JPS5944624B2 - Photographic sheet for color diffusion transfer method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photographic light-sensitive sheet for color diffusion transfer.

In particular, the present invention relates to a silver halide photographic light-sensitive sheet for color diffusion transfer, which contains an azo dye image-forming compound having a novel redox matrix.

JP-A-48-33826, JP-A No. 49-114424,
No. 49-126331, No. 49-126332-,
No. 50-115528, No. 51-104343, U.S. Patent No. 3928312, No. 3931144, No. 39
No. 54476, and [Research Disclosure]
(Research DisclOsure) Magazine 1302
4 (1975) describes a color diffusion transfer color image formation process using dye-releasing redox compounds. here"
Dye-releasing redox compound? is a compound in which a group called a redox nucleus and a dye (including its precursor) are bonded. This redox mother nucleus initially immobilizes this redox compound by the action of the ballast group bonded thereto, but due to redox reaction under alkaline conditions, it splits itself and forms a compound containing a dye moiety ( It acts to release pigment compounds). That is, when a sensitive material having a photosensitive silver halide emulsion layer combined with this redox compound is exposed and developed with an alkaline processing solution, the redox compound itself is oxidized depending on the amount of developed silver halide, and further It is split into a pigment compound and a non-diffusible quinone compound by an alkaline treatment solution. As a result, this dye compound diffuses into the image-receiving layer and provides a transferred image thereto.

Examples of redox compounds that release magenta dye include JP-A-50-115528 and JP-A-49-114424.
No., U.S. Pat. No. 3,932,380, U.S. Pat. No. 3,931,144,
Some are described in Japanese Patent Application Laid-Open No. 53-46730.

However, when the magenta dye-releasing redox compounds specifically described in these prior documents are used, the stability of the transferred color image is insufficient (for example, the light fastness is insufficient, and the magenta dye-releasing redox compound is The color image was also significantly faded).
Furthermore, there were technical problems such as insufficient transfer of the dye portion. For example, regarding fading of transferred color images, when a polymeric acid (e.g., polyacrylic acid, a copolymer of acrylic acid and butyl acrylate, etc.) is used in the neutralization layer as disclosed in U.S. Pat. No. 3,362,819 (described later), It has been found that residual monomers (such as acrylic acid or butyl acrylate) worsen the fading of transferred color images.

In particular, the remaining butyl acrylate monomer was found in the prior patent (
For example, U.S. Pat.
Subsequent research has revealed that this greatly worsens the fading of magenta images obtained from the method (No. 30). However, it is technically very difficult to suppress such residual monomers to an amount that does not affect the fastness of the image when producing the polymeric acid for the neutralization layer. Therefore, it is desired to develop a redox compound that releases a dye compound that is difficult to react with such monomers. Furthermore, when the dye-releasing redox compound of the above-mentioned prior patent was used, subsequent research revealed that the visible spectrum of the transferred image was wide and this affected color reproduction. The first object of the present invention is to provide an azo dye image-forming compound that provides a stable magenta dye image.

The second objective is to provide an azo dye image-forming compound that has a good hue in the dye portion.

Thirdly, the present invention provides an azo dye image-forming compound in which the hue of a transferred color image does not change due to...

Fourthly, the present invention provides a photosensitive sheet for color diffusion transfer, which contains an azo dye image-forming compound that provides a magenta transfer dye image of sufficient density even in the presence of a relatively small amount of silver halide.

Fifth, the present invention provides a photosensitive sheet for the so-called 6-negative color diffusion transfer method in which a photosensitive element can also be used.

As a result of various studies, the present inventors have found that a photographic photosensitive sheet for color diffusion transfer method containing an azo dye image-forming compound of the following general formula effectively achieves the above objectives and is fully satisfactory. It was discovered that it has photographic performance.

However, [Q1 is a hydrogen atom, a halogen atom, -SO2NR3R4
A sulfamoyl group represented by (where R3 represents a hydrogen atom, an alkyl group, or a substituted alkyl group, R4 represents a hydrogen atom or R4a, and R4a represents an alkyl group, a substituted alkyl group, an alkenyl group, a cycloalkyl group) , an aralkyl group (eg, benzyl group), a substituted aralkyl group (eg, substituted benzyl group), or an aryl group (eg, phenyl group); represents a substituted aryl group (eg, substituted phenyl group).

1R3 and R4 may be linked directly or via an oxygen atom to form a ring), -SO2R5 (R5 represents an alkyl group, a substituted alkyl group or an aralkyl group),
carboxyl group, -COOR6 (R6 represents an alkyl group, substituted alkyl group, phenyl group, substituted phenyl group)
, or represents a group of -CONR3R4 (R3 and R4 are as defined above); Q2 is at the 5th or 8th position with respect to G
position, hydroxyl group or -NH-COR4a or -N
represents a group of HSO2R4a (in the formula, R4a has the same meaning as above); Rla is an alkylene group having 2 or more carbon atoms; R2a is an alkyl group or a substituted alkyl group; m and q are O or 1
represents; J represents a divalent group selected from sulfonyl or carbonyl; Z represents a hydrogen atom, an alkyl group or a substituted alkyl group; X represents the formula -A, -(L)n-(
A2), -(In the formula, Al and A2 are each the same or different, and are an alkylene group.

or an arylene group, L represents a divalent group selected from oxy, carbonyl, carboxamide, carbamoyl, sulfonamide, sulfamoyl, sulfinyl or sulfonyl, and n and p do not represent O or 1. ) represents a divalent bonding group; G represents a hydroxyl group, a salt thereof, or the formula 10CE represents -0C0E (wherein E represents an alkyl group, a substituted alkyl group, or an aryl group);

) represents a hydrolyzable acyloxy group. Y represents a component that, as a result of development under alkaline conditions, provides an azo dye compound having a diffusivity different from that of the azo dye image-forming compound represented by formula 6 (1) (provided that the component has a ballast group).

(except when it is a mono- or p-hydroxyarylsulfamoyl group). ] Among the compounds represented by general formula (1),
Compounds represented by the following general formula () or general formula (l) are preferred.

However, [Ql, Q2, Rla, R2a and Y are general formulas (
It has the same meaning as in 1).

Rlb is synonymous with Rla and R2b is synonymous with R2a. ] (In the following explanation, R1 and R2 are respectively Rla.ll!: Rlb and R2a unless otherwise indicated.
and R2b.

) In the above general formula, the dye moiety (particularly the moiety derived from the diazo component) is characterized by the presence of a group -0-R1-0-R2.

The second feature is that this -0-Rla-0-R2a group is at the 4th position with respect to the azo group, and the -SO2NH- group (included in Y in formula ()) is in the azo group. against 3
It can be mentioned that it is in the highest rank. In particular, in the compound of formula (1), it is important that -0-Rla-0-R2a and Y have an ortho positional relationship. It is thought that this strengthens the function of Y as a redox nucleus and enables the dye compound to be released more effectively, thereby improving transferability. If there is actually another substitution relationship (for example, if the group {-Rla-0-R2a is 2 to the azo group)
and Y occupies the 5th position relative to the azo group)
Such an effect of improving transferability (particularly an effect of improving transferability in a low pH region) was not observed. Also in the compound of formula (l), -0-Rlb! {-R2b
It is important that ' and Y are in an ortho positional relationship.

This provides the effect that the hue of the transferred image from the compound of formula () does not change depending on the pH.
There are various possible causes for this, but one explanation is that intramolecular hydrogen bonds are involved (-SO2N
The effect of suppressing the dissociation of H- is mentioned.

In fact, even if a compound (having O-Rla-0-R2a) has other substitution relationships (for example, -O-R
The group la-0-R2a occupies the 2nd position with respect to the azo group,
-SO2NH occupies the 5th position relative to the azo group)
It was found that the hue of the transferred image changes depending on the pH. Furthermore, it was found that the visible absorption spectrum of the transferred image provided by the compound of the present invention was sharp, and had a favorable effect on color reproduction.

The alkylene group having 2 or more carbon atoms represented by R1 may be linear or branched, and preferably has 2 to 8 carbon atoms.

(However, branched alkylene groups that form an acetal bond are not included). As a particularly preferable example of R1,
-CH(CH3)CH2
-, kylene groups (not including those forming an acetal bond). R because of the ease of obtaining raw materials
It is particularly advantageous if 1 is -CH2CH2-. R
When 1 is a methylene group, it becomes an acetal bond such as -0-CH2-0-R2, which is chemically unstable (especially in acidic conditions) and decomposes during the synthesis process, which is not preferable.

