom, an alkyl group, or a substituted alkyl group, and Y ⁴ represents a hydrogen atom or an alkyl group). , represents a substituted alkyl group, an aralkyl group, or an aryl group. ^{Y 3} and Y ⁴ may be connected directly or via an oxygen atom to form a ring); M is a hydrogen atom, an alkyl group, Substituted alkyl group, alkoxy group, substituted alkoxy group, -
A sulfamoyl group represented by SO ₂ NY ³ Y ⁴ (Y ³ and Y ⁴ are the same as above), a group represented by -COOY ⁶ (Y ⁶ is an alkyl group, a substituted alkyl group, a phenyl group, or a substituted phenyl group) ) or a halogen atom; Q ¹ is a hydrogen atom, a halogen atom, a group represented by -SO ₂ NY ³ Y ⁴ (Y ³ and Y ⁴ are the same as above), -SO ₂ Y ⁵
(Y ⁵ represents an alkyl group, substituted alkyl group or aralkyl group), a group represented by COOY ⁶ (Y ⁶ is the same as above), -CONY ³ Y ⁴ group (Y ³ and Y ⁴ are (synonymous with the above), alkyl group, substituted alkyl group, alkoxy group, substituted alkoxy group,

Represents a group represented by [Formula]; Q ² is a cyano group, a trifluoromethyl group, -
SO ₂ Y ⁵ group (Y ⁵ has the same meaning as above), -SO ₂ NY ³ Y ⁴
(Y ³ and Y ⁴ are the same as above), a group represented by -
A group represented by COOY ⁶ (Y ⁶ has the same meaning as above), -
A group represented by CONY ³ Y ⁴ (Y ³ and Y ⁴ are the same as above) represents a halogen atom; q represents 0 or 1; J represents a divalent group selected from sulfonyl or carbonyl; Z represents a hydrogen atom, an alkyl group, or a substituted alkyl group; R and ^R each represent an atomic group necessary to complete a 5- or 6-membered heterocycle; Y is self-cleaved as a result of a redox reaction and becomes diffusible. Represents a redox center that has the function of releasing a dye. Among Q, in the case of a carbamoyl group represented by the formula -CO-NY ³ Y ⁴ , Y ³ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms), or an alkyl residue. A substituted alkyl group having 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms) is preferred. Y ⁴ is a hydrogen atom, carbon number 1-8
(more preferably a carbon number of 1 to 4) alkyl group,
Preferred are substituted alkyl groups in which the alkyl residue has 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms), benzyl groups, phenyl groups, and substituted phenyl groups in which the alkyl residues have 6 to 9 carbon atoms. Further, Y ³ and Y ⁴ may be bonded directly or via oxygen to form a 5- to 6-membered ring.
When Y ³ and Y ⁴ are both hydrogen atoms, or at least one of Y ³ and Y ⁴ is a hydrogen atom and the other is an alkyl group having 1 to 4 carbon atoms, or Y ³ and Y ⁴ is an alkyl group having 1 to 4 carbon atoms, which is particularly preferable because it is inexpensive and easily available and has good transferability. As Q, a cyano group is particularly preferable from the viewpoint of fastness of the transfer dye compound. The alkyl group and substituted alkyl group represented by M preferably have 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms) in the alkyl moiety. Examples of substituents for substituted alkyl include those listed below in the case of Y ³ -Y ⁵ . The alkoxy group and substituted alkoxy group represented by M have an alkyl moiety containing 1 to 1 carbon atoms.
8 (more preferably 1 to 4) is preferred.
Examples of the substituents of the substituted alkoxy group are Y ³ ~
The things listed in case of Y ⁵ can be mentioned. Among M, in the case of a sulfamoyl group represented by the formula -SO ₂ NY ³ Y ⁴ , Y ³ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms), or an alkyl residue. A substituted alkyl group having 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms) is preferred. ^Y4 is hydrogen, an alkyl group having 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms), and an alkyl residue having 1 to 8 carbon atoms (more preferably 1 carbon number).
~4) Substituted alkyl groups, benzyl groups, phenyl groups, and substituted phenyl groups having 6 to 9 carbon atoms are preferred.
Further, Y ³ and Y ⁴ may be bonded directly or via oxygen to form a 5- to 6-membered ring. Among these, both Y ³ and Y ⁴ are hydrogen atoms, or
It is particularly preferable that at least one of Y ³ and Y ⁴ is a hydrogen atom and the other is an alkyl group having 1 to 4 carbon atoms, from the viewpoint of being inexpensive and easily available and having good transferability. A preferable example of Y ⁶ in −COOY ⁶ is a carbon number of 1 to
8 (more preferably 1 to 4 carbon atoms) alkyl group, a substituted alkyl group in which the alkyl residue has 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms), phenyl group, substituted phenyl group having 6 to 9 carbon atoms The basics are given. Examples of the substituents for the substituted alkyl in ^Y3 to ^Y5 above include a cyano group, an alkoxy group, a hydroxyl group, a carboxyl group, a sulfo group, and a tetrahydrofurfuryl group. Examples of the substituent of the substituted phenyl group in Y ⁴ , Y ⁵ and Y ⁶ include a hydroxy group, a halogen atom, a carboxy group, a sulfo group, and a sulfamoyl group. The halogen atom represented by M is particularly preferably a chlorine atom. J is CO or _SO2 , preferably _SO2 . The alkyl group represented by Z may be linear or branched, preferably has 1 to 8 carbon atoms, and is particularly preferably an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group). , n-propyl group, isopropyl group, n-butyl group, etc.). The substituted alkyl group represented by Z is preferably a substituted alkyl group in which the alkyl residue has 1 to 8 carbon atoms,
Particularly preferably, the alkyl residue is a substituted alkyl group having 1 to 4 carbon atoms. Examples of the substituents of the substituted alkyl group include a cyano group, an alkoxy group, a hydroxyl group, a carboxyl group, and a sulfo group. Among Q ¹ and Q ² , in the case of a sulfamoyl group represented by the formula -SO ₂ NY ³ Y ⁴ , Y ³ is a hydrogen atom or a carbon atom with 1 to 8 carbon atoms (more preferably 1 to 8 carbon atoms).
4) The alkyl group or alkyl residue has 1 carbon number
A substituted alkyl group having 8 to 8 carbon atoms (more preferably 1 to 4 carbon atoms) is preferred. Y ⁴ is hydrogen, carbon number 1
-8 (more preferably 1 to 4 carbon atoms) alkyl group, substituted alkyl group whose alkyl residue has 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms), benzyl group, phenyl group, 6 to 4 carbon atoms The substituted phenyl group of 9 is preferred. Further, Y ³ and Y ⁴ may be bonded directly or via oxygen to form a 5- to 6-membered ring. In particularly preferred embodiments, Y ³ and Y ⁴ are both hydrogen atoms, or at least one of Y ³ and Y ⁴ is a hydrogen atom and the other is an alkyl group having 1 to 4 carbon atoms, or Y ³ and Y 4 are hydrogen atoms. ⁴ is carbon 1~
The alkyl group of No. 4 is particularly preferable because it is inexpensive and easily available and has good transferability. −CONY ³ Y ⁴
The same applies to the group . When Q ¹ and Q ² are -SO ₂ Y ⁵ groups, Y ⁵ is preferably an alkyl group whose alkyl moiety has 1 to 8 carbon atoms, a substituted alkyl group, or a benzyl group. In particular, alkyl groups having 1 to 4 carbon atoms and benzyl groups are preferred because they are inexpensive, easily available, and have excellent transferability. −COOY ⁶
Preferred examples of Y ⁶ include an alkyl group having 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms), and an alkyl group having 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms);
4) Substituted alkyl group, phenyl group, carbon number 6-
9 substituted phenyl groups are mentioned. Examples of substituents for the substituted alkyl in Y ³ to ^{Y 6} above include cyano group, alkoxy group, hydroxyl group, carboxyl group, sulfo group, and tetrahydrofurfuryl group (however, phenyl (excluding groups). Further, examples of the substituent of the substituted phenyl group in Y ⁴ , Y ⁵ and Y ⁶ include a hydroxy group, a halogen atom, a carboxy group, a sulfo group, a sulfamoyl group, an alkyl group, an alkoxy group, and the like. In order to prevent these compounds from being diffused or washed out as they are by the alkali used during the development of the light-sensitive material, they require a ballast group that substantially prevents them from being diffused or washed out. The size of the group or number of carbon atoms required for the ballast group varies depending on the conditions of use, such as processing time and alkali concentration, as well as the number and type of water-soluble groups in the dye part. If the number of carbon atoms in the ballast group becomes larger than necessary, it becomes disadvantageous in terms of solubility and extinction coefficient, but there is no upper limit to the number of carbon atoms in principle. Generally, the total number of carbon atoms in the ballast group is 8
The desirable range is 50 to 50, preferably 8 to 32. In the above general formula [],

The presence of the group [formula] is one of the major characteristics, and it is possible not only to improve the light resistance of the transfer dye obtained by the present invention and to achieve the synthetic advantages described later.

