JPS612151A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the light fastness and heat fastness of yellow color picture image by incorporating a specified phenolic compd. to a layer contg. a yellow coupler having an N-phenylcarbamoyl group, or to an adjacent layer. CONSTITUTION:The yellow coupler expressed by formula I (wherein R1 is an N- phenylcarbamoyl group; R2 is 4-20C tertiary alkyl, or phenyl; X1 is a group eliminable in the stage of coupling reaction with an oxidized body of a developing agent) such as a compd. expressed by formula II or III, is incorporated into a silver halide emulsion layer. Further, a compd. expressed by formula IV(wherein R19 and R20 are tertiary alkyl; R21 is an alkyl) specifically a compd. expressed by formula V and VI, is incorporated into a layer contg. the yellow coupler or into an adjacent layer to prevent discoloration of yellow picture image. Further, the amt. of the compd. IV to be used in usually 0.5-200wt% basing on the amt. of the coupler.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a silver halide photographic light-sensitive material, and particularly to a silver halide color photographic light-sensitive material in which fading of yellow images (IJs) is prevented. It is.

(Prior Art) Generally, the quality of photographic slag obtained from silver halide photographic light-sensitive materials is not permanent, and deteriorates over time during storage. In particular, azomethine dyes formed by the reaction of aromatic primary amine developing agent brews with casolers,
Or, if a color photograph with an image composed of indoor dyes is exposed to light for a long period of time or stored under high temperature and high humidity, the dye image may fade or discolor, and even the white background may become discolored (yellow stain). It is normal for this to occur, resulting in deterioration of image quality.

Such deterioration in image quality is a fatal drawback for recording materials, and improvements are desired.

On the other hand, color photography generally uses cyan, magenta, and yellow dye images, and among these dyes, magenta dye is the weakest to light, followed by yellow dye.

Among these three types of dyes, cyan dye is the strongest. Hitherto, various studies have been conducted to improve the fastness of magenta dye, which is the most vulnerable to light trapping, and it has become possible to make it fast to a considerable level. For this reason, the fading of the yellow dye has become noticeable. However, the reality is that almost no research has been conducted on fastening to yellow dyes.

A method of using antifading agents to improve the light and heat fastness of yellow images is known, and hindered amines and phenols have been used in British Patent No. 13, No. 13/JJg313, and No. Ke1074 Yumi No., U.S. Patent No. 3334133, U.S. Patent No. 2trs23, Special Publication No. 417-J/Koj6, U.S. Patent No. 3
1-/≠20, same jλ-6623, JP-A-Sho, tir
-ii MiG 03, same j? -j4 (proposed in No. 26) Although these compounds do have the effect of improving the light and heat fastness of yellow dyes, the effect may be small or may have other properties (for example, changes in hue, occurrence of fog, precipitation in the coating film, gradation change of the sensitive material, etc.)
It may even make things worse.

On the other hand, various additives have been proposed to improve the fastness of magenta dyes, but although these compounds are certainly effective in fastening magenta dyes, they have little effect on yellow dyes. There are some that do not show this effect and, on the contrary, promote discoloration.

(Object of the Invention) Therefore, the first object of the present invention is to provide a silver halide color photographic light-sensitive material 1 in which the fastness of a yellow dye image is improved.

A second object of the present invention is to incorporate a stabilizer into a photographic layer that is sufficiently effective in improving the fastness of yellow dye images without causing any change in hue, formation of fog, poor dispersion, or crystallization. The object of the present invention is to provide a silver halide color photographic material in which a yellow image is stabilized.

A third object of the present invention is to provide a color photographic material in which the color balance of the three fading colors is improved by improving the light and heat fastness of the yellow dye image.

(Structure of the Invention) As a result of various studies, the present inventors have found that at least one of the layers containing at least one yellow coupler represented by the following general formula (I) or its adjacent layer has the following general formula (
It has been found that the five objects of the present invention can be achieved by containing at least one of the compounds represented by II).