For the same reason, it is also not preferable when the two oxygen atoms of the -0-R1-0-R2 group are bonded to the same carbon atom in R1 (acetal bond).

The alkyl group represented by R2 may be linear or branched, and preferably has 1 to 8 carbon atoms.

From a synthetic standpoint, R2 is preferably an unsubstituted alkyl group, and particularly preferred examples thereof include linear or branched alkyl groups having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, n-propyl group, isopropyl group). group, n-butyl group, etc.). Examples of substituents for the substituted alkyl group include alkoxy groups (eg, methoxy, ethoxy, etc.) and dialkylamino groups (eg, diethylamino, etc.). Among Q1, in the case of a sulfamoyl group represented by the formula -SO2NR3R4, R3 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms), or an alkyl residue having 1 to 8 carbon atoms ( More preferably, a substituted alkyl group having 1 to 4 carbon atoms is preferred.

R4 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.
Substituted alkyl group (more preferably having 1 to 4 carbon atoms), alkenyl group having 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms), cycloalkyl group having 3 to 8 carbon atoms (more preferably 5 to 8 carbon atoms) A benzyl group, a substituted benzyl group having 7 to 12 carbon atoms, a phenyl group, and a substituted phenyl group having 6 to 9 carbon atoms are preferred. Further, R3 and R4 may be bonded directly or via oxygen to form a 5- to 6-membered ring. In a particularly preferred embodiment, both 1R3 and R4 are hydrogen atoms, or at least one of 2R3 and R4 is a hydrogen atom and the other is an alkyl group having 1 to 4 carbon atoms, since this is inexpensive and easily available. It is particularly preferable from the viewpoint of excellent transferability and transferability. The same applies to the group -CONR3R4. One S
In the case of O2R5 group, R5 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. Preferred examples of R6 in -COOR6 include an alkyl group having 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms), and a substituted alkyl group in which the alkyl residue has 1 to 8 carbon atoms (more preferably 1 to 4 carbon atoms). group, phenyl group, carbon number 6~
9 substituted phenyl groups are mentioned. Examples of the substituent for the substituted alkyl in R3 to R6 and R4a above include a cyano group, an alkoxy group, a hydroxyl group, a carboxyl group, a sulfo group, and a tetrahydrofurfuryl group (however, the substituent is phenyl (excluding groups). Furthermore, examples of the substituent of the substituted phenyl group in R4, R4a and R6 include a hydroxy group, a halogen atom, a carboxy group, a sulfo group, a sulfamoyl group, an alkyl group, and an alkoxy group.

The substituted benzyl group for R4 preferably contains one or two substituents, and the substituents include a hydroxy group, a halogen atom, a carboxy group, a sulfo group, a sulfamoyl group,
Alkyl groups, alkoxy groups, methylenedioxy groups, etc. (
Preferred examples include hydroxy group, alkoxy group having 1 to 4 carbon atoms, and methylenedioxy group.

Examples of such substituted benzyl groups include o-, m-,
or p-hydroxybenzyl group, o-, m-, or p-methoxybenzyl group, 3-hydroxy-4methoxybenzyl group, 4-hydroxy-3-methoxybenzyl group, 2-hydroxy-3-methoxybenzyl group, 2 ,5-
Examples include dimethoxybenzyl group, 3,4-dimethoxybenzyl group, and methylenedioxybenzyl group. 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 a substituted alkyl group in which the alkyl residue has 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. Examples of the compound of formula (1) include non-diffusible image-forming substances (dye-releasing redox compounds) that are oxidized and self-destructed to provide diffusive 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 as indicated by -0G1 or -NHG. Here, G1 represents a group that produces a hydroxyl group when hydrolyzed, and is preferably a group represented by -CG3 or -C-0-G3. Here, G3 is an alkyl group, particularly an alkyl group having 1 to 18 carbon atoms such as a methyl group, ethyl group, or propyl group, or an alkyl group having 1 to 18 carbon atoms such as a chloromethyl group or a trifluoromethyl group.
18 represents a halogen-substituted alkyl group, phenyl group, or substituted phenyl group. In addition, G2 is a hydrogen atom, and the number of carbon atoms is 1 to
Represents 22 alkyl groups or hydrolyzable groups. The most preferred hydrolyzable group for G2 is a group represented by -CG4, -SO2G5 or -SOG5.

Here, G4 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 groups; substituted phenyl groups such as nitrophenyl groups and cyanophenyl groups; phenyloxy groups substituted or unsubstituted with lower alkyl groups or halogen atoms; carboxyl groups;
Represents an alkyloxycarbonyl group; an aryloxycarbonyl group; an alkylsulfonyl ethoxy group or an arylsulfonyl ethoxy group. Further, G5 represents a substituted or unsubstituted alkyl group or aryl group. Furthermore, b is 0.1
or an integer of 2.

However, in the above α, an alkyl group that makes the compound represented by the general formula (4) immobile and non-diffusible as G2 of -NHG2 as described above may be introduced. except when α is a group represented by 0G1 and when α is represented by 1NHG2 and G2
When is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a hydrolyzable group, b is 1 or 2, preferably 1.

Ball represents a ballast group. The ballast group will be explained in detail later. Specific examples of this type of Y are described in JP-A-48-33826 and JP-A-53-50736.

Another example of Y suitable for this type of compound is the following formula (8
). In the formula, Ball, α,
b has the same meaning as in formula (4), and β5 represents an atomic group necessary to form a carbocycle, for example, a benzene ring, and a carbocycle or a heterocycle is further fused to the benzene ring to form a naphthalene ring or a quinoline ring. A ring, a 5,6,7,8-tetrahydronaphthalene ring, a chroman ring, etc. may be formed.

Further, in the various rings mentioned above, 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. Specific examples of this type of Y are described in JP-A-51-113624 and US Pat. No. 4,053,312.

Further examples of Y suitable for this type of compound include the groups represented.

In the following equation (6), Ball and b have the same meanings as in equation (4), and α
5 represents a hydroxyl group or has the same meaning as α.

β7 represents an atomic group necessary to form a heterocycle, such as a pyrazole ring or a pyridine ring, and a carbon ring or a heterocycle may be further fused to the heterocycle, and furthermore, to the various rings described above, the formula ( The ring may be substituted with the same type of substituent as the substituent on the ring described in B). A specific example of this type of Y is described in JP-A-51-104343. Furthermore, as Y which is valid for this type of compound, formula a)
).

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 -0
G7, -S-G7 or (G7 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 G8 (G8 represents the same group as the above G7 group, or G8 represents an acyl group derived from an aliphatic or aromatic carboxylic acid or sulfonic acid, G9 represents hydrogen or an unsubstituted or substituted alkyl group); δ is a fused Represents the residues necessary to complete the benzene ring, so this fused benzene ring has 1
or more substituents; and the substituent on the fused benzene ring completed by γ and/or δ is or contains a ballast group.

Specific examples of this type of Y are described in JP-A-51-104343 and JP-A-53-46730. Furthermore, examples of Y suitable for this type of compound include a group represented by formula (E).

In the formula, BaII has the same meaning as in formula (A), and ε is
1 oxygen atom or =NG'' group (G'' represents a hydroxyl group or an amino group which may have a substituent), especially ε
When is =NG'' group, GI is typically G'' in =C=NG/' group, which is formed as a result of the dehydration reaction of a carbonyl reagent H2N-GI with a ketone group; Examples of the compound H2N-G// include hydroxylamine, hydrazines, semicarbazides, thiosemicarbazides, etc. Specifically, the hydrazines include hydrazine, phenylhydrazine, or a phenyl group with an alkyl group, an alkoxy group, Examples include substituted phenylhydrazine having a substituent such as a carbalkoxy group or a halogen atom, as well as isonicotinic acid hydrazine.

Examples of semicarbazides include phenyl semicarbazide or substituted phenyl semicarbazides having substituents such as alkyl groups, alkoxy groups, carbalkoxy groups, and halogen atoms, and thiosemicarbazides include various derivatives similar to semicarbazide. can be given. In addition, β''5 in the formula is a 5-, 6-, or 7-membered saturated or unsaturated non-aromatic hydrocarbon ring, specifically, for example, cyclopentanone, cyclohexanone, cyclohexenone, cyclopentylene Representative examples include non, 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, a condensed ring formed by fusing benzene and the above-mentioned 5- to 7-membered non-aromatic hydrocarbon ring, such as indanone, benzcyclohexenone, benzcycloheptenone, etc., is more preferred in the present invention. 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 group. nitro group, amino group, alkylamino group, arylamino group, amido group, alkylamido group, arylamide group, cyano group, alkylmercapto group, alkyloxycarbonyl group, etc. good.