By introducing the group [Formula], Dmax improvement at high temperature is achieved. By the way, according to the present invention

The effect of the group [formula] is not described or taught at all in the prior art cited above (for example, US Pat. No. 3,929,760, US Pat. The carbon atom chain represented by R and R ¹ and which may contain at most one oxygen atom is, for example, an alkylene group having 4 to 6 carbon atoms (for example, -(CH ₂ ) ₄
−, −(CH ₂ ) ₅ −, −CH ₂ CH ₂ CH ₂ CH ₂ CH (CH ₃ )
−, −CH ₂ CH ₂ CH ₂ CH(CH ₃ )CH ₂ −, −
CH ₂ CH ₂ CH (which can complete a 5- or 6-membered ring with a nitrogen atom, such as CH ₃ )CH ₂ CH ₂ -), -CH ₂ CH ₂ -O-CH ₂ CH ₂ -, -
Examples include carbon atom chains containing oxygen atoms, such as _CH2CH ( _CH3 )-O-CH( _CH3 ) _CH2- . The heterocycle completed by each of R and R ¹ may have a substituent such as an alkyl group (eg, methyl). Compounds of formulas () and () include non-diffusible image-forming substances (dye-releasing redox compounds) that are oxidized and self-destructed to provide diffusible dyes as a result of development. Valid Y for this type of compound is an N-substituted sulfamoyl group.
For example, Y can include a group represented by the following formula (A). In the formula, β represents a group of nonmetallic atoms necessary to form a benzene ring, and a carbocycle or a heterocycle is fused to the benzene ring to form, for example, a naphthalene ring, a quinoline ring, or a 5,6,7,8-tetrahydronaphthalene ring. A ring, a chroman ring, etc. may be formed. Furthermore, the benzene ring or the ring formed by condensing a carbocycle or heterocycle with the benzene ring includes a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a nitro group, an amino group, an alkylamino group. , an arylamino group, an amide group, a cyano group, an alkylmercapto group, a keto group, a carbalkoxy group, a heterocyclic group, etc. may be substituted. α represents a group represented by -OG ¹ or -NHG ² . where -OG ¹ represents a hydroxyl group, a group that can be hydrolyzed to produce a hydroxyl group, preferably

[Formula] or

It is a group represented by [Formula]. Here, G ³ is an alkyl group, particularly an alkyl group having 1 to 18 carbon atoms such as a methyl group, an ethyl group, or a propyl group, a halogen-substituted alkyl group having 1 to 18 carbon atoms such as a chloromethyl group or a trifluoromethyl group, or phenyl. group, represents a substituted phenyl group. or,
G ² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or a hydrolyzable group. here above
Preferred hydrolyzable groups for ^G2 are:

[Formula] A group represented by -SO ₂ G ⁵ or -SOG ⁵ . Here, G ⁴ is an alkyl group having 1 to 4 carbon atoms such as a methyl group; a halogen-substituted alkyl group such as a mono-, di- or trichloromethyl group or a trifluoromethyl group; an alkylcarbonyl group such as an acetyl group; an alkyloxy group ; Substituted phenyl groups such as nitrophenyl groups and cyanophenyl groups; Unsubstituted phenyloxy groups substituted with lower alkyl groups or halogen atoms; Carboxyl groups; Alkyloxycarbonyl groups; Aryloxycarbonyl groups; Alkylsulfonyl ethoxy groups or arylsulfonylethoxy groups represents. Also, G ⁵
represents a substituted or unsubstituted alkyl group or aryl group. Furthermore, b is an integer of 0.1 or 2. However, the above α
In some cases, an alkyl group corresponding to the alkyl group that makes the compound represented by the general formula (A) immobile and non-diffusible is introduced as G ₂ of -NHG ₂ , as described above. , that is, α is −OG ¹
When α is -NHG _{2 and G 2 is} a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrolyzable group, b is 1 or 2, preferably It is 1. Ball represents a ballast group. The ballast group will be explained in detail later. A specific example of this type of Y is shown in the U.S. patent
No. 3928312, No. 4076529, No. 4152153, No.
No. B351673, No. 4135929, No. 4258120, JP-A-Sho
48-33826 and Japanese Patent Application Publication No. 53-50736, Patent Application No. 1987-
96339. For example, the following is a typical example. Another example of Y suitable for this type of compound is a group represented by the following formula (B). In the formula, Ball, a, and b have the same meanings as in formula (A), and β' represents an atomic group necessary to form a carbocyclic ring, for example, a benzene ring, and a carbocyclic or heterocyclic ring is added to the benzene ring. The rings may be fused to form a naphthalene ring, a quinoline ring, a 5,6,7,8-tetrahydronaphthalene ring, a chroman ring, or the like.
Furthermore, halogen atoms, alkyl groups,
alkoxy group, aryl group, aryloxy group,
A nitro group, an amino group, an alkylamino group, an arylamino group, an amide group, a cyano group, an alkylmercapto group, a keto group, a carbalkoxy group, a heterocyclic group, etc. may be substituted. Specific examples of this type of Y include U.S. Pat.
56-16130, 56-16131, 56-12642
No. 4,053,312 and Japanese Patent Application No. 74,109.
It is described in No. 55-96339. For example, the following examples are typical. Furthermore, another example of Y suitable for this type of compound is a group represented by the following formula (C). In the formula, α, Ball, and b have the same meanings as in formula (A). β'' represents an atomic group necessary to form a heterocycle, such as a pyrazole ring or a pyridine ring,
A carbocycle or a heterocycle may be further fused to the heterocycle, and the above various rings may be further fused with formula (B).
The ring may be substituted with the same type of substituent as the ring substituent described in . A specific example of this type of Y is described in JP-A-51-104343. Further, as Y effective for this type of compound, there is one represented by formula (D). In the formula, γ preferably represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group or a heterocyclic group, or -CO- ^G6 ; ^G6 is ^-OG7 , -S- ^G7 or

[Formula], (G ⁷ represents hydrogen, an alkyl group, a cycloalkyl group, or an aryl group, and the alkyl group, cycloalkyl group, and aryl group may have a substituent, and G ⁸ is G represents the same group as the ⁷ group, or G ⁸ represents an acyl group derived from an aliphatic or aromatic carboxylic acid or sulfonic acid, G ⁹ represents hydrogen or an unsubstituted or substituted alkyl group); δ is , represents the residues necessary to complete the fused benzene ring,
The fused benzene ring may therefore carry one or more substituents; and the substituents on said fused benzene ring completed by γ and/or δ are or contain a ballast group. It includes. Specific examples of this type of Y include U.S. Pat.
46730. Furthermore, examples of Y suitable for this type of compound include a group represented by formula (E). In the formula, Ball has the same meaning as in formula (A), and ε is an oxygen atom or a =NG'' group (G'' represents a hydroxyl group or an amino group which may have a substituent), and in particular, ε is = In the case of NG'', G'' is typically G'' in the =C=N-G'' group formed as a result of the dehydration reaction of the carbonyl reagent H ₂ N-G'' with a ketone group; Examples of H ₂ N−G'' compounds include hydroxylamine, hydrazines, semicarbazides, thiosemicarbazides, etc.
Specifically, examples of hydrazines include hydrazine, phenylhydrazine, substituted phenylhydrazine having a substituent such as an alkyl group, alkoxy group, carbalkoxy group, or halogen atom on the phenyl group, and isonicotinic acid hydrazine. Can be done. Examples of semicarbazides include phenyl semicarbazide or substituted phenyl semicarbazides having substituents such as alkyls, alkoxy groups, carbalkoxy groups, and halogen atoms, and thiosemicarbazides include various derivatives similar to semicarbazide. can be given. Further, β in the formula is a 5-, 6-, or 7-membered saturated or unsaturated non-aromatic hydrocarbon ring, specifically, for example, cyclopentanone, cyclohexanone, cyclohexenone, cyclopentenone, Representative examples include cycloheptanone and cycloheptenone. Furthermore, the 5- to 7-membered non-aromatic hydrocarbon ring may be fused with another ring at an appropriate position to form a condensed ring. Here, the other rings may be various rings, regardless of whether they exhibit aromaticity or not, and regardless of whether they are hydrocarbon rings or heterocycles, but when forming a condensed ring, For example, in the present invention, fused rings such as indanone, benzocyclohexenone, benzocycloheptenone, etc., which are formed by fusing benzene with the above-mentioned 5- to 7-membered non-aromatic hydrocarbon ring, are more preferred. The 5- to 7-membered non-aromatic hydrocarbon ring or the fused ring is an alkyl group, an aryl group, an alkyloxy group, an aryloxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, or a halogen atom. , a nitro group, an amino group, an alkylamino group, an arylamino group, an amide group, an alkylamido group, an arylamido group, a cyano group, an alkylmercapto group, an alkyloxycarbonyl group, and the like. G ¹⁰ represents a hydrogen atom or a halogen atom such as fluorine, chlorine, or bromine. A specific example of this type of Y is described in JP-A-53-3819. In addition, examples of Y in the compound of the present invention include, for example, JP-B No. 48-32129, JP-A No. 48-39165, JP-A No. 49-Sho.
64436 and US Pat. No. 3,443,943. As specific examples of Y represented by general formulas (C), (D), and (E), the following are representative. Another type of compound represented by formula () or () releases a diffusible dye by self-ring closure under alkaline conditions, but does not substantially cause dye release when reacting with an oxidized developer. Examples include non-diffusible imaging compounds such as those that disappear. Y that is effective for this type of compound includes, for example, the formula
The things listed in (F) can be mentioned. In the formula, α″ is an oxidizable nucleophilic group such as a hydroxyl group, a primary or secondary amino group, a hydroxyamino group, a sulfonamide group, or a precursor thereof, and is preferably a hydroxyl group. , dialkylamino group or any group defined for α'', preferably a hydroxyl group. G ¹⁴ is an electrophilic group such as -CO- or -CS-, preferably -CO-. G ¹⁵ is an oxygen atom, sulfur atom, selenium atom, nitrogen atom, etc., and in the case of a nitrogen atom, it is a hydrogen atom, a carbon atom 1
Alkyl groups or substituted alkyl groups containing up to 10 carbon atoms may be substituted with aromatic residues containing 6 to 20 carbon atoms. Preferred G ¹⁵ is an oxygen atom. G ¹³ is an alkylene group having 1 to 3 carbon atoms, and a represents 0 or 1, preferably 0. ^G13 is a substituted or unsubstituted alkyl group containing 1 to 40 carbon atoms, or 6 to 40 carbon atoms;
40 substituted or unsubstituted aryl groups, preferably alkyl groups. G ¹⁶ , G ¹⁷ and
G ¹⁸ is a hydrogen atom, a halogen atom, a carbonyl group, a sulfamyl group, a sulfonamide group, an alkyloxy group containing 1 to 40 carbon atoms, or G ¹³
G ¹⁶ G ¹⁷ may together form a 5- to 7-membered ring. Also G ¹⁷ is

