JPS6123151A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable a color image durable for long period storage to be obtained by incorporating a specified cyan dye forming coupler. CONSTITUTION:A silver halide photographic sensitive material contains at least one of cyan dye forming couplers represented by the formula in which R1, R3 are each independently an optionally substd. aliphatic, aryl, or heterocyclic group; R2 is an optionally substd. aliphatic or alkoxy group; Z is H or a group releasable by coupling; m, n are each 0 or 1, and when m and n are both 0, and both of R2 and R3 are each nonsubstd. alkyl, the total C number of them is >=3, or R1 is an optionally substd. aryl or heterocyclic group, and R2, R3 may be each a nonmetallic atomic group combining with each other and forming a 5--7-membered ring.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material containing all novel cyan dye-forming couplers.

(Prior art) When a silver halide photosensitive material is exposed to light and then subjected to color development processing, a developing agent such as an aromatic-class amine oxidized by silver halide reacts with a dye-forming coupler, resulting in color development. An image is formed. Generally, in this method, a subtractive color reproduction method is used, and in order to reproduce blue, green, and red, images of yellow, magenta, and cyan, which are complementary colors, are formed, respectively.

(Problems to be Solved by the Invention) Phenols or naphthols are often used as cyan image forming couplers.

However, several problems remain in the storage stability of color images obtained from conventionally used phenols and naphthols. For example, U.S. Patent No. 2.3t7,3
3/No. 2.3t9, 922, No. 2, 'A23.
No. 730 and No. 2, ! "0/.

The color images obtained from the λ-acylaminophenolic cyan couplers described in U.S. Pat. No. 2,772.112 and U.S. Pat. , 2, described in No. 1126! - Color images obtained with diacylaminophenolic cyan couplers generally have poor light fastness, and /-hydroxy-λ-naphthamide cyan couplers generally have poor both light and heat (particularly moist heat) fastness. .

The object of the present invention is to provide a cyan dye-forming coupler which overcomes these drawbacks and which provides color images that can withstand longer storage times.

(Means for Solving the Problems) The object of the present invention is to solve the problem by reducing the number of
This is accomplished by using two photographic couplers and a silver halide color light-sensitive material containing them.

[In the formula, R1 and R31d independently represent a substituted or unsubstituted aliphatic, aryl, or heterocyclic group, R2 represents a substituted or unsubstituted aliphatic group or alkoxy group, and Z is a hydrogen atom or a developing agent. represents a group that can be separated during an oxidative coupling reaction with
It can be linear, branched or cyclic, and saturated or unsaturated (, m and ni, respectively, O
or /i, with the proviso that m and n are both zero, and R
When 2 and R3 are unsubstituted alkyl, the total number of carbon atoms is 3 or more, or Rxfd represents a substituted or unsubstituted aryl or heterocyclic group), and R2 and R3 together represent a j- to 7-membered It may also be a nonmetallic atom (group) forming a ring. ] Next, R l in the general formula [, I)
, R2, R3, and Z will be explained in detail.

In general formula (I), R1 and R3 are linear or cyclic, saturated or unsaturated, preferably having 1 to 32 carbon atoms.
aliphatic groups (e.g., methyl group, dityl group, tridecyl group, allyl group, propargyl group, cyclohexyl group, etc.)
, represents an aryl group (e.g., phenyl group, naphthyl group, etc.) or a heterocycle (e.g., λ-pyridyl group, coimidazolyl group, λ-furyl group, t-quinolyl group, etc.), and these represent seven or more alkyl groups. , aryl group, heterocyclic group, alkoxy group (e.g., methoxy group, λ-methoxyethyne group, etc.), aryloxy group (e.g., λ, t-
di-tert-amylphenoxy group, λ-chlorophenoxy group, guccianophenoxy group, etc.), alkenyloxy group (for example, λ-propenyloxy group, etc.), acyl group (for example, acetyl group, benzoyl group, etc.), ester groups (e.g., butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, phenylsulfonyl group, toluenesulfonyloxy group, etc.), amide group (e.g., acetylamino group, ethylcarbamoyl group, dimethyl car/gumoyl group, methanesulfonamide group, butylsulfamoyl group, etc.), sulfamide group (e.g., dipropylsulfamoylamino group, etc.), imide group (e.g., succinibado group, higntoynyl group, etc.), ureido group (e.g., phenylureido group, dimethylureido group, etc.), aliphatic or aromatic sulfonyl group (e.g. methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio group (
For example, ethylthio group, phenylthio group, etc.), hydroxyl group, cyano group, carboxy group, nitro group, sulfo group, halogen atom, etc. The times may be the same or different.