Gl also 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. Other examples of Y in the compound of the present invention include those described in Japanese Patent Publications No. 48-32129, No. 48-39165, No. 49-64436, and U.S. Pat. No. 3,443,943.

Another type of compound represented by formula (1) releases a diffusible dye by self-ring closure under alkaline conditions, but when it reacts with an oxidized developer, it substantially stops releasing the dye. Examples include non-diffusible image-forming compounds.

Examples of Y that are effective for this type of compound include those listed in formula (F).

In the formula, α7 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.

α″5 is a dialkylamino group or any group defined for α7, preferably a hydroxyl group.

Gl4 is an electrophilic group such as -CO- or -CS, preferably -CO-. Gl5 is an oxygen atom, a sulfur atom,
A selenium atom, a nitrogen atom, etc., and in the case of a nitrogen atom, it is substituted with a hydrogen atom, an alkyl group or substituted alkyl group containing 1 to 10 carbon atoms, or an aromatic compound residue containing 6 to 20 carbon atoms. It's okay. Gl5 is preferably an oxygen atom, Gl3 is an alkylene group having 1 to 3 carbon atoms, and a represents O or 1, preferably 0. Gl3 is a substituted or terminally substituted alkyl group containing 1 to 40 carbon atoms, or a substituted or unsubstituted aryl group containing 6 to 40 carbon atoms, preferably an alkyl group. Gl6, Gl7 and Gl8 are each a hydrogen atom, a halogen atom, a carbonyl group, a sulfamyl group, a sulfonamide, an alkyloxy group containing 1 to 40 carbon atoms, or the same as Gl3, and Gl6 and Gl
7 may together form a 5- to 7-membered ring. Also Gl7G
l3 may be one (Gl2) -N-Gl4-Gl5-.

a However, at least one of Gl3, Gl6, Gl7 and Gl8 represents a ballast group.

A specific example of this type of Y is described in JP-A-51-63618. The formula (
An example is the group represented by In the formula, BalJβ5
are the same as those in formula (3), and Gl9 is an alkyl group (including a substituted alkyl group).

For a specific example of this type of Y, see Japanese Patent Application Laid-Open No. 53-3553.
It is described in 3.

As Y suitable for this type of compound, there is also a group represented by the formula (au).

υ where BalJJβ5 are the same as those in equation (8), and G! 9 is the same as that in formula G.

For a specific example of this type of Y, see Japanese Patent Application Laid-Open No. 49-1116.
28 and 52-4819. Yet another type of compound that can be used in 1) is a non-diffusible compound (dye compound) that releases a diffusible dye upon coupling reaction with the oxide of a color developing agent oxidized by silver halide. The emission force (Brain) can be mentioned.

Typical examples of Y that are effective for this purpose include the groups listed in US Pat. No. 3,227,550. For example, as Y, the formula (
J) can be mentioned. (Ball-CO
up) 1-Link- 0) In the formula, COup is a coupler residue capable of coupling with the oxide of the color developer, such as a 5-pyrazolone type coupler residue, a phenol type coupler residue, a naphthol type coupler residue, and a 6-indanone type coupler residue. Represents a coupler residue or an open-chain ketomethylene coupler residue.

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 (1) having the group represented by formula 0 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, -0-, -H7-, an alkylidene group, -S-, -S-S- or -NHSO
2nd place 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 is C
Oup is a phenol-type coupler residue, a naphthol-type coupler residue, or an indanone-type coupler residue, and Li
nk is -NHSO2-.

Yet another type of compound represented by formula (1) is a compound (dye developer) that is initially diffusible under alkaline conditions but becomes non-diffusible upon oxidation during development. Typical examples of Y that are effective for this type of compound include those listed in US Pat. No. 2,983,606.
Particularly desirable among the above compounds are dye-releasing redox compounds, and an effective group as Y is an N-monosubstituted sulfamoyl group.

The N-substituent of the N-substituted sulfamoyl group is preferably a carbocyclic group or a heterocyclic group. As examples of the N-carbocycle-substituted sulfamoyl group, among the above, those represented by formulas (A) and (B) are particularly preferred. Examples of the N-heterocyclic-substituted sulfamoyl group include (C
) and (D) are particularly preferred. In the group represented by the general formula (self), an embodiment in which γ is -COR6 will be described below. G7 represents hydrogen or an alkyl group having 1 to 32 carbon atoms (e.g. methyl group, ethyl group, isopropyl group, n-
Octadecyl group] represents a cycloalkyl group (e.g. cyclohexyl group) or an aryl group (e.g. phenyl group), and the above alkyl group, cycloalkyl group and aryl group may have a substituent, for example, the alkyl group may have a hydroxyl group. group, alkoxy group, aroxy group,
The aryl group may be substituted with a halogen, a carboxyl group, or a sulfo group, and the aryl group may be substituted with a halogen, an alkyl group, an alkoxy group, a dialkylamino group, an acylamino group, a carboxyl group, or a sulfo group.

G8 represents any of the groups mentioned in the definition of G7 above, or G8 represents an acyl group derived from an aliphatic or aromatic carboxylic acid or sulfonic acid.

G9 represents hydrogen or an unsubstituted or substituted alkyl group having 1 to 32 carbon atoms.

The fused benzene ring completed by the radical δ may carry one or more substituents, for example: halogen, eg chlorine, bromine: carbon, 32 atoms. Alkyl groups such as methyl, butyl, hexadecyl groups; aryl groups such as phenyl groups (the aryl groups may carry substituents, examples of which include: halogen; alkyl groups, alkyl groups, alkoxy groups, dialkylamino groups, acylamino groups); aralkyl groups such as benzyl groups; cycloalkyl groups such as cyclohexyl groups;
Alkoxy groups such as methoxy, ethoxy, dodecyloxy, hexadecyloxy; aralkoxy groups such as benzyloxy, acylamino or acyl groups (the acyl group being derived from an aliphatic or aromatic carboxylic acid or a sulfonic acid) cyano group, sulfo group, carboxyl group, sulfamoyl group, carbamoyl group (one or more hydrogen atoms on the nitrogen atom of the carbamoyl group or sulfamoyl group may be optionally substituted); or any atoms or groups of atoms necessary to complete a fused carbocycle or heterocycle.

When the fused benzene ring completed by the group δ has several substituents, these substituents need not all be the same.

The dye-releasing redox compounds of this invention must not diffuse through the photographic layer prior to processing.

For this purpose, the compounds have a ballast group, for example in residue G6 or in a substituent on the fused benzene ring completed by δ. Even if the substituent on the fused benzene ring completed by δ or G6 does not contain a long chain alkyl group, the dye-releasing redox compound may retain sufficient diffusion resistance.

This is because the molecule can be made sufficiently large depending on the size of the dye residue. Alternatively, by appropriately selecting a sufficiently large ballast group,
This dye-releasing redox compound can be provided with sufficient diffusion resistance. Ballasting groups are groups which are inserted into the compounds of the invention in order to enable them to exist in the form of diffusion-resistant substances in the hydrophilic colloids commonly used in photographic materials. . The group used for this purpose is preferably an organic residue having 8 to 32 carbon atoms.
Such organic residues generally include linear or branched aliphatic groups, but may also include carbocyclic, heterocyclic, or aromatic groups. This residue is
It may be directly or indirectly bound to the "remaining part" in the molecule. In the case of an indirect bond, the bond may be, for example, via one of the following intervening groups: -NHCO-, NHSO2-, -NR-, where R represents hydrogen or an alkyl group. , -O-, -S-
, -SO, -0 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. Diffusibility (or diffusion resistance) depends on the size of the molecule of the compound, so if the entire molecule is sufficiently large, it may be sufficient to use a relatively short group as a ballast group. It is also possible. When the substituent on the fused benzene ring in the indole group or G6 is a divalent group, this is a divalent group.
It may be one that connects two indole rings, for example, as shown below.

Bone [However, in DyeG human formula (1), it represents the part excluding Y, L is the divalent group of the substituent of the benzene ring completed by δ (described above), and Gf5' is the divalent group of G6. represent.

] Specific examples of the compounds of the present invention include the following.

(However, R2=CH3) Compound 2 Compound 3 in the formula of Compound 1 Compound 4 (However, R3=H) Compound 5 A compound in which R3=CH3 in the formula of Compound 4 Compound 6
In the formula of compound 4, R3=(n) {4H9 f deadly compound 7 compound 8 compound 12 compound 13 (however, R3=R4=CH3) compound 14 In the formula of compound 13, R3=R4=C2H5 compound 15 compound 18 When the compound of the present invention is oxidized under alkaline conditions, it releases a novel magenta dye compound as shown in the following formula (IV), particularly preferably a compound shown in formula () or (VI).

[However, Ql, Q2, G, Rla, R2a, J9Z, X, m and q have the same meanings as in general formula (1).

] [However, Ql, Q2, Rla, Rlb, R2a and R2j are the same as in the case of formula (4) or (assistant).] The compound of the present invention is a sulfonyl halide represented by formula () and a formula () or It is obtained by a condensation reaction with an amine represented by the formula ().Other compounds can also be synthesized in accordance with this method. [However, Q!, Q2, Rla, Rlb, R
2a, R2b, and Y have the same meanings as in formula (1) or (1), and δ and G6 have the same meanings as in formula (self).

X1 is a halogen atom (e.g. chlorine atom, fluorine atom)
] 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 Amines (e.g. N
, N-diethylamine, etc.), heteroaromatic amines such as (pyridine, quinoline, α-, β-, or γ-picoline, lutidine colicin, 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.). When X1 is chlorine, that is, when the formula () is sulfonyl chloride, a heteroaromatic amine (preferably pyridine) is particularly preferred among the above.
The diazo component () required to synthesize formula () can be synthesized as follows.

r-: To the gate n)') [However, the sign has the same meaning as in the case of formula () or (4).

] The first step is a reaction between (X) and R2-0-R1-0, but in the latter, the alcohol R2-0-R1-0H is treated with metallic sodium or sodium hydride, etc. obtained by doing.

In the reaction for obtaining (to), it is preferable to use excess R2-0-R1-0H as a solvent. Another method for obtaining the compound of formula 0(1) is to convert compound (X) into R2-0-R1
-0H (used as solvent), manganese dioxide or sodium silicate (Na2O.NSiO2,
However, there is a method of reacting with sodium hydroxide in the presence of n=about 1 to about 3). This method is advantageous in that it does not use flammable substances such as sodium metal or sodium hydride. Representative examples of reduction reactions to obtain the compound of formula () include reduction with iron powder, catalytic hydrogenation (Raney nickel or palladium on carbon catalyst), and hydrazine reduction (Raney nickel, palladium on carbon or activated carbon catalyst). be.

The diazo component () is diazotized and coupled with a compound (coupler or coupling component) represented by formula (Xl) to obtain an azo dye represented by formula (X).

By converting the sulfonic acid group of this azo dye into a sulfonyl halide using a chlorinating agent, a compound represented by the formula () can be synthesized. [However, the symbol has the same meaning as in the case of formula () or II).

] In order to convert the compound of formula (X) into the compound of formula (), it is preferable to use phosphorus oxychloride (POCt3), thionyl chloride (SOct2), or phosphorus pentachloride (PC4) as a chlorinating agent.

At this time, N-N-dimethylacetamide, . It is preferable to carry out the reaction in the presence of an NN-disubstituted carbamide (catalyst) such as NN-dimethylformamide or N-methylpyrrolidone. The amine represented by the formula () is, for example,
The one described in Japanese Patent Application Laid-Open No. 53-46730 is representative.

A typical method for synthesizing the amine represented by the formula αD is the following schematic route.

In order to obtain the compound represented by formula (X) from the compound represented by formula (to), a chlorinating agent as described in the synthesis of compound () above may be used.

In this case as well, it is desirable to carry out the reaction in the presence of the N,N-disubstituted carbamide as described above. Formula (X)
It has a sulfonyl chloride and a ballast group. To obtain a compound of formula (X) by a condensation reaction with a compound of formula (), the compound of formula () and formula (Vll)
It is preferable to carry out the condensation reaction in the presence of a basic substance as described in the case of the condensation reaction with the compound (). Typical examples of the reduction reaction to obtain the compound of formula () include catalytic hydrogenation, reduction with iron powder, and hydrazine reduction (Raney nickel, palladium-carbon or activated carbon catalyst). In compound (), R2 occupying the p position
We would like to emphasize that the basicity of the amino group is increased due to the group b-0-Rlb-0-. Therefore, there is an advantage that the condensation reaction with the sulfonyl halide () in the next step proceeds easily. Representative synthetic examples of the azo dye image-forming compound and its intermediates used in the present invention will be described in detail below. Synthesis Example 1: Synthesis of sodium 2-(2-methoxyethoxy)-5-nitrobenzenesulfonate (method 1) 7.3t sodium hydride in 300ml methyl cellosolve (14.6V in the form of a 50% liquid paraffin suspension) )
While stirring, 55 r of sodium 2-chloro-5-nitrobenzenesulfonate was added to the sodium-2-methoxyethylate solution prepared by adding.

The reaction mixture was heated and stirred at 80-85° C. for 30 minutes in a water bath. After hot filtration, 1.5 t of isopropyl alcohol was added to the mother liquor for crystallization. The precipitated crystals were collected and washed with 100 ml of isopropyl alcohol. Yield 5
9t0 (Method 2) Sodium 2-chloro-5-nitrobenzenesulfonate 5.2t1 Manganese dioxide 0.6r1 Methyl cellosolve 15ml, Water 1ml and Sodium hydroxide 0.95t
were mixed and stirred at 75°C for 40 minutes.

After cooling, insoluble materials were removed and the solution was poured into 100 ml of isopropyl alcohol. Filter out the precipitated crystals,
4.8y of sodium 2-(2-methoxyethoxy)-5-nitrobenzenesulfonate was obtained. (Method 3) Method 2
Sodium silicate (No. 3;
Using Na2O-NSiO2; n2 about 3) 0.87,
By exactly the same treatment, 2-(2-methoxyethoxy)
Sodium -5-nitrobenzenesulfonate 4,8r was obtained.

(The same results as above were obtained using Na2O.NSiO2 with n=about 1, about 2, or about 2.5.) Synthesis Example 2: 2-(2-ethoxy-ethoxy) -Synthesis of sodium 5-nitrobenzenesulfonate Sodium mono-2-ethoxyethylate solution prepared by adding 7.3y of sodium hydride (14,67 in the form of a 50% liquid paraffin suspension) in 300ml of ethyl cellosolve. Inside, 2-chloro-
Sodium 5-nitrobenzenesulfonate 557 was added.

This reaction mixture was heated and stirred for 30 minutes while being kept at 80 to 85°C. After the reaction was completed, insoluble matter was separated, and 150 ml of ethyl cellosolve was distilled off from the oral liquid under reduced pressure. 300 ml of isopropyl alcohol was added to the concentrated liquid and cooled on ice. The precipitated crystals were separated, washed with 1007n1 of isopropyl alcohol, and air-dried. Yield: 331 Synthesis Example 3: Synthesis of sodium 2-(2-butoxyethoxy)-5-nitrobenzenesulfonate The title compound was obtained by the same treatment using ethylene glycol monobutyl ether in place of methyl cellosolve in Synthesis Example 1 (Method 2). The compound was obtained.

Synthesis Example 4: Synthesis of sodium salt of 5-amino-2-(2-methoxyethoxy)benzenesulfonic acid 2-(2-
methoxyethoxy)-5-nitrobenzenesulfonic acid 3
A mixed solution of 0r, reduced iron 307, ammonium chloride 0.6V, and water 60ml was heated and stirred for 2 hours while being kept at 80 to 85°C.

After the completion of the reaction, the insoluble matter was removed from each household, and 200 ml of isopropyl alcohol was added to the aqueous solution, which was then cooled on ice. The precipitated crystals were collected, washed with 50 ml of isopropyl alcohol, and air-dried. Yield 237. Synthesis Example 5: Synthesis of Compound 1 (1) 2-(N-Tert-butylsulfamoino(
c) Synthesis of -4-[4-(2-methoxyethoxy)-5-sulfophenylazo]-5-methanesulfonamide-1-naphthol Sodium hydroxide 1.7t, water 80W1
5-amino-2-(2-methoxyethoxy) in the solution of 1
9.9 r of benzenesulfonic acid was added, and an aqueous solution (10 d) of 2.8 t of sodium nitrite was further added.

Separately, a solution of 18a of concentrated hydrochloric acid and 70mj of water was prepared, and the above solution was added dropwise at 5°C or lower. Thereafter, the mixture was stirred at 5° C. or lower for 30 minutes to complete the reaction. Separately sodium hydroxide 8.

0f, 40ml water, and 150ml methyl alcohol
Prepare a solution of 2-t-butylsulfamoyl-5-
14.9 t of methanesulfonamide-1-naphthol was added, and the diazo solution prepared above was added dropwise at 10°C or lower.

After dropping, stir at 10℃ or less for 30 minutes and add 20ml of concentrated hydrochloric acid.
1 was added. Collect the precipitated crystals and add 200ml of acetone.
1 and air dried. Yield 197.2) 2-(N-
Tert-butylsulfamoyl)-4-[4-(2-
Synthesis of methoxyethoxy)-5-chlorosulfonylphenylazo]-5-methanesulfamide-1-naphthol 2-(N-Tert-butylsulfamoyl)-4-[4-( 2-methoxyethoxy)-5-
Sulfophenylazo]-5-methanesulfonamide-1
-N,N-dimethylacetamide 2 in a mixed solution of naphthol 19r acetone 100ml, phosphorus oxychloride 20a
0a was added dropwise at a temperature below 50°C.

After the dropwise addition, the mixture was stirred for 1 hour and gradually poured into 500 ml of ice water. After separating the precipitated crystals, they were washed with 50 d of acetonitrile and air-dried. Yield: 147.3) Synthesis of Compound 1 To 40ml of N,N-dimethylacetamide, add 3-amino-5-methoxy-1-(N-octadecylcarbamoyl)indole obtained by the method of JP-A No. 237-46730 and the above. 2-(N-Tert- of 13V obtained in (2)
butylsulfamoyl)-4-4[4-(2-methoxyethoxy)-5-chlorosulfonylphenylazo]-5
-methanesulfonamide-1-naphthol.

Add 10ml of pyridine dropwise while stirring, and add 3ml of pyridine at room temperature.
Stir for hours. The reaction mixture was poured into 10a of hydrochloric acid and 200ml of ice water, and the precipitated crystals were collected and washed with water. After air drying, N
, N-diethylacetamide and methyl alcohol. Yield: 6.0y Synthesis Example 6: Synthesis of Compound 3 (1) 2-pyrrolidinosulfonyl-4-[4-(2-
methoxyethoxy)-5-sulfophenylazo]-5-
Synthesis of methanesulfonamide-1-naphthol Sodium hydroxide 0.9V, water 40ml! 5-amino-
2-(2-methoxyethoxy)benzenesulfonic acid 4.
A solution of 1.4 t of sodium nitrite and 5 ml of water was added.

Separately, prepare a solution of 9 ml of concentrated hydrochloric acid and 36 ml of ice water, and
The above solution was added dropwise below. Thereafter, the mixture was stirred at 5° C. or lower for 30 minutes to complete the reaction. Sodium hydroxide 4.0f7
, 7.4 t of 2-pyrrolidinylsulfamoyl-5-methanesulfonamide-1 naphthol was added to a solution of 20 ml of water and methyl alcohol.

The diazo solution prepared above was added dropwise to this solution while keeping it at 10° C. or lower. After the dropwise addition, stir for 30 minutes and add 10% of concentrated hydrochloric acid.
m1 was added. After filtering out the precipitated crystals, add 100% acetone.
Washed with m1 and air dried. Yield 8.770 (2) 2-
Synthesis of pyrrolidinosulfonyl-4-[4-(2-methoxyethoxy)-5-chlorosulfonylphenylazo]-5-methanesulfonamido-1-naphthol (1)
2-pyrrolidinylsulfamoyl-4-[4-(
2-methoxyethoxy)-5-sulfophenylazo]-
5-methanesulfonamido-1-naphthol 8.7y,
Add N to a mixed solution of 40 d of acetone and 9 ml of phosphorus oxychloride.
, N-dimethylacetamide (9 ml) was added dropwise at a temperature below 50°C.

After dropping, the mixture was stirred at room temperature for 1 hour and poured into 200 ml of ice water. The precipitated crystals were filtered out and washed with 20 ml of acetonitrile. Yield 5.07. (3) Synthesis of compound 3 N,N
-3-amino- in dimethylacetamide 20Tn1
5-methoxy-2-(N-octadecyloxycarbamoyl)indole 3.57 and 2-pyrrolidinosulfonyl-41 obtained in (2) above [4-(2-methoxyethoxy)-5-sulfochlorophenylazo] 5.0 y of -5-methanesulfonamido-1-naphthol was added.

Add 3.6 ml of pyridine dropwise while stirring, and add 2 ml of pyridine at room temperature.
Stir for hours. After the reaction is complete, methanol 30ml, water 1
0 ml was added to the reaction solution. The precipitated crystals were filtered out and washed with 50 ml of methanol. After air drying, recrystallization was performed using N,N-dimethylacetamide, methanol, and a small amount of water. Yield 3.57. Reproduction of natural colors by the subtractive color method requires a photosensitive element consisting of at least two combinations: an emulsion with selective spectral sensitivity in a certain wavelength range and a compound that provides a dye with selective spectral absorption in the same wavelength range. used. In particular, combination units of a blue-sensitive silver halide emulsion and a compound that provides a yellow dye, combination units of a green-sensitive silver halide emulsion and a compound that provides a magenta dye, and combination units of a red-sensitive silver halide emulsion and a cyan dye. Photosensitive elements comprising units in combination with compounds that provide . It goes without saying that the azo dye image-forming compound of the present invention can be used as the compound that provides the dye. In these combination units of emulsions and dye-providing compounds, the silver halide emulsion layer and the dye-providing compound-containing layer may be coated in a layered manner in a face-to-face relationship, or the silver halide and The dye-providing compounds may be mixed in a binder, each in the form of particles, and applied as a single layer. In a preferred multilayer structure, from the exposure side, a blue-sensitive emulsion combination unit, a green-sensitive emulsion combination unit,
The red-sensitive emulsion combination units are arranged one after the other, and especially in the case of a layer of high-speed silver halide emulsion, it is preferable to arrange a layer of yellow filter between the blue-sensitive emulsion combination unit and the green-sensitive emulsion combination unit.

The yellow filter layer 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 combinations of different color sensitivities. The intermediate layer may be a hydrophilic polymer such as gelatin, polyacrylamide, or partially hydrolyzed polyvinyl acetate, US Pat. No. 3,625.
685, a polymer with pores formed from a latex of a hydrophilic polymer and a hydrophobic polymer;
or by polymers alone or in combination, such as polymers that become progressively more hydrophilic with the treatment composition, such as calcium alginate described in US Pat. No. 3,384,483. In order to prevent the oxidized form of the developer from diffusing into other color-sensitive emulsion combination units, a compound (which has the function of capturing such oxidized form) is added to the intermediate layer.
For example, 2,5-di(Sec-dodecyl)hydroquinone,
A mixing inhibitor such as 2,5-di(t-pentadecino(ha)hydroquinone) may be included.

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, and has a halogen composition. is selected depending on the purpose of use and processing conditions of the photosensitive material, but the iodide content is from 0 mol% to 10 mol% (the chloride content is 30 mol% or less), and the remainder is bromide. Silver bromide, silver iodobromide or silver chloroiodobromide emulsions are particularly preferred. The grain size of the silver halide used may be a normal grain size or a fine grain size. These silver halide emulsions can be prepared according to conventional methods. The silver halide emulsion used in the present invention can be sensitized using a chemical sensitizer.

As a chemical sensitizer, Product Licensing Index (PLl). Volume 92 (published December 1971) NQ9232, page 107, 1. Chemical
Those described in the section of nsi-TizatiOn can be used.

The silver halide emulsion used in the present invention is an antifoggant. A stabilizer and a spectral sensitizer may be contained as necessary. Antifoggants and stabilizers include V●AntifOgg on page 107 of Product Licensing Index (PLI) Volume 92 (published in February 1971) NQ9232.
Those described in the section ants and stabilzers can be used.

As a spectral sensitizer, Product Licensing Index (PLI) Volume 92 (published in December 1971)
NQ. '9232, pages 108-109, XV. Spe
Those described in the section on ctralsensitization can be used.

The azo dye image-forming compound used in the present invention can be dispersed in a hydrophilic colloid carrier by various methods depending on the type of the compound.

For example, a compound having a dissociable group such as a sulfo group or a carboxyl group can be dissolved in water or an alkaline aqueous solution and then added to the hydrophilic colloid solution. Azo dye image-forming compounds, which are difficult to dissolve in aqueous media and easily soluble in organic solvents, are added to a hydrophilic colloid solution in the form of a solution obtained by dissolving them in the organic solvent, and then dispersed into fine particles by stirring or the like. to be dispersed.

For more information on such dispersion methods, see U.S. Pat.
It is described in No. 2027, No. 2801171, No. 2949360, and No. 3396027.

In order to stabilize the dispersion of the azo dye image-forming compound and promote dye image formation, the azo dye image-forming compound is dissolved in a high-boiling solvent that is substantially insoluble in water and has a boiling point of about 200° C. or higher at normal pressure. It is advantageous to incorporate the photosensitive element into the photosensitive element. Suitable high-boiling solvents for this purpose include triglycerides of higher fatty acids; aliphatic esters such as dioctylthiadipate; phthalate esters such as di-n-butyl phthalate; tri-0-cresyl phosphate, tri- -phosphoric acid esters such as n-hexyl phosphate; amides such as N,N-diethyl laurylamide; 2,
Examples include hydroxy compounds such as 4-di-n-amylphenol. Furthermore, it is advantageous to incorporate a solvent-philic polymer along with the azo dye image-forming compound into the photosensitive sheet in order to promote dye image formation with stabilized dispersion of the azo dye image-forming compound. Examples of solvent-philic polymers suitable for this purpose include: sierac; phenol-formaldehyde condensates; poly-n-butyl acrylate; copolymers of n-butyl acrylate and acrylic acid; copolymers of n-butyl acrylate, styrene, and methacramide. etc. These polymers may be dissolved in an organic solvent with an azo dye image-forming compound and then dispersed in a photographic hydrophilic colloid such as gelatin, or they may be emulsified in a hydrophilic colloid dispersion of an azo dye image-forming compound. The polymer may be added in the form of a hydrosol prepared by polymerization or other means. Dispersion of azo dye imaging compounds is generally achieved effectively under high shear forces. For example, high-speed rotating mixers, colloid mills, high-pressure milk homogenizers, high-pressure homogenizers as disclosed in British Patent No. 1304264,
Ultrasonic emulsifiers are useful.

Dispersion of azo dye imaging compounds is greatly aided by the use of surfactants as emulsification aids. Surfactants useful in dispersing the azo dye image-forming compounds used in the present invention include sodium triisopropylnaphthalenesulfonate, sodium dinonylnaphthalenesulfonate, sodium p-dodecylbenzenesulfonate,
There are anionic surfactants disclosed in dioctyl sulfosuccinate sodium salt, cetyl sulfate sodium salt, and Japanese Patent Publication No. 39-4293 and British Patent No. 1138514. For use with esters, U.S. Patent 36
As disclosed in No. 76141, it exhibits particularly good emulsifying ability. Furthermore, Japanese Patent Publication No. 13837, U.S. Patent Nos. 2992104, 3044873, and 3061
The dispersion methods disclosed in No. 428, No. 3832173, etc. are also effective for dispersing the compound of the present invention. Silver halide emulsion layer used in the present invention: A layer containing an azo dye image-forming compound: A processing liquid permeable layer such as a protective layer or an auxiliary layer such as an intermediate layer contains a hydrophilic polymer as a binder. There is.

As the hydrophilic polymer, it is advantageous to use gelatin, but other hydrophilic polymers may also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc., single or copolymers thereof. I can do it.

In addition to lime-processed gelatin, acid-processed gelatin and Bull. SOc. Sci. PhOt. Japan
n. Enzyme-treated gelatin as described in NQl6, p. 30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

Gelatin derivatives can be obtained by reacting gelatin with various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetazaka alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds. The one obtained by doing so is used. Specific examples are U.S. Patent Nos. 2,614,928 and 313.
No. 2945, No. 3186846, No. 3312553, British Patent No. 861414, No. 1033189, No. 1
It is described in No. 005784, Japanese Patent Publication No. 42-26845, etc.

The gelatin graft polymer is a gelatin grafted with a single (homo) or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. can be used. Particularly preferred are graft polymers with polymers which are compatible with gelatin to some extent, such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates and the like. Examples of these are U.S. Pat. No. 2,763,625, U.S. Pat.
It is described in No. 6884, etc.

Typical synthetic hydrophilic polymer substances include, for example, West German Patent Application (0LS) No. 2312708 and U.S. Patent No. 3620751.
No. 3879205 and Japanese Patent Publication No. 7561/1983.

A silver halide emulsion layer used in the photographic light-sensitive sheet of the present invention,
The layer containing the azo dye image-forming compound or other hydrophilic colloid layer may contain coating aids, inorganic or organic hardeners, and the like.

As a coating aid, Product Licensing Index (PL), Volume 92 (1971, December issue) N
Q9232a) Those described in the COati-Ngajds section on page 108 can be used.

As a hardening agent, PL, Vol. 92, Kan 9232, p. 108, H
Those described in the section on ardeners can be used.

The photosensitive sheet of the present invention has at least one layer of light-sensitive silver halide photographic emulsion combined with the azo dye image-forming compound of the present invention applied directly or to a planar material that does not undergo significant dimensional changes during processing. It is applied indirectly.

Such supports include product licensing,
The one described in the XSuppOrts section on page 108 of Index (PLI) Volume 92 (published in December 1971) NQ9232 is used. Examples of methods for obtaining color diffusion transfer images using azo dye image-forming compounds include JP-A-49-114424 and JP-A-48-3.
There are those described in Pelkey Patent No. 788268, No. 3826, and the like.

These methods can be used in combination with the azo dye imaging compounds of this invention. Using the azo dye imaging compounds of the present invention, such as dye-releasing redox compounds,
Examples of methods for obtaining color diffusion transfer images include the following processes. (A) at least one light-sensitive silver halide emulsion layer (hereinafter referred to as a light-sensitive element) in combination with a dye-releasing redox compound of the present invention;
Exposure of a photosensitive sheet made of a support having .

(8) Spreading an alkaline processing composition on the photosensitive silver halide emulsion layer and developing each photosensitive silver halide in the presence of a silver halide developer.

(6) As a result, the oxidized product of the developer generated depending on the amount of exposure cross-oxidizes the dye-releasing redox compound.

(D) Cleaving the oxidized form of the dye-releasing redox compound to release a diffusible dye.

(Field) The released dye diffuses into the image layer to form a transferred image on the image-receiving layer (in direct or indirect contact with the photosensitive layer). In the above process, the dye-releasing redox compound can be cross-oxidized. Any silver halide developer can be used, so long as it is present.

Such developing agents may be included in the alkaline processing composition or in appropriate layers of the photosensitive element.
Examples of developing agents that can be used in the present invention are as follows. Hydroquinones, aminophenols (e.g. N-methylaminophenol), pyrazolidones (e.g. phenidone, 1-phenyl-3-pyrazolidone), dimezone (1-phenyl-4,4-dimethyl-3-
pyrazolidone), 1-phenyl-4-methyl-4-oxymethyl-3-pyrazolidone), phenylenediamines (e.g. N,N-diethyl-p-phenylenediamine,
3-methyl-N,N-diethyl-p-phenylenediamine, 3-methoxy-N-ethoxy-p-phenylenediamine), etc.

Of those listed herein, black and white developers are particularly preferred as they generally have properties that reduce stain formation in the image receiving layer more than color developers such as phenylene diamines.

When a dye-releasing redox compound is used as the azo dye image-forming compound of the present invention, if an ordinary surface latent image type emulsion is used and a reversal mechanism is not used, the transferred image will be a negative image and the residual image will be a positive image.

The silver halide emulsion is a direct positive silver halide emulsion (direct positive emulsions also include emulsions in which a direct reversal positive image can be obtained by fogging during development after exposure. For example, internal latent image emulsions or solar emulsions) (e.g., a resection type emulsion), a positive image can be obtained at the image receiving site. The solarization type emulsion mentioned above is described in "The Ory of the Photographics" edited by Mees.
OfthePhOtOgraphicPrOcess”
(1942: Macmillan New York McMilla
nCO. NewYOrk), pages 261-297, are useful. For its preparation method,
For example, British Patent Nos. 443245 and 462730, US Patent Nos. 2005837, 2541472, and 33
No. 67778, No. 3501305, No. 3501306
No. 3501307, etc. The internal latent image type emulsion advantageously used in the present invention is described in US Pat. No. 2,592,250 and the like.

As a fogging agent for this type of emulsion, US Pat.
982, hydrazines described in 2563785, hydrazides and hydrazones described in 3227552, British Patent No. 1283835, Japanese Patent Publication No. 1983-38
No. 164, U.S. Pat. No. 3,734,738, U.S. Pat. No. 3,719,949
The quaternary salt compounds described in No. 4 and No. 3,615,615 are representative.

Furthermore, the DIR inverted emulsion system as described in U.S. Pat.
Reversal emulsion systems with solution physical development, such as those described in US Pat. No. 3,364, can also be combined with dye-releasing redox compounds.

Image-receiving elements which can be used in combination with the above photosensitive elements include mordants such as poly-4-vinylpyridine-latexes (especially in polyvinyl alcohol) as described in U.S. Pat. No. 3,148,061, polyvinyl pyridine as described in U.S. Pat. It is essential to have a mordant layer containing pyrrolidone, polymers containing quaternary ammonium salts, such as those described in US Pat. No. 3,239,337, alone or in combination.

As a mordant, U.S. Patent Nos. 2,882,156 and 362
Basic polymers described in No. 5694 and No. 3709690 are also effective. Other U.S. Patents No. 2484430, U.S. Patent No. 3271147, U.S. Patent No. 3184309, U.S. Patent No. 327
Mordants described in No. 1147 and the like are also effective. The photosensitive sheet of the present invention preferably has a function of neutralizing alkali brought in from the processing composition. For this purpose, a neutralization layer containing a sufficient amount of acidic substance to neutralize the alkali in the processing solution, that is, an acidic substance with an area concentration equal to or higher than the alkali in the developed processing solution, is applied to the photosensitive sheet. Advantageously, it can be incorporated (for example in a cover sheet or image-receiving element). Another advantageous method of using the cover sheet with the neutralizing layer is to apply it to the peeled-off image-receiving element. Preferred acidic substances include US Pat. No. 298
Typical examples include those described in No. 3606, No. 2584030, and No. 3362819.

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 U.S. Pat. No. 3,557,237. . Acidic substances can be incorporated into photosensitive sheets in microencapsulation as described in German patent application (0LS) 2038254. The neutralization layer (or acidic substance-containing layer) used in the present invention is preferably separated from the developed treatment liquid layer by a neutralization rate adjusting layer (timing layer).

Examples of timing layers include gelatin, polyvinyl alcohol or U.S. Pat.
No. 30, No. 3785815, Patent Application 1978-JMo V946
No. 50-90616, Japanese Unexamined Patent Publication No. 48-92022
No. 49-64435, No. 49-22935, No. 51-JMo V333, Special Publication No. 44-15756, No. 4
No. 6-12676, No. 48-41214, West German patent application (0LS) No. 1622936, No. 2162277,
Research Disclosure “ResearchDi”
There are compounds described in ``SclOsure'', Vol. 151, 15162 (1976). This timing layer functions to delay the decrease in pH of the processing solution caused by the neutralization layer, thereby allowing the required development and transfer to proceed sufficiently. In a preferred embodiment of the invention, the image-receiving element is arranged on a support in sequence.
It has a multilayer structure consisting of a neutralizing layer, a timing layer, and a mordant layer (image receiving layer).

Details of the image receiving element can be found in Japanese Patent Application Laid-Open No. 47-13285, U.S. Patent No. 3.
It is described in No. 295970, British Patent No. 1187502, etc. The processing composition constituting the processing element that can be used in the present invention is a liquid composition containing processing components necessary for developing a silver halide emulsion and forming a diffusion transfer dye image.
The main solvent is water, and may also contain other hydrophilic solvents such as methanol and methyl cellosolve.

The processing composition maintains the pH necessary for development of the emulsion layer and removes acids generated during the development and dye image formation processes (e.g., hydrohalic acids such as hydrobromic acid, carboxylic acids such as acetic acid). Contains a sufficient amount of alkali to neutralize acids (acids, etc.). As the alkali, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide dispersion, tetramethylammonium hydroxide, sodium carbon, phosphoric acid 3
hydroxides or salts of alkali metals or alkaline earth metals such as sodium, diethylamine, etc.;
or amines are used, preferably about 1 at room temperature.
It is desirable to contain a caustic alkali having a pH of 2 or higher, particularly at a concentration of PH14 or higher. More preferably, the treatment composition contains a hydrophilic polymer such as high molecular weight polyvinyl alcohol, hydroxyethyl cellulose, sodium carboxymethyl cellulose. These polymers give the treatment composition a viscosity of 1 poise or more at room temperature, preferably several hundred (500 to 600) to 1000 poise, and not only facilitate the uniform spread of the composition during treatment, but also facilitate the uniform distribution of the composition during treatment. During the process, the aqueous solvent migrates to the photosensitive element and the image receiving element, concentrating the processing composition.
It forms a non-flowing film that helps the elements come together after processing. This polymer film can serve to inhibit further migration of colored components to the image-receiving layer and prevent image alteration after formation of the diffusion-transferred dye image is substantially completed. The processing composition also contains T to prevent fogging of the silver halide emulsion by external light during processing.
It is sometimes advantageous to include light-absorbing substances such as iO2, carbon black, PH indicator dyes, and desensitizers such as those described in US Pat. No. 3,579,333.

Furthermore, a development inhibitor such as benzotriazole can be added to the processing liquid composition. The above treatment compositions are disclosed in U.S. Pat. No. 2,543,181, U.S. Pat.
It is preferable to use it in a rupturable container as described in No. 91, No. 3056492, No. 3152515, etc.

When the photographic light-sensitive sheet of the present invention is in the form of a photographic film unit, that is, after being exposed to imagewise
In the case of a film unit configured to perform photographic processing by passing the film unit between a pair of juxtaposed pressing members, for example, the following elements: 1) support 2) the above-mentioned 3) image-receiving components as described above; 4) processing requirements as described above; and 5) developer (in the processing element or in the photosensitive element).

In one embodiment of the film unit, the light-sensitive element and the image-receiving element are stacked face-to-face, and after exposure the element is processed by spreading an alkaline processing composition between the two elements. Ru. On this occasion. The image-receiving element may be peeled off after transfer of the image, as described in U.S. Pat.
As described in No. 5, the image may be viewed without peeling off. In another embodiment, the image receiving element and the photosensitive element can be integrally arranged in this order on the support.

For example, as disclosed in Pelkey Pat. It is effective if applied sequentially. After the photosensitive element has been exposed to light, it is placed face-to-face with a process sheet that is sufficiently opaque to block light, and a processing composition is spread between the two. The most recommended embodiment of the overlapping and integrated type for applying the present invention is disclosed in Pelkey Patent No. 757,959.

According to this embodiment, an image-receiving layer, a substantially opaque light-reflecting layer (such as those described above), on a transparent support,
The above-mentioned single or plural photosensitive layers are applied one after another, and a transparent cover sheet is further superimposed face-to-face on this. A rupturable container containing an alkaline processing composition containing an opacifying agent (eg, carbon black) for blocking light is placed adjacent the top layer of the photosensitive layer and the transparent cover sheet. Such a film unit is exposed to light through a transparent cover sheet, and when taken out from the camera, the container is ruptured by a pressing member, and the processing composition (including the opacifying agent) is transferred between the photosensitive layer and the cover sheet. It spreads over a whole area in between. 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).

Also, another useful laminated integration form in which the azo dye imaging compounds of the present invention can be used is U.S. Pat.
No. 15644, No. 3415645, No. 34156
No. 46, No. 3647487, and No. 363570
No. 7, German patent application (0LS) 2426980.

Among the azo dye image-forming compounds of the present invention, dye-releasing redox compounds are particularly preferred. More preferred compounds of the present invention are represented by the above general formula () or (4),
and each symbol in the formula is a compound as shown below: [
R1 is -CH2CH2-; R2a and R2b may be the same or different and each represents a straight chain or branched alkyl group having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, n-propyl group, isopropyl group); ,n
-butyl group, etc.) (Yes; Q1 is a hydrogen atom or -
SO, NR3R4 sulfamoyl group (R3 and R4 may be the same or different, each represents a hydrogen atom or R4a, R4a has 1 carbon number)
-4 alkyl group, or alkyl residue has 1 to 4 carbon atoms
represents a substituted alkyl group, and examples of the substituents of the substituted alkyl include a cyano group, an alkoxy group, a hydroxyl group, a carboxyl group, and a sulfo group.

Further, R3 and R4 may form a 5- to 6-membered ring directly or via oxygen. ); Q2 represents a hydroxyl group or a -NHsO2R4a group substituted at the 5-position (R4a has the same meaning as above); Y represents the general formula (A), (B);
, (0, (D), (E), (F), (Cj, (has) or 0).

[Rla is -CH2CH2-; Q1 is a hydrogen atom or a sulfamoyl group represented by -SO2NR3R4 (R3 and R4 may be the same or different, and each is an alkyl group having 1 to 4 carbon atoms, or an alkyl residue) The group represents 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 hydroxy group, a carboxy group, and a sulfo group. In addition, R3 and R4 may be bonded directly or via oxygen to form a 5- to 6-membered ring); Q2 is a hydroxyl group or -NHSO2R4 substituted at the 5-position (R4a has the same meaning as above); Y represents the general formula (A), (B), (0, ([), (E
), (F), (G), l or GJ).

] Effects and advantages obtained by the present invention (especially by introducing the R2-0-RLO- group) include the following.

First, since the dye released has good light resistance, it is possible to obtain a color image with little photofading.

Second, the released dye has a good hue (does not change with pH), so when combined with other azo dye image-forming compounds with good hue, it is possible to obtain high quality color images. I can do it. Third, the transferability of the released dye is good, so that there is very little residual dye in the exposed areas of the photosensitive element.

Therefore, if necessary, it is effective to peel off the photosensitive element and subject it to desilvering treatment to obtain a negative color image (negative use) based on unreacted azo dye image-forming compounds.

Fourth, the released dye is less susceptible to fading due to vinyl monomers such as acrylic acid and butyl acrylate remaining in the neutralization layer.

Example 1 Dye Compound A Released from Compound 1: Dye Compound A was dissolved in 10-3MC1)N,N-dimethylsulformamide (DMF).

Add 0.25 ml of this solution to DMFll. 5d and then butyl acrylate 10-1M0)DMFl. 25m
l and PH5. O5 buffer (BrittOn-RObi
A mixture of nsOn buffer) 12.5d was added. This was left at room temperature (25 to 29 C), and the decrease in absorbance at the visible absorption maximum wavelength was measured. From this measurement value,
The residual rate of dye compound A was determined. Furthermore, a pseudo-first-order reaction rate constant k was determined assuming that the decrease in the survival rate was pseudo-first-order. Similarly, the residual rate and k of dye compound B: released from compound 18 were determined.

For comparison, the residual rate and k were determined for Comparative Compound C-E using the same procedure.

Table 1 shows the results. Comparative Compound C Comparative Compound D Comparative Compound E As is clear from Table 1, Compounds A and B have much better fastness than Comparative Compounds CE.

Regarding actual transferred images, corresponding to the results in Table 1, it was found that the dyes of compounds A and B are not susceptible to dark fading due to vinyl monomers such as acrylic acid and butyl acrylate remaining in the neutralization layer. I understand. Example 2 A photosensitive sheet was prepared by sequentially coating the following layers on a polyethylene terephthalate transparent support.

(1) The following mordant 3.0y/Rrf and gelatin 3.
0? A mordant layer containing /m''. A white reflective layer containing y/M2.

(3) A light-shielding layer containing 2.707/M2 of carpon plaque and 2.70 t/n1'' of gelatin.

(4) Magenta dye-releasing redox compound 1 of the present invention (
0.80t/m, diethyl laurylamide (0.40
7/m and a layer containing gelatin (1.081").

(5) Green-sensitive internal latent image type direct reversal silver iodobromide emulsion (halogen composition in silver halide: iodine 1 mol %, silver amount: 1.
87/M3, 1.3 t/m of gelatin), a layer containing a fogging agent of the following formula (0.0287/m) and sodium dodecylhydroquinone sulfonate (0.13 y/M°).

(6) Layer containing gelatin (0694 t/m).

Furthermore, the following treatment liquid and cover sheet were prepared. Treatment liquid 0.8 t of the treatment liquid having the above composition was filled into a container that can be broken under pressure.

Cover sheet Polyacrylic acid (viscosity approximately 1,000 cp in a 10% by weight aqueous solution) 15y/M2 as an acidic polymer layer (neutralization layer) on a polyethylene terephthalate support and acetylcellulose (100t of acetylcellulose) as a timing layer thereon. (hydrolyzes to produce 39.4t acetyl groups) 3.81 and 2 and styrene-maleic anhydride copolymer (composition ratio, styrene:maleic anhydride = approximately 60:40, molecular weight approximately 50,000) 0.27/ A cover sheet was prepared by applying m゛.

Processing process A film unit in which the above cover sheet and the above photosensitive sheet are stacked is exposed using wedges with different densities in a stepwise manner from the cover sheet side, and then 85μ of the above processing solution is applied between the two sheets. It was spread out until it was thick (the development was done with the help of a pressurized opening).

Treatments were carried out at 25°C. After processing, the transferred image was observed through the transparent support of the photosensitive sheet. Compound 1 of the present invention
The magenta dye image transferred from
The change in hue was small with respect to the change in H (9 to 4), and the dark fading resistance was also excellent.

Similar experiments were conducted with other exemplified compounds, but
In all cases, robust images with beautiful hues were obtained. Example
3 In the same manner as shown in Example 2, the mordant layer, titanium oxide layer, and carbon black layer were coated on a transparent support in this order, and the following cyan dye-releasing redox compound (0.54 f7/m) and diethyl laurylamide (0.54 f7/m) were coated on a transparent support. ．．
257/m” and a layer containing gelatin (1.14y/m”).

(5) Red-sensitive internal latent image type direct reversal silver iodobromide emulsion (halogen composition in silver halide: 2 mol% iodine, 1.9 r/m silver amount, 1.47/m gelatin and Example 2
fogging agent (0.028f/g) and sodium dodecylhydroquinone sulfonate (0.13t/g) shown in
A layer containing Nf).

(6) A layer containing gelatin (2.6 r/m) and 2,5-di-t-pentadecylhydroquinone (0.8 t/m).

(7) Compound 1 of the present invention (0.45 t/M°), diethyl laurylamide (0.107/m, 2,5-di-t
- Layer containing butylhydroquinone (0.00747/m) and gelatin (0.767/Rrf) (8) Green-sensitive internal latent image type direct reversal silver iodobromide emulsion (halogen composition of silver iodobromide: iodine 2 mol %, silver content 1.47/M2, gelatin 1.0 f/m, the same fogging agent used in Example 2 (0.024 t/Rrf) and sodium dodecylhydroquinone sulfonate (0.11 t/m ”).

(9) Layer containing gelatin (2.67/m) and 2,5-di-t-pentadecylhydroquinone (0.8 r/m).
(substitute) The following yellow dye-releasing redox compound (0.
78y/m, diethyl laurylamide (0.16t/
m, 2,5-di-t-butylhydroquinone (0.0
A layer containing 12 V/m and gelatin (0.78 y/m).

Claims (1)

[Scope of Claims] 1 having at least one photosensitive silver halide emulsion layer,
And at least one of the emulsion layers has a general formula (I)▲A mathematical formula, a chemical formula, a table, etc.▼(I) However, [Q^1 is a hydrogen atom, a halogen atom, -SO_2NR^]
Sulfamoyl group represented by 3R^4 (where R^3
represents a hydrogen atom, an alkyl group, or a substituted alkyl group, R^4 represents a hydrogen atom or R^4^a,
R^4^a represents an alkyl group, a substituted alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group, a substituted aralkyl group, an aryl group, or a substituted aryl group. R^3 and R^4 may be connected directly or through an oxygen atom to form a ring), -SO_2R^5 (R^5
represents an alkyl group, substituted alkyl group, or aralkyl group), carboxyl group, -COOR^6 (R^6 represents an alkyl group, substituted alkyl group, phenyl group, or substituted phenyl group), or -CONR^3R^4 The base of (R^
3, R^4 is the same as above), and Q^2 is,
Located at the 5th or 8th position with respect to G, hydroxyl group or -NH-
Represents a group of COR^4^a or -NHSO_2R^4^a (in the formula, R^4^a has the same meaning as above); R^1^a
is an alkylene group having 2 or more carbon atoms; R^2^a is an alkyl group or a substituted alkyl group; m and q represent 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; X represents the formula -A_1-(L)_n-(A_
2)_p- (wherein A_1 and A_2 are the same or different and represent an alkylene group or an arylene group, L is oxy, carbonyl, carboxamide, carbamoyl,
It represents a divalent group selected from sulfonamide, sulfamoyl, sulfinyl or sulfonyl, and n and p represent 0 or 1. ) represents a divalent bonding group; G is a hydroxyl group, its salt, or a formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, E is an alkyl group, a substituted alkyl group or an aryl group.) represents a hydrolyzable acyloxy group. Y represents a component that, as a result of development under alkaline conditions, provides an azo dye compound with diffusivity different from that of the azo dye image-forming compound represented by formula (I) (provided that the o- or p-hydroxyarylsulfamoyl group). ] A photographic light-sensitive sheet characterized by being combined with a compound represented by the following.