JPS5944618B2 - Color diffusion transfer method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to color diffusion transfer processes, and more particularly to color diffusion transfer processes using novel color imaging materials.

There are various methods of color diffusion transfer depending on the manner in which the color imaging material releases the diffusible dye upon development of the silver halide.

The first typical method is the so-called dye developer method,
A dye developer is a compound that has both a dye part and a silver halide developer part in one molecule, and as a result of oxidation of the dye developer as a color image forming material by silver halide, it has a diffusive property. There will be a change in the This type of color diffusion transfer method is covered by many patents, such as British Patent No. 804,
It is described in the specification of No. 971, etc. In the dye developer method described above, the dye developer diffusely transferred to the image-receiving layer has a silver halide developer portion and is highly reactive.

Therefore, reactions such as air oxidation after transfer may affect the dye image, such as color staining or color change. A typical second method is that a silver halide color developing agent oxidized by silver halide undergoes a coupling reaction with a non-diffusible color image-forming substance or further undergoes a ring-closing reaction to release a diffusible dye. The material is used as a color image forming material.

This type of color diffusion transfer method is described, for example, in U.S. Pat.
No. 27,550, No. 3,443,940, No. 3,227,551, British Patent No. 90
It is described in the specification of No. 4,365, etc.

In the second method, it is essential to use a silver halide color developing agent, and p-phenylenediamine compounds and the like are usually used as the silver halide color developing agent. The above-mentioned p-phenylenediamine compounds generally cause severe color staining due to their oxidized products, and often have an undesirable effect on dye images.

Furthermore, the above-mentioned p-phenylenediamine compounds have the disadvantage that they tend to cause dermatitis when used. In contrast to the first and second systems, a typical third system is a non-diffusible color image-forming material that is directly oxidized with silver halide.

Alternatively, a silver halide developing agent oxidized by silver halide undergoes a reaction such as an oxidation ring reaction, resulting in ring closure or decomposition with an alkali to release a diffusible dye or its precursor (dye-releasing property). Redox compound, DyeReleasingRedOxCOm-POu
nds (hereinafter referred to as DRR compound).
This type of color diffusion transfer method is described, for example, in US Pat.
Specification No. 98,897, Specification No. 3,725,062, Specification No. 3,728,113, Specification No. 3,245
, 789 specification, 3,443,939 specification,
Specification No. 3,705,035, JP-A-48-338
Publication No. 26, Publication No. 50-118723, Publication No. 47-2
Publication No. 327, Publication No. 49-64436, Special Publication No. 1973
-39165, Japanese Patent Application Specification ([Color Diffusion Transfer Method]) dated July 1, 1975, etc.

In the third method described above, what is transferred to the image-receiving layer is a dye part (G), which consists only of its precursor part and does not have a silver halide developer part, and also contains a p-phenylenediamine-based compound. It is not essential to use a color developing agent such as, but in a preferred embodiment, it is possible to use a black and white silver halide developing agent, with the advantage that a dye image with less color staining is obtained. , which is advantageous over the first and second methods. In the third method, that is, the so-called DRR method, a light-sensitive silver halide emulsion layer and a non-diffusive color image forming substance, namely D
A photographic element containing an RR compound is exposed to light to form a latent image in a light-sensitive silver halide and then processed with an alkaline processing solution, optionally in the presence of a silver halide developing agent. . During processing with this alkaline processing liquid, the photographic element and the image-receiving layer are in a superimposed state, and as a result of the processing with the alkaline processing liquid, the diffusible dye released from the non-diffusible DRR compound or its The precursor material is transferred by diffusion to the image receiving layer to obtain a dye image. The DRR1 compound suitable for use in the above DRR system has (a) ease of dispersion of the compound into a hydrophilic colloid, (b) good transfer efficiency of the dye portion or its precursor to be transferred to the image-receiving layer; and (c) the dye portion to be transferred to the image-receiving layer or its precursor has good dyeing properties to the image-receiving layer, (d) absorption after transfer is of a favorable color tone, and (e) An essential requirement is that the dye image formed on the image-receiving layer is sufficiently stable. Furthermore, when the above DRR compound is used in combination with a light-sensitive silver halide emulsion having substantially spectral sensitivity in its light-absorbing region, it is also possible to add or DR in the same layer as the photosensitive silver halide emulsion
If an R compound is included, the number of photons absorbed by the light-sensitive silver halide emulsion decreases due to the light absorption of the DRR compound itself, resulting in desensitization.

In order to prevent this desensitization, we use a DRR compound that temporarily shifts the light absorption spectrum to increase the quantum efficiency during exposure and at a certain stage after exposure, change the temporarily shifted light absorption spectrum back to the original light absorption spectrum. A so-called DRR shift type color diffusion transfer method has been developed, which utilizes the principle of irreversibly returning to the original state. In addition to the above-mentioned requirements a) to (e), the shift-type DRR compound suitable for use in the above-mentioned DRR-type shift-type color diffusion transfer method has (f) a sufficiently large light absorption so as not to impair the sensitivity of the silver halide emulsion. (g) to quickly and irreversibly return to the original light absorption spectrum at a certain stage after exposure;
h) The essential requirements include not returning to the original light absorption spectrum before exposure. Conventionally,
DRR compounds having an azo dye moiety, particularly those similar to the DRR compounds used in the present invention, include:
DRR compounds having an azo dye moiety having a dimethylamino group, an acetamide group, or a benzamide group are known. However, the above-mentioned DRR compounds do not meet the requirements (a) that the DRR compound should satisfy, for example, the absorption after transfer does not have a desirable color tone, or the dye image formed on the image-receiving layer is not sufficiently stable. to (e)
It cannot be said that everything is fully equipped. Furthermore, shift type D
As RR compounds, compounds having an azo dye moiety and an acyloxy group within the dye moiety are known.

However, this conventionally known shift type DRR compound cannot satisfy the above-mentioned requirements (a) to (h).
There is no known RR compound similar to the shifted DRR compound having an azo dye moiety used in the present invention and having an aromatic compound residue and an amino group substituted with an acyl group.

Accordingly, it is an object of the present invention to provide a new color diffusion transfer process using a new color imaging material, and in particular a new color diffusion transfer process using a new DRR compound. In other words, an object of the present invention is to provide a new color diffusion transfer method using a new DRR compound that fully satisfies all of the above requirements (a) to (e) that the DRR compound should satisfy, and furthermore, A new shift-type color diffusion transfer using a new shift-type DRR compound that fully satisfies all of the above requirements a) to (h), which has as its basic structure a new DRR compound that fully satisfies all of the requirements a) to (e). It is about providing law. Another object of the present invention is to obtain a dye image with clear and stable color tone by using the above color diffusion transfer method.

The above object and other objects of the present invention which will become apparent hereinafter are to provide an image-forming photographic element containing at least one light-sensitive silver halide emulsion layer and a non-diffusible compound represented by the following general formula []. and developing the photographic element with an alkaline processing solution in the presence of a silver halide developing agent to release a diffusible dye from the compound and to diffuse the diffusible dye into the image-receiving layer in response to the imagewise exposure. This is achieved by a color diffusion transfer method, which is characterized in that the image is transferred.

[In the formula, Al represents an aromatic hydrocarbon group, A3 represents an aromatic hydrocarbon group, and M represents a diffusible dye from the compound represented by the general formula [1] by oxidation under alkaline conditions. represents a monovalent moiety that releases X1 and X
2 each represents a divalent group, l is a hydrogen atom or a formula Y
It represents a group represented by CO-, and YCO represents a group whose bond with a nitrogen atom is cleaved at a hydroxyl ion concentration of 10-5 to 2 mol/2.

m and n are each O or 1, and m+n=1, q and r are each 0 or 1, R(1),
R(2) and R(5) are each a hydrogen atom, a halogen atom, a nitro group, an alkyl group, a hydroxyl group, a group represented by the formula 10C0Y' (here, Y'CO is a hydroxyl ion concentration of 10-
Represents a group whose bond with an oxygen atom is cleaved at 5 to 2 mol/l. ). Alternatively, R(1) and R(2) may bond to each other to form a naphthalene nucleus. Furthermore,
w is an integer of 1 or 5. Furthermore, the compound represented by the above general formula [1] will be explained in detail. In the above formula,
Al represents an aromatic hydrocarbon group.

Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group, and examples of the substituted aromatic group include a phenol group, a naphthol group, an aniline group, a naphthylamine group, a diphenylamine group, a monoalkylaniline group,
A dialkylaniline group and the like can be mentioned. The aromatic hydrocarbon groups listed above may be further substituted with other substituents.

The substituent here may be a variety of groups, including an alkyl group, an aromatic hydrocarbon group, an alkyloxy group, an aryloxy group, a halogen atom, a nitro group, a cyano group, an acylamino group, and an amino group. , alkylamino group, arylamino group, acyl group, acyloxy group, aralkyl group, hydroxyl group, carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group, amide group, Examples include sulfonamide groups, carboxyl groups, sulfo groups, halogen-substituted alkyl groups, alkylsulfonyl groups, arylsulfonyl groups, carboxylic acid ester groups, alkylcarbonyl groups, arylcarbonyl groups, or groups in which these are substituted with each other. can be mentioned. The group represented by A1 has been described in detail above, but among the above, the most preferable effect in the method of the present invention is achieved when the group represented by At is a phenyl group or a naphthyl group.

In the above general formula [1], A3 represents an aromatic hydrocarbon group.

Examples of the aromatic hydrocarbon group here include phenyl group, naphthyl group, etc. as in A1 above, and this aromatic hydrocarbon group may be substituted with one or more various groups. Among them, substituents that exhibit preferable effects in the present invention include alkyl groups, aromatic hydrocarbon groups, alkyloxy groups,
Aryloxy group, halogen atom, nitro group, cyano group, acylamino group, amino group, alkylamino group, arylamino group, acyl group, acyloxy group, aralkyl group, hydroxyl group, carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, Sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group, amide group, sulfonamide group, carboxyl group, sulfo group, halogen-substituted alkyl group, alkylsulfonyl group, arylsulfonyl group, carboxylic acid ester group, alkylcarbonyl group, These include arylcarbonyl groups, etc., or groups in which these are mutually substituted. M1 represents a monovalent moiety which releases a diffusible dye from the compound represented by the above general formula [1] upon oxidation under alkaline conditions, particularly at a hydroxide ion concentration of 10-5 to 2 mol/l. Typical M1 moieties of the DRR compound represented by the above general formula [1] used in the present invention include those represented by the following general formulas [] to 00.

General formula [] 11▲10υ2 In the above, Q preferably forms a 6-membered aromatic ring such as a benzene ring, or preferably a 10-membered aromatic group such as a naphthalene ring or a quinoline ring. (optionally substituted with a halogen atom, a lower alkyl group, a lower alkyloxy group, etc.), and B represents a hydroxyl ion concentration of 10-52, especially under alkaline conditions.
It represents an organic group that makes the compound represented by the above general formula [1], which has a group represented by the general formula [] as M1, immobile and non-diffusible under the condition of mol/1.

The organic group is a long-chain alkyl group or a benzene group,
Aromatic compound residues such as naphthalene, or suitable divalent groups, such as long-chain alkyl groups bonded to one end of the group represented by -X1 in the above general formula [1], which will be detailed later, or benzene, naphthalene, etc. Mention may be made of aromatic compound residues. Preferred examples of the organic group represented by B in the compound represented by the general formula [1] according to the present invention include 1H, a substituted or unsubstituted alkyl group having 8 to 22 carbon atoms, and -C -, -N-,
-CH2 coffenylene group, -01 or -SO, - at the terminal of a divalent group formed by arbitrary combinations of substituted or unsubstituted alkyl groups with alkyloxy groups having 8 to 22 carbon atoms, etc. The same applies to a group to which a phenyl group or naphthyl group substituted with an alkyloxy group or the like or unsubstituted is bonded.

D represents a group represented by -0R1 or -NHR2. Here, R1 is a hydrogen atom or a group whose bond between R and O is cleaved under conditions of a hydroxide ion concentration of 10-52 mol/l, as shown in Table 8.
It is preferably a hydrogen atom, a group represented by -CR3 or -C-0-R3.

Here, R3 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 1 carbon atoms such as a chloromethyl group or a trifluoromethyl group.
8 represents a halogen-substituted alkyl group, phenyl group, or substituted phenyl group. In addition, R2 is a hydrogen atom, and has 1 to 2 carbon atoms.
Represents a group in which the bond between R2 and N is cleaved under conditions of two alkyl groups or a hydroxyl ion concentration of 10-5 to 2 mol/2. Here, the above-mentioned cleavable group is preferably one CR
4,-SO2R is a group represented by -SOR5. Here, R4 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, or a nitrophenyl group. and substituted phenyl groups such as cyanophenyl groups,
Lower alkyl group or halogen atom-substituted or unsubstituted phenyloxy group, carboxyl group, alkyloxycarbonyl group, aryloxycarbonyl group,
Represents an alkylsulfonyl ethoxy group or an arylsulfonyl ethoxy group. Further, R5 represents a substituted or unsubstituted alkyl group or aryl group. Furthermore, X is 0, 1 or 2
is an integer. However, in D above, organic groups that make the compound represented by the general formula [1] immobile and non-diffusible may be introduced as →R2 and R2 as described above. , except in that case, i.e. when D is -
When it is a group represented by 0R1, and D is represented by -NHR2, and R2 is a hydrogen atom, and the hydrogen ion concentration is 10-5 to 2
When the bond between R2 and N is a group that is cleaved under conditions of mol/l or an alkyl group having 1 to 7 carbon atoms, X is 1 or 2, preferably 1. M1 represented by the above general formula []
Preferred specific examples of the moiety in the present invention include the following. In the above formula, B, Rl, Q and X
is the general formula [synonymous with B, Rl, Q, and x in the old formula.

L represents -SO2-S1 or -0-. Preferred specific examples of the general formula [M] in the present invention include the following: In the above formula, R6 represents a hydrogen atom, an amino group, an alkyl group, or an aryl group,
R7 and R each represent a hydrogen atom, an alkyl group or an aryl group, and R8 represents a hydrogen atom, a hydroxyl group, an alkyl group or an aryl group.

However, when R6 is a hydrogen atom, an alkyl group or an aryl group, R8 is a hydroxyl group.翫v was.

Here, R, R, and O each represent an alkyl group or an aryl group, or R and RlO may form a pyridinium divalent group or a piperazine divalent group together with the N atom. It also represents an AnOh acid anion. In addition, R6
, one or two of R7, R8 and R9 is the above general formula []
A group represented by B in is preferable.

Specific examples of the M1 portion represented by the above general formula [] include the following.

In the above formula, B and B', Q and q, and X and x7 are respectively synonymous with B, Q and x in the general formula [], and are t.

L7 represents -C1 or -SO2-, and Rll represents a hydrogen atom or an alkyl group. represents a hydrogen atom, a /hydroxy group, an acyloxy group, or a group represented by the formula N, and V represents a hydroxy group, an acyl/oxy group, or a group represented by the formula N
represents a group represented by

\Here, Rl2 and Rl3 each represent a hydrogen atom, an acyl group or a hydrocarbon group.

Specific examples of the M1 portion represented by the above general formula [] include the following.

1r1) A In the above formula, Rl4 represents a hydrogen atom, an alkyl group, an aralkyl group, or an amino group, Rl5 represents an alkyl group, an aralkyl group, an aryl group, an acyl group, or an amino group, and R,4 and Rl5 may be bonded together to form a hydrocarbon ring or a heterocycle.

L7 represents one -C group or one -SO2 group, and y is O or an integer of 1. B and x have the same meanings as B and x in the general formula []. Specific examples of the M1 portion represented by the crest in the above general formula include the following.

In both of the above formulas, B has the same meaning as B in the general formula [].

L7 is -0-, -S-, -CO-, -S92, -CON
R16- or -SO2NR16- (R,6 represents a water carbon atom or an alkyl group), and W represents an oxygen atom, a sulfur atom or an imino group. Further, y is an integer of O or 1. The above general formula [] and [VI! I] denoted by M,
Specific examples of the parts include the following.