General formula (in IJ, R2 preferably has 7 to 2 λ carbon atoms)
represents an aliphatic group or an alkoxy group, and these (,'l
R1 may have a permissible substituent.

In the general formula [IJ, z represents a hydrogen atom or a coupling-off group, examples of which include a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), an alkoxy group (e.g., an ethoxy group, (dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxyzoJ pyruoxy group, methylsulfonyl ethoxy group, etc.), iri-ruoxy, & (e.g., 4'-chlorophenoxy group,
≠-methoxyphenoxy group, ≠-carboxyphenoxy group, etc.), acyloxy group (e.g., acetoxy group, tetradecanoyloxy group, benzoyloxy group, etc.),
Sulfonyloxy groups (for example, methanesulfonyloxy & I-luenesulfonyloxy groups, etc.), amide groups (
For example, dichloroacetylamino group, heptafluorobutyrylamino group, methanesulfonylamino group? , toluenesulfonylamino group, etc.], alkoxycarbonyloxy groups (e.g., ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy groups (e.g., phenoxycarbonyloxy group, etc.), and aliphatic groups. Aromatic (e.g., ethylthio group, phenylthio group, tetrazolylthio group, etc.),
Examples include ibado groups (eg, succinimide group, hydantoinyl group, etc.), aromatic azo groups (eg, phenylazo group, etc.), etc. These leaving groups may contain photographically useful groups.

In the general formula (IJ, m and n are each 0 or /all, and if both m and n are zero, fl, R2 and R
When both of 3 are unsubstituted alkyl groups, R2
and R3 have a total number of carbon atoms of 3 or more, or R1 is substituted or Vf, unsubstituted aryl or heterocyclic group
.

In the general formula [IJ, R2 and R31d may be nonmetallic atoms (group) that combine with each other to form a 7-membered ring.

In general formula (I), R and R3 are preferably substituted or unsubstituted alkyl or aryl groups.

In general formula (1), R2 is preferably a substituted or unsubstituted alkyl group.

In the general formula [I′J(・, preferable Z is a hydrogen atom,・
- Preferred are rogene atom (of which fluorine atom and chlorine atom are preferred), alkoxy group, aryloxy group, sulfonamide group, acyloxy group, and alkoxycarbonyloxy group.

In the general formula (13), preferred is nnO, and preferred is 0.

In the general formula [IJ, RzH-substituted alkyl group or alkyl having 2 or more carbon atoms is particularly preferable, and the substituent in this case is preferably an alkylthio group, an arylthio group, an alkyloxy group, an aryloxy group, or an acylamino group.

In general formula (I), R2 and R3g are also preferably nonmetallic atoms (group) that combine with each other to form a 7-membered ring.

Next, cyan couplers included in the present invention will be specifically listed, but the present invention is not limited thereto.

α 0CH2CH2CH2COOH α Next, an example of coupler synthesis will be shown.

Synthesis example O-(α-(21 μm di-tert-amylphenoxy)-butanoylamino)-λ-butanoylamino-
Chloro-3-methylphenol (exemplary coupler (1))
1) Synthesis of 2-amino-≠-chloro-3-methylphenol Non-nitro-terchloro-3-methylphenol 37.
! GFZ water, 200 rnl, and methanol 20 ml were dispersed, and while heating and stirring on a steam path, hydrosulfite toner 7011f was gradually added. After heating and stirring for about 30 minutes, it was cooled to room temperature, the precipitated crystals were filtered, and dried.
-Methylphenol (pale yellow crystals) 2jfi was obtained.

2) Synthesis of 2-butanoylamino-≠-chloro-3-methylphenol λ-amino-chloro-3-methylphenol, 2
The mixture was heated and dissolved in 100 ml of 0gf acetonitrile, and butanoyl chloride/4tgf was added dropwise while heating under reflux on a steam path. After dropping, the mixture was refluxed for 30 minutes, cooled to room temperature, poured into 300 ml of water, and all precipitated crystals were collected by filtration. The crude crystals were recrystallized from acetonitrile to give 2-butanoylamino-Hiro-chloro-3-methylphenol (white 1fls crystals) 23 .