[Formula] may be used. However, at least one of G ¹³ , G ¹⁶ , G ¹⁷ and G ¹⁸ represents a ballast group. Ar represents an aryl group,
Z is synonymous with formula (). Ar is preferably
pim; or θ-phenylene group with 1 carbon number
-4 alkyl groups, C1-4 alkoxy groups, C1-6 alkoxyalkoxy groups, and halogen atoms (particularly chloro atoms) may be substituted. A specific example of this type of Y is JP-A No. 51-63618.
There is a description in . For example, the following are representative examples. Oxidized product of the group represented by formula (F) - i.e. (F')
can also be used as Y in the present invention. When reduced, it returns to (F) and has the function of releasing a diffusible dye. (However, α ⁴ is a group that produces α″ when reduced, α ⁵
is a group that produces α when reduced, and the other symbols have the same meanings as in formula (F). ) Specific examples of this type of Y are described in JP-A-53-110827 and US Pat. No. 4,278,750. for example; Further, as Y suitable for this type of compound, formula (G)
Examples include groups represented by . In the formula, Ball and β' are the same as those in formula (B). G ¹⁹ is an alkyl group (including substituted alkyl groups)
It is. A is a divalent group such as an alkylene group (having 1 to 6 carbon atoms) or Ar. Z is the formula ()
Synonymous with. For specific examples of this type of Y, see
No. 53-35533, No. 53-110828, No. 53-110827, and US Pat. No. 4,278,750. for example; Further, as Y suitable for this type of compound, the formula (H)
There is a group represented by In the formula, Ball and β′ are the same as those in formula (B), and G ¹⁹ is the same as that in formula (G). A has the same meaning as formula (G), and Z has the same meaning as formula (). For specific examples of this type of Y, see JP-A-49-111628 and JP-A-52-4819.
There is a description in . for example, Yet another type of compound represented by formula () or () is a non-diffusible compound that releases a diffusible dye upon coupling reaction with the oxide of a color developer oxidized by silver halide. (dye-releasing couplers). Typical examples of Y that are effective for this purpose include the groups listed in US Pat. No. 3,227,550. For example, Y may be represented by formula (J). (Ball-Coup) t-Link- (J) In the formula, Coup is a coupler residue that can couple with the oxide of the color developer, such as a 5-pyrazolone coupler residue, a phenol coupler residue, or a naphthol coupler residue. group, an indanone-type coupler residue, an open-chain ketomethylene coupler residue, etc. Ball represents a ballast group. Link is bonded to the active point of the Coup portion, and when the dye image-forming compound represented by formula (I) having the group represented by formula (J) above as Y performs a coupling reaction with the oxide of the color developer. represents a group whose bond with the Coup moiety can be cleaved, such as an azo group, an azoxy group, -O-, -Hg-, an alkylidene group, -S-, -S-S- or _-NHSO2 , etc. can be mentioned. t represents 1 or 2 when Link is an alkylidene group, and 1 when Link is any of the above groups. Among Y represented by the above formula (J), preferred are those where Coup is a phenol type coupler residue, naphthol type coupler residue or indanone type coupler residue, and Link is -NHSO ₂ -. As another type of compound represented by formula () or (), the group Y described in the following listed patents can be utilized: JP-A-54-
130927, No. 53-69033, West German application (OLS)
No. 3008588, No. 3014699. Ballast groups are residues inserted into the compounds of the invention in order to enable them to be present in the form of diffusion-resistant substances in the hydrophilic colloids commonly used in photographic materials. . The residues used for this purpose have 8 to 50 carbon atoms, preferably 8 to 32 carbon atoms.
is preferably an organic residue. Such organic residues generally include linear or branched aliphatic groups, but may also include carbocyclic, heterocyclic, or aromatic groups. This residue may be attached directly or indirectly to the "rest of" the molecule. In the case of an indirect bond, the bond may be, for example, via one of the following intervening groups: -NR ^a CO-, -
NR ^a SO ₂ -, -NR ^a - (where R ^a represents a hydrogen alkylaryl group), -O-, -S-, -SO ₂ -. This ballast group may further contain a water solubility imparting group in addition to the above-mentioned groups, examples of which include a sulfo group and a carboxyl group. This water solubility imparting group may be present in the form of an anion. Diffusivity (or diffusion resistance) depends on the size of the molecule of the compound, so if the entire molecule is sufficiently large, only a relatively short group can be used as the residue for imparting diffusion resistance. may be sufficient. Particularly desirable among the above compounds are dye-releasing redox compounds, in which the group effective as Y is N
-Substituted sulfamoyl group. The N-substituent of the N-substituted sulfamoyl group is preferably a carbocyclic group or a heterocyclic group. Among the above examples of the N-carbocyclic-substituted sulfamoyl group, those represented by formulas (A) and (B) are particularly preferred. Among the above examples of the N-heterocycle-substituted sulfamoyl group, those represented by formulas (C) and (D) are particularly preferred. The features achieved by the present invention appear particularly prominently when Y is represented by the following formula (K) among Y represented by formula (B). However, G represents a hydroxyl group or a group that provides a hydroxyl group by hydrolysis, and R ^1a and R ^2a may be the same or different,
Each may be an alkyl group, or R ^1a and R ^2a may be linked to form a ring. R ^3a represents a hydrogen atom, an alkyl group or an aromatic group. R ^4a represents an alkyl group or an aromatic group. R ^5a represents a hydrogen atom, an alkyl group, an alkyloxy group, a halogen atom, an acylamino group or an alkylthio group; and R ^5a and R ^3a , R ^5a
and R ^4a , R ^4a and R ^3a may be linked to form a ring, or R ^1a and R ^2a and R ^3a may be linked to form a bicyclo ring or a tricyclo ring. n represents 1 or 2. Specific examples of G include, in addition to a hydroxyl group, carbon atoms having 2 to 40 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 8 carbon atoms.
4 alkyl -COO- group (e.g. acetoxyl group, propionyloxy group, etc.),
Examples include aromatic carbonyloxy groups having 7 to 40 carbon atoms, preferably 7 to 15 carbon atoms, and more preferably 7 to 9 carbon atoms (eg, benzoyl group, substituted benzoyl group, etc.). The alkyl group represented by R ^1a (and R ^2a , R ^3a or R ^4a ) has 1 to 40 carbon atoms, preferably 1 to 24 carbon atoms.
It may be linear, branched, or cyclic, and may be further substituted with a substituent (for example, an alkoxy group, a cyano group, a hydroxyl group, a halogen atom, a phenoxy group, a substituted phenoxy group, an acylamino group, etc.) You may do so. R ^1a (and R ^2a ,
Preferred examples of the alkyl group for R ^3a or R ^4a ) include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, undecyl, pentadecyl, heptadecyl; isopropyl, isobutyl, t-butyl, t-butyl; -branched alkyl groups such as amyl and neopentyl; Examples of the aromatic group represented by R ^1a (and R ^2a , R ^3a or R ^4a ) include phenyl group, substituted phenyl group, naphthyl group, and substituted naphthyl group. Examples of substituents for these substituted phenyl groups or naphthyl groups include alkoxy groups, cyano groups, hydroxyl groups, nitro groups, and alkyl groups. When R ^1a and R ^2a combine to form a ring, it is desirable that they form a 5- to 40-membered ring, preferably a 5- to 12-membered ring (among these, a saturated ring is particularly preferred). Regarding the alkyl moiety of the alkyl group, alkyloxy group, and alkylthio group represented by R ^5a , the alkyl moiety has 1 to 40 carbon atoms, preferably 1 to 24 carbon atoms, and may be linear or branched. It may be cyclic, and further substituents (for example,
(alkoxy group, cyano group, hydroxyl group, halogen atom, phenoxy group, substituted phenoxy group, acylamino group, etc.) may be substituted. Preferred examples of the alkyl group for R ^5a include those specifically described in the explanation of R ^1a . The arylthio group represented by R ^5a is preferably a phenylthio group, a substituted phenylthio group, or a heterocyclic thio group. Typical examples of the acylamino group represented by R ^5a include an alkyl-CONH- group and a (substituted or unsubstituted) phenyl-CONH- group. Examples of the substituents in the substituted phenylthio group of R ^5a and the substituted phenyl-CONH- group of R ^5a include those described as examples of the substituents of the substituted aryl group of R ^1a and R ^2a . Examples of the heterocyclic thio group for R ^5a include those commonly known as development inhibitor releasing groups. Examples of the halogen for R include fluorine, chlorine, and bromine. R ^4a and R ^5a ; R ^1a and R ^4a ; or R ^1a and R ^5a may form a condensed ring, and the ring is preferably 5- to 6-membered.
Furthermore, the ring formed by R ^1a and R ^5a may be a heterocycle (heteroatoms include O, N, etc.) (forming an aromatic hydrocarbon condensed ring is preferable since color staining occurs in the remaining portion). do not have.). More preferably in general formulas () and ()

[Formula] is an isopropyl group, a t-butyl group, a t-amyl group, a cyclohexyl group, a 1-ethyl-1-methylpentyl group, a t-octyl group,
or