General formula (I) R2-COC)1-R1 In the formula, R1 represents a substituted or unsubstituted N-phenylcarbamoyl group. R2 represents a tertiary alkyl group having from -0 carbon atoms or a substituted or unsubstituted phenyl group. Xl represents a group that can be separated during the coupling reaction with the oxidized form of the developing agent. R1b R2 or X may form a comer or higher multimer.

General formula (n) R21 In the formula, bR19 and R20 each represent a tertiary alkyl group, and R21 represents an alkyl group.

To describe the yellow coupler represented by general formula (I) in more detail, the substituent for R1 (N-phenylcarbamoyl group) includes substituents well known in yellow couplers, such as an alkyl group, an alkenyl group, an alkoxy group, and an alkoxycarbonyl group. group, halogen atom, alkoxycarbamoyl group, aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group, alkylureido group.

Alkyl-substituted succinimide group, aryloxy group, carbonyl group, arylcarbamoyl group, arylamide group, arylsulfamoyl group, arylsulfonamide group, arylureido group, carboxy group, sulfo group, nitro group , cyan group, thiocyano group, etc., there may be two or more substituents, and in that case, they may be the same or different from each other.

The tertiary alkyl group having μ to λO carbon atoms in R2 is.

For example, t-butyl group, t-amyl group, t-octyl group%
/,/-diethylpropyl group % 1.1-dimethylhexyl group, 1,1,3.3-tetramethelhexyl group,
are listed as representative examples. Representative examples of the substituent for the substituted phenyl group of R2 include the substituents shown for R1.

The coupling-off group of Xl may be a hydrogen atom, but preferably a coupling-off group forming a λ-equivalent yellow coupler, such as the following general formulas [III], [IV),
Represents a group represented by (V) or [■].

0R16 [111] R represents an aryl group or a heterocyclic group which may be substituted with 16 digits.

R17 and RlB are each a hydrogen atom, a hydrogen atom, a carboxylic acid ester group, an amine group, and an alkyl group.

It represents an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl group, or a multiple ring, and these groups may be the same or different.

Represents a nonmetallic atom required to form a ring or a t-membered ring.

A preferred yellow coupler for use in the present invention is represented by the following general formula [■].

In the formula, R3 represents a tertiary alkyl group having q to l carbon atoms, a phenyl group substituted with a halogen atom, an alkyl group, or an alkoxy group, or an unsubstituted phenyl group. R4 represents a halogen atom or an alkoxy group. R5 represents a hydrogen atom, a halogen atom, or an alkoxy group which may have a substituent.

R6 is an anrulamino group, an alkoxycarbonyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an alkylsulfonamide group, an arylsulfonamide group, an alkylureido group, which may have a substituent, or an alkyl ureido group.
Represents a roureido group, succinimide group, alkoxy group, or aryloxy group.

X2 is the following general formula [■] [■] [X) or [XT
') represents a group.

In the formula, R7 represents a substituted or unsubstituted alkylsulfonyl group, arylsulfonyl group, acyl group, hydroxy group, or a substituent represented by R1 above. t is 2.3%
μ or j, and when t is 3 or more, %R7 may be the same or different.

R9ru10 In the formula, s n8. R9 each represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydroxy group. R10h Rl 1 and 1 (tz each represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or an acyl group. W2 represents an oxygen or sulfur atom.

A particularly preferred yellow coupler used in the present invention is represented by the following general formula [■].

General formula [■] In the formula, R13 represents an alkyl group or a phenyl group which may have a substituent. X3 is represented by the following general formula (XIIT
) or the general formula (IX) [X) or [
■] represents.

In the formula, %R14 represents a hydrogen atom, a halogen atom, a cyano group, an optionally substituted acylamino group, an alkyl or arylsulfamoyl group, or an alkyl or arylsulfonyl group.

R15 represents a hydrogen atom, a cyan group, an optionally substituted alkyl or arylsulfonyl group, an alkyl or arylsulfamoyl group, an alkyl or arylsulfonamido group, an acyl group, an alkyl or aryloxycarbonyl group, or a carboxy group, and R14,
Of R15, at least /a represents an optionally substituted alkyl or arylsulfonyl group, an alkyl or arylsulfamoyl group, an alkyl or arylsulfonamido group, an alkyl or aryloxycarbonyl group, or a carboxy group.

Specific examples of the yellow coupler represented by the general formula (I) used in the present invention are shown below, but are not limited thereto.

H (Y-2) (Y-,?1 H (Y-μ) (Y-, t) H (Y-11 fY-7) (yr) (Y-ta) H (Y-//) l (Y-/ ko) (Y-/3) (Y-/g) (Y-zjl H3 (Y-/, 61 (Y-/7) (JH (Y-7g) (Y-/ ta) H SO2C)-13 (Y-,zO) (Y-,2/ I H H3 (Y-22) (Y-23) (Y-koj) 0OH (Y-,2&) (Y-27) (Y- ,2f) HCOOH Cl2l-125 (Y-!ri) (Y,?(7) (Y-J/) (Y-,?,2) (Y-,?J) H (Y-3μ) C/ CH3 -C-Tian CH2CH20C2H5 ('f-Js) CH3-C-NH CH3 (¥-36) C/ H (J)OCH3 UOH " CH3 (Y-≠≠) (Y-Hiroj) (¥-g6) (Y-Gua) (Y-Hir) (Y-4'ri) (Y-jO) S02 H (Y-j/] N (Y-j)) c7! H (Y-s3) α -56- (i) These yellow couplers are, for example,
No. 13, same-t/-J J 4t/ No. 0, same ji
-, 2j 7 J,,, No. 2, JP-A-4T7-. 2A
/33, 1it-7J/@7, ti-ioa
Number Otsu 3.

Same j O-/-? θ1- issue, same! 0-1s3111,
Same, tQ-/ 2 J J 4I: +2, same 3t-+
zll+No.27.

3O-17t30, 3.2-12M211.

Same J Co. 113 Coll., British Patent/No. 4t2j010, West German Patent/J≠7161, West German Application Publication, 2. ! /
No. 2917, same λ coro 73I! l1 No. 2 Hiroshi/goo
It can be synthesized according to the method described in No. t.

Next, a typical synthesis example of the yellow coupler used in the present invention will be shown.

Synthesis of Exemplary Couplers (Y-j) α-Chloro-α-hibaloyl-λ-chloroj-(n-
hexadecanosulfonamide) acetanilide 4'4'
S', j, J'-dichloro-≠, y'-dihydroxydiphenylsulfone ti2Yf')) tylacetamide λ
It was dissolved in μOCC and acetonitrile-21θd under reflux.

2.7 cc of triethylamine was slowly added dropwise to the mixture, followed by reaction under reflux for 5 hours.

Reaction mixture tj% hydroxide) IJum solution j.

0 ml and extracted with ethyl acetate J 00 ml.

The oil layer 'f was washed with water λ times, dried over magnesium sulfate, and concentrated under reduced pressure to obtain a residue 607.

The residue was subjected to silica gel chromatography, the part containing the product was concentrated under reduced pressure, and the residue was chromatographed with n-hexane/
Crystallization from ethanol (I0/l volume ratio) gave an exemplary coupler (Y-j) 2asy (melting point 7-23°C).

Representative examples of the compound represented by the general formula (III) of the present invention are shown below, but the compounds are not limited thereto.

CH3 OH OH OH OH OH QCs H1y(n) C2H5 OH OH OH OH OH OH OH OH C2H5 Among the compounds represented by general formula (II), R19゜R2
A compound in which the total number of carbon atoms in the alkyl groups of 0 and R21 is 10 or more is particularly preferred in terms of the effects of the present invention.

These compounds represented by general formula (n) are disclosed in British Patent 2
066ri7s (A) No., US Patent Hong Jl! ',! ′μ
A combination with a magenta coupler is known for the θμ issue.

As mentioned above, a material that exhibits an excellent fading prevention effect for a magenta color image r# does not necessarily have an excellent fading prevention effect for a yellow color image.

The compound represented by the general formula (TI) of the present invention showed an excellent effect on light and heat fastness with respect to the yellow coupler of the general formula (II) used in combination.

Although the compound used in the present invention varies depending on the type of coupler used in combination, it is appropriate to use the compound in an amount of 01-200% by weight, preferably 1 to 130% by weight, based on the coupler. If it is less than this range, the fading prevention effect is extremely small and is not suitable for practical use. Moreover, if it is too large, the progress of development will be inhibited.

This may cause a decrease in color density.

The compounds used in the present invention may be used alone or in combination of two or more. Moreover, it can also be used in combination with a known anti-fading agent.

The compound of the general formula (TI) used in the present invention is the compound of the general formula (I
) has excellent anti-fading effect when co-emulsified with yellow coupler.

In addition to the yellow coupler, the following magenta and cyan couplers can be used in the present invention to produce a color photographic material.

Magenta coloring couplers include pyrazolone compounds,
Indacylon compounds, cyanoacetyl compounds, pyrazolotriazole compounds, etc. can be used, and pyrazolone compounds are particularly advantageous. Specific examples of magenta color-forming couplers that can be used include U.S. Patent λ,l,00,7gg
No., same λ, r3, A01, same 3, Ot2.633
No. 3゜/2'7, JA No. 3,3/
No. 1,417, No. 3, Hiroshi 79, No. 3, No. 3. j／
ri, t Kota No. 3,631, 3/ri No. 3, j
t2.322, same 3. T/! , 307. No. 3.1
311-. 90g issue, same J, g9/'+4
No. 14, μ, 367.

, 2gλ issue, 1.3tl, 2.37, u, 3
3/, Zari No. 7, same u, 311,393, same μ.

,2μ/,/1. if No., West German Patent/, 110. Hiro6μ
No., West German patent application (OLS l, 2, μOza, 44
J-No., same, 2.9/7. No. 4'j, 2. <7/l
/, Ri No. 39, same! , gu2≠, ≠No. 67, special public showμ0−
t03/issue, Tokukaisho, g/-201+2A issue, same +2
No. -51922, No. 51922, No. 410.27, No. 410.27, No. 410.27, No. 410.27, No. rO-/! No. 933, same! ,
No. 2-172/2/, No. 119-717021, No. s
o-Otsu No. 0-33, same, t/-2454t1, same jj
-3! This is described in No. 1-λ.

These magenta couplers can be used in combination with antifade agents.

As an anti-fading agent, see US Pat. No. 333t/3jt.

No. 31A3+2300, No. 3, t 7 j Oj
No. 0, No. 357 Hiroshi 627, No. 37004133, No. 376μ337, No. 393jO/4, No. 3912.
9ug issue, Dokei Jj41.2/4 issue, Dokei ≠ λ7 Tatata 0
No., British Patent/3177! JLR No. 2062/#g
No. 20At973, No. 20774t, f,! r number.

Special request! ;I-+20. f27g issue, JP-A Show jx-i
s, 2) J, No. 3, same! f3-/77.2 No., same j3
--〇No. 3.27, same j 4t-/ & jt j j
No. 0, same j! -6327, same jjt-J/00'
No. 1, Jza-λ41114/No. 1033, Tokuko Shogu♂-3//, 2. ! r number, same jμmt2
Compounds described in No. 337 can be used.

As the cyan color-forming coupler, a phenol thread compound, a naphthol compound, etc. can be used. A specific example is US Patent λ, 369. 2,113μ
, No. 37.2, same λ, 47μ, No. 23, same, r+2
i, No. 20g, 2, 193.

No. 3,0311,12λ, No. 3,3/l
, ≠ 7, same 3. It! 31jf, 3゜4L
7A,,jt3, same 3. jza3. No. 71, 3.
39/, 31j, 3,767.4t//.

&, No. 0017.929, It, 3A2,110
No., same g, JAza, J, 17, same u, 344/, 1f
t4L issue, Dokei issue, 333.222, same μ, 34'2
.

Ir, ljt No.*, 3a, t, olj No., West German Patent Application (OLS), z, g/u, No. ♂30, 2. μju, No. 329, Japanese Patent Application Publication No. 7J'-69131, No./-2t034, No. μza-joss, No. s
i-/gAfJf, jco 62t cog, jλ-
It is described in No. 90ri No. 31.

Colored couplers include 1, for example, U.S. Pat.
7A,, 1tAo No. 2. jJ, /, 901Jj+
, 3.03u, 1r92, Special Publication No. 4141-2
No. 01, No. 3g-ko + No. 233j, No. 01, No. 3g-ko + 233j, Koko //30
V issue, same≠Hiroshi-3J, 4Ll, / issue, JP-A-31-26
034 in the specification, J Co. 4t, 2/λ1 specification,
West German patent application (OLS) 2. You can use the one listed in air, qjy issue d8e.

As a DIR coupler, for example, US% 3°227.
3jμ issue, same 3. Otsu/7.2ri No. 1, 3.70/,
7ffJ issue, 3, 7rio, JRE issue, 3.63
Ko, No. 344j, μ, 3! tj, No. 100, μ, λ
4At, Ri No. 42, West German Patent Application (OLS) J, μlμ
, oot issue, same co, 4tj Hiroshi, JQ1 issue, same λ, 4tj
u, J Kota, same 3. Koori.

No. 11, British Patent No. 4tj4A, Japanese Patent Publication Showjλ
-6962 gu, same≠tar/Jko 331, special public show 5i
-i(, those described in iai issue can be used.

In addition to the DIR coupler, the light-sensitive material may contain a compound that releases an event suppressor upon the occurrence of an event. For example, as described in US Pat. λri 7,4Aμj.

3.379, J-ta, West German patent application (OLS)
λ,gu/7. ? llA issue, JP-A-ShojJ-/! The materials described in +27/No. J3-T II6 can be used.

Two or more of the above couplers can be contained in the same layer.

The same compound may be contained in different layers or layers. These couplers are generally added in an amount of coxlO mole to 5xio' mole, preferably 1xlO mole to jxlO-1 mole, per mole of silver in the emulsion layer.

Yellow couplers of general formula (i) of the present invention and general formula (
The method of introducing the compound (TI) into the silver halide emulsion layer is a known method, for example, as described in the US patent! .

The method described in No. 3.22,027 can be used.

For example, phthalate alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.)% phosphate esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate)% citric acid esters (e.g. acetyl tribunal citrate), % benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide) % fatty acid esters (e.g. dibutoxyethersuccinate), trimesic acid esters, or organic solvents with a boiling point of about 3θ~/jo0c For example, after dissolving in lower alkyl acetate such as ethyl acetate, butyl acetate, enal propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc.
Dispersed in hydrophilic colloids. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

Also % special public Akira! No. l-39133, JP-A-J/-J Wata 4
The dispersion method using polymers described in No. t3 can also be used.

Gelatin is advantageously used as the binder or storage colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, but other hydrophilic colloids can also be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated.

In the photographic emulsion layer used in the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the silver halide. The preferred silver halide is silver chlorobromide containing a bromide group on the order of 0%. Especially preferred! It is silver chlorobromide containing silver bromide of θ molar ratio to O molar ratio.

The average grain size of the silver halide grains in a photographic emulsion (grain diameter for spherical or near-spherical grains).

In the case of cubic particles, the edge length is taken as the particle size, and it is expressed as an average based on the projected area. ) is not particularly limited, but is preferably 3μ or less.

The particle size may be narrow or wide.

Silver halide grains in photographic emulsions may have regular crystal bodies such as cubic or octahedral, or may have spherical,
It may have an irregular crystalline shape such as a plate shape, or it may have a composite shape of these crystalline shapes. It may also consist of a mixture of particles of various crystalline forms.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of at least j times the grain thickness occupy 30% or more of the total projected area.

The silver halide grains may have different phases inside and on the surface. 'Furthermore, it may be a particle in which latent particles are formed as a king on the surface, or a particle in which latent particles are formed in a king in the inside of the particle.

In addition, in the process of silver halide grain formation or physical ripening, t”b such as cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or a complex salt thereof, rhodium salt or a complex salt thereof, iron salt or iron complex salt, etc. It could be something you made.

After the emulsion is precipitated or physically ripened, soluble salts are usually removed, and for this purpose, the Tardel water washing method or the flocculation method may be used.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, see, for example, "D" edited by H. Frleser.
ie Qrundlagen der Photog
raphischenprozesse mit S
ilberhalogeniden” (Akademi
sche Verlagsgesellschaft
.

The method described in 41') pages 676-73 can be used.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used are cyanine pigments and merocyanine pigments.

Included are complex cyanine dyes, complex merocyanine dyes, poropolar-cyanine dyes, hemicyanine dyes, steryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyania dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with sensitizing dyes, dyes that do not themselves have a spectral sensitizing effect or substances that do not substantially absorb visible light, 1
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, those described in U.S. Pat. acid formaldehyde condensates (e.g. U.S. Pat. No. 3.7μ3.sio
(described in the above issue), cadmium salts, azaindene compounds, etc. US Patent 3. tis, 6μ3 issue,
Same 3. tljt, 6μ7, same 3. A/7゜-ta No. J,
Same 3. The combinations described in No. A3j, 7λ1 are particularly useful.

The invention is also applicable to multilayer, multicolor photographic materials having at least λ different spectral sensitivities on the support. A multilayer natural color photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support.

The order of these layers can be arbitrarily selected as required. An emulsion layer having the same color sensitivity may be divided into λ layers, three or more unit emulsion layers each having a different sensitivity.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, aryl group-substituted be/citriazole compounds (e.g., those described in U.S. Pat. No. 3,33,7944), t-teazolidone compounds (e.g., U.S. Pat. % cinnamic acid ester compounds (such as those described in US Pat.
7oz, Roj No. 707.376), butadiene compounds (e.g., U.S. Pat. No. 707.376);

Ops...! , No. 22), or benzoxidol compounds (e.g., those described in U.S. Pat. No. 3,700,
≠ those described in No. 63) can be used. Additionally, U.S. Patent J, &ji? , 7t.

r- can also be prepared by using the method described in Japanese Patent Application Laid-open No. JP-A-ShojμmarsJj. UV-absorbing couplers (for example, cyan dye-forming couplers based on 1-naphthol);

Ultraviolet absorbing polymers may also be used. These ultraviolet absorbers may be mordanted in specific layers.

The photosensitive material produced using the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer for the purpose of preventing irradiation and other various purposes. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, melonanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In the photosensitive material produced using 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.

The photographic material of the present invention is a color negative film.

Color can be used for general silver halide color photosensitive materials such as color positive film, color reversal film for slides, color reversal film for movies, and color reversal film for TV, but especially for high sensitivity, It is useful for color negative films and color reversal films that require high image quality.

The photographic emulsion used in the present invention is used for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or for stabilizing the photographic performance.

Various compounds can be included. That is, azoles 1 such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , benzotriazoles,
Benzotriazoles, mercaptotetrazoles (especially l-phenyl-j-mercaptotetrazole)
Mercaptopyrimidines; Mercaptotriazines; Thioketo compounds such as oxadorintheone;
．． 3a, 7) Tetraazaiintene u4), pentaazaindenos; many compounds known as anti-capri agents or stabilizers such as henzene sulfonic acid, benzene sulfinic acid, benzene sulfonic acid amide, etc. Compounds can be added.

For more detailed examples of these and how to use them, see, for example, US Patent No. 3. rijμ, μ7 hiro issue, same 3. Rigλ, Rit7, Tokkosho, t, 2-. Those described in No. 2g, 6tO can be used.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization.

For the purpose of increasing sensitivity, increasing contrast, and promoting fAflJ, the photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, and It may also contain ammonium salt compounds, urethane derivatives, urea salt conductors, imidazole derivatives, 3-pyrazolidones, and the like. For example, US Patent 2. μ00
, No. 332, same λ, gx3. sari issue, 2,711
．． , No. 06, 3. A/7. ．． No. 210, J.
772.

No. 02'/No. 3, III, No. 003, British Patent/
.

Those described in Hiro tr, Tata No. 1, etc. can be used.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability.

For the photographic processing of the layer consisting of the photographic emulsion produced using the present invention, any of the known methods and known processing solutions as described, for example, in Research Disclosure/No. 74, page 30, may be applied. can do. The processing temperature is usually chosen between l♂0C and so'C, but %1i
The temperature may be lower than 0c or higher than 5o0c.

The color development generally consists of an alkaline aqueous solution containing one color developing agent. The color developing agent is a known primary aromatic amine developer such as phenylene diamines (e.g. t-amino-N, N-diethylaniline, 3-methyl-
≠-amino-N,N-diethylaniline%l-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-aminoheethyl-N-β-hydroxyethylaniline, 3-methyl-μmamino-N-ethyl-N-β-methanesulfamide ethylaniline.

guamino-3-nonal-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, L, F', A, Pho by Mason
tographicProcessing Chem
istry (published by Focal Press, t966), P22t~1λ, U.S. Pat. a
Those described in RI No. 33 may also be used.

The color developing solution may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. It may contain inhibitors and the like. Also, if necessary, use hard water (or other agents).

Preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol.

promoters such as polyethylene glycols, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride,
It may also contain an auxiliary developer such as l-phenyl-3-pyrazolidone, a viscosity imparting agent, a polycarboxylic acid chelating agent, an antioxidant, and the like.

Specific examples of these additives can be found in Research Disclosure/
No. 74/77, l/-3, as well as U.S. Pat.

No. 013.723, West German Open (OLS), z, x2co,
50, etc.

The photographic emulsion layer after color development is usually bleached.

The bleaching process may be performed simultaneously with the fixing process.

It may also be done individually. As a bleaching agent, for example, iron (m
), cobalt (■), chromium (■11. copper (l■)
Compounds of polyvalent metals such as, peracids, quinones, nitroso compounds, etc. are used.

For example, ferricyanide, dichromate, iron (III)
14 or Kobal) (III), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 13-diamino-coprolξnortetraacetic acid, or organic acids such as citric acid, tartaric acid, malic acid, etc. Complexes; persulfates, permanganates; nitrosophenols, etc. can be used. Among these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate (I), and ammonium ferric ethylenediaminetetraacetate (I) are particularly useful. Iron ethylenediaminetetraacetate (iJ
I) Complex salts are useful both in stand-alone bleach solutions and in -bath bleach-fix solutions.

(Example) The present invention will be described below with reference to specific examples, but is not limited thereto.

Example 1 The coupler of the present invention (Y-4t was dissolved by heating in 10 ff dibutyl phthalate!tnl and 10 ml ethyl acetate, and mixed with sodium dodecylbenzenesulfone 0872.
The mixture was mixed with 100 ml of an aqueous solution of θ gelatin and stirred and mixed using a homogenizer rotating at high speed at SOoC to obtain a coupler emulsion dispersion. This dispersion and silver chlorobromide emulsion 1. tOf
λ-hydroxy-4<,4-dichloro-8
- Add 3 ml of a 2% aqueous solution of trianne sodium salt and 6 tnlyjz of a multi-aqueous solution of saponi, and deposit the amount of silver on the cellulose triacetate film. / m 2 , and a gelatin protective layer having a dry film thickness of lμ was applied thereon to prepare a sample Ak.

In the same manner, when preparing the above emulsified dispersion, the compounds of the present invention and comparative compounds were added to the above coupler and the coupler pressure of Y-/ as shown in Table 1, but otherwise the same as Sample A. Samples B-M' were prepared by applying the method described in the following.

Samples A to M were subjected to stepwise exposure for sensitometry and then subjected to the following development treatment.

Process Temperature Time color development, 310C, 3 minutes water washing, 1 minute bleach fixing
Wash with water for 1 minute and 30 seconds
The composition of the 1-minute color developing solution was as follows.

Benzyl alcohol /jrnl diethylene glycol I ml sulfate v sodium sulfite λ ghydroxylamine sulfate 3 ? potassium carbonate
Add 30 f water
pH (adjustment)
The composition of the bleach-fix solution is as follows.

Ethylenediamine - Acetic acid - λ 2 λ - Sodium salt Ethylenediamine - μ - Acetic acid - ≠ 02 2 - Ferrous salt Sodium sulfite j7 Sodium theosulfate 70 9 Add water
/1pH4, to check the light resistance of each sample obtained in this way. It was shown in

In addition, in order to investigate heat resistance, the initial concentration of 1. The dye residual rate in OK was expressed as a sludge fraction. The obtained results are shown in Comparative Compound (a) Compound described in US Pat. No. 3≠32300! , Comparison compound described in No. 2-1.4.23 (
e) Comparative compound of the compound described in British patent IJJA♂r? I(b) Comparative compound (d
) From this result, 1
It can be seen that the compounds of the present invention are extremely effective in preventing photofading of color stains compared to comparative compounds. Not only that, but it also shows excellent effects in preventing thermal fading.

Example 2 A color photographic material (sample N) was prepared by sequentially coating the following first layer (lowest layer) to sixth layer (top layer) on a paper support laminated on both sides with polyethylene. (mg7m2 in Table 2 represents the coating amount) Table 2 (-X-/) Sensitizing dye: Botacium λ-[j-(≠-
(6-Methyl-3-bentylbenzothiazoline-coylidene) -2-menal-coptenylidene)-3-rhodanine] acetate (arrow λ) coupler nicor [α-(co, q-tert)
-ba7terphenoxy)butanamide)-4,4-dichloro-j-methylphenol (-X-,,?li mnitrinonyl phosphate (arrow μ) UV absorber: J-(,2-hydroxy-3-
sec-butyl-j-tert-butylphenol)benzotriazole (arrow j) coupler: l-(,2,g,A-trichlorophenyl 1-J-(L2-chloro-y-tetradecanamide) ayuline 2-pyrazolone-j - ON (arrow t) anti-fade agent, !-tert-hexylhydroquinone (-%-7) solvent nitricresyl phosphate (arrow ♂) coupler: Y-ke 6 Similarly, the first layer of sample N While leaving the yellow coupler as it is, apply various anti-fading agents to the yellow coupler.
Multilayer samples (O to R) containing O molar addition were prepared.

After giving each sample a minute blue light exposure through a continuous wedge,
Genzawa treatment was carried out using the following treatment steps.

Processing process Color development 33°0 3 minutes 30 seconds Bleach fixing
Washing with water at 33°C for 7 minutes and 30 seconds 300C3 revolution Dry color development Liquid composition Benodyl alcohol ijml Sodium sulfite Dipotassium dibromide 01μm Hydroxylamine sulfur akM, 2SI〃-amino-3-methyl-N-ethyl-N-β (Methanesulfonamide) λ1 Sodium carbonate (l hydrate) Add 30f water, /θ
00rul pH 1o, l Bleach-fix solution composition Ethylenediamine≠ Iron salt for acetic acid Guj7 Sodium sulfite /Qf Ammonium thiosulfate 70 Multi-aqueous solution 160ml Ethylenediamine 4 Vinegar ea Sodium salt js' Add water IOooml pH 6,1 Obtained in this way For each sample, light resistance and sound were measured according to the test method used in Example 1, and the results are summarized in Table 3.

From these results, it can be seen that the compound of the present invention is extremely effective in preventing photofading of color 1 walls even in single layer coated samples.

Claims (1)

[Scope of Claims] A layer containing at least one yellow coupler represented by the following general formula (I) or at least one layer adjacent thereto contains at least one compound represented by the following general formula (II). A silver halide color photographic light-sensitive material. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, R_1 represents a substituted or unsubstituted N-phenylcarbamoyl group. R_2 represents a tertiary alkyl group having 4 to 20 carbon atoms or a substituted or unsubstituted phenyl group. X_1 represents a group that can be separated during the coupling reaction with the oxidized form of the developing agent. R_1, R_2 or X
_1 may form a dimer or more multimer. General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, R_1_9 and R_2_0 each represent a tertiary alkyl group, and R_2_1 represents an alkyl group.