JPH0619534B2 - Color photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a color photographic material, particularly a color photographic material, which is subjected to a development process to obtain a faded and non-colored portion (hereinafter referred to as a white background) of a dye image finally obtained. The present invention relates to prevention of discoloration.

[Prior art]

Generally, the quality of photographic images obtained with silver halide photographic materials is not permanent and deteriorates with storage. In particular, a color photograph having an image composed of an azomethine dye or an indoaniline dye formed by the reaction of an oxide of an aromatic primary amine developing agent and a coupler is exposed to light for a long period of time or under high temperature and high humidity. When it is stored, it usually causes discoloration or discoloration of the dye image, and further discoloration of white background (yellow stain), which causes deterioration of image quality.

Such deterioration of image quality is a fatal defect for recording materials. To eliminate these drawbacks,
Many proposals have been made in the past. Among them, the most effective method is a method of using a color image stabilizer together.

As color image stabilizers, hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, spiroindans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, Methylenedioxybenzenes,
Aminophenols, hindered amines and phenolic hydroxyl groups of these compounds are silylated, acylated,
There are alkylated ether or ester derivatives, and metal complexes are also known.

For example, hydroquinones are described in U.S. Pat. No. 2,360,29.
No. 0, No. 2,418, 613, No. 2,700, 4
No. 53, No. 2,701,197, No. 2,728,
No. 659, No. 2,732,300, No. 2,73
No. 5,765, No. 3,982,944, No. 4,4
30,425, British Patent 1,363,921, US Pat. Nos. 2,710,801, 2,816,028 and the like, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans are US Patent 3,432,
No. 300, No. 3,573, 050, No. 3,57
No. 4,627, No. 3,698,909, No. 3,7.
64,337, JP-A-52-152225, etc.,
Spiroindanes are described in US Pat. No. 4,360,589, p-alkoxyphenols are described in US Pat.
5,765, British Patent No. 2,066,975 (B),
Hindered phenols are disclosed in U.S. Pat. No. 3,70,70 in JP-A-59-10539 and JP-B-57-19764.
No. 0,455, JP-A-52-72225, U.S. Pat. No. 4,228,235, Japanese Patent Publication No. 52-6623, etc., gallic acid derivatives, methylenedioxybenzenes and aminophenols are described in U.S. Pat. 3,457,0
No. 79, No. 4,332,886, Japanese Patent Publication No. 56-21
144, etc., hindered amines are described in US Pat.
336,135, 4,268,593, British Patents 1,326,889, 1,354,313,
No. 1,410,846, Japanese Patent Publication No. 51-1420,
JP-A-58-114036 and 59-53846,
No. 59-78344 and the like, ether and ester derivatives of phenolic hydroxyl groups are disclosed in US Pat. No. 4,155,76.
No. 5, No. 4,174,220, No. 4,254,2
16, No. 4,264,720, JP-A-54-14.
No. 5530, No. 55-6321, No. 58-10514
No. 7, No. 59-10539, Japanese Patent Publication No. 57-37856
No. 4,279,990, Japanese Patent Publication No. 53-3
No. 263, etc., metal complexes are disclosed in US Pat. No. 4,050,93.
No. 8, No. 4,241,155, British Patent No. 2,02
7, 731 (A) and the like.

[Problems to be solved by the invention]

However, although these compounds are effective in preventing discoloration and discoloration of the dye image, their effect is small,
As a color image stabilizer for photographic use, which is effective in preventing discoloration, it exerts overall excellent effects by deteriorating the hue, causing fog, causing poor dispersion, and causing crystals. Is insufficient.

[Object of the Invention]

Accordingly, it is a first object of the present invention to provide a silver halide photographic material containing a stabilizer which prevents deterioration of the image quality of a photographic image over time.

The second object of the present invention is that there is no change in hue or fog,
Furthermore, by providing a photographic layer with a stabilizer having a sufficient effect of preventing discoloration or change of a color image without causing poor dispersion or crystals, it is intended to provide a color photographic material in which a color image is stabilized. is there.

The third object of the present invention is to provide a color photographic material in which the above-mentioned stabilizer is contained in the photographic layer so that the unexposed portion of the light-sensitive material after development processing does not generate yellow stain to light, heat and humidity. To do.

[Means for solving problems]

As a result of various studies, the inventors of the present invention have found that the object of the present invention can be achieved by incorporating at least one compound represented by the following general formula (I) into the photographic layer.

General formula (I) In the formula, R ₁ and R ₂ represent a hydrogen atom, an aliphatic group, a heterocyclic group, a R ₇ CO— group, a R ₈ SO ₂ — group or a R ₉ NHCO— group, and R ₃ represents
Represents a hydrogen atom or an aliphatic group, R ₄ represents a hydrogen atom, an aliphatic group or an aliphatic oxy group, R ₅ and R ₆ represent a hydrogen atom, an aliphatic group or an aryl group, R ₇ , R ₈ And R ₉ represents an aliphatic group, an aryl group or a heterocyclic group, R ₃ and R ₄ may be ring-closed, and the aliphatic group, the aryl group and the heterocyclic group each have a substituent. You may have. However, R ₁ and R ₂ are not hydrogen atoms at the same time, and R ₁ and R ₄ are not ring-closed.

The substituent of the general formula (I) will be described.

The aliphatic group is a linear, branched or cyclic aliphatic hydrocarbon, and includes saturated and unsaturated groups such as alkylalkenyl and alkynyl, and the aryl group may be monocyclic or polycyclic. The ring group is a heteroatom (N, S,
O, P, Si, Se, Te, Ge, etc.). It is a monocyclic or polycyclic saturated or unsaturated group. Any of these aliphatic groups, aryl groups or heterocyclic groups may have one or more substituents. When there are two or more substituents, they may be the same or different.

Examples of the aliphatic group include a methyl group, a butyl group, a tridecyl group, a cyclohexyl group, and an allyl group.
Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the heterocyclic group include a 2-pyridyl group, a 2-imidazolyl group, a 2-furyl group and a 6-quinolyl group. Substituents allowed for these groups include alkyl groups, aryl groups, heterocyclic groups, alkoxy groups (eg, methoxy group, 2-methoxy group, etc.), aryloxy groups (eg, 2,4-di-tert-group). Amylphenoxy group, 2-chlorophenoxy group, 4-cyanophenoxy group, etc.), alkenyloxy group (eg, 2-propenyloxy group, etc.), acyl group (eg, acetyl group,
Benzoyl group), ester group (eg, butoxycarbonyl group, phenoxycarbonyl group, acetoxy group,
Benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group etc.), amide group (eg acetylamino group, methanesulfonamide group, dipropylsulfamoylamino group etc.), carbamoyl group (eg dimethylcarbamoyl group, ethylcarbamoyl group) Such),
Sulfamoyl group (eg, butylsulfamoyl group), imide group, (eg, succinimide group, hydantoinyl group, etc.), ureido group (eg, phenylureido group, dimethylureido group, etc.), aliphatic or aromatic sulfonyl group (eg, , Methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio group (eg, ethylthio group, phenylthio group, etc.), hydroxy group, cyano group, carboxy group, nitro group, sulfo group, halogen atom, etc. .

Specific examples and preferred ranges of the substituents of R ₁ to R ₉ are shown below.

R ₁ and R ₂ are a hydrogen atom, an alkyl group (for example, methyl,
Ethyl, propyl, n-octyl, tert-octyl, benzyl, hexadecyl), an alkenyl group (eg, allyl, octenyl, oleyl), a heterocyclic group (eg, tetrahydropyranyl, pyrimidyl) or R ₇ CO—R ₈ SO
_2- , or a group represented by R ₉ NHCO-. Where R
₇ , R ₈ and R ₉ are alkyl groups (for example, methyl, ethyl,
n-propyl, n-butyl, n-octyl, tert-octyl, benzyl), alkenyl group (eg, allyl, octenyl, oleyl), aryl group (eg, phenyl, methoxyphenyl, naphthyl), or heterocyclic group ( For example, pyridyl and pyrimidyl). Also R ₁ , R
₂ may be the same group or different, but R ₁
And R ₂ are not hydrogen atoms at the same time. R ₃ is a hydrogen atom, an alkyl group (eg, methyl, ethyl, n-butyl, benzyl), or an alkenyl group (eg, allyl,
Hexenyl, octenyl), R ₄ is a hydrogen atom,
Alkyl group (eg, methyl, ethyl, n-butyl, benzyl), alkenyl group (eg, allyl, hexenyl, octenyl), alkoxy group (eg, methoxy,
Ethoxy, benzyloxy) or an alkenoxy group (eg, 2-propenyloxy, hexenyloxy), which may be ring-closed with R ₃ and R ₄ . However, R ₄ is the aforementioned R ₁
It never closes. R ₅ and R ₆ are a hydrogen atom, an alkyl group (for example, methyl, ethyl, n-butyl, benzyl), an alkenyl group (for example, 2-propenyl, hexenyl, octenyl), or an aryl group (for example, phenyl, methoxyphenyl, Chlorophenyl, naphthyl).

R ₁ and R ₂ are preferably a hydrogen atom (however, not simultaneously a hydrogen atom), a substituted or unsubstituted alkyl group, an aliphatic carbonyl group or an aliphatic sulfonyl group, and more preferably the total carbon number contained. Is a 1-20 substituted or unsubstituted alkyl group, an aliphatic carbonyl group, or an aliphatic sulfonyl group. R ₃ and R ₄ are preferably a hydrogen atom, a lower alkyl group (having 1 to 6 carbon atoms) or a lower alkoxy group (having 1 to 6 carbon atoms). R ₅ and R ₆ are preferably a hydrogen atom or a lower alkyl group (having 1 or 2 carbon atoms).

Next, typical examples of these compounds are shown below, but the compounds used in the present invention are not limited thereby.

(1) (2) (3) (Four) (Five) (6) (8) (9) (Ten) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (twenty one) (twenty two) (twenty three) (twenty four) (twenty five) (26) (27) (28) (29) (30) The compound represented by the general formula (I) of the present invention is 6,6′-
4,7,4 ', 7'-Tetrahydroxy-obtained by acid-catalyzed rearrangement of dihydroxy-2,2'-spirobischroman or its phenolic hydroxyl group substitution product
1,1 injection-spirobisindane or 4,4 '
It is obtained by etherifying the phenolic hydroxyl group of -dihydroxy-1,1'-spirobisindane.

4,7,4 ', 7'