7g was obtained.

3), 2-Butanoylamino-≠-chloro-3-methyl-t-nitrophenol synthesis λ-butanoylamino-Hiro-chloro-3-methylph
23 ji 'f, dissolved in 70 ml of acetic anhydride, water-cooled ''F (0~j0C), acetic acid, nitric acid (d=/.

0) 7ml of the mixed solution was slowly added dropwise - then stirred at r'C for 30 minutes. The reaction mixture was poured into ice water, and the precipitated crystals were collected by filtration and dried to obtain coptanoylamino-v-rero-3-methyl-6-nitrophenol (yellow crystals) 211, J'gf.

4) -Amino-λ-butanoylamino-chloro-
3-Methylphenol Synthesis λ-Butanoylano<<-Chloro-3-methyl-t
- Nitrophenol 2179 in water, zooml.

Disperse in 20 ml of methanol and add 100 ml of hydrosulfide soda while heating and stirring on a steam path.
f was added gradually. After heating and stirring for about 30 minutes, it was cooled to room temperature, and the precipitated crystals were filtered and dried.
-Methylphenol/A, ≠g was obtained.

5) Synthesis of coupler (1) t-Amino-λ-butanoylamino-Hiro-chloro-3-
Methylphenol/Jj; if acetonitrile AOml
, dissolved in dimethylacetamide 4d and heated under reflux, α
-(λ,≠-di-tert-amylphenoxy)-butanoyl chloride 2≠,♂I was added dropwise, and then further,
Reflux was performed for 7 hours. After the reaction was completed, the mixture was extracted with ethyl acetate, washed with water, dried (anhydrous sodium sulfate), and concentrated.

The resulting residue was recrystallized from total acetonitrile to give 4-(α-
(K, Hiroshi-ter t-amylphenoxy)-butanoylamino)-λ-butanoylamino-chloro-
Obtained 2tg (white crystals) of 3-methylphenol (Carl-1-Ra-(11)).Melting point /36~/31C Elemental analysis results (204α to C31H45) (in percent) Calculated value C: t1.30 H:I, 32 N:
! . /41 Actual value C: l, 1.3za H:,! ',≠O
N:! . Other couplers can be similarly synthesized.

The coupler of the present invention can be introduced into the silver halide emulsion layer by a known method. At that time, couplers, solvents, ultraviolet absorbers, protective colloids, which can be introduced together with the couplers of the present invention,
Binders, antifoggants, color mixing inhibitors, antifading agents, sensitizing dyes, dyes, bleaching agents, etc., as well as methods for forming silver halide photosensitive materials (methods for forming photographic emulsions, methods for introducing couplers, etc., support) i'L Re5earch Disclos
ure, /ri71r/February, item/7A It
3 (Industrial Opportunity
s Ltd,, UK)% Tokukaisho! It is possible to use the substances and methods described in No. 6-tj/3 Hiroshi and Japanese Patent Application Laid-open No. 333/1999, or in the cited documents.

The amount of the coupler of the present invention added is generally from 1 x 10 -3 mol to 7 x 10 1 mol per mol of silver in the emulsion layer, preferably from 1 x 10 mol to 7 x 10 mol! X10 is 1 mole.

Couplers that can be used in the present invention will be explained in more detail.

A typical example of a yellow coupler is U.S. Patent U, 17
No. 1.037, No. 2,1107.2 IO, No. 3. λt
T, to4 issue, 21.22.

Hiro 4I3, 3.0 Hiroza, / Rihiro, 31μ≠7.
2.2 is described in the number etc. Among these yellow couplers, acylacetamide derivatives such as benzoylacetanilide and piparoylacetanilide are preferred.

As a yellow coupler, the following general formula [11] is also used,
Z' represents a hydrogen atom or a coupling-off fund. (
Below is the general formula (same up to XJ).

Here, R11u represents the diffusion resistance with a total carbon number of g to 32, and R12fl-j: hydrogen atom, 1 or more halogen atoms, lower alkyl group, lower alkoxy group, or resistance with a total carbon number of t to 3λ. Represents a diffusible group. When there are two or more R12's, they may be the same or different.