^{[ Formula} : This is the case when it represents an alkoxy group (those having a total carbon number of 1 to 24 are particularly preferred). Specific examples of the dye-releasing compound of the present invention are illustrated below. Compound 1 Compound 2 Compound 3 Compound 4 Compound 5 Compound 6 Compound 7 In the formula of compound 6, M=2-Cl Compound 8 M=2- _CH3 compound 9 M=3- _CH3 compound 10 M=4- _CH3 compound 11 compound 12 compound 13 compound 14 compound 15 compound 16 Compound 17 In the formula of compound 16, R ² =CH ₃ , R ³
= C ₂ H ₅ Compound 18 In the formula of compound 16, R ² = CH ₃ , R ³
= _CH2 -C( _CH3 ) _3Compound 19 In the formula of compound ₁₆ , ^R2 = _C2H5 , ^R3
= _{C4H9 -} n Compound 20 In the formula of compound 16, ^R2 = _CH3 , _R3
=H Compound 21 compound 22 Compound 23 In the formula of compound 22, R ¹ =CH ₃ , R ²
= CH ₃ , R ³ = CH ₂ -C(CH ₃ ) ₃ Compound 24 In the formula of compound 22, R ¹ = CH ₃ , R ²
= C ₂ H ₅ , R ³ = C ₄ H ₉ -n Compound 25 In the formula of compound 22, R ¹ = CH ₃ , R ²
=CH ₃ , R ³ =H Compound 26 In the formula of compound 22, R ¹ , R ² =
(CH ₂ ) ₅ , R ³ = H Compound 27 In the formula of compound 22, R ¹ , R ² =
(CH ₂ ) ₄ , R ³ = H Compound 28 In the formula of compound 22, R ¹ , R ² =
(CH ₂ ) ₅ , R ³ = CH ₃ Compound 29 In the formula of compound 22, R ¹ , R ² =
(CH ₂ ) ₄ , R ³ = CH ₃ Compound 30 In the formula of compound 22, R ¹ = R ² = R ³ =
_CH3 compound 31 compound 32 compound 33 Compound 34 In the formula of compound 33, Ball=CON(C ₁₈ H ₃₇ -n) ₂ Compound 35 compound 36 In the present invention, the compound represented by the general formula is generally an azo dye halide () or () and an amine derivative () having various organic ballast groups.
It can be synthesized by condensation reaction with (However, Hal is a halogen atom, and the other symbols have the same meanings as in formula () or ().) This condensation reaction is usually preferably carried out in the presence of a basic substance. Examples of such basic substances include alkali metal or alkaline earth metal hydroxides (e.g., sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, etc.), aliphatic amines (e.g., triethylamine, etc.), aromatic Heteroaromatic amines such as (pyridine, quinoline, α-, β-, or γ-
Picoline, lutidine, collidine, 4-(N・N-
(dimethylamino)pyridine, etc.), and heterocyclic bases (1,5-diazabicyclo[4,3,0]
Nonene-5.1.8-diazabicyclo [5.4.
0] Undecene-7, etc.). That is, when formula () or () is a sulfonyl chloride, a heteroaromatic amine (preferably pyridine) is particularly preferable among the above. The following schematic route is a typical method for synthesizing the amine represented by formula (). The first step is () and

This substitution reaction easily proceeds at temperatures below 100°C, but if excess

It is preferable to use [Formula] as a solvent. To convert a compound of formula () into a compound of formula (), it is preferable to use phosphorus oxychloride (POCl ₃ ), thionyl chloride (SOCl ₂ ), or pentachloride (PCl ₅ ) as a chlorinating agent. . At this time, N・N-dimethylacetamide, N・
It is preferable to carry out the reaction in the presence of N-dimethylformamide or N-methylpyrrolidone.
In order to obtain a compound of formula () by a condensation reaction between a sulfonyl chloride represented by formula () and an amine having a ballast group and yielding Y, condensation of the compound of formula () with the compound of formula () is performed. It is desirable to carry out the condensation reaction in the presence of a basic substance as mentioned in the reaction. Typical examples of reduction reactions to obtain the compound of formula () include catalytic hydrogenation, reduction with iron powder, and hydrazine reduction (Raney nickel, palladium on carbon or activated carbon catalyst). In the compound (), it occupies the p position