[-1]-CONHNH-SO2-C,7H3, (n)
In the above formula, B has the same meaning as B in the above general formula [].

f is an oxygen atom or a =NRI7 group (R, 7 represents a hydroxyl group or an amino group which may have a substituent), and especially when I is a =NRl7 group, Rl7 is H2N-Rl
Rl7 in the C=N-Rl7 group formed as a result of the dehydration reaction of carbonyl reagent 7 with a ketone group is typical, and examples of the compound H2N-R,7 in this case include hydroxylamine, hydrazine, semicarbazide, There are thiosemicarbazide and the like.Specifically, examples of hydrazine include hydrazine, phenylhydrazine, or their two formulas, where B, L and y are the above general formula [] or [
] has the same meaning as B, f, and y.

Z7, in conjunction with carbon atoms and nitrogen atoms, has 5-membered, 6-membered,
Represents a nonmetallic atom necessary to form a 9- or 10-membered heterocycle. Specific examples of the M moiety represented by the above general formulas [] and [X] include the following.

Examples include substituted phenylhydrazine having a substituent such as an aryl group, an alkoxy group, a carbalkoxy group, or a halogen atom in the group, as well as isonicotinic acid hydrazine. Examples of thiosemicarbazide include phenyl semicarbazide or substituted phenyl semicarbazide having a substituent such as an alkyl group, an alkoxy group, a carbalkoxy group, or a halogen atom, and thiosemicarbazide also includes various derivatives similar to semicarbazide. can be given. In addition, q in the formula is a 5-, 6-, or 7-membered saturated or unsaturated non-aromatic hydrocarbon ring, specifically, for example, cyclopentanone, cyclohexanone, cyclohexenone, cyclopentynon,
Representative examples include cycloheptanone and cycloheptenone.

Further, the 5- to 7-membered non-aromatic hydrocarbon ring may be further fused with other molecules at appropriate positions to form a condensed ring.

Here, the other rings may be various rings, regardless of whether they exhibit aromaticity or whether they are hydrocarbon rings or heterocycles, but when forming a condensed ring, for example, indanone, etc. 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 benzene, benzcyclohexenone, and benzziglo\xenon, 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. It may have one or more substituents such as atoms, nitro groups, amino groups, alkylamino groups, arylamino groups, amide groups, alkylamido groups, arylamide groups, cyano groups, alkylmercapto groups, and alkyloxycarbonyl groups. .

Rl8 represents a hydrogen atom or a halogen atom such as fluorine, chlorine, or bromine.

Specific examples of the M1 portion represented by the above general formula 00 include the following.

Although the M1 moiety has been described in detail above, the most preferable effect in the present invention is achieved when the M moiety in the compound represented by the general formula [1] is represented by the general formula 1].

In the above general formula [1], X1 and X2 each represent a divalent group.

In the present invention, preferred X1 and X2 are -0-, -S
-, -C-, -SO2-, Rl9-SO-RA1N-TS1CR2OR2l-RA1CR2OCR2l- (here, R
, , represent a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and R2O and R2l each represent a hydrogen atom, a halogen atom, an alkyl group or an aromatic hydrocarbon group.

), substituted or 11r8/ a\ unsubstituted aromatic divalent group, -NN-, \ / (where X7 and r are respectively -0-, -S-, -C
R2OR2l or a divalent group formed by any combination of 1 or 2 to 4 of the above -CR2O=CR2,-, and a is O
or 1, and X' and r together with N and/or C form a 5- or 6-membered ring as a whole.

) as a constituent element, and is a divalent group consisting of one of these or a combination of a plurality of these in an arbitrary linear chain. Furthermore, in the present invention, more preferable X1 and X
2 is a group represented by the formula Dn.

Here, E1 and E2 each represent an alkylene group or a phenylene group having 1 to 8 carbon atoms, and this alkylene group or phenylene group may be substituted with a halogen atom, an alkyl group, or an aromatic hydrocarbon group. R22 and R
227 each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aromatic hydrocarbon group having 6 to 13 carbon atoms, such as a phenyl group, tolyl group, naphthyl group, etc. 1N''-4' 1-Otsu 1N'-1
5--4 Represents a halogen atom-substituted or unsubstituted alkylene group having 1 to 8 carbon atoms, a phenylene group, or a substituted phenylene group.

J2 represents -SO2- or -C-. b and c are integers of O or 1, respectively; when b is 1, c is 1, and when b is O, c is O or 1. (However, c
When is 1, the total number of carbon atoms of E and E2 is 14 or less. ). D, e and f are each O or 1. However, the sum of d and e is 1. In the above general formula [1], Z represents a hydrogen atom or a group represented by the formula YCO-. YCO- has a hydroxyl ion concentration of 10-5 to 2 mol/
' represents a group whose bond with the nitrogen atom is cleaved, and in this case, a compound represented by the general formula [1]: so-called shift-type DRR
It becomes a compound. Y that has a preferable effect in the present invention
The group Y represented by CO includes a methyl group, an ethyl group,
Alkyl groups having 11 to 5 carbon atoms such as propyl group and isopropyl group; chloromethyl group, dichloromethyl group,
Trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, trifluoromethyl group, α-
A halogen-substituted alkyl group at the α-1 or β-1 position having 1 to 5 e carbon atoms, such as promoethyl group, α-prombutyl group, pentafluoroethyl group, α-bromoisopropyl group;
A substituted or unsubstituted alkyloxy group having 1 to 5 carbon atoms, such as a methoxymethyl group, a proboxymethyl group, a phenoxymethyl group, or an α-phenoxyethyl group, or a substituted or unsubstituted aryloxy group at the α-1 or β-1 position. Substituted alkyl group having 1 to 5 carbon atoms, alkyl group having 1 to 5 carbon atoms substituted with a hydroxyl group at the α-1 or β-1 position such as a hydroxymethyl group; β-methylvinyl group, β
- Vinyl group substituted with substituted or unsubstituted alkyl group having 1 to 5 carbon atoms or aryl group such as phenylvinyl group; 1 to 3 substituents including halogen atom, nitro group, cyano group or trifluoromethyl group or a group represented by the formula -0R23 or -C-0R24 (herein, R23 represents a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms or a phenyl group, and R24
represents the group represented by R23 or a hydrogen atom.

Preferred substituents for the alkyl group include an alkylsulfonyl group having 1 to 5 carbon atoms, an amide group, a hydroxy group, a carboxyl group, an alkoxy group, and a halogen atom.
Further, as a substituent for the phenyl group, a halogen atom, a nitro group, a cyano group, a trifluoromethyl group, and a methyl group are preferable, and it is preferable that 1 to 3 substituents exist.
These include ethoxy group, β-methylsulfonylethoxy group, phenyloxy group, p-chlorophenyloxy group, and ethoxycarbonyl group. Among Y in the group represented by YCO- above, in the present invention, a more preferable one is an alkyl group having 1 to 5 carbon atoms substituted with a halogen atom at the α-1 position or β-1 position, or the formula -0R23 or the formula -C-0 -R2
Among the groups represented by 4, the most preferred is a trifluoromethyl group. In the above general formula [1], m and n are each O or 1, and m+n=1.

In the present invention, more preferably n is O and m is 1, or m is O and n is 1, and N
Compounds in which the groups represented by 1 and A3 are aromatic hydrocarbon groups exhibit the highest effects in the present invention. In the above general formula [1], q and r are each 0 or 1.

Also, R(1),,R(2'S and R3 are each hydrogen atom, halogen atom, nitro group, alkyl group, hydroxyl group, formula -
A group represented by 0C0Y7 (here, Y!CO represents a group whose bond with an oxygen atom is cleaved at a hydroxyl ion concentration of 10-5 to 2 mol/l.
The group represented by 0nR(6)C1 or R4-0-c-
This is a group represented by

Here, RΦ) is an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms substituted with halogen,
Represents a phenyl group or substituted phenyl group having 6 to 18 carbon atoms. ). Alternatively, R(1) and R(2) may bond to each other to form a naphthalene nucleus. At this time, 翿) is bonded to any position of the naphthalene nucleus. Above, the compound represented by the general formula [1] used in the present invention has been described in detail, but among these, the compound that exhibits even more preferable effects is one in which A3 is a substituted or unsubstituted phenyl group, and R (1) , R(2), or R1 is a hydroxyl group, a group represented by the above formula -0C0Y7, and Z' is a halogen-substituted group having 1 to 5 carbon atoms at the α-1 or β-1 position. The carbonyl group to which an alkyl group is bonded is the above formula -COR23 or the above formula -CC-0-R2
4 (most preferably a trifluoroacetyl group).

Typical specific examples of the compound represented by the general formula [1] that can be advantageously used in the present invention are shown below, but the compounds according to the present invention are not limited to these.

Exemplary Compound The compound represented by the general formula [1] used in the present invention is synthesized according to the following synthesis method.

A diazotized product of the above-mentioned Z-substituted amine, which is a disubstituted aromatic compound residue having or not having a reactive group for a joint, and an aromatic amine having or not having a reactive group for a joint. (At least one of the Z-substituted amine and the diazotide has the reactive group for the di-joint.

) to synthesize a shifted or unshifted azo dye having a reactive group for the joint. Conversely, an aromatic group-disubstituted amine having or not having a reactive group for the joint in the aromatic compound residue and the above-mentioned YCO-substituted amine (in this case, at least one of the aromatic compound residues has an -NH2 group) Coupling of a diazotide of (having) with a diazo coupler (X1 above) having or not having a reactive group for a joint, (at least one of the diazotide and the diazo coupler has a reactive group for a joint). A shifted azo dye having a reactive group for joints can also be synthesized by reaction. Here, the reactive group for a joint is one that can participate in the formation of the X (X, or X2) moiety in the above general formula.

Next, an M (M1) moiety is introduced into an azo dye having or not having a reactive group for a joint to obtain a shifted or unshifted DRR compound.

In addition, if a portion of M-X is introduced into a compound that can become a diazotide and/or a diazo coupler from the beginning, then a directly shifted or unshifted DRR compound can be obtained by simply performing a coupling reaction similar to the above. can be obtained. A reactive group for the joint in place of the disubstituted amine of the above aromatic compound residue, or a monosubstituted aromatic compound residue with or without the above M-X moiety and the above Z
The above reaction is carried out using a substituted amine, and the aromatic compound residue is later introduced into the amino group by reacting it with a halogen-substituted aromatic compound at an appropriate step during the process, resulting in a shifted or non-shifted amine. It is also possible to obtain DRR compounds without any. In the above reaction, if YCO has not been introduced into the amino group of the aromatic compound residue-substituted amine, the amino group can be converted to YCO (for example, acylated) at an appropriate reaction step to shift the amino group. DRR compounds can be obtained.

An unshifted DRR compound can also be obtained by hydrolyzing a shifted DRR compound. Next, a specific synthesis example of the compound represented by the above general formula [1] used in the present invention will be shown.

Synthesis Example 1 Synthesis of Exemplified Compound (1) To a solution of 5.09 g of β-4-aminophenylpropionic acid dissolved in 100 ml of water containing 20 ml of concentrated hydrochloric acid, 10 g of water was added.
ml of sodium nitrite 2.

An aqueous solution in which 39 was dissolved was added dropwise at 0 to 5°C.

After stirring for 20 minutes, 0.29 g of sulfamic acid was added followed by 20.09 g of sodium acetate.

On the other hand, 15 WL of trifluoroacetic acid and 15 d of trifluoroacetic anhydride were added to 5.79 of 3-anilinophenol.
Refluxed for an hour.

Trifluoroacetic acid and excess trifluoroacetic anhydride were distilled off under reduced pressure, and the residue was dissolved in 100 ml of ethanol. Aqueous ammonia was added to this solution, and the above diazonium salt solution was added dropwise while maintaining the pH at about 9. After stirring for 30 minutes, the mixture was neutralized with acetic acid and the resulting oil was extracted with ethyl acetate.

After washing with water, it was dried and the solvent was distilled off. The remaining oil was purified by silica gel column chromatography, and the melting point was 161.
~165°C pale yellow substance [compound (4) below] 8,69
I got it. Compound (A) 0,99 and the above compound (B) 1,
39 was dissolved in 3ml of tetrahydrofuran.

A solution of 0.49 of synchhexylcarbodiimide dissolved in 1 ml of tetrahydrofuran was added to this under ice cooling.
Stir for hours. After stirring for 4 hours at room temperature, the resulting white precipitate was filtered, the filtrate was concentrated, and purified by silica gel chromatography. Further, it was reprecipitated from ethylene glycol monomethyl ether monohydrate, with a melting point of 107~
Pale yellow substance at 112°C [Exemplary compound (1)] 0.74
I got a 9. Synthesis Example 2 Synthesis of Exemplified Compound (1) Compound (A) 0.99 and Compound (B) 1.

N-ethoxycarbonyl-2-ethoxy-1,3-dihydroquinoline dissolved in 5 ml of dry dimethylformamide was added to the solution.

After stirring at room temperature for 6 hours, it was cooled in an ice bath and an aqueous solution of 1.59 sodium bicarbonate dissolved in 50 TfL1 of water was added. The resulting precipitate was filtered, washed with water, and then dried. The product purified by silica gel column chromatography was reprecipitated from ethylene glycol monomethyl ether and water to obtain a pale yellow substance with a melting point of 104-110°C [Illustrative Compound (1)
)] 0.829 was obtained. Synthesis Example 3 Synthesis of Exemplified Compound (29) The above compound (A) 2.0f! 60m of ethyl alcohol
1 and 2 ml of a 2N aqueous potassium caustic solution was added.

After stirring at room temperature for 30 minutes, the mixture was neutralized with acetic acid and extracted with ethyl acetate. The extract was washed with water, dried, concentrated, and purified using silica gel column chromatography. After distilling off the organic solvent from the eluate, n-hexane was added to reduce the melting point to 1.
Red and colored crystals of 38-141heC [the following compound (0) 1
,29 was obtained. Compound (00.7f1 and compound (B)1
．． 39 was dissolved in 3ml of tetrahydrofuran. A solution prepared by dissolving 0.49 of synchhexylcarbodiimide in 1 ml of tetrahydrofuran was added to this under ice cooling, and the mixture was stirred for 4 hours. After stirring at room temperature for 4 hours, the resulting white precipitate was filtered, and the filtrate was concentrated and purified by silica gel column chromatography. Further, it was reprecipitated from ethylene glycol monomethyl ether monohydrate, with a melting point of 102 to 1.
0.869 of a yellow substance [exemplified compound (29)] at 06°C was obtained. Synthesis Example 4 Synthesis of Exemplified Compound (29) 0.3 g of Compound (1) was dissolved in ethylene glycol monomethyl ether 10T1Le, 0.5 ml of 2N potassium potassium aqueous solution was added, and the mixture was stirred at room temperature for 10 minutes.

After neutralization with acetic acid, water was added, and the resulting precipitate was filtered, washed with water, and dried. After purification by silica gel column chromatography, reprecipitation was performed from ethylene glycol monomethyl ether monohydrate to obtain 0.29 of a yellow substance [Exemplary Compound (29)] with a melting point of 103 to 107°C. In this way, various compounds represented by the above general formula [1] can be synthesized according to the above synthesis method. Among the compounds synthesized in this way, the elemental analysis values of the exemplified compounds The results of the measurements are shown below.

Now, the present invention will be explained in more detail.

The photographic element according to the present invention contains a silver halide emulsion layer and a compound represented by the above general formula [1] as a DRR compound.

Silver halide emulsions are hydrophilic colloids of silver bromide, silver iodide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodide, silver chloroiodobromide, and mixed silver halides. It is a dispersion,
In addition to ordinary emulsions, they may be manufactured using any of a variety of methods, such as so-called conversion emulsions, Lippmann emulsions, prefogged or internal latent image type direct positive emulsions, and photographic emulsions. The grain size, content, mixing ratio, etc. of silver halide differ depending on the type of material.

As the hydrophilic protective colloid, which is a dispersant for silver halide, various natural or synthetic colloidal substances such as gelatin, gelatin derivatives, and polyvinyl alcohol are used alone or in combination. In addition, this silver halide is
activated gelatin, sulfur sensitizers such as allylthiocarbamide, thiourea, cystine, selenium sensitizers, noble metal sensitizers such as gold sensitizers and sensitizers such as ruthenium, rhodium, iridium, etc. alone. Chemical sensitization can be carried out by using or in combination as appropriate.

Furthermore, silver halide emulsions can be optically sensitized, for example, with cyanine dyes and merocyanine dyes, and color photographic light-sensitive materials are generally made using three types of silver halide emulsions each having a different sensitivity wavelength range. can get. This silver halide emulsion also contains triazoles, tetrazoles,
It can be stabilized with imidazoles, azaindenes, quaternary benzothiazolium compounds, zinc or cadmium compounds, and can also contain sensitizing compounds of the quaternary ammonium salt type or polyethylene glycol type.

It may also contain suitable gelatin plasticizers such as glycerin, dihydroxyalkanes such as 1,5-pentadiol, esters of ethylene bisglycolic acid, bis-ethoxydiethylene glycol succinate, amides of acrylic acids, latex, etc. It can also contain formaldehyde, halogen-substituted fatty acids like mucopromic acid,
Compounds with acid anhydride groups, dicarboxylic acid chlorides,
Gelatin hardeners such as biesters of methanesulfonic acid, sodium bisulfite derivatives of dialdehydes in which the aldehyde groups are separated by 2 or 3 carbon atoms, or spreading agents such as saponins, or coatings such as sulfosuccinates. Various photographic additives Oσ such as auxiliaries can be contained.

Furthermore, various additives commonly used in photography, such as antifoggants and ultraviolet absorbers, can also be included, if necessary.
In the present invention, as described above, various silver halide emulsions can be used, and when a negative silver halide emulsion is used, a negative color diffusion transfer image can be obtained.

Positive color diffusion transfer images can be obtained by various methods. For example, U.S. Pat. No. 3,227,552, U.S. Pat. No. 2,592,250, U.S. Pat. No. 2.005,
Specification No. 837, Specification No. 3,367,778, Specification No. 3,761,276, British Patent No. 1,011
, 062, Japanese Patent Publication No. 41-17184, Japanese Patent Application Laid-Open No. 50-8524, etc., or a method using a direct positive silver halide emulsion, or British Patent No. 904,364. , a method using physical development described in Japanese Patent Publication No. 47-325, etc., or Japanese Patent Publication No. 43-21778, U.S. Patent No. 3,227,55
As described in Specification No. 4, Specification No. 3,632,345, etc., a color image forming substance is added to a fogged emulsion layer, and as an adjacent layer, it is reacted with an oxidized form of a developing agent. ,
It can be obtained by a method such as using a negative silver halide emulsion layer containing a compound that releases a development inhibitor.

As described above, various methods can be used to obtain a positive color diffusion transfer image, but a method using a direct positive silver halide emulsion is preferred. Direct positive silver halide emulsions include, for example, silver halide emulsions whose entire surface is made developable by prior exposure or chemical treatment, and whose entire surface becomes undevelopable by imagewise exposure. Another direct positive type silver halide emulsion is a direct positive type silver halide emulsion which has photosensitivity mainly inside the silver halide grains. In the present invention, the latter direct positive type silver halide emulsion is preferred.
When this direct positive silver halide emulsion is imagewise exposed, a latent image is formed mainly inside the silver halide grains.
A positive silver image is formed when the surface is developed under foggy conditions. There are various methods for developing under such fogging conditions. For example, West German Patent No. 850,383
The so-called air fog developer described in US Pat. This method is described in West German Patent No. 854,888, US Pat. It is described in the specification of No. 029. Furthermore, development may be carried out in the presence of a fogging agent, and examples of fogging agents that can be used for this include hydrazine compounds and N
There are substituted quaternary ammonium salts, etc., and these can be used alone or in combination. These fogging agents are described in U.S. Patent Nos. 2,588,982 and 3,227,552.
No. 3,615,615, No. 3,719,49
No. 4, No. 3,734,738, No. 3,718,4
It is described in No. 70, etc. The amount of the fogging agent can vary widely depending on the purpose, but generally when added to the developing solution, it is 0.1 to 2.0% per 11 of the developing solution.
9, and when added to a photographic element it is 0.9 mm per square meter.
01 to 0.29. In the present invention, the photographic element is a combination of the above silver halide emulsion and a compound represented by the above general formula [1] or [formula] as a DRR compound.

By using one or two combinations of this silver halide emulsion and a DRR compound, it is also possible to obtain monochrome or, for example, two-color dye images for pseudocolor photography. Also, for use in multicolor subtractive color diffusion transfer processes, for example, blue-sensitive, green-sensitive and red-sensitive silver halide emulsions are combined with yellow, magenta and cyan DRR compounds, respectively. A preferred multilayer structure is one in which a blue-sensitive emulsion, a green-sensitive emulsion, and a red-sensitive emulsion are coated in this order from the exposed side, and a single layer of yellow filter is disposed between the blue-sensitive emulsion and the green-sensitive emulsion. good.

The photosensitive silver halide emulsion and the DRR compound may be combined, for example, by adding them to separate adjacent layers.
Short wavelength-shifted DRRs such as those represented by O
When the compound is used, it is advantageous because it does not reduce the sensitivity of the emulsion and can therefore be added to the silver halide emulsion layer. Alternatively, two or more of each of a silver halide emulsion and a DRR compound may be coated in a single layer by the mixed packet method described in, for example, U.S. Pat. Nos. 2,800,458 and 3,466,662. It can also be used as

The DRR compound used in the present invention is dissolved in as small an amount of an organic solvent as possible and in a hydrophilic protective colloid such as gelatin or polyvinyl alcohol, which is a carrier for the silver halide emulsion layer or its adjacent layer in a photographic element. distributed to

As the organic solvent, a high boiling point solvent, a low boiling point solvent that can be removed from the dispersion by evaporation, or an organic solvent easily soluble in water can be used alone, or in combination. Particularly useful high-boiling solvents in the present invention include N-n-butylacetanilide, diethyl laurylamide, dibutyl laurylamide, dibutyl phthalate, l.licresyl phosphate, and the like.

Ethyl acetate, methyl acetate, cyclohexanone, etc. are useful as low boiling point solvents. These low boiling point solvents can be removed by evaporation during drying after coating the layer, or can be removed by the method described in US Pat. No. 2,801,171 and the like before coating. Further, as the organic solvent that is easily soluble in water, 2-methoxyethanol, dimethylformamide, etc. can be used. Also, various lipophilic polymers can be used instead of or in addition to the high boiling point solvent.

As the lipophilic polymer, polyvinyl acetate, polyacrylic acid ester, polyester made of polyhydric alcohol and polybasic acid, etc. can be used. Special Public Service 1977-
No. 13837, No. 48-32131, U.S. Patent No. 3,832,173, JP-A-17-1983
The method described in Japanese Patent No. 637 and the like is useful in the present invention for dispersing the DRR compound according to the present invention.

Further, among the compounds represented by the above general formula [1], D having a water-soluble group such as a carboxyl group or a sulfo group
The RR compound may be dissolved in water or an alkaline aqueous solution, then dispersed in a hydrophilic protective colloid, and neutralized if necessary.

The amount of DRR compound used in the present invention can vary widely depending on the compound used and the desired result, but for example, about 0.5% of the water-soluble organic cocide coating solution to be applied.
Preferably, from about 10 weight percent is used.

When performing multicolor color diffusion transfer processes, it is advantageous to use an interlayer in the photographic element.

In addition to hydrophilic polymers such as gelatin, polyacrylamide, calcium alginate, partially hydrolyzed polyvinyl acetate, and hydroxypropyl cellulose, the intermediate layer
It is constructed from a polymer with pores formed from a latex of hydrophilic and hydrophobic polymers as described in U.S. Pat. No. 3,625,685. Furthermore, U.S. Patent Nos. 3,384,483 and 3,421
, Specification No. 892, Specification No. 3,427,158,
Specification No. 3,121,011, No. 3,043,6
Specification No. 92, Specification No. 3,069,263, Specification No. 3,615,422, Specification No. 3,625,685
Specification No. 3,756,816, No. 3,
The compounds disclosed in the specification of No. 069,264 etc.
Can be used in the middle layer.

In photographic elements, couplers are used in interlayers and in the layer between the silver halide emulsion layer and the image-receiving layer to prevent color mixing and color contamination due to diffusion of oxidized developing agent into other layers.
It is preferable to add the amidrazone compound described in JP-A-48-15532, the hydrazone compound described in German Patent No. 2,123,268, or a non-diffusible hydroquinone derivative.

A non-diffusible hydroquinone derivative may also be added to the silver halide emulsion layer. As supports for the photographic elements of this invention, various natural or synthetic polymers can be used, such as paper, glass, cellulose nitrate, cellulose acetate, polyvinyl acetal, polycarbonate, polystyrene, polyethylene terephthalate, polypropylene, polyethylene, etc., and may be transparent or transparent depending on the purpose. It may be transparent or opaque.

Water vapor permeable supports or oxygen barrier supports as described in US Pat. No. 3,573,044 can also be advantageously used.

Further, when a transparent support is used, it is preferably colored to an extent that does not hinder exposure and observation of formed images, but prevents the emulsion layer from being covered during processing due to light rays passing from the edges of the support. . In the present invention, the photographic element described above is imagewise exposed and developed with an alkaline processing solution described below in the presence of a silver halide developing agent described below.

By this development, the compound of general formula [1] above and other DRR compounds incorporated into the photographic element imagewise release the diffusible dye. The diffusible dye is diffusely transferred to the image receiving layer which is placed in superimposed relationship with the photographic element at least during development and is then dyed into that layer to form a color image. The image-receiving layer preferably contains a mordant. As a mordant suitable for the image-receiving layer, any mordant can be used as long as it has a favorable mordant effect on the diffusible dye or its precursor that is diffused and transferred, and examples thereof include poly-4-vinylpyridine, Poly-4-vinyl-N-benzylpyridinium-valatoluenesulfonate, cetyltrimethylammonium bromide, and the like are useful. U.S. Patent No. 2,882,156
Pelkey Patent No. 729,202, U.S. Pat. No. 3,488,706, U.S. Patent No. 3,859
,096 specification, 3,788,855 specification,
Specification No. 3,227,148, No. 3,271,1
Specification No. 47, Specification No. 3,709,690,
Specification No. 3,625,694, No. 3,770,4
The mordants described in Patent No. 39, Patent No. 3,756,814, and Japanese Patent Application Laid-open No. 50-61228 can be advantageously used in the present invention. The above mordants are usually used in various dispersants such as gelatin, polyvinyl alcohol, polyvinylpyrrolidone, completely or partially hydrolyzed cellulose esters, and examples include poly-N-methyl-2-vinylpyridine, N-methoxymethane, etc. Chi-polyhexylmethyleneazibamide, vinyl alcohol and N-
Copolymers or polymer mixtures of vinylpyrrolidone, partially hydrolyzed polyvinyl acetate, acetyl cellulose, gelatin, polyvinyl alcohol, guanyl hydrazone derivatives of acylstyrene polymers, and only dispersants with mordant effect. It is also possible to constitute an image-receiving layer.

Further, as a special example, a mordant may be included in the tercalic treatment liquid as described in JP-A-50-47626.

The image-receiving layer may further contain various additives commonly used in photographic technology, such as ultraviolet absorbers and fluorescent brighteners.

After the diffusible dye is diffusely transferred to the image-receiving layer by application of an alkaline processing solution and the formation of the dye image is substantially completed,
It is necessary to lower the ... in the film unit to near neutrality to increase the stability of the dye image and to virtually stop further image formation to prevent discoloration and staining of the image that occurs at high pH.

For this reason, it is advantageous to use a neutralizing layer containing a substance that lowers the pH sufficiently. Such substances include, for example, polymeric acids or their partial esters or acid anhydrides as shown in U.S. Pat. No. 3,362,819;
or higher fatty acids as described in U.S. Pat. No. 2,983,606 or U.S. Pat. No. 2,584,0
Solid acid metal salts such as those shown in No. 30 are useful in the present invention. Also, U.S. Patent No. 3,576,62
Microencapsulation is also possible as described in No. 5. Furthermore, it is preferable to use a timing layer to control the rate of pH decrease, and materials for this purpose include, for example, gelatin, hydroxypropyl cellulose, partially hydrolyzed polyvinyl acetate acrylic latex, polyacrylamide, acetyl cellulose, and polyvinyl. Alcohols, partially acetalized polyvinyl alcohol, etc. and mixtures thereof may be used.

The alkaline processing solution used in the present invention contains components necessary for developing the silver halide emulsion and forming a diffusible dye, and has strong alkalinity, generally higher than PHLO.

The alkaline treatment liquid used in the present invention contains hydroxides of alkali metals and alkaline earth metals, such as compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and lithium hydroxide, or sodium carbonate, diethylamine, and the like.

Further, it is preferable that the alkaline processing liquid contains a silver halide developing agent.

Examples of the silver halide developing agent that can be used in the present invention include hydroquinone, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxy Methyl-
3-pyrazolidone, ascorbic acid, aminophenol, N-methylaminophenol, N,N-diethyl-p
-phenylenediamine, 3-methyl-N,N-diethyl p-phenylenediamine, 3-methoxy-Nethyl-N
-ethoxy-p-phenylenediamine and the like.

As mentioned above, various silver halide developing agents can be used, but a black and white silver halide developing agent is particularly preferred in order to reduce the occurrence of staining in the dye image area to be formed.

The above-mentioned silver halide developing agent is generally contained in an alkaline processing solution, but it is also possible to contain it in advance in the photographic element. Furthermore, they can be included both in the alkaline processing solution and in the photographic element. When included in advance in the photographic element, it may be included in the form of a precursor. Further, it is preferable to add a compound such as hydroxyethyl cellulose or carboxymethyl cellulose sodium salt to the alkaline processing liquid as a thickener. Furthermore, sodium sulfite, potassium bromide, triazole compounds, mercapto compounds, or compounds suitable for improving photographic properties such as color balance may also be added to the alkaline processing solution.

The alkaline processing liquid can be applied to the photographic element in a variety of forms, but is preferably maintained in a rupturable container;
After exposure of the photographic element, the rupturable container may be ruptured by a pressure member within the camera and/or attached to the film unit cartridge and applied to the exposed photographic element.

U.S. Patent No. 2,543,181 is a rupturable container.
Specification No. 2,643,886, No. 2,
Containers described in Japanese Patent No. 723,051, Japanese Patent No. 3,056,492, Japanese Patent No. 3,152,515, etc. can be used.

The film unit used in the present invention is composed of the above photographic element, an image-receiving layer, and a rupturable container, but the photographic element and the image-receiving layer may be separated before exposure, or they may be combined into one. It can also be a unit.

After processing, the photographic element and the image-receiving layer may be integrated;
Alternatively, the photographic element and image-receiving layer may be peeled off. If the photographic element and image-receiving layer are separated before exposure, or if the film unit is used in such a way that the photographic element and image-receiving layer are peeled off after processing, the image-receiving layer may be on a separate support from the photographic element. It is necessary to provide

The support for the image-receiving layer may be the same as that for the photographic element, and may be transparent or opaque depending on the purpose. The image-receiving layer can also be provided on the support of the photographic element, in which case a support separate from the support of the photographic element, a so-called cover sheet, is usually used to apply the alkaline processing solution to the photographic element. It is preferable to use

This support can also be the same as the support for the photographic element. As a background for the formed image, it is preferable to provide a light reflecting agent layer with high whiteness on the opposite side of the viewing direction with respect to the image receiving layer.

The position of the light reflector layer is not particularly limited, but
If the photographic element and image-receiving layer are not separated after processing,
A light reflecting agent layer may be provided between the photographic element and the image receiving layer. The light-reflecting agent layer may be provided as a layer in advance, or the light-reflecting agent layer may be formed in the alkaline processing solution by containing the light-reflecting agent during processing. As the light reflecting agent, titanium dioxide, zinc oxide, barium sulfate, silver flakes, alumina, barium stearate, zirconium oxide, etc. can be used alone or in combination of two or more. When provided as a layer in advance, it may be dispersed in any dispersant permeable to an alkaline solution, such as gelatin or polyvinyl alcohol. In addition, as a method for forming a light reflecting agent layer, for example, Japanese Patent Application Laid-open No. 46
Methods such as those described in Japanese Patent No. 486 and Japanese Patent No. 47-477 may also be used.

The light reflecting agent layer may further contain stilbene, coumarin, etc. as a whitening agent. When the silver halide emulsion is developed in a bright place after exposure, it is preferable to provide an opacifier layer to protect the silver halide emulsion from light. The opacifying agent layer may be provided as a layer in advance, or
It may also be formed during processing. As the opacifying agent, carbon black, JP-A-47-26, JP-A-47-2
Indicator dyes such as those described in Publication No. 7 and Publication No. 47-28 may also be added. Also, U.S. Patent No. 3,57
It is also advantageous to use desensitizers such as those described in US Pat. No. 9,333. The light reflecting agent layer and the opacifying agent layer may be present as the same layer, or may be present as separate adjacent layers.

Various layer configurations can be used for the film unit, such as those described in U.S. Pat. No. 3,415,644, U.S. Pat.
Specification No. 646, Specification No. 3,473,925, Specification No. 3,573,042, Specification No. 3,573,04
Specification No. 3, Specification No. 3,594,164, Specification No. 3
, 594,165, 3,615,421, 3,576,626, 3,6
Specification No. 58,524, Specification No. 3,635,707, Specification No. 3,672,890, Specification No. 3,730
, 718 specification, 3,701,656 specification,
Specification No. 3,689,262, JP-A-50-633
Any of the film units described in Pelkey Patent No. 757,959 or Pelkey Patent No. 757,960 can be used in the present invention.

In the various film units mentioned above, a filter dye suitable for improving photographic properties may be added to the silver halide emulsion at any position on the light incident side during exposure, if necessary. .

As a filter dye, it is stable at normal pH, but
It is also possible to use a dye that becomes colorless due to decomposition or the like when it comes into contact with an alkaline processing solution. Also, after diffusion transfer of the dye image to the image-receiving layer, the photographic element contains a pigment corresponding to the diffusion transfer image.
Image remains due to silver image and dye or dye breakers.

This residual silver and silver halide can be removed by treatment with a bleaching bath and a fixing bath or a bleach-fixing bath, and if necessary, a treatment can be applied to convert the dye breaker into a dye, thereby removing the remaining silver and silver halide from the image-receiving layer soil. It is also possible to obtain a dye image that is inverted with respect to the dye image that was previously obtained. The present invention will be explained below with reference to examples, but the present invention is not limited to the description of the following examples.

Example 1 Photographic element (1) was prepared by sequentially coating the following layers on a 110 μm thick transparent polyethylene terephthalate film support.

(1) Blue-sensitive silver iodobromide emulsion (113W19 in terms of silver)
/100d) and gelatin (12.2 mineral 100d) with a dry thickness of 1.1 μm, (2) Exemplary compound (1)
(8.0mg/100d), tricresyl phosphate (4.
0w/100cd) and gelatin (14.0W9/10
0d) with a dry thickness of 1.5 μm; (3) a protective layer with a dry thickness of 0.9 μm made of terminally hardened gelatin (10.07r19/100d).

Exemplary compound (6), exemplary compound (9), exemplary compound (29), exemplary compound (34), and exemplary compound (37) were used instead of exemplary compound (1) of Yoshin element (1). Similarly to element (1), create photo element (), photo element (
), Photographic Element QV), Photographic Element (V), and Photographic Element (Y) were created.

The layers containing the exemplified compounds of each photographic element were prepared in the following manner. First, each exemplified compound was dissolved in ethyl acetate and tricresyl phosphate, and this was emulsified and dispersed in an aqueous gelatin solution containing alkanol.XC (manufactured by DuROnt) as a dispersant, and applied.

Next, an image-receiving sheet was prepared by sequentially coating each of the layers described below on a baryta paper support coated with cellulose acetate.

(1) Polyacrylic acid (24.8TI79/100Cf
(2) a timing layer of cellulose acetate (5.0η/100cT1) with a dry thickness of 3.0 μm; (3) styrene and N-
1:1 copolymer of benzyl-N,N-dimethyl 4-N-(3-maleimidopropyl) ammonium chloride (22.0rf19/100cd) and gelatin (22.0rf19/100cd)
．． Image receiving layer with a dry film thickness of approximately 2.0 μm.

Photographic elements (1) to (9) are exposed to light from the support side through a total of 30 stages of light wedges consisting of silver wedges with a density difference of 0.15 per stage, and then the above image-receiving sheets are superimposed, and the following steps are performed between them: The treatment was carried out by developing 1.0 ml of the alkaline treatment solution described above.

Alkaline processing liquid After 2 minutes, the image receiving sheet was peeled off from the photographic element and allowed to dry.

The maximum density (Dmax) and minimum density (Dmin) of the resulting transferred image were measured using a blue filter. The measurement results are shown below. Next, photographic elements (1) to (
VI) was exposed to light in the same manner as above from the side opposite to the support, and the same treatment was performed. After 2 minutes, the image receiving sheet was peeled off from the photographic element and allowed to dry.

The reflection density of the resulting transferred image was measured using a blue filter, and the degree of decrease in sensitivity when exposed from the side opposite to the support was determined compared to when exposed from the support side. The results obtained are shown below. From the above results, shift type DR
Photographic elements (1), () and (l) using Exemplified Compound (1), Exemplified Compound (6) and Exemplified Compound (9) which are R compounds are Exemplified Compound (29) which is a non-shift type DRR compound; Exemplified Compound (34) and Exemplified Compound (37)
It was found that the degree of decrease in sensitivity was significantly smaller than that of photographic elements (5) and (and) using the following materials.

Furthermore, similar results were obtained even when the following method was used to prepare the layers containing the exemplified compounds of the above photographic elements (1) to ().

Each exemplified compound was dissolved in acetone, and the resulting solution was filtered to remove acetone-insoluble compounds.

The obtained filtrate was dropped into water to precipitate the above exemplary compound. The precipitate was collected by filtration, and the resulting filtered mass was washed with water.
7% by weight of the exemplified compound was added to water containing 10% by weight of alkanol/XC based on the exemplified compound to form an aqueous slurry, which was ultrasonically dispersed using an ultrasonic homogenizer, dispersed in an aqueous gelatin solution, and then coated. Example 2 Carbon black on one side (25m9/100c: 7l)
A laminated multicolor photographic element was prepared by sequentially applying the following layers to the other side of a 110 .mu.m thick polyethylene terephthalate film support coated with 45.0 w/100 c7i and gelatin (45.0 watts/100 c7i).

(1) Cyan DRR compound having the structural formula shown below (13.
2Tf19/100C71) and gelatin (17.0m
g/100c! l) a layer with a dry film thickness of 1.5 μm,
(2) Red-sensitive internal latent image type silver iodobromide emulsion (14 in terms of silver).

3w/100d), 2-octadecylhydroquinone-5
- Potassium sulfonate (0.7W/100d), formyl-45-methylphenylhydrazide (0.14η/1
(3) 2,5-di-Te
rt-octylhydroquinone (6.0Tn9/100(
7L), di-n-butyl phthalate (6.0T19/10
0d) and gelatin (12.0η/100d) with a dry film thickness of 1.0 μm, (4) a magenta DRR compound having the structural formula (10.0η/100d) and gelatin (15.0Tn9/100c1i). (5) Green-sensitive internal latent image type silver iodobromide emulsion (14.0W19/100CTL in terms of silver)
), potassium 2-octadecylhydroquinone-5-sulfonate (1.0W9/100CTL), formyl-45
-methylphenylhydrazide (0.13TI19/10
0CIi) and gelatin (15.5w/100(:d)
(6) 2,5-di-Tert-octylhydroquinone (6.0Tf19/
100cr1,), di-n-butyl phthalate (6.0 instant/100~), and gelatin (12.0~/100d)
An intermediate layer with a dry film thickness of 1.0 μm consisting of (7) Exemplified Compound (61) (8.3η/100d) and gelatin (12
．． 5m9/100cT1) dry film thickness 1.1μm
layer (8) blue-sensitive internal latent image type silver iodobromide emulsion (14 in terms of silver).

5W19/100cd), potassium 2-octadecylhydroquinone-5-sulfonate (0.7T!Z9/100
(9) Gelatin (10.0w/
100cri1) protective layer with a dry film thickness of 0.9 μm.

In the laminated multicolor photographic element described above, the cyan DRR compound, magenta DRR compound, and exemplified compound (29) were dispersed as follows.

First, the cyan DRR compound, the magenta DRR compound, or the exemplary compound (29) was dissolved in acetone, and the resulting solution was filtered to remove ascent-insoluble substances. The obtained filtrate was dropped into 125 ml of water to precipitate the above compound. The precipitate was collected by filtration and the filtered mass was washed with water. 7 in weight
% cyan DRR compound, magenta DRR compound or exemplified compound (29) and cyan DRR compound, magenta DRR compound or exemplified compound (29)
An aqueous slurry containing 0% by weight alkanol.XC was formed.

The mixture was subjected to ultrasonic dispersion using an ultrasonic homogenizer and dispersed in an aqueous gelatin solution. Next, the following layers were sequentially coated on a transparent polyethylene terephthalate film support having a thickness of about 100 Itm to prepare an image receiving sheet.

(1) Neutralizing layer made of polyacrylic acid (24.8W19/100d) with a dry film thickness of 25.0 μm, (2) Dry film thickness 3 made of cellulose acetate (5.0W19/100d)
．． 0 μm timing layer, (3) 1:1 copolymer of styrene and N-benzyl-NN-dimethyl-N-(3-maleimidopropyl) ammonium chloride (22.
0η/100CTI) and gelatin (22.0rf19
/100d) with a dry film thickness of approximately 2.0 μm.

The laminated multicolor photographic element thus obtained is subjected to light wedge exposure through blue, green, red, yellow, magenta and cyan filters, and then the image receiving sheet is superimposed;
Furthermore, a rupturable container containing 1.0 ml of the alkaline processing solution described below was attached in between to form a film unit.

The film unit is then passed between a pair of pressurized juxtaposed rollers having a gap of about 80 μm to rupture the rupturable container and dump its contents between the element and the image receiving sheet. Expanded.

After about 8-10 minutes of alkaline processing solution, a good dye image was observed through the transparent support of the image receiving sheet.

Example 3 A laminated multicolor photographic element was prepared by sequentially coating the following layers on a 100 μm thick transparent polyethylene terephthalate film support.

(1) 1:1 copolymer of styrene and N-vinylbenzyl-N,N,N trihexylammonium chloride (
2.2η/100c! l) and gelatin (22W9/1
An image-receiving layer with a dry film thickness of 2.0 μm consisting of (00cIL), (
2) Dry film thickness 7μ made of titanium dioxide (220η/1000f1) and gelatin (22W9/100cr1)
m light reflective layer, (3) carbon black (20.5W1
9/100cri! L) and gelatin (42.

(4) Red-sensitive internal latent image type silver iodobromide emulsion (14,3W19/100~ in terms of silver), 2-octadecylhydroquinone- Potassium 5-sulfonate (0.7η/100
C71L), formyl-45-methylphenylhydrazide (0.14Tf19/100cTi1), a cyanide DRR compound having the following structural formula (8.0I/100cr1L)
), a layer with a dry film thickness of 2.5 μm consisting of tricresyl phosphate (4.0 m9/100 cd) and gelatin (22.5 W19/100 c71), (5) 2,5-di-Ter
A dry film with a dry thickness of 1.0 μm consisting of t-octylhydroquinone (6.0η/100d), di-n-butyl phthalate (6.0T!7i!/100CTL) and gelatin (12.0T!7i!/100CTL) Intermediate layer, (6) green-sensitive internal latent image type silver iodobromide emulsion (14.0Tn9/10 in terms of silver)
0cri1), potassium 2-octadecylhydroquinone-5-sulfonate (1.0Tf19/100CTII)
, formyl-4'-methylphenylhydrazide (0.1
3w/100d), magenta DRR having the structural formula below
Compound (10.0W19/100cd), dicresyl phosphate (5.0Im/100 (1-J mo VI) and gelatin (
25.3T19/100Cd) dry film thickness 2.7
μm layer, (7) 25-di-Tert-octylhydroquinone! (6.0W!9/100cd), di-n-butyl phthalate (6.0W/100d), yellow colloidal silver (3.5~/100CTIL) and gelatin (12.0
~Re2100 (1-JMoVf) dry film thickness 1.0μ
m intermediate layer, (8) blue-sensitive internal latent image type silver iodobromide emulsion (
14.5W19/100cT1), potassium 2-octadecylhydroquinone-5-sulfonate (0
．． 7TR9/100C71), formyl-45-methylphenylhydrazide (0.14η/100d), Exemplary Compound (1) (13.0~/100(-11L)), Tricresyl phosphate (6.

0wa/100cr11) and gelatin 26.0~/10
(9) A protective layer of gelatin (10.0W19/100cTI1) with a dry thickness of 0.9 μm.

The layer containing the cyan DRR compound, the magenta DRR compound, and the exemplary compound (1) was created as follows.

First, cyan DRR compound, magenta DRR compound or exemplified compound (1) is dissolved in ethyl acetate and tricresyl phosphate, and this is used as a dispersant in alkanol/XC.
(manufactured by DuPOnt) was emulsified and dispersed in an aqueous gelatin solution.

Next, a water-methanol (1:1) solution of potassium 2-octadecylhydroquinone-5-sulfonate was emulsified and dispersed in an aqueous gelatin solution containing alkanol.XC. Each of the obtained dispersions was mixed with an internal latent image type silver iodobromide emulsion containing a methanol solution of formyl-4'-methylphenylhydrazide immediately before coating, and then coated. Next, the following layers were sequentially applied onto a transparent polyethylene terephthalate film support having a thickness of 100 μm to prepare a cover sheet.

(1) Neutralizing layer with a dry thickness of 25.0 μm made of polyacrylic acid (25.1I/100d), (2) Timing layer with a dry thickness of 3.0 μm made of cellulose acetate (5.5W19/100cr1i) .

The laminated multicolor photographic element thus obtained is subjected to a light wedge exposure through blue, green, red, yellow, magenta and cyan filters, after which it is overlaid with the above-mentioned cover sheet, during which it is subjected to an alkaline treatment as described below. liquid 1.0ml
A rupturable container containing the film was attached to form a film unit.

The film unit is then passed between a pair of pressurized juxtaposed rollers having a gap of about 80 μm to rupture the rupturable container and dump its contents between the element and the cover sheet. Expanded.

A good dye image was observed through the transparent support of the photographic element after about 8-10 minutes of alkaline processing solution.

Claims (1)

[Scope of Claims] 1. A photographic element containing at least one light-sensitive silver halide emulsion layer and a non-diffusible compound represented by the following general formula [I] is imagewise exposed, and the photographic element is subjected to silver halide development. A color diffusion transfer method characterized by developing with an alkaline processing solution in the presence of a base agent, releasing a diffusible dye from the compound, and diffusing and transferring the diffusible dye to an image-receiving layer in response to the imagewise exposure. . General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A_1' represents an aromatic hydrocarbon group, A_3 represents an aromatic hydrocarbon group, and M_1 represents a represents a monovalent moiety that releases a diffusible dye from the compound represented by the general formula [I], and X_1
and X_2 each represent a divalent group, Z' represents a hydrogen atom or a group represented by the formula YCO-, and YCO has a hydroxyl ion concentration of 10^-^5 to 2 mol/l and bonds with nitrogen atoms. Represents a group that is cleaved. m and n are each 0 or 1, and m+n=1, q and r are each 0 or 1, and R^(^1
^), R^(^2^) and R^(^5^) are a hydrogen atom, a halogen atom, a nitro group, an alkyl group, a hydroxyl group, a group represented by the formula -OCOY' (here, Y'CO is represents a group whose bond with an oxygen atom is cleaved at a hydroxyl ion concentration of 10^-^5 to 2 mol/l. Also, R^(
^1^) and R^(^2^) may combine with each other to form a naphthalene nucleus. Further, w is an integer of 1 or 5. ]