A typical example of a magenta coupler is the US patent λ.

No. 1.00,711, No. 2,362. μr issue, same, 2
．． 3≠3.703, 2,3//, 012, 3.
/! λ, number t, same 3. Yorori, ≠λ, same 3. O
62,t! No. 3, same 2. It is described in RiOza, No. 573, etc. In addition to this, as a magenta coupler,
7-33g! Issue, special request! The arylthio group-eliminating pyrazolone magenta couplers described in I-/103?4, Oyo and Id. (
/, 2-b3 pyrazoles, /H-pyrazolo (/, j-
b3 pyrazoles, Research Disclosure 24
/H-pyrazolo(/, t-dJ Tetrazoles, /H-pyrazolo('r' CJ ('r,
2+Hiro] Triazoles and patent application Shojza-/3131
/H-pyrazoloCi, z-b) (1, z
, G] Pyrazoloazole magenta couplers such as triazoles can also be preferably used in the present invention.

Therefore, magenta coupler ([I]) (!:L”C
are preferably represented by the following general formulas (IV), (V) and (Vl).

R14 7, / \-person Here, R13U represents all diffusion-resistant groups with a total carbon number of lr to 32, R14 C, l or more...rogen atom, lower alkyl group, lower alkoxy group, phenyl group, or represents a substituted phenyl group. A represents a group of non-metallic atoms necessary to form a 5-membered azole ring containing λ~g nitrogen atoms, and the azole ring is a substituent (fused ring).
It may have.

In addition to the cyan coupler of the present invention, other known cyan couplers can be used in combination. Typical examples of such cyan couplers are U.S. Pat.
2. ♂2ta, 12otsu, 3゜OQ2. lr3 No. 3.03≠, r9.2 No. 2, Hiroshi 74', Jri No. 3,
Same No. 13,730, Same Ko, JA7 No. 531,
and 3.0μ/.

, 23, etc. Among these cyan couplers, phenols and naphthols are preferred.

Therefore, as the cyan coupler (Cp), those represented by the following general formulas [■], [■], (IX'J and [XJ) are suitable.

H H 2' H 4' H 2' Here, R15 represents a substituent having 3 or more carbon atoms in total and may have diffusion resistance. It represents a lower alkyl group or a lower alkoxy group, and when there are two or more R15 or R16 in the molecule, they may be the same or different.

Particularly preferred couplers for use in combination with the coupler of the present invention and other cyan couplers include those represented by the following general formula [AJ].

H In the formula, R17 and RBU represent an aliphatic group, an aryl group or a heterocyclic group, each of which is substituted or unsubstituted. R191'ff represents a hydrogen atom, a rogen atom, an alkyl group, or an azilamino group, and R19 is 11
8 along with nitrogen! Alternatively, a group of nonmetallic atoms forming a t-membered ring may be formed.

Z' represents a hydrogen atom or a fund that can be separated during an oxidative coupling reaction with a developing agent. neo or /.

The above-mentioned "aliphatic group" includes saturated and unsaturated groups such as alkyl, alkenyl, and alkynyl groups, including any of straight-chain, branched, or cyclic groups.

Specific examples of the coupler represented by the general formula [A] include Japanese Patent Application 'd (91-, 20113, No. 2, 61-4.2 & 7).
/ issue and same! Also included are the compounds described in No. 1-/33) No. 23. Typical examples of the general formula (AJ) are shown below, but the invention is not limited thereto.

(A-/] [8-2] [A-j) i-C5H11 (A=73 [A-ta] (A-15 [8-/za') CH3 [A-/ri] [A-λO] ( A-, 2/J [A-λλ] α [:A-, 23] (A, -21A] α (A-, 2, 4) (A-, 27) t-C5H1゜t-CgH17 0-t -C4H9 In order to introduce the cyan coupler of the present invention or magenta and yellow couplers to be used in combination into the emulsion layer, for example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, +1 phenyl phosphate, etc.), phate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), phenols (
For example, high boiling point organic solvents with boiling point/AO0C or higher such as λ,≠-di(1)amylphenol), lower alkyl acetates such as ethyl acetate, butyl acetate, 70 ethyl pionate, secondary butyl alcohol, methyl in butyl ketone , β-Etogyokudiethyl acetate Methylseronlube acetate, etc., a low boiling point organic solvent with a boiling point of 300c~/jO0C is used alone or in combination as necessary, and then dissolved, and then emulsified and dispersed in an aqueous hydrophilic colloid solution in advance. It is preferable.

The photosensitive material of the present invention may contain a special casoler 't- other than the coupler of the present invention represented by the above general formula, if necessary. For example, in the green-sensitive emulsion layer,
A colored magenta coupler can be included to provide a masking effect. In addition, a development inhibitor-releasing coupler (DI
R coupler), development inhibitor releasing hydroquinone, etc. can all be used in combination. The development inhibitor released from these compounds during development brings about interlayer effects such as improving the sharpness of the image, making the image finer, and increasing the monochromatic saturation.

In the photographic emulsion layer of the present invention or its adjacent layer, a coupler that releases a development accelerator or a nucleating agent upon silver development is added to improve photographic sensitivity, improve graininess of color images, and improve gradation. It is also possible to obtain effects such as increasing the tone.

The present invention can be used for general silver halide color photosensitive materials such as color negative film, color pano ξ-, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, etc. It is especially suitable for use in color negative films and various color reversal films that require high sensitivity and high image quality. It can also be used on colored paper.

In the conventional light-sensitive material layer structure of color paper, any one of the layers on both sides adjacent to the red-sensitive emulsion layer containing the cyan coupler, preferably both layers, entirely contains the ultraviolet absorber. When an ultraviolet absorber is added to the intermediate layer between the green interlayer and the red-sensitive layer, it may be co-emulsified with a color mixing inhibitor. When a UV absorber is added to the protective layer, another protective layer may be applied as the outermost layer. This protective layer can contain a matting agent of any particle size.

The above-mentioned ultraviolet absorber, like the coupler, is dissolved in a single or mixed solvent of a high boiling point organic solvent and a low boiling point organic solvent, and is dispersed in a hydrophilic colloid.

Although there are no particular limitations on the amounts of the high-boiling organic solvent and the ultraviolet absorber, the high-boiling organic solvent is usually used in an amount of 0.4 to 300% based on the weight of the ultraviolet absorber.

It is preferable to use compounds that are liquid at room temperature alone or in combination.

When the above-mentioned benzotriazole ultraviolet absorber is used in combination with the coupler combination of the present invention, it is possible to improve the storage stability, especially the light fastness, of chromophore images, especially cyan images. This ultraviolet absorber and cyan coupler may be co-emulsified.

The amount of ultraviolet absorber applied should be sufficient to impart photostability to the cyan dye image, but if too much is used, it may cause yellowing of the unexposed areas (white areas) of the color photographic light-sensitive material. Therefore, it is usually preferable to use 17/X/0
'-E nyl/m2-2 x 10-3 mol/m2, especially t
xio 'mol/m2~/.

! ×10 moles/77! It is set in the range of .

In order to improve the storage stability of chromophore images, especially yellow and magenta images, various organic and metal complex fading inhibitors can be used in combination. Organic anti-fading agents include hydroquinones, gallic acid derivatives, p-
There are alkoxyphenols, p-oxyphenols, etc., and patents for dye image stabilizers, stain inhibitors, and antioxidants are cited in Research Disclosure/7A Hiro J. Further, metal complex-based antifading agents are described in Research Disclosure/J/12 and the like.

In order to improve the heat and light fastness of yellow images, polyamides belonging to the group of phenols, hydroquinones, hydroxychromans, hydroxycoumarans, hindered amines and their alkyl ether, silyl ether or hydrolyzable precursor derivatives are added. Compounds of (can be used).

Various silver halides can be used in the silver halide emulsion layer of the color photographic light-sensitive material according to the present invention. Examples include silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Silver iodobromide containing silver iodide in an amount of 0 to 20 moles, and silver chlorobromide containing silver bromide in an IO to 0 mole ratio are preferred. ...There are no limitations on the crystal form, crystal structure, grain size, grain size distribution, etc. of the silver halide grains. ...A silver halide crystal may be a normal crystal or a twin crystal, and may be hexahedral, octahedral, or /<<hedral. The grains may be tabular grains having a thickness of 06S microns or less, a small diameter (both o' and t microns, and an average aspect ratio of 5 or more) as described in Research Disclosure 22j3μ.

The crystal structure may be uniform, or the inside and outside may have different compositions (or may have a layered structure, or the composition may differ due to epitaxial bonding) ~ Even if silver halide is bonded. (The latent image may be composed of a mixture of particles of various crystal forms. Also, the latent image may be formed mainly on the surface of the particle or may be formed inside the particle.

Grain size of silver halide f-1,0. The emulsion may be fine particles with a diameter of /ζ゛ron or less or dog-sized particles with a projected area diameter of up to 3 microns, a monodisperse emulsion with a narrow distribution, or a polydisperse emulsion with a wide distribution.

These silver halide grains can be produced by known methods commonly used in the art.

The above silver halide emulsion can be sensitized by conventional chemical sensitization, ie, sulfur sensitization, noble metal sensitization, or a combination thereof. Furthermore, the silver halide emulsion according to the present invention can be imparted with color sensitivity in a desired wavelength range by using a sensitizing dye. Dyes that can be advantageously used in the present invention include methine dyes and styryl dyes such as cyanine, hemicyanine, logocyanine, merocyanine, oxonol, and hemioxonol, which will be detailed later. The above can be used in combination.

The support used in the present invention is polyethylene tele7
Any of the transparent supports such as L/-t or cellulose triacetate and the reflective supports described below may be used. Reflective supports are more preferred, such as baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyethylene terephthalate, and cellulose triacetate. There are polyester films such as cellulose, polyamide films, polycarbonate films, polystyrene films, etc., and these supports can be appropriately selected depending on the purpose of use.

The blue-sensitive, green-sensitive and red-sensitive emulsions of the present invention are spectrally sensitized with methine dyes and others so that they have color sensitivity. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

In addition to the above-mentioned constituent layers of the color photographic light-sensitive material of the present invention, auxiliary layers such as an undercoat layer, an intermediate layer, and a protective layer may be provided. Further, if necessary, a λ-th ultraviolet absorbing layer may be provided between the red-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer. Although it is preferable to use the above-mentioned ultraviolet absorber for this ultraviolet absorbing layer VC, other known ultraviolet absorbers may also be used.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, white matter such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly(+)-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl pyrrolidone
/L/ (Can be used on a variety of synthetic hydrophilic polymeric materials such as single or copolymers of midazole, polyvinylpyrazole, etc.).

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, and Phot.

Enzyme-treated gelatin as described in Japan, A6/A, p. 30 (/ri 66) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

In the photographic material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. These brighteners may be water-soluble, or water-insoluble brighteners may be used in the form of a dispersion. Specific examples of fluorescent brighteners are given in U.S. Patent λ.

1.32.70/issue, 3.2t9. l1tO No. 3
．． 3jri, No. 102, British patent? No. 62,073, same/
, 3/ri, No. 763, Research Disclos
ure / 76 volumes / 71, 1A3 ( / 7g year / 2
Monthly issue) ≠ Brighten on the left column of the page ~ line 3
It is described in the description of ers, etc.

In the photographic material of the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like. For example, British Patent No. 7j, U.S. Patent No. 476, J
/4 issue, same co, 13ri, 4AO/ issue, same x, rrx, i
rt, 3101tr, ur7, 3. /za44
, No. 309, No. 3, Li'A, No. 231, West German Patent Application (Of, S)/, Lilμ, No. 3, JP-A-ShojtO-
Polymers described in Hiroshi 7t Cori No., Hiroshi Ta 0-7/332, etc. can be used.

The photosensitive material of the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid enzyme derivative, etc. as a color antifogging agent. No. J, 33
4,32.7, 2゜1IO3, 72/No. s, a
ir, t, i3, same, 2. t7j, 3/11. No. λ, 701. /ri No. 7, 2,701/-, 7/3 No.
2,72Ir, No. 66, same, No. 732,300,
Same +2,73j,7t! No., Japanese Patent Publication No. Jθ-Tako 2gt, No. J'O-Ta λ Rizari, No. j0-23 λ, No. J0-/10337, No. jλ-/$12jj, No. J'O -I Jza No. 73, etc.

In addition to the above, the color photographic material of the present invention may contain various photographic additives known in this field, such as stabilizers, antifoggants, surfactants, couplers other than those of the present invention, filter dyes, and irradiation preventive agents. Dyes and developing agents can be added as necessary, examples of which are described in Research Disclosure 17Aμ3VC.

Furthermore, depending on the case, fine particles having substantially no photosensitivity may be present in the silver halide emulsion layer or other hydrophilic colloid layer.
- A silver halide emulsion (for example, a silver chloride, silver bromide, or silver chlorobromide emulsion with an average grain size of 0.20 μm or less) may be added.

The color developing solution that can be used in the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As a color developing agent, q-amino-N, N-diethylaniline, 3-methyl-44-N,
N-diethylaniline, ≠-aminohethyl β-hydroxyethylaniline, 3-methyl-≠-aminohethyl β-hydroxyethylaniline, 3
Typical examples include -Menal-Hiro-Amino-H-Ethyl-H-β-methanesulfonamidoethylaniline, and Hiroshi-Amino-3-methyl-N-ethyl-N-β-methoxyethylaniline.

The color developing solution contains pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, and development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. can be included. Also, if necessary,
Water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol,
Development accelerators such as polyethylene glycols, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron octide, /
- Auxiliary phenomena such as phenyl-3-pyrazolidone, viscosity imparting agents, polycarboxylic acid chelating agents described in U.S. Pat.
22. It may also contain an antioxidant described in No. J-0.

The photographic emulsifier layer of the color developer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (■), cobalt (■), chromium (Vl), and copper (II), peracids, quinones, and nitrone compounds. For example, ferricyanide, dichromate,
organic complex salts of iron (III) or copal) (III);
For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid,
7. Ai such as 3-diamino-2-propatoltetraacetic acid
Complex salts of noboricarboxylic acids or organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates; nitronephenol, and the like can be used. Among these, potassium ferricyanide, iron ethylenediaminetetraacetate (
[1) Sodium and iron ethylenediaminetetraacetate (■)
Ammonium is particularly useful and the 6° ethylenediaminetetraacetic acid iron (III) i14 salt is useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

It may be washed with water after color development or bleach-fixing treatment.

Color development can be carried out at any temperature between troc and 5z0c. Preferably 1jJO'c or more, particularly preferably j
Color development is performed at j'c or higher.

The development time is preferably as short as about 3 minutes to about 1 minute. Liquid replenishment is preferable for continuous development processing, and 330CC to i(, oaa
, preferably less than 1 ooca. Benzyl alcohol Bzmt in the developer is preferably 71 or less.

The bleaching process can be carried out at any temperature from /1r0C to ro0C, but preferably 300C or higher. When the temperature is 3j0C or more, the processing time can be reduced to 7 minutes or less, and the amount of liquid replenishment can be reduced. The time required for washing with water after color development and bright white fixing is usually within 3 minutes, and a stabilizing bath can also be used to make the washing substantially waterless.

Colored pigments not only deteriorate due to light, heat, or temperature, but also deteriorate and fade due to mold during storage. It is preferable to use an anti-mold agent, especially since the deterioration caused by mold is very serious in the case of cylindrical color images. Specific examples of antifungal agents are disclosed in JP-A No. 3-7-/17λ
There are corchiazolylbenzimidazoles as described in μ≠. The antifungal agent may be incorporated into the photosensitive material (or may be added externally during the development process, or may be added at any step if the processing agent coexists with the photosensitive material).

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto.

EXAMPLE Coupler according to the invention (1) 10I, trioctyl phosphate 10fl and ethyl acetate 20ml 1fj00C
10 g of gelatin and 0.0 g of dodecylbenzenesulfonic acid. The mixture was added to 100 of an aqueous solution containing 1 g, stirred, and then preheated and passed through a colloid mill 5 times to emulsify and disperse finely.

Add all of this emulsion to 27 g of silver chlorobromide and gelatin.
and μ as a hardening agent.
After adding , t-dichloroμm bitroxytriazine, 2% aqueous solution JOml, the turbidity (7>pH was adjusted to 4.o and then uniformly coated on a triacetic acid fiber-based film base. Let's call it sample A.

In place of the above coupler (1), the same molar coupler (3),
(j), (/ri), the film is t by the same operation.
I did i14N. These are designated as samples B%C and D, respectively.

For comparison, films were prepared by the same procedure using the same mole of comparative couplers (10/N, (102), (103)) in place of coupler (1). do.

<ioυ Cs Hll(t) (103) U.S. Patent No. 3. Coupler α cited in Tata F, No. 444λ These samples were exposed using a continuous wedge for sensitometry and then subjected to the following color development process.

Color development processing process (33°C) 1. Color development 3 minutes 30 seconds λ, bleach fixing 1 minute 30 seconds 3
, water washing 2 minutes 30 seconds The treatment steps used in each step are as follows.

Color developer benzyl alcohol /! , 0ml
Diethylene glycol 1.0tnl ethylenediamine 4A acetic acid s, og sodium sulfite ko, og anhydrous potassium carbonate
30fl Hydroxylamine sulfate 3,09 Potassium bromide o, +g≠-amino-N-ethyl-N~ (β-methanesulfonamidoethyl)-m-toluidine sesquisulfate monohydrate j, 0g Add water /1 (pH 1O02 ) Bleach-fix solution ethylenediamine≠acetic acid <<, og ethylenediamine chloride acetic acid ferric salt 4top sodium sulfite! , θy sodium thiosulfate (
70%) /JO1d Add water
71 Next, each developed film was tested for fastness. When the sample was left in the dark at 1000C for 6 days, when the sample was left in the dark at 1000C for 6 weeks, and when the sample was left in the dark at
When exposed to light for t days at 10,000 lux), the fastness of each material was shown in Table 1 as initial density/, density reduction rate at 0.

It is clearly seen from Table 1 that the couplers of the present invention have excellent heat, moist heat and light fastness properties.

Table 2 tert-pentyloxy)butanamide]acetanilide (1υ solvent dioctylbutyl phosphate Example
A glass photographic light-sensitive material (Sample H) was prepared by sequentially coating the following layers from the first layer (bottom layer) to the seventh layer (top layer) on a paper support laminated on both sides with 2° polyethylene. (Table 2: Indicates the coating amount of rn9/rrL2 in the table) Cyan coupler (
$3) Sample ① was prepared in the same manner as Sample H except that ffi was replaced with the coupler of the present invention.

After giving each sample a red light exposure through a continuous wedge,
Development processing was performed using the following processing steps.

Treatment Step (33°C) The components of each treatment step are as follows.゛Color developer benzyl alcohol l! d diethylene glycol 3ml potassium carbonate
, 2j9 sodium chloride
θ, /I sodium bromide
o, sg anhydrous sodium sulfite
2g Hydroxylamine fm acid salt-2j; 1-h-ethyl-N-β-methanesulfonamidoethyl-3-methyl-aminoaniline sulfate ≠g Water is added to adjust to /l and NaOHf is added to adjust the pH to 10.

Bleach-fixing solution Ammonium thiosulfate /, 2≠, jg Sodium metabisulfite / 3.3ji Anhydrous sodium sulfite J, 7g EDTA ferric ammonium salt tsg Add water to lr to pH 6, l
Adjust to r.

The robustness of the samples after treatment was tested. Sample 2ioo
When left in the dark at 0c for 0 and μ days, toOc,
Table 3 shows the concentration reduction rate at the initial concentration /, 0 when left in a dark place at 70% RH for 7 and t weeks, and when exposed to light for 1 and 2 days using a xenon tester (10,000 lux). show.

Table 3 shows that the color images obtained from the couplers of the present invention have excellent fastness to light, heat, and moist heat.

Patent applicant: Fuji Photo Film Co., Ltd. Showa! October/f3rd

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material containing at least one cyan dye-forming coupler represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, R_1 and R_3 independently represent a substituted or unsubstituted aliphatic, aryl, or heterocyclic group, and R_
2 represents a substituted or unsubstituted aliphatic or alkoxy group, Z represents a hydrogen atom or a group that can be separated during an oxidative coupling reaction with a developing agent, and the above aliphatic group may be linear or branched. Alternatively, it may be cyclic, saturated or unsaturated, and m and n each represent 0 or 1 (provided that when m and n are both zero and R_2 and R_3 are unsubstituted alkyl) , the total number of carbon atoms is 3 or more, or R_1 represents a substituted or unsubstituted aryl or heterocyclic group), R_2
and R_3 may be a nonmetallic atom (group) that together form a 5- to 7-membered ring. ]