We would like to emphasize that the basicity of the amino group is increased due to the group of [Formula]. Therefore, there is an advantage that the condensation reaction with the sulfonyl halide () or () in the next step proceeds easily. Representative syntheses of dye-releasing redox compounds and intermediates thereof used in the present invention are described in detail below. Synthesis Example 1 Synthesis of sodium 2-morpholino-5-nitrobenzenesulfonate 82.5 g (0.3
mol) of sodium 2-chloro-5-nitrobenzenesulfonate was added, and the reaction mixture was gradually heated in a steam bath and stirred at 85-90°C for 30 minutes. After cooling, the precipitated crystals were collected and washed with acetone to obtain 90 g of sodium 2-morpholino-5-nitrobenzenesulfonate (yield 92%).
I got it. mp206-209℃ Synthesis Example 2 Synthesis of 2-pyrrolidinium-5-nitrobenzenesulfonate Suspend 100g of sodium 2-chloro-5-nitrobenzenesulfonate in 500ml of acetonitrile, add 100ml of pyrrolidine with stirring, and add 100ml of pyrrolidine to this mixture. The mixture was heated to reflux for 1 hour. After cooling, by pouring into 1.5 cold, 2N hydrochloric acid
-Pyrrolidinium-5-nitrobenzenesulfonate 97.3g (yield 93%) was obtained. mp205−210℃
(dec) Synthesis Example 3 Synthesis of 2-morpholino-5-nitrobenzenesulfonyl chloride 31 g (0.1 mol) of sodium 2-morpholino-5-nitrobenzenesulfonate obtained in Synthesis Example 1 and 92 ml (1 mol) of phosphorus oxychloride were added. The mixture was added to 320 ml of acetonitrile and heated under reflux for 2 hours. After cooling, the reaction product was added to 600 ml of ice water and the precipitated crystals were collected to obtain 20.3 g of 2-morpholino-5-nitrobenzenesulfonyl chloride (yield:
66%). mp117−120℃ Synthesis example 4 4-tert-butyl-2-(2'-morpholino-5'-
Synthesis of nitrobenzenesulfonamide)-5-hexadecyloxyphenol 9.2 g (0.03 mol) of the 2-morpholino-5-nitrobenzenesulfonyl chloride obtained above and
To a 70 ml solution of 13.3 g (0.03 mol) of 2-amino-4-tert-butyl-5-hexadecyloxyphenol hydrochloride in N/N-dimethylacetamide at room temperature, 15 ml of pyridine was added dropwise at room temperature, and after the addition was complete, the mixture was allowed to cool to room temperature. Stirring was continued for 1 hour. The reaction mixture was added to hydrochloric acid water (250 ml of ice water, 50 ml of concentrated hydrochloric acid) while stirring, and the precipitated crystals were collected. Yield 19g (95%) mp95-98℃ Synthesis Example 5 4-tert-butyl-2-(2'-morpholino-5'-
Synthesis of (aminobenzenesulfonamide)-5-hexadecyloxyphenol 20.3 g (0.03 mol) of 4-tert-butyl-2-
(2'-morpholino-5'-nitrobenzenesulfonamide)-5-hexadecyloxyphenol, 20
g reduced iron, 0.5 g ammonium chloride, 17 ml water
was added to 70 ml of isopropyl alcohol, and heated under reflux in a steam bath for 3 hours. Heating the reaction mixture, cooling the mother liquor on ice, collecting precipitated crystals, washing with 30 ml of isopropyl alcohol, and air drying yielded 18.2 g.
The title compound (yield 94%) was obtained. mp150~155
°C Synthesis Example 6 Synthesis of Compound 30 4-tert-Butyl-2-(2'-morpholino-5'-
5 ml of pyridine and 20 ml of N.N-dimethylacetamide were added to 6.5 g (0.01 mol) of 4-(4'-chlorosulfonylphenylazo)-5-hexadecyloxyphenol, and then 4-(4'-chlorosulfonylphenylazo)-3- 3.9 g (0.01 mol) of cyano-1-phenyl-5-pyrazolone was added, and the mixture was stirred at room temperature for 1 hour. After the reaction is complete, extract with ethyl acetate,
Crystallization was performed by adding methyl alcohol to the extract. After collecting the precipitated crystals, they were air-dried to obtain 6.5 g (yield: 65%) of the title compound. m.
p.128～133℃ εAcetone ₄₁₂ 2.27×10 ⁴ Synthesis Example 7 4-Cyclohexyl-2-(2'-morpholino-
Synthesis of 5'-nitrobenzenesulfonamide)-5-hexadecyloxyphenol 197 g of 2-morpholino-5-nitrobenzenesulfonyl chloride, 234 g of 2-amino-4-cyclohexyl-5-hexadecyloxyphenol, 166 ml of pyridine and N.N- Dimethylacetamide 1 was added and stirred at room temperature for 1 hour. After the reaction was completed, 1.2 ml of ethyl acetate and 1.2 ml of water were added for extraction, and 3.2 ml of methyl alcohol and 100 ml of water were added to the extract for crystallization. After removing the precipitated crystals,
Air drying gave 298 g (85% yield) of the title compound. mp52～55℃ Synthesis Example 8 4-Cyclohexyl-2-(2'-morpholino-
Synthesis of 5'-aminobenzenesulfonamide)-5-hexadecyloxyphenol 4-cyclohexyl-2-(2'-morpholino-
5'-nitrobenzenesulfonamide)-5-hexadecyloxyphenol 39g, reduced iron 39g, ammonium chloride 1g, isopropyl alcohol 140g
ml and 35 ml of water were added and heated under reflux for 2 hours. After the reaction, filter, collect the precipitated crystals, and air dry.
35 g (95% yield) of the title compound was obtained. mp180
~185℃ Synthesis Example 9 Synthesis of Compound 26 4-Cyclohexyl-2-(2'-morpholino-
27 g of 5'-aminobenzenesulfonamide)-5-hexadecyloxyphenol, 80 ml of N.N-dimethylacetamide, 20 ml of pyridine, 4-(4'-chlorosulfonylphenylazo)-3-cyano-5
- 15.6 g of pyrazolone was added and stirred at room temperature for 1 hour. After the reaction was completed, the mixture was extracted with 150 ml of ethyl acetate and 150 ml of water, and methyl alcohol was added to the extract for crystallization. The precipitated crystals were collected and air-dried to obtain 28 g (yield 68.5%) of the title compound. mp124-128℃ εAcetone ₄₁₂ 2.28×10 ⁴ Compounds represented by formulas () and () are:
It can be synthesized according to the following formula: and (However, the symbol has the same meaning as formula () or ().) Diazotization of compound (L) is described, for example, in Yutaka Hosoda's "New Dye Chemistry" Gihodo (1963) pp. 114-120, Hiroshi Horiguchi's "Synthesizing Synthesis". Dye” Sankyo Publishing (1970), 114-124
This can be done using the method described on the page. Among these, it is preferable to diazotize the diazo component (L) by a method usually called a reversed method. In this method, 1 mole of the diazo component (L), about 1 mole of sodium nitrite, and about 1 mole of sodium hydroxide (or other alkali or alkaline earth metal hydroxide) are dissolved in water, and this mixture is Add to cooled mineral acid water (e.g. dilute hydrochloric acid, dilute sulfuric acid, etc.). The amounts of sodium nitrite and sodium hydroxide are preferably the above amounts, but may be added in excess. The solution of the diazonium salt thus obtained is mixed with about 1 mol of an organic solvent, solution, or aqueous solution of the coupler compound (N) to carry out a coupling reaction. The organic solvent for dissolving the coupler is preferably one that mixes with water, such as alcohols (methanol, ethanol,
-propanol, methoxyethanol, ethoxyethanol, etc.), carbonamides (N/N-
(dimethylacetamide, N.N-dimethylformamide, etc.), carboxylic acid salts (acetic acid, propionic acid, etc.) are preferred. Further, the compound (N) may be dissolved in these mixed solvents. Furthermore, the compound (N) may be used as an alkaline aqueous solution. During this coupling reaction, it is preferable to coexist a basic substance. Desirable basic substances include sodium acetate, potassium acetate, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and the like. Compound (S) can also be synthesized according to the above method. However, conditions for diazotization must be selected depending on the properties of the diazo component (R). In this case, the above-mentioned books by Hosoda and Horiguchi are helpful. The details of the coupling reaction will be described in the following specific example, but please refer to pages 124-129 of Horiguchi's book mentioned above.
“Fundamental Process of Dye Chemistry” by HEFierz-David and L. Blangy
Interscience Publishers Inc., New York
(1949), pp. 239-297, The Chemistry of Synthetic Dyes, by K. Venkataraman.
Academic Press Inc., New York (1952), No. 11
I will also list the chapter descriptions as they may be helpful. In order to obtain a compound represented by formula () or (), the sulfonic acid group of the compound represented by formula (O) or (S) may be replaced with a halogenosulfonyl group. In particular, the case of Hal=Cl is preferable, so
I will talk about this synthesis method. Examples of the chlorinating agent for converting the sulfonic acid group of formula (O) or (S) into a chlorosulfonyl group include compounds such as phosphorus oxychloride, phosphorus pentachloride, thionyl chloride, and chlorosulfonic acid. This reaction proceeds smoothly when a carboxylic acid amide such as N.N-dimethylacetamide, N.N-dimethylformamide or N-methylpyrrolidone is present. The required amount of the above chlorinating agent is determined by stoichiometry;
It is often desirable to use an excess (1.5 to 50 times the theoretical amount, preferably 1.5 to 10 times) of the chlorinating agent. This reaction often proceeds satisfactorily at room temperature (approximately 25°C). If the reaction is intense, it is also possible to cool it to about 0°C. On the other hand, if the reaction is slow, heating may be performed in the range of 25° to 150°C (preferably 25°C to 100°C). E. Miiller also applies when Hal is other halogen.
Houben−Weyls Methodender Organishen
Chemie, Vol. 557-598 (1955). For the synthesis of compounds () and (), please refer to JP-A-Sho.
The descriptions in 52-7727 and 54-111344 are listed here as they are helpful. In the case of q=0 among the compounds represented by (), the compound (however, Z=H, protect the Y part if necessary) is diazotized in the same manner as above and reacted with the coupler (N). Synthesize by The compound of the present invention is combined with a light-sensitive silver halide emulsion to constitute a photographic light-sensitive material. After exposure, when processing is performed with an alkaline processing solution, the compound of the present invention undergoes oxidation and then hydrolyzes to release the dye in the areas where silver development occurs, so this released dye can be transferred or washed with water. A color image distribution can be obtained even if the photosensitive material removed by the method is subjected to bleaching and fixing processes. If a so-called ordinary emulsion is used, which develops depending on the amount of exposure, the transferred image will form a negative image and the residual image will form a positive image. Direct reversal emulsions and U.S. patents 3227551 and 3227554,
Using a DIR reversal emulsion system, such as that described in British Patent No. 3364022, or a reversal emulsion system using dissolution physical development, such as that described in British Patent No. 904364, the transferred image is a positive image and the residual image is a negative image. Become. Any one or combination of either type of yin-yang may be utilized as desired.
In developing the photosensitive material described herein, the processing is carried out in the presence of an auxiliary developer in order to facilitate electron transfer between the relatively immobile compound of the present invention and the silver halide grains. It is desirable that this be done. The following can be exemplified as the auxiliary developer that can be used. Black and white developer 1-phenyl-3-pyrazolidinone, 1-phenyl-4,4-dimethyl-3-pyrazolidinone, 1-phenyl-4-methyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-hydroxymethyl- Pyrazolidinones such as 3-pyrazolidinone, 1-(p-tolyl)-4-methyl-4-hydroxymethyl-3-pyrazolidinone; p-amino-phenol, N-methyl-p-aminophenol, N・N-diethylamino- Aminophenols such as phenol; Hydroquinones such as p-tolylhydroquinone; etc. Color developer: Phenylene diamines such as N/N-diethyl-p-phenylene diamine, 6-hydroxy-1, 2, 3, 4-tetrahydroquinoline, etc. Of those listed herein, black and white developers are particularly preferred over color developers such as phenylene diamines, which generally have the property of reducing stain formation in the image receiving layer. Among black and white developers, pyrazolidinones are particularly suitable for use in combination with the dye-releasing compounds of this invention. Among these, it is advantageous to combine with a 1-aryl-3-pyrazolidinone developer, especially one represented by the following formula. In the formula, W ¹ and W ² may be the same or different,
Each includes a hydrogen atom, an optionally substituted alkyl group (suitably having 1 to about 37 carbon atoms, including straight chain, branched, and cyclic ones), or an optionally substituted aryl group (preferably a carbon number 6 to 20, including phenyl and naphthyl).
Further, W ¹ and W ² may be connected to each other to form a 4- to 8-membered (preferably 6-membered) carbon ring (preferably a saturated ring). Substituents in substituted alkyl groups and substituted aryl groups include lower alkyl groups (having 1 to about 6 carbon atoms), hydroxy groups, and alkoxy groups (suitably having 1 to about 20 carbon atoms, preferably 1 to about 20 carbon atoms). 6 lower alkoxy group), amino group (unsubstituted amino group, mono- or dialkyl-substituted amino group, arylamino group, amino group substituted with alkyl group and aryl group; carbon number of these substituted amino groups is 1 to Approx. 36 is suitable), sulfo group, halogen atom (chlorine,
Examples include bromine and iodine atoms), alkyl or aryl ester groups (suitably having 1 to about 20 carbon atoms), and the like. Among W ¹ and W ² , a hydrogen atom, an alkyl group, or a hydroxyalkyl group (eg, hydroxymethyl, hydroxyethyl) is preferable. Further, W ³ represents a hydrogen atom or a substituent having a negative Hammett's σ (sigma) constant, and m represents an integer of 1 to 5. Specific examples of substituents for ^W3 include alkyl groups (e.g. methyl group, ethyl group), alkoxy groups (e.g. methoxy group, ethoxy group), hydroxy group, amino group,
Mention may be made of aryl groups (eg phenyl groups). An example of the substituent for W ³ when m is 2 is a methyl group. Among these, the half-wave potential of polarography is about -80mV to about -200mV (vs.SCE, PH11.0
) (preferably about -100 mV to
-150 mV) is useful for (i) rapid development of silver halide grains and (ii) its oxidized form cross-oxidizes sufficiently efficiently with the o-sulfonamidophenol derivatives of the present invention. This is particularly useful in that it is possible to shorten the time required to complete an image. When the compound of the present invention is used in a diffusion transfer method, it is preferable to use a combination of hydroquinones (for example, methylhydroquinone, t-butylhydroquinone, etc.) in addition to the above-mentioned pyrazolidinones as a developer. It is particularly good at adjusting the tone. The dye-releasing compound of the present invention is generally dispersed in a hydrophilic colloid carrier in the following manner. That is, a solution obtained by dissolving a dye-releasing compound in an organic solvent is added to a solution of a hydrophilic colloid and dispersed as microdroplets. Easily volatile solvents such as ethyl acetate, tetrahydrofuran, methyl ethyl ketone, etc. may be used during the drying process of the photographic layer or
