JPS61281238A - Color photographic sensitive material - Google Patents

Abstract

PURPOSE:To form a yellow dye image good in hue and high in Dmax by incorporating a specified compound in a photosensitive silver halide emulsion layer. CONSTITUTION:The color photographic sensitive material contains an azo dye image forming compound represented by formula I, and embodied by the compound 1, preferably, in an amount of 2X10<-4>-2X10<-3>mol/m<2>. The photosensitive silver halide emulsion contains, especially preferably, silver bromide, iodobromide, or chloroiodobromide contg. iodide in an amount of <=10mol% and chloride in an amount of <=30mol%.

Description

[Detailed description of the invention] (Technical field of application of invention) The present invention relates to color photographic materials.

In particular, the invention relates to a color diffusion transfer method or a heat-developable silver halide photographic light-sensitive material containing a novel yellow dye image-forming compound.

(Prior art) Force 2 - Diffusion transfer method C2 utilizes the difference in diffusivity between a dye image-forming compound and a dye compound derived from it (which forms a color image in an image-receiving layer) to create a color image. Dye developing agents, dye releasing couplers (DDR couplers), and dye releasing redox compounds (DRR compounds) are well known as representative examples of dye image forming compounds [for example, "Photographic Image Forming Compounds"]. Science and Engineering (photo
graphic 5aience andli:n
gineering) J Vol. 20, No. /j1~/44
Page 1 / 2 / 2 / 2 / 2 / 'The Theory of the Photographic Process ('l'he'l'h')
theory of 'l'he photography
cPrOCel! 8) Edited by T. H. James (Macmillan Noblitzing Company, Inc.)
illan publishing (Co, inc.)
It is described in /ri 1972 jtt-page 32.2.

(Problems to be Solved by the Invention) Yellow dye-releasing redox compounds include, for example, U.S. Pat.
issue and US Patent Application Publication (USB) j! Azopyrazolone-type yellow dye developers and yellow dye-releasing redox compounds having an aryl group at the 7-position of the pyrazolone nucleus described in 6-3 are known, but the dyes formed from the compounds described herein are There were technical problems such as poor hue and low maximum transferred image density (Dmax). In addition, an improved yellow dye-releasing redox compound is described in Japanese Patent Application Laid-Open No. 1996-34-34, but further improvements are desired.

(Objective of the Invention) Therefore, the object of the present invention is to provide good hue and Dmax.
An object of the present invention is to provide a color photographic material containing a compound that forms a yellow dye (image) with high yellow color.

(Means for Solving the Problems) As a result of various studies, the present inventors have found that the use of an azo dye image-forming compound of the following general formula (I) in a color photographic material can effectively achieve the above purpose. It has been found that the photographic performance has been achieved and has sufficiently satisfactory photographic performance.

In addition to the effects mentioned above, effects such as i) good light resistance, ii) high transfer speed, and 111) small pH dependence of the hue of the dye image can be obtained.

11i′! 1 In general formula (1), E is added to the dye part (diazo component).
It is characterized by the presence of l and R2 groups.

The above-mentioned superior effects of this group are
0/J, 633 and Tokkai Shoj Goo///.

This was completely unexpected from the compound described in No. 3 Doug.

100NRIR2 represented by Q is R1 and R described later
It has the same meaning as 2, and Q is particularly preferably a cyano group from the viewpoint of light fastness of the transferred dye image.

The alkyl group or alkoxy group represented by El may be linear or branched, and preferably has a carbon number of /~? Particularly preferably carbon number/~g (
Examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, methoxy group, ethoxy group, propoxy group, butoxy group, etc.).

In the substituted alkyl group or substituted alkoxy group represented by El, the alkyl residue has a carbon number/~? Substituted alkyl groups are preferred, and particularly preferred are those in which the alkyl residue has a carbon number of /~. Examples of substituents for the substituted alkyl group and substituted alkoxy group include those listed below as substituents for R1 and R4.

A preferred example of R3 of one COOR3 represented by R2 is:
An alkyl group with carbon number/~r (more preferably carbon number/~4t), an alkyl residue with carbon number/~? Examples include a substituted alkyl group having (more preferably carbon number/~4t), a phenyl group, and a substituted phenyl group having carbon number t~.

When R2 is a carbamoyl group represented by -CONRIR2, R1 is a hydrogen atom or a carbon number/~? (more preferably carbon number/~4t) or a substituted alkyl group in which the alkyl residue has carbon number/~r (more preferably carbon number t-4t).

R2 is a hydrogen atom, an alkyl group having a carbon number of ♂ to ♂ (more preferably a carbon number of ≈4t), and an alkyl residue having 7 or more carbon atoms. A substituted alkyl group (more preferably carbon number/~4t), benzyl group, phenyl group, and substituted phenyl group having carbon number g to wa are preferable. Further, R1 and R2 may be bonded directly or via oxygen to form a j-6 membered ring. Among these, it is inexpensive and easy to obtain when ■R1 and R2 are both hydrogen atoms, or ■R'' *At least one of R2 is a hydrogen atom and the other is an alkyl group with carbon number/~ It is particularly preferred from the viewpoint of good spots and transferability (-).

In the case of a sulfonyl group represented by -8O2R4, R4 is the number of carbon atoms/~? (more preferably carbon number/~g)
Examples include an alkyl group, a substituted alkyl group in which the alkyl residue has a carbon number of /~/ (more preferably a carbon number /~4t), a phenyl group, and a substituted phenyl group that has 6 to 4 carbon atoms.

Examples of the substituent for the substituted alkyl in R1 and R4 above include a cyan group, an alkoxy group (which may be substituted with a halogen atom, etc.), a hydroxy group, a carboxyl group, a sulfo group, a halogen i-atom, etc. I can do it.

Examples of the substituent of the substituted phenyl group in R2-R4 include a hydroxy group, a halogen atom, a carboxy group, a carbamoyl group, a sulfo group, and a sulfamoyl group (which may be substituted with an alkyl group, etc.).

The alkyl group and substituted alkyl group in 2 have the same meaning as explained for El.

In the formula -AI-(L)-(A2)- represented by X, n
p Among the groups represented by AI and A2, preferable examples include an alkylene group having a carbon number of 1 to 1, a substituted alkylene group having a carbon number of 1 to 10 (substituents include an alkoxy group having a carbon number of 3 to 3, a hydroxyl group, ), rogen atom, etc.), arylene group, substituted arylene group with 6 to /θ carbon atoms [Substituents include alkyl groups with 1 to 3 carbon atoms, alkoxy groups with 3 carbon atoms, 3 to 3 carbon atoms] ! alkoxyalkoxy group (especially preferred is methoxyethoxy7), hydroxyl group, halogen atom, -NH8O2R5 (R5 is the number of carbon atoms
-NHCO
A group represented by R5 (R5 has the same meaning as above),
A cyan group, a group represented by S 02 R5 (R5 has the same meaning as above), a group represented by -COR5 (R5 has the same meaning as above), and a hydrogen atom, a substituted or unsubstituted alkyl having a carbon number of / to B, respectively. represents a group, or R6 and R
7 are connected to each other,! Represents the atomic group necessary to form a 6-membered or 6-membered heterocycle. Among these, a particularly preferred one is a morpholino group. Among the groups represented by L, particularly preferred are -3O2NH-
It is.

The compound of formula (1) is a negative non-diffusible image-forming substance (DR) which is oxidized and self-cyclates to give a diffusible dye as a result of development using an alkaline processing solution or heat treatment.
R compound).

Another type of compound represented by formula (I) releases a diffusible dye by self-ring closure under alkaline conditions, but when it reacts with an oxidized developer, it does not substantially produce several dye colors. Examples include positive non-diffusible image forming compounds (DRR compounds) such as: Specific examples of Y suitable for these types of compounds are found in U.S. Pat. No. 3,92. ! ”, 3/2
No.3, 3,993°? No., same g, θ2≦, j2 ri, same 4t, /! No. 2.733, same group, 061.4t2r
No., same gu.

0! ! , 3/2 issue, same da, /9♂, 23ta issue, same da,
/7ri, 2ri7, samegu, /4t9, ? No. 92...
Same 3? 4t4t, No. 776, 3.4t 3. Free 3, same 3.7! /, 4t06, same 3, 4t 3. 3rd, 3rd and 4th grade 3. ri 4to issue, same 3. Otsu 2! .

,the law of nature! No. 2, 3. Wa? 0,4t7ri issue, same gu, /rj
, 7! ! No. 41. /4t21L! r9/issue, same gu.

27? , No. 7jO, No. 739, No. 379, No. 41
．． 2/r, Jtr, same! , 4t2/, No. 9641, same da, /ri? , 3J-1, same gu, /9ri, 3? Gu issue,
Same da, /Jj, octopus 9, same Z, 33 otsu, 3ko λ, same gu, /3 ri, 3? No., Tokukaisho! 3-! No. 0236, No. 104t3, No. 3, No. 730/22, No. 730/22, No. 730/22, No. 10/27, No. 2 of J, No. 2, No. 2, No. 2 of 2t4t2, No. 2!
6-/Otsu/3/ issue, same j7-4t04t3 issue, same! 2-
Otsu! θ No., same Ta 7-ko θ23! Same issue! 3-≦ri033
Same issue! Ku/30ri No. 27, same evening≦-/Go4tj4t
No. 2, same! 2-//rij4tj, etc.

Among Y of the negative dye-releasing redox compound, a particularly preferable group is an N-substituted sulfamoyl group (the N-substituent is a group derived from an aromatic hydrocarbon ring or a heterocycle).

Typical groups for Y are illustrated below, but are not limited to these.

Further, two typical examples of Y in the positive dye-releasing redox compound are shown below.

When compounds of this type are used, they are preferably used in combination with diffusion-resistant electron donor compounds (known as ED compounds) or their precursors.

Examples of ED compounds include, for example, U.S. Pat.
No. 393, same group, 27♂.

No. 7J-0, JP-A-Shojj-/31736, etc. (=described.

Yet another type of compound of formula (I) is a non-diffusible compound (dye compound) which releases a diffusible dye upon coupling reaction with the oxide of a color developing agent oxidized by silver halide. emitting couplers). This (= valid Y is U.S. Patent J, 227,
The groups listed in No. J-j-0 are representative.

Yet another type of compound represented by formula CI) is a compound that is initially diffusible under alkaline conditions but becomes non-diffusible upon oxidation upon development (dye developers). Y that is effective for this type of compound is U.S. Patent Co., Der 3. t.

The one listed in No. 6 is representative.

Among the azo dye image-forming compounds of the present invention, DRR compounds are preferred.

More preferred compounds of the present invention are represented by the above general formula (I), and specific examples of the compounds represented by the general formula (I) are listed below.

Compound / Compound co-compound viJ3 Compound g compound! Compound 10 Compound/λ Compound //Compound R=OCH3 Representative synthesis examples of the dye-releasing redox compound used in the present invention and intermediates thereof will be described in detail below.

Synthesis of compound/) Synthesis of 3-cyano-g(2,!-dimethyl-gousulfophenyl 7')-r-hirazolone containing 10 g of p--+silidine-gousulfonic acid and 2 g of sodium hydroxide Add 20rnl of an aqueous solution containing 3.4tg of sodium nitrite dissolved in the aqueous solution JOml, and add t'C
It was then added dropwise into 1 rnl of concentrated hydrochloric acid and 100 ml of water. Thereafter, the mixture was stirred for 30 minutes below z'C.

J-'/7. ／−／−Fenny Lou! -Hirazolone? ,
Jg was dissolved in 30 mJ of methyl alcohol, sodium acetate/g was added, and the diazo solution prepared above was added below lo'c. After stirring for 7 hours, it was filtered and dried.

Yield 23.6g m,p,cozooc2) Synthesis of 3-cyano-g(co,j-dimethyl-derchlorosulfonylphenylazo)-z-pyrazolone/) Pyrazolone dye 23-&gs acetonitrile 700mJl and N , N-dimethylacetamide 2q
ml was put into a 200 ml Mitsuro flask, and 4 tml of phosphorus oxychloride, Z, was added dropwise at below jOoC. then 7
The mixture was stirred for an hour, poured into ice water, and the precipitated crystals were filtered off.

Yield /ri, tg m, p, ltj ~ /qr 'C 3) Synthesis of compound / co-amino-tert-butyl-! -Pyrazolone dye obtained with -hexadecyloxy/-phenol r, rg, a)? , Jg and N,N-dimethylacetamide θml were added dropwise to a 100ml Mitsuro flask (both male and female).Then, the mixture was stirred for 7 hours, poured into hydrochloric acid, filtered, and N,N-dimethyl It was recrystallized from a mixed solution of acetamide romit and 200 ml of methanol.

Yield 70g m, p, itotsu~/j7°C Synthesis of compound λ/) Synthesis of 3-cyano-g(termethoxycomethyl-goosulfophenylazo)-j-hirazolone 7.3 g of sodium hydroxide and water Comethoxy! to 20ml of solution! - Add 10 ml of an aqueous solution containing 7.3 g of methylsulfanilic acid and 2.3 g of sodium nitrite, and add concentrated hydrochloric acid/
/ml and zoml of water at a temperature below j'C. After the dropwise addition, the mixture was stirred for 30 minutes.

3-cyano-/-phenyl-! -Dissolve 4゜1g of pyrazolone in tOml of methyl alcohol, dissolve sodium acetate//,
Added 7g. Then, the diazo solution prepared above was added to /θ0
C or less, stirred for 7 hours, and precipitated crystals were separated by filtration.

Yield: 7.7 g m, p, 2j O°C or higher2) 4.4 g of pyrazolone dye synthesized with 3-cyano-g(j-methoxy-methyl-terchlorosulfonylphenyl-yso)-, r-pyrazolone synthesis/) , Acetonitrile 33m! and N,N-dimethylacetamide 7 mJ
was placed in a 100rnll Mitsuro flask, oxychloride phosphor mz was added at below jo0c, and the mixture was stirred for 30 minutes. It was poured into ice water and the precipitated crystals were separated by filtration.

Yield: 6.3g m, p, /rit~/rir 0C 3) Synthesis of compound ko, pyrazolone dye obtained in 2)! g,2-aminodarte
rt-methyl-! -hexadecyloxy-7-phenol Jr, 7g and N,N-dimethylacetamide, 2
0 mjl was put into a 100 ml Mitsuro flask, pyridine z and tml were added, and the mixture was stirred for 30 minutes. Methyl alcohol was added to the reaction solution, and the precipitated crystals were filtered off and then recrystallized from a mixed solvent of ethyl acetate and methyl alcohol.

Yield 4tg m, p, /44♂~/! θ 0Cε acet7 2.2/×104 4t4tJ' nm Other compounds can also be easily synthesized according to the above synthesis method.

The color photographic material of the present invention can be used, for example, for heat development.

The layer structure of the sensitive material and other additives suitable for this purpose are described in European Patent Application Publications Ep7j and 4t?λA2, etc.

When the color photographic light-sensitive material of the present invention is applied to color diffusion transfer photography, it may be of the peel-off (beer-apart) type or Japanese Patent Publications No. 4TJ-16314, No. 33697,
Japanese Patent Application Publication No. Sho J-0-/j04tθ and British Patent/, 3
30, an integrated type as described in No. J241, JP-A-J7-//3G! It is possible to adopt a structure of a film unit that does not require peeling as described in No. Alternatively, it may be an integrated film unit that can be peeled off as desired (JP-A-Sho! 6-
67r4tO and Tokukai Sho! Tar 2207 Co No. 7, etc.).

In any of the above formats, JP-A-Shoj Law/4tj2/7, JP-A-J3-72622, JP-A-41-'
;#/30, same jg-73r4t3 and same ju
-/374t No. 33 and other fused latex polymer monolayers or JP-A-Sho! t-z4t, t<ti issue and “Research Disclosure Y-J (Rese
arch])isclosure)A/♂.

The use of a polymeric acid layer protected by a temporary barrier layer, such as the lactone ring-containing polymers disclosed in 4tjl (/79), shortens the neutralization timing time at high processing temperatures, may be useful if the processing temperature is acceptable. This is advantageous in increasing the width.

The photosensitive silver halide emulsion used in the present invention includes silver chloride,
A hydrophilic colloidal dispersion of silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, or a mixture thereof, in which the halogen composition is selected depending on the intended use and processing conditions of the photosensitive material. However, silver bromide, silver iodobromide or silver chloroiodobromide having an iodide content of /θmole% or less and a chloride content of jOmole% or less are particularly preferred.

In the present invention, either a negative type emulsion that forms a surface latent image or a direct reversal type emulsion can be used. The latter emulsion includes an internal latent image type emulsion and a pre-fogged direct reversal type emulsion.

Internal latent image type silver halide emulsions can be advantageously used in the present invention; examples of this type of emulsion include, for example, U.S. Pat.
2.23-0 issue, same! ,, 20 Go, No. 373, same j,
4t4t7, Octopus No. 7, same 3.74/, No. 27,
and 3. Ri3! Examples include conversion type emulsions, core/shell type emulsions, emulsions containing different metals, etc., which are indicated by , 0/, etc.

As a nucleating agent for this type of emulsion, US Patent 2°! ♂1,
Hydrazines described in No. 912, No. λ, No. 7/♂; Hydrazides and hydrazones described in No. 227, No. JJ-2: British Patent/, No. 3. ♂
3! No., Special Public Sho Geta-3 // Bu Z No., U.S. Patent Da, //
j, /22, same 3゜23g, 73? Issue, 3.7/ri, 4t? Da issue, same J, t/! ,≦/! Quaternary salt compounds described in US Patent No. 3,7/♂, No. 4T No.
Sensitizing dyes having substituents in the dye molecule: U.S. Pat.
θ30゜゛ Ta2! No. 4t, θ31. /Koku-go, Do-gu, λ-gu! , No. 032, No. 2jj, No. j//, No. 032, No. 032, No. 032, No. Typical examples include thiourea-linked acylhydrazine compounds described in θ/3, 276.364, and the like.

The silver halide emulsions of the present invention (bilaterally coated) can have color sensitivities extended by spectral sensitizing dyes, if desired.

As the spectral sensitizing dye, cyanine dyes, merocyanine dyes, etc. can be used as appropriate.

The dyes formed from the magenta and cyan dye-providing compounds used in combination in this invention may be preformed dyes or may alternatively be dye precursors that can be converted into dyes in the photographic processing step or in additional processing steps. and the final image dyes may or may not be metal chelated. Representative magenta and cyan dye structures useful in this invention include azo dyes, azomethine dyes, anthraquinone dyes, phthalocyanine dyes, triphenyl dyes. Mention may be made of metal-chelated or non-metal-chelated dyes such as methane dyes and indigoid dyes.Any known dye-providing compounds can be used in the present invention.

Also, as a type of dye precursor, a dye-donating compound having a dye moiety that temporarily shifts light absorption in a light-sensitive element can also be used in this patent; No. 330, No. j-j-j-332, U.S. Pat. ! 7ri,
No. 33, 3. Riko.

It is described in British Patent No. 4TG, British Patent No. 7,377.

The coating amount of the dye-providing compound is /x10-4 to /X102
mole/m2, preferably λ×/θ-4 to JX10
It is 3 mole/m2.

The dye-providing compound used in this invention can be dispersed in the hydrophilic colloid in a variety of ways depending on the type of compound. For example, a compound having a dissociable group such as a sulfo group or a carboxy group can be dissolved in water or an alkaline aqueous solution and then added to the hydrophilic colloid solution and dispersed. On the other hand, compounds that are difficult to dissolve in aqueous media but easy to dissolve in organic solvents can be dispersed by the following method.

(2) A method in which a solution of a compound dissolved in a substantially water-insoluble high-boiling solvent is added and dispersed in a hydrophilic colloid solution.
Same, 13! , No. J-/4, same.

70/, No. 177. Further, if necessary, a low boiling point solvent or an organic solvent easily soluble in water may be used, and these solvents are removed by drying (volatilization by drying, washing with water, etc.).

■ A method in which the compound is dissolved in a water-miscible solvent and then dispersed in a hydrophilic colloid solution.

■ A method in which a lipophilic polymer is used instead of or in combination with a high-boiling point solvent in the above (■).This method is described, for example, in US Patent J', J/? ,/9! No., West German patent/
, rij7,4t≦7.

■ A method in which a compound is dissolved in a water-miscible solvent and then an aqueous latex is gradually added to the solution to obtain a dispersion in which the compound is contained in latex particles.
For example, it is described in Japanese Unexamined Patent Publication No. 7/1994t3.

In addition, hydrosil, a lipophilic polymer described in Japanese Patent Publication No. Shoj/-3973j, for example, may be added to the hydrophilic colloid dispersion obtained above.

Dispersion of the dye-providing compound is effective using surfactants as emulsification aids. Useful surfactants are described, for example, in the above-mentioned patent specifications and Japanese Patent Publication No. 3 Wagde No. 23, U.S. Patent No. 3. 74, /'I1.

Hydrophilic colloids used to disperse the dye-providing compounds used in the present invention include, for example, gelatin, colloidal albumin, casein, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, agar, sodium alginate, starch derivatives, etc. sugar derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol, polyN-
Examples include vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide, and derivatives thereof (for example, partial hydrolysates). Compatible mixtures of two or more of these colloids may be used if desired. Among these, gelatin is most commonly used, but gelatin may be partially or completely replaced with a synthetic hydrophilic colloid.

Processes for obtaining color diffusion transfer images using dye-donating compounds are described in Photographic Science and Engineering J.
graphic 5science and engineering
neer ing) magazine, vol. 20, A: 4t, /jj~
Published on page 64, July/R issue/2g.

Any silver halide developer can be used in the above process as long as it is capable of cross-oxidizing the dye-providing compound. Such developing agents may be included in the alkaline processing composition or in appropriate layers of the photographic element. Examples of developing agents that can be used in the present invention are as follows.

Hydroquinones, aminephenols, phenylenediamines, pyrazolidinones [e.g. /-phenyl-3-pyrazolidinone, /-7enyl-4t, 4t-dimethyl-3- Pyrazolidinone, /-p-1rerudermethyl-g-hydroxymethyl-3-pyrazolidinone, /-(4t'-methoxyphenyl)-coumethyl-g-hydroxymethyl-3-
pyrazolidinone, /-phenyldermethyl-derhydroxymethyl-3-pyrazolidinone], etc.

Among those listed here, black and white developers (among them pyrazolidinones) are particularly preferred over color developers such as phenylenediamines, which have the property of reducing stain formation in the image-receiving layer.

The processing composition used to process the photographic light-sensitive material of the present invention preferably contains a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, or sodium phosphate and has a pH of about 10% or higher; Preferably // has an alkaline strength of 1 or more.

The treatment composition may contain antioxidants such as sodium sulfite, ascorbate, piperidinohexose reductone, and may also contain silver ion concentration regulators such as potassium bromide. It may also contain viscosity increasing compounds such as hydroxyethyl cellulose and sodium carboxymethyl cellulose.

The alkaline processing composition may also contain a compound such as benzyl alcohol, which has the effect of accelerating development or promoting dye diffusion.

Reproduction of natural colors using subtractive color method (2) A photosensitive material consisting of at least two combinations: an emulsion with selective spectral sensitivity in a certain wavelength range and a dye-donating compound with selective spectral absorption in the same wavelength range. is used.

In particular, light-sensitive materials comprising a combination of a blue-sensitive silver halide emulsion and a yellow-donating compound, a combination of a green-sensitive emulsion and a magenta dye-providing compound, and a combination of a red-sensitive emulsion and a cyan dye-providing compound are useful.

These combination units of the emulsion and the dye-providing compound may be coated face-to-face in a layered form (they may be coated in double layers) or in the form of individual grains (the dye-providing compound and the silver halide grains are in the same grain). ) may be mixed and applied as a single layer.

Between the intermediate layer and the layer containing the dye-donating compound
A separating layer may be provided as described in No. -J-20!6. Also, in the middle class, is the Japanese Patent Application Publication JT-47? ! A silver halide emulsion may be added as described in No. 0.

Regarding the mordant layer, neutralization layer, neutralization speed control layer (timing layer), processing composition, etc. that can be used in the light-sensitive material for the color diffusion transfer method of the present invention, for example, Japanese Patent Application Laid-Open No. 13-13-4T932
Those described in item r can be applied.

The polymer mordants used in the present invention include polymers containing secondary and tertiary amine groups, polymers having a nitrogen-containing heterocyclic moiety, polymers containing these da-class cation groups, etc., with a molecular weight of J-, ooo or more, Particularly preferably 10,
000 or more.

For example, US Patent 2. j4tl,! No. 64, same.

Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in 4tJO, J, /4#, 06/, 7j6.r/41, etc.: U.S. Patent Q, / Vinylimidazolium cationic polymer disclosed in 24t, No. 316 specification, etc.; U.S. Patent, !, 62!, t tag number, same J, rj9
, No. 096, same gu, l co? .

! Polymer mordant crosslinkable with gelatin etc. disclosed in U.S. Pat. Rijr, No. 991, 2.7J/,
No. 162, 2nd and 7th issue? , No. 063, Unexamined Japanese Patent Publication No. 74T-/
/j22r issue, same! Ku/4tjj Kota issue, same! Ku 7
2go 022, same j4t-/J-J-rJj, same! Aqueous sol type mordant disclosed in the specification of No. 1/731.2 etc.: U.S. Patent No. 3. Water-insoluble mordants disclosed in the specifications of /ri♂, θt♂, etc.: U.S. Patent g, /(/, 97
No. 4, same da.

Coθ/J4tO, a reactive mordant capable of covalently bonding with the dye disclosed in the specification, etc., and US Pat. No. 3.70
ri, No. 690, 3, 7? ? ,♂! ! No. 3.
t'12, 4t♂ko No. 3. Gr? , 70 Otsu No. J, JJ No. 7.066, JJ No. 3.27/, /RI No. 7, Same No. 3, 27/, /4t♂ No., Same! ! -30! , 27
No., same jλ-/jJr! No. 2, No. j3-/2j, No. 2, ! -102g issue, same! 3-/θ7/3! No., British Patent Co., Ltd., 0t4t.

Examples include mordants disclosed in Japanese Patent No. 702 and the like.

Other US patents No. 2, j7J-, 3/, same.

712, /J- can also be mentioned as a mordant as described in the specification.

In addition to the above-mentioned formats, color photographic materials that can be used in the present invention include a method in which a photosensitive sheet without an image-receiving layer is developed in a tank to elute the soluble dye compound, and the remaining insoluble (non-diffusible) dye compound is utilized. Therefore, the present invention can be applied to any method that utilizes dye diffusion. Of course, conventional color photography (Conventional Color Photography)
Needless to say, it can also be used for photography.

Specific examples showing the effects of the present invention will be described below, but the scope of the present invention is not limited thereto.

Example 1 A photosensitive sheet, an image receiving sheet, and a processing liquid were prepared as follows.

Preparation of photosensitive sheet Each layer was coated on a polyethylene terephthalate transparent support in the following order.

(1) Yellow dye-releasing redox compound with the following structure (
/, θX103mol/m2), tricyclohexyl phosphate (θ, org/m2), Co.

r-sheet t e r t-, z-tadecylhydroquinone (0,00/g/m2), and gelatin (θ, jg/m2)
m2).

(2) Silver halide emulsion (silver amount: 0, r 2 g
/m2), a layer containing gelatin (0,9 g/m2).

(3) A protective layer containing gelatin θ·j g/m2.

Preparation of image-receiving sheet Polyethylene terephthalate transparent support (2, copoly(styrene-N-vinylindyl-N-methylpiperidinium chloride) 3.0 g/m2, gelatin 3.0
An image-receiving layer containing g/m 2 was applied.

After exposure, each of the photosensitive sheets A/~Aj is overlapped with the image-receiving sheet/The processing liquid is spread uniformly between both sheets through a pair of pressure rollers, and after /θ minutes, the image-receiving sheet is peeled off. After soaking in 2-thiacetic acid solution, the sample was thoroughly washed with water. Next is pHj's McEngine's Buffer.
After soaking, it was air dried. At this time, all the image receiving sheets were uniform with no stains. The visible spectral absorption of these image receiving sheets was measured using a Cary spectrophotometer. At this time, an untreated image receiving sheet was used as a control. The results are shown in Table 1 (hue of transferred image).

As is clear from the results in Table 1, the absorption (λ1/
2 long wavelength side), the corresponding di-substituted product of the present invention (E
The absorption (λ1/2 long wavelength side) of the leaving dye (which is also substituted with 'l E z) is considerably shifted to the long wavelength side, and exhibits a preferable hue as a yellow dye.

Similarly, in the yellow hue, as shown in Table 1, the wavelength expressed on the λ1/2 long wavelength side is more important than λmax,
This value is 4t99~! The present invention of θrnm is preferable.

Example 2 A photosensitive sheet, a cover sheet, and a processing solution for use in a photographic material for color diffusion transfer were prepared as follows.

Photosensitive sheet A photosensitive sheet t// was prepared by coating the following layers on a polyethylene terephthalate transparent support.

(1) Kohori [Styrene-N-vinylbenzyl-N
.

Image-receiving layer containing 3.0 g/m2 of gelatin.

(2) Titanium dioxide 20g7m2, gelatin, θg/
A white reflective layer containing m2.

(3) A light-shielding layer containing 2.0 g/m2 of carbon black and gelatin/j g/m2.

(4) The following cyan dye-releasing redox compound 0°4t
4tg/m2, tricyclohexyl phosphate θ, 0
9g/m2.2. J--Gt--<npdecylhydroquinone 0.0θJ'g/m2, and gelatin θ,
/g, /m2 containing layer.

(5) Red-sensitive inner layer type direct positive silver bromide emulsion (according to the amount of silver/
03g/m2), gelatin/, 2g/m2, the following nucleating agent θ, 0gmg/m2 and courseluho, 1-n-
Pentadecylhydroquinone sodium salt 0.13g
A red-sensitive emulsion layer containing 7 m2.

(6), 2. J--G1-<ntadecylhydroquinone 0. ￥3g/m2, trihexyl phosphate θ, /
layer containing g7m2 and gelatin 0.4tg/m2.

(7) Magenta dye-releasing redox compound of the following structural formula (2) (0.27 g/m2), magenta dye-releasing redox compound of the structural formula (2) (0,7727 m2), tricyclohexyl phosphate<0.0rg7m2), 2.7- - Tadecylhydroquinone (0,θ0g/m
2) and a layer containing gelatin (0°9g/m2).

Structural formula■ Structural formula■ (8) Green-sensitive green-sensitive inscribed positive silver bromide emulsion (08 in terms of silver content)
22g7m2), gelatin (o, 51g/m2)
), a green-sensitive emulsion layer containing the same nucleating agent as layer (5) (0,03 mg/m2) and 2-sulfo-t-n-d-ntadecylhydroquinone sodium salt (0,otrg/m2).

(9) Same layer as (6).

α Moan Yellow dye-releasing redox compound listed in Table 1 (7,6X10-4 mol/m2), tricyclohexyl phosphate (O,/jg/m2), co,! -d-t-pentadecylhydroquinone (θ, θ/4t-g/
m 2) and a layer containing gelatin (0,7 g/m 2).

αυ Blue-sensitive blue-sensitive inscribed positive silver bromide emulsion (7.0% silver content)
097m2), gelatin (/, /g/m2), layer (5)
The same nucleating agent ((7, o4tmg7m2) and 2-
Sulfo-j-n--e entadecylhydroquinone
Blue-sensitive emulsion layer containing sodium salt (θ, Ozg/m2).

(l of gelatin (0, tg/m2), polymethyl methacrylate tex (θ, 04 g/m2) and triacryloyl triazine (0,02 g 7 m2) as a hardening agent.
2) A protective layer containing:

Construction of Cover Sheet A cover sheet was prepared by sequentially coating the following layers (/') to (3') on a transparent polyethylene terephthalate support.

(/') acrylic acid and butyl acrylate tro pair 20
(weight ratio) copolymer (2,zg/m2) and H/,4
t-bis(2,3-epoxypropoxy)-butane (o
, 4tg/m2).

(,2') Acetylcellulose (hydrolyzes 700g of acetylcellulose to produce 3,4tg of acetyl groups) (,?,?g/m2) and 10 to 0 of styrene and maleic anhydride. (weight ratio) copolymer (molecular weight approx. 10,000) with methanol ring-opened product (0.23 g/m
2) and r-(x-cyano-/-methylethylthio)-/-phenyltetrazole (o, ij4tg7m2
).

(3') Data of styrene-n-butyl acrylate-acrylic acid-N-methylolacrylamide, 7 vs. 4tJ
, j vs. 3 vs.! (Weight ratio) Copolymer latex and methyl methacrylate-acrylic acid-N-methylol acrylamide glue 3:y:3 (weight ratio)The solid content ratio of the former latex and the latter latex is g:4tζ A 2μ thick layer applied by mixing two parts.

Composition after treatment Example - Same as /.

After the photosensitive sheet t~// was exposed to light through a continuous wedge, the processing liquid was spread between the photosensitive sheet and the cover sheet by passing it between /pair of pressure rollers. One hour after development, the concentration was measured and I) max was determined.

From Table 2, it can be seen that the dye image-providing compounds of the present invention which are di-substituted have a higher I) ma compared to the corresponding conventional mono-substituted
It can be seen that x is given (for example, I6 vs. Haruka 7.4/θ vs. Bi2.ya// vs. A/).

(Effects of the present invention) Combining Example 1 and Example 2, it can be seen that the compound of the present invention is an excellent compound that can achieve both good hue and high I)max.

Table 2 EI E2 Comparative -C1 (H # -D CHa H , -EcJH Compounds A/, 2 and 2 in the table indicate the □ compounds of the present invention exemplified above.

Claims (1)

[Scope of Claims] A color photographic light-sensitive material, characterized in that it has at least one light-sensitive silver halide emulsion layer, and at least one of the emulsion layers is combined with a compound represented by general formula (I). . ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) However, Q is a cyano group, trifluoromethyl group, or -
A carbamoyl group represented by CONR^1R^2 (where R^1 represents a hydrogen atom, an alkyl group, or a substituted alkyl group, and R^2 represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aralkyl group, or an aryl group) Indicates.R^
1 and R^2 may be linked directly or through an oxygen atom to form a ring; E^1 is a halogen atom, an alkyl group, a substituted alkyl group, a hydroxyl group, an alkoxy group, or Represents a substituted alkoxy group; E^2
represents a substituent defined in the above E^1 section, or an electron-withdrawing group selected from the following group; cyano group, trifluoromethyl group, -SO_2R^4 (R^4 is an alkyl group, (represents a substituted alkyl group, phenyl group or substituted phenyl group), a group represented by -COOR^3 (represents R^
3 represents a hydrogen atom, an alkyl group, a substituted alkyl group, a phenyl group or a substituted phenyl group), -CONR^1R
^2 (R^1, R^2 are the same as above), sulfo group, -S
O_2NR^1R^2 (R^1 and R^2 are the same as above)
represents; 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;
, A_2 are the same or different and each represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group,
L represents a divalent group selected from oxy, carbonyl, carboxamide, carbamoyl, sulfonamide, sulfamoyl, sulfinyl or sulfonyl, and n and p represent 0 or 1. ) represents a divalent bonding group;
Y represents a component that provides an azo dye compound having different diffusivity from the azo dye image-forming compound represented by formula (I) as a result of development.