It can be removed by the method described in U.S. Pat. It is removed by washing with water. However, in order to stabilize the dispersion of the dye-releasing compound and accelerate the dye image forming process, it is advantageous to incorporate the dye-releasing compound into a solvent that is substantially insoluble in water and has a boiling point of 200° C. or higher at normal pressure. Examples of this type of solvent include dibutyl phthalate, tricresyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, N·N-diethyl lauramide, and the like. In order to accelerate the dissolution process of the dye-releasing redox compound, it is desirable to supplementally use a volatile or water-soluble solvent such as those mentioned above. Furthermore, instead of or in addition to the high-boiling solvent, a lipophilic polymer can also be used. As a lipophilic polymer suitable for this purpose, for example, a polyester resin obtained by polycondensation of a polyhydric alcohol and a polybasic acid is used. Other polymers include polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl propionate,
polyvinyl butyral, polyvinyl chloride,
Polyacrylic ester, polymethacrylic ester, nitrocarboxymethyl cellulose, N-
Vinylpyrrolidone-acrylic acid copolymer, N-vinylpyrrolidone-acrylic acid-methyl acrylate copolymer, vinyl phthalimide-acrylic acid copolymer, cellulose acetate hydrogen phthalate, poly-N-methyl methacrylamide, dimethylaminoethyl methacrylate - Acrylic acid copolymers and the like can be used. Generally, a colloid mill, a high-pressure homogenizer, an ultrasonic emulsifier, a high-speed rotating mixer, etc. are used for dispersion into minute droplets, and an anionic surfactant is preferably used as the emulsification aid. Surfactants useful in dispersing the compounds of the invention include sodium triisopropylnaphthalene sulfonate, sodium dinonylnaphthalene sulfonate, sodium p-dodecylbenzenesulfonate, dioctyl sulfosuccinate sodium salt, cetyl sulfate sodium salt, Formalin condensate in which the ratio of p-nonylphenol to sodium p-nonylphenoxybutylsulfonate is about 55 to about 45 (average degree of condensation about 3.4), p-tert-octylphenoxydiethoxyethylsulfonic acid There are anionic surfactants disclosed in Sodium, Japanese Patent Publication No. 39-4293 and British Patent No. 1138514. The combination of these anionic surfactants and higher fatty acid esters of anhydrohexitol has been patented in the US.
As disclosed in No. 3676141, it exhibits particularly good emulsifying ability. Furthermore, U.S. Patent Publication No. 43-13837, U.S. Patent No. 2992104, U.S. Patent No. 3044873, U.S. Patent No. 3061428, U.S. Pat.
The dispersion method disclosed in No. 3832173 and the like is also effective for dispersing the compound of the present invention. Hydrophilic colloids used to disperse the dye-releasing compounds of the invention include, for example, gelatin, colloidal albumin, casein, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, agar, sodium alginate, and sugar derivatives such as starch derivatives. , synthetic hydrophilic colloids such as polyvinyl alcohol, polyN-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide, and derivatives and partial hydrolysates thereof. If desired, compatible mixtures of two or more of these colloids are used. Among these, gelatin is most commonly used, but gelatin may be partially or completely replaced with a synthetic polymer substance. A light-sensitive element for color diffusion transfer is a combination of a silver halide emulsion and a dye-releasing compound of the present invention. The silver halide emulsion used in the present invention is a hydrophilic colloidal dispersion of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, or a mixture thereof, which contains halogen The composition is selected depending on the purpose of use of the photosensitive material and processing conditions, but if the iodide content is 10
Particularly preferred are silver bromide, silver iodobromide or silver chloroiodobromide emulsions in which the remainder is bromide under mol% (chloride content is 30 mol% or less). The grain size of the silver halide used may be a normal grain size or a fine grain size, but preferably has an average grain size in the range of about 0.1 micron to about 2 micron. Furthermore, depending on the intended use of the photosensitive material, it is desirable that the particle diameter be uniform. The crystal shape of the particles used may be cubic, octahedral or mixed crystal. These silver halide emulsions are used, for example, in Chimie Photographique by P. Glafkides.
(2nd edition, 1957: Paul Montel, Paris) Chapters 18 to 23 can be prepared by known and commonly used methods. The silver halide emulsion used in the present invention includes a natural sensitizer contained in gelatin, a sulfur sensitizer such as sodium thiosulfate or N.N.N'-triethylthiourea, a thiocyanate complex salt of monovalent gold, It is preferable that the film be chemically sensitized using a gold sensitizer such as a thiosulfate complex, or a reduction sensitizer such as stannous chloride or hexamethylenetetramine. The present invention also uses silver halide emulsions that easily form latent images on the grain surfaces, as described in US Pat. No. 2,592,550 and
In addition to internal latent image type silver halide emulsions such as those described in No. 3206313, direct reversal silver halide emulsions using desensitizing dyes and solarization type silver halide emulsions can also be used. The above solarization type silver halide emulsions are described in "The Theory of the Photographic Process" edited by Mees.
(1942: McMillan Co. New York) pages 261-297 are useful. Regarding the preparation method, for example, British Patent No. 443245, British Patent No. 462730,
US Patent No. 2005837, US Patent No. 2541472, US Patent No. 3367778
No. 3501305, No. 3501306, and No. 3501305, No. 3501306, and No.
It is described in No. 3501307 etc. The internal latent image type silver halide emulsion that is advantageously used in the present invention mainly has a photosensitive center inside the silver halide emulsion grains, and selectively forms a latent image thereon by exposure. On the other hand, the degree of latent image formation on the particle surface is low. Such an internal latent image type silver halide emulsion is based on the Theory of
Photographic Process (4th edition, 1977, TH
James (ed.), pp. 171-176, the amount of silver in the image (corresponding to the surface latent image) obtained by developing with a surface developer after exposure is the same as that of the image obtained with an internal developer. It is characterized by a clearly low value compared to the amount of silver (corresponding to the entire latent image). Internal latent image type silver halide emulsions can be made by various methods. For example, Burton's emulsion, which has a high iodine content and is made by the ammonia process (EJWall, Photographic Emulsions, pp. 35-36, 52-
53 pages American Photographic Publishing Co.,
(1929)) and U.S. Patent No. 2497875, 2563785
), a large-grain primitive emulsion with a low iodine content made by the ammonia method (West German Patent Application (OLS) No. 2728108), and a large-grain primitive emulsion with a low iodine content made by the ammonia method (West German Patent Application (OLS) No. 2728108). Emulsions made by precipitation (US Pat. No. 3,511,662), a carrier that first creates grains of highly soluble silver salts such as silver chloride and then converts them to less soluble silver salts such as (iodine) silver bromide. Convergence emulsion by Tastrophy precipitation method (US patent)
No. 2592250), a core-shell emulsion in which a silver halide shell is coated on the core grains by mixing a chemically sensitized large grain core emulsion with a fine grain emulsion and ripening the core emulsion (US Pat. No. 3,206,313). british patent
No. 1011062), a soluble silver salt solution and a soluble halide solution were simultaneously added to a chemically sensitized monodisperse core emulsion while keeping the silver ion concentration constant to coat the core particles with a silver halide shell. core·
Shell emulsion (UK patent 1027146, US patent
3761276), a localized halogen emulsion in which the emulsion grains have a laminated structure of two or more layers, and the first and second phases have different halogen compositions (US Pat. No. 3935014);
There is an emulsion (US Pat. No. 3,447,927) in which silver halide grains are formed in an acidic medium containing trivalent metal ions to incorporate different metals. Fogging agents (nucleating agents) for this type of emulsion include hydrazines described in US Pat. No. 2,588,982 and US Pat. −38164, U.S. Patent No. 3734738, U.S. Patent No. 3719494
A typical example is the quaternary salt compound described in No. 3615615. Furthermore, U.S. Patent No. 3227551, U.S. Patent No. 3227554, U.S. Pat.
DIR reversal emulsion systems, such as those described in US Pat. No. 3,364,022, or reversal emulsion systems by solution physical development, such as those described in British Patent No. 904,364, can also be combined with the dye-releasing compounds of the present invention. . The silver halide emulsion used in the present invention is 4-
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 5-nitroimidazole, 1-phenyl-5-mercaptotetrazole, 8-chloromeric quinoline, benzenesulfinic acid,
Pyrocatechin, 4-methyl-3-sulfoethylthiazolidine-2-thione, 4-phenyl-3-
It may also be stabilized by additives such as sulfoethylthiazolidine-2-thione. In addition, inorganic compounds such as cadmium salts, mercury salts, and complex salts of platinum group elements such as chlorocomplex salts of palladium are also useful for stabilizing the photosensitive material of the present invention. Furthermore, the silver halide emulsion used may contain a sensitizing compound such as a polyethylene oxide compound. The silver halide emulsions used in the present invention can have color sensitivity expanded by spectral sensitizing dyes, if desired. Useful spectral sensitizers include cyanines,
These include merocyanines, holoporacyanines, styryls, hemicyanines, oxanols, and hemioxanol. Specific examples of spectral sensitizers include the above-mentioned P.
Chapters 35-41 of Glafkides' book and FM Hamer's The Cyanine and Related Compounds.
Related Compounds” (Interscience). In particular, cyanines in which the nitrogen atom of the basic heterocyclic nucleus is substituted with an aliphatic group (e.g., an alkyl group) having a hydroxyl group, a carboxyl group, or a sulfo group;
For example, US Patent No. 2503776, US Patent No. 3459553, US Patent No.
3177210 are particularly useful in embodiments of the present invention. The photosensitive element of the photosensitive material for color diffusion transfer according to the present invention is a planar material that does not undergo significant dimensional changes during processing, such as cellulose acetate film, polystyrene film, polyethylene terephthalate, which are commonly used in photographic photosensitive materials. It is applied to films, polycarbonate films, laminates thereof, thin glass films, etc. When the adhesive strength between the support and the photographic emulsion layer is insufficient, a layer having adhesive properties to both is provided as an undercoat layer. In addition, to further improve adhesion, the surface of the support was treated with corona discharge.
Preliminary treatment such as ultraviolet irradiation or flame treatment may be performed. In addition, as the support, paper or paper whose surface is laminated with a water-impermeable polymer such as polyethylene can be used. The dye-releasing compound of the present invention can be used in general photosensitive materials, but can also be used in photosensitive materials for color diffusion transfer. Hope
No. 49-106404 and US Pat. No. 3,594,164 may also be used. Color photosensitive elements to which the present invention can be applied include a combination of a silver halide emulsion and a dye-releasing redox compound. The combination of the color sensitivity of the silver halide emulsion and the spectral absorption of the dye image is appropriately selected depending on the intended color reproduction. Reproduction of natural colors by the subtractive color method requires at least two combinations of an emulsion that has selective partial photosensitivity in a certain wavelength range and a compound that provides a dye image that has selective spectral absorption in the same wavelength range. element is used. In particular, it consists of a combination of a blue-sensitive silver halide emulsion and a yellow dye-releasing redox compound, a combination of a green-sensitive silver halide emulsion and a magenta dye-releasing redox compound, and a combination of a red-sensitive silver halide emulsion and a cyan dye-releasing redox compound. Photosensitive elements are useful. These combined units of emulsion and dye-releasing redox compound may be coated in layers in a face-to-face relationship in the photosensitive element, or they may be formed into particles and mixed and coated as a single layer. . In a preferred multilayer structure, a blue-sensitive silver halide emulsion combination unit, a green-sensitive silver halide emulsion combination unit, and a red-sensitive silver halide emulsion combination unit are sequentially arranged from the exposure side, and in particular, a high-sensitivity emulsion containing silver iodide. In this case, a yellow filter layer may be disposed between the blue-sensitive silver halide emulsion combination unit and the green-sensitive emulsion silver halide combination unit. The yellow filter contains a yellow colloidal silver dispersion, a dispersion of an oil-soluble yellow dye, an acidic dye mordanted with a basic polymer, or a basic dye mordanted with an acidic polymer. Advantageously, each emulsion combining unit is separated from each other by an interlayer. The interlayer prevents undesirable interactions between emulsion combination units of different color sensitivities. The intermediate layer may include hydrophilic polymers such as gelatin, polyacrylamide, and partially hydrolyzed polyvinyl acetate, as well as pores formed from a latex of hydrophilic and hydrophobic polymers as described in U.S. Pat. No. 3,625,685. The hydrophilicity of the polymer is made up of polymers that become progressively more hydrophilic with the treatment composition, such as calcium alginate described in US Pat. No. 3,384,483. Furthermore, a layer (for example, a gelatin layer) is provided between the intermediate layer and the layer containing the dye-releasing redox compound to isolate the two, thereby preventing the dye-releasing redox compound itself from migrating to the intermediate layer and becoming ineffective. May be prevented. In order to prevent the oxidized form of the developer from diffusing into other color-sensitive emulsion combination units, the intermediate layer contains a compound (for example, 2,5-di Color mixing inhibitors such as (sec-dodecyl)hydroquinone and 2,5-di(tert-pentadecyl)hydroquinone) may be included. The dye-releasing compounds of this invention are used in amounts such that the molar ratio of silver to dye-releasing compound in the silver halide emulsion with which it is combined ranges from about 50 to 0.5, preferably from about 20 to 2. The yellow dye-releasing compound of the present invention may be mixed or mixed with other yellow dye-releasing compounds as necessary (for example, to adjust solubility, prevent crystal precipitation after application, or finely adjust hue). Can be used together (separate layers). Examples of yellow dye-releasing compounds that can be used in combination or in combination include US Pat. No. 4,013,633, US Pat.
Disclosure16475 (1977), U.S. Patent No. 4245028,
No. 4245028, No. 4268625, JP-A-53-149328,
No. 55-43585, No. 56-12642, No. 51-114930, No. 51-114930, No.
55-134849, 56-16130, 56-16131, 56-
71072, 56-25737, 55-138744, 56-
71072, 56, 25737. Also,
Two types of yellow dye-releasing compounds according to the present invention can also be used together or in combination. Examples of magenta dye-releasing compounds that can be used in the photographic material of the present invention include, for example, U.S. Pat.
No. 3932380, No. 3931144, No. 3954476, No. 3932380, No. 3931144, No. 3954476, No.
No. 4242435, No. 4255509, No. 4268624, 4250246
No. 1986-73057, 56-71060, 56-
16130, 56-16131, 56-12642, 55-
35315, 55-134850, 55-36804, 55-
40402, examples of cyan dye-releasing compounds used in the photographic light-sensitive materials of the present invention are, for example, U.S. Pat.
No. 3942987, No. 4013635, No. 4273708, 4268625
No. 56-71061, 56-16130, 56-
16131, 56-12642, 55-40401, 52-
8827, 53-143323. The receiving element may be a poly-4-vinylpyridine latex (particularly in polyvinyl alcohol) as described in U.S. Pat. No. 3,148,061, a polyvinylpyrrolidone as described in U.S. Pat. It is essential to have a mordant layer, such as a salt-containing polymer. In addition to the above, basic polymers described in US Pat. No. 2,882,156, US Pat. No. 3,625,694, US Pat. Additionally, U.S. Patents No. 2484430, U.S. Patent No. 3271147, U.S. Patent No. 3184309,
The mordant described in No. 3271147 is also effective. The color photographic material containing the dye-releasing compound of the present invention preferably has the function of neutralizing alkali carried over from the processing composition. The processing composition contains an alkali in order to provide a high pH of 10 or more, preferably 11 or more, which is sufficient to promote the "image forming process" consisting of development of the silver halide emulsion and dye release and diffusion of the dye-releasing redox compound. Contains. After the formation of the diffusion transfer image is substantially completed, the pH within the film unit is neutralized to around neutrality, that is, 9 or less, preferably 8 or less, to virtually stop any further image formation process. This prevents changes in image tone over time, suppresses discoloration of images caused by high alkalis, and contamination of brown and white areas. For this purpose, a neutralization layer containing an acidic substance in an amount sufficient to neutralize the alkali in the processing solution to the above pH, that is, an acidic substance with an area concentration equal to or higher than the alkali in the developed processing solution. It is advantageous to incorporate this into the film unit. Preferred acidic substances include substances with a pKa of 9 or less that contain an acidic group (or a precursor group that provides such an acidic group upon hydrolysis), and more preferably oleic acid as described in U.S. Pat. No. 2,983,606. Higher fatty acids and US patents
Examples include polymers of acrylic acid, methacrylic acid, or maleic acid and their partial esters or acid anhydrides, which are described in No. 3362819. Specific examples of polymeric acidic substances include copolymers of vinyl monomers such as ethylene, vinyl acetate, and vinyl methyl ether with maleic anhydride, and their n-
These include butyl half ester, copolymer of butyl acrylate and acrylic acid, cellulose, acetate/acid phthalate, etc. In addition to these acidic substances, the neutralizing layer may contain polymers such as cellulose nitrate, polyvinyl acetate, and may also contain plasticizers as described in US Pat. No. 3,557,237. Further, the neutralization layer may be cured by a crosslinking reaction using a polyfunctional aziridine compound, an epoxy compound, or the like. A neutralizing layer is disposed in the image receiving element and/or the photosensitive element. It is particularly advantageous if it is located between the support of the image-receiving element and the image-receiving layer. West German patent application (OLS)
Acidic substances can be microencapsulated and incorporated into film units as described in US Pat. No. 2,038,254. The neutralization layer or acidic substance content in the above case is preferably separated from the developing treatment liquid layer by a neutralization rate regulating layer (timing layer). This neutralization rate adjusting layer has the function of delaying the neutralization of the processing solution by the neutralizing layer and allowing the desired development and transfer to proceed sufficiently. Neutralization rate controlling layers include, for example, gelatin, polyvinyl alcohol, polyvinyl propyl ether, polyacrylamide, hydroxypropyl methylcellulose, isopropyl cellulose, partially polyvinyl butyral, partially hydrolyzed polyvinyl acetate, β-hydroxyethyl methacrylate and ethyl・Constructed mainly of polymers such as copolymers with acrylates. These polymers are usefully cured by cross-linking reactions using aldehyde compounds such as formaldehyde or N-methylol compounds. Examples of neutralization rate adjusting layers include U.S. Pat. No. 3,455,686, U.S. Pat.
No. 49-64435, No. 49-22935, No. 51-77333, Japanese Patent Publication No. 44-15756, No. 46-12676, No. 48-41214, West German Patent Application (OLS) No. 1622936, No. 2162277
There are compounds described in Research Disclosure 15162 No. 151 (1976) and others. Preferably, the neutralization rate controlling layer has a thickness of 2 microns to 20 microns. The processing compositions constituting the processing elements used in the present invention contained the processing components necessary for the development of the silver halide emulsion and the formation of a diffusion transferred dye image or a dye image that remains after runoff of the released dye. It is a liquid composition, and the main solvent is water, and may also contain a hydrophilic solvent such as methanol or 2-methoxyethanol. The processing composition maintains the pH necessary for development of the emulsion layer and neutralizes acids (e.g., hydrohalic acids such as hydrobromic acid) generated during the development and dye image formation processes. Contains a sufficient amount of alkali to Examples of alkalis include alkali metal or alkaline earth metal salts or amines such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide dispersion, tetramethylammonium hydroxide, sodium carbonate, trisodium phosphate, and diethylamine. used,
In particular, when used in the diffusion transfer method, it is desirable to contain caustic alkali at a concentration such that it has a pH of about 12 or more, particularly 13 or more, at room temperature. More preferably in this case the treatment composition contains a hydrophilic polymer such as high molecular weight polyvinyl alcohol, hydroxyethyl cellulose, sodium carboxymethyl cellulose. These polymers give the processing composition a viscosity of at least 1 poise at room temperature, preferably on the order of 500 to 1000 poise, and not only facilitate uniform spread of the composition during processing, but also viscosity of the photosensitive element during processing. When the aqueous solvent is transferred to the image receiving element and the processing composition is concentrated, it forms a non-flowing film which helps the film units to be integrated after processing. This polymer film can also be used to inhibit further migration of colored components to the image-receiving layer after the formation of the diffusion-transferred dye image is substantially completed, thereby preventing changes in the image. Other processing compositions used in the diffusion transfer method include:
Carbon black, to prevent the silver halide emulsion from being exposed to external light during processing.
Light blocking substances such as TiO ₂ and PH indicators and US patents
It may be advantageous in some cases to contain desensitizers such as those described in No. 3,579,333. The above treatment composition is described in US Pat. No. 2,543,181,
No. 2643886, No. 2653732, No. 2723051, No.
It is preferable to use it in a rupturable container as described in No. 3056491, No. 3056492, No. 3152515, etc. When the photosensitive material of the present invention is in the form of a photographic film unit, that is, it can be photographically processed by passing the film unit between a pair of juxtaposed pressing members after imagewise exposure. In the case of a film unit having the following structure, for example, the following elements: (1) a support, (2) a photosensitive element as described above, (3) an image receiving element as described above, and (4) an image receiving element as described above. and (5) developer (in the processing element or photosensitive element). The most recommended embodiment of the overlapping and integrated type for applying the present invention is disclosed in Belgian Patent No. 757959. According to this embodiment, on the transparent support, an image receiving layer,
A substantially opaque light-reflecting layer (e.g. _two TiO layers and a carbon black layer) and one or more photosensitive layers (photosensitive elements) as described above are applied in sequence, and a transparent cover sheet is applied on the surface. It is superimposed on A rupturable container containing an alkaline processing composition containing an opacifying agent (e.g. carbon black) for blocking light is placed adjacent the top layer (protective layer) of the photosensitive layer and the transparent cover sheet. A film unit like this,
The container is exposed to light through a transparent cover sheet, and the container is ruptured by a pressing member when taken out from the camera.
A processing composition (including an opacifying agent) is spread across the area between the photosensitive layer and the cover sheet. As a result, the photosensitive element is shielded from light in the form of a sandwich, and development proceeds in a bright place. It is recommended that the film units of these embodiments incorporate a neutralization mechanism as described above. Among these, it is preferable to provide a neutralizing layer on the cover sheet (if desired, further provide a timing layer on the side where the processing liquid is spread). Other useful laminated and integrated forms in which the redox compounds of the present invention can be used include U.S. Pat.
3647487 and 3635707, German Patent Application (OLS) No. 2426980. In another preferred embodiment, an image-receiving element having a multilayer structure having an arrangement of a support, a neutralizing layer, a neutralization rate controlling layer, and a mordant layer, and one or more photosensitive layers (photosensitive elements) sequentially formed on the support. The coated elements are placed one on top of the other in a face-to-face relationship, and the above-mentioned alkaline treatment liquid is also spread between these two elements. In this case, the image-receiving element may be peeled off after transfer, or the image-receiving layer support may be made transparent and a reflective layer may be provided between the image-receiving layer and the photosensitive layer, as described in US Pat. No. 3,415,645. The image may be able to be inspected as it is without being peeled off. The invention will be further illustrated by the following specific examples. (The dye-releasing redox compound is hereinafter referred to as a DRR compound) Example 1 A photosensitive sheet was prepared by sequentially coating the following layers on a transparent polyester support. (1) The following mordant (3.0g/m ² ) and gelatin (3.0g/m 2 )
g/m ² ). (2) White reflective layer containing titanium dioxide (20 g/m ² ) and gelatin (2.0 g/m ² ). (3) A light shielding layer containing carbon black (2.70g/m ² ) and gelatin (2.70g/m ² ). (4) The following cyanide DRR compound (0.44g/m ² ), tricyclohexyl phosphate (0.09g/m 2 )
m ² ), 2,5-di(t-pentadecyl)hydroquinone (0.01 g/m ² ) and gelatin (0.8
g/m ² ). (5) Red-sensitive internal latent image type direct reversal silver bromide emulsion (silver content 1.03 g/m ² ), gelatin (1.2 g/m ² ),
The following nucleating agent (0.05 mg/m ² ) and sodium pentadecylhydroquinone sulfonate (0.13
g/m ² ). (6) 2,5-di(tert-pentadecyl)hydroquinone (0.71 g/m ² ), copolymer of vinylpyrrolidone and vinyl acetate (molar ratio 7:3) (0.24 g/m 2 )
m ² ) and a layer containing gelatin (0.6 g/m ² ). (7) Layer containing gelatin (0.4 g/m ² ). (8) The following magenta DRR compound (0.36g/m ² ),
Tricyclohexyl phosphate (0.08g/
m ² ), 2,5-di(tert-pentadecyl)hydroquinone (0.01 g/m ² ) and gelatin (0.6
g/m ² ). (9) Green-sensitive internal latent image type direct reversal silver bromide emulsion (silver content 0.82 g/m ² ), gelatin (0.9 g/m ² ),
Layer containing the same nucleating agent (0.03 mg/m ² ) and sodium pentadecylhydroquinone sulfonate (0.08 g/m ² ) as layer (5). (10) 2,5-di(tert-pentadecyl)hydroquinone (0.71 g/m ² ), copolymer of vinylpyrrolidone and vinyl acetate (molar ratio 7:3) (0.24 g/m 2 )
m ² ) and a layer containing gelatin (0.6 g/m ² ). (11) Layer containing gelatin (0.4 g/m ² ). (12) The following yellow DRR compound (0.58 g/m ² ),
Tricyclohexyl phosphate (0.13g/
m ² ), 2,5-di(tert-pentadecyl)hydroquinone (0.01 g/m ² ) and gelatin (0.7
g/m ² ). (13) Blue-sensitive internal latent image direct reversal silver bromide emulsion (silver content 1.09 g/m ² ), gelatin (1.1 g/m 2 );
m ² ), a layer containing the same nucleating agent as layer (5) (0.04 mg/m ² ) and sodium pentadecylhydroquinone sulfonate (0.07 g/m ² ). (14) Layer containing gelatin (1.0g/m ² ). A rupturable container was filled with 0.8 g of a treatment solution having the following composition. Treatment liquid 1-(p-tolyl)-4-hydroxymethyl-4-
Benzyl alcohol 1.5cc H ₂ O 580c.c. A cover sheet was prepared by sequentially applying the following layers on a transparent polyester support. (1) 80:20 (weight ratio) copolymer of acrylic acid and butyl acrylate (22 g/m ² ) and 1.4-
Layer containing bis(2,3-epoxypropoxy)-butane (0.44 g/m ² ). (2) Acetylcellulose (100g of acetylcellulose is hydrolyzed to produce 39.4g of acetyl groups) (3.8g/m ² ) and a 60:40 (weight ratio) copolymer of styrene and maleic anhydride. coalescence (molecular weight approximately 50,000) (0.2 g/m ² ) and 5-(β-
Layer containing cyanoethylthio)-1-phenyltetrazole (0.115g/ ^m2 ). (3) Copolymer latex of vinylidene chloride, methyl acrylate, and acrylic acid in a ratio of 85:12:3 (weight ratio) (2.5 g/m ² ) and polymethyl methacrylate latex (particle size 1 to 3 microns)
(0.05g/m ² ). The photosensitive material is Sample A, and the layer (12) is yellow.
Samples B, C, and D were prepared in which only the DRR compound was replaced with the compound shown in Table 1. After exposing samples A to D, they were integrated with the processing solution and cover sheet, and the processing solution was spread to a thickness of 80 μm using a pressing member at 10°C, 25°C, and 35°C, respectively, to form a transferred color image. I got it. The results are shown in Table-1. As is clear from Table 1, compared to Samples A and B, Samples C and D gave good characteristic values with higher maximum reflection density (Dmax) at low temperature (10°). Comparative compound y:

Table: Example 2 The following layers were applied in sequence onto a transparent polyester support. (1) Layer (2) (2) (2) (3) (3) (4) (13) (5) (14) (6) The above implementation Layer (14) of Example 1 The photosensitive material thus prepared is referred to as A',
Samples B', C', and D' were prepared in which only the yellow DRR compound in layer (4) was replaced with the compound shown in Table 2. After exposing samples A' to D', they were integrated with a processing liquid cover sheet in the same manner as in Example 1 to obtain transferred images at 10°C, 25°C, and 35°C, respectively. The results are shown in Table-2. As is clear from Table 2, at low temperature (10°C), C is more important than D than A.
A higher Dmax has been achieved than B.

【table】

Claims (1)

[Claims] 1 General formula () or (): However, Q is a cyano group, a trifluoromethyl group, or a carbamoyl group represented by -CONY ³ Y ⁴ (where Y ³ represents a hydrogen atom, an alkyl group, or a substituted alkyl group, and Y ⁴ represents a hydrogen atom or an alkyl group). , represents a substituted alkyl group, an aralkyl group, or an aryl group ( ^{Y 3} and Y ⁴ may form a ring connected directly or via an oxygen atom); M represents a hydrogen atom, an alkyl group, a substituted Alkyl group, alkoxy group, substituted alkoxy group, -
A sulfamoyl group represented by SO ₂ NY ³ Y ⁴ (Y ³ and Y ⁴ are the same as above), a group represented by -COOY ⁶ (Y ⁶ is an alkyl group, a substituted alkyl group, a phenyl group, or a substituted phenyl group) ) or a halogen atom; Q ¹ is a hydrogen atom, a halogen atom, a group represented by -SO ₂ NY ³ Y ⁴ (Y ³ and Y ⁴ are the same as above), -SO ₂ Y ⁵
(Y ⁵ represents an alkyl group, substituted alkyl group or aralkyl group), a group represented by COOY ⁶ (Y ⁶ has the same meaning as above), -CONY ³ Y ⁴ group (Y ³ and Y ⁴ are (synonymous with the above), alkyl group, substituted alkyl group, alkoxy group, substituted alkoxy group,
Represents a group represented by [Formula]; Q ₂ is a cyano group, a trifluoromethyl group, -
SO ₂ Y ⁵ group (Y ⁵ has the same meaning as above), -SO ₂ NY ³ Y ⁴
(Y ³ , Y ⁴ are the same as above), -
A group represented by COOY ⁶ (Y ⁶ has the same meaning as above), -
A group represented by CONY ³ Y ⁴ (Y ³ and Y ⁴ are the same as above) represents a halogen atom; q represents 0 or 1; J represents a divalent group selected from sulfonyl or carbonyl; Z represents a hydrogen atom, an alkyl group, or a substituted alkyl group; R and R ¹ each represent an atomic group necessary to complete a 5- or 6-membered heterocycle; Y represents self-cleavage as a result of a redox reaction. Represents a redox center that has the function of releasing a diffusible dye. A photographic material containing at least one of the compounds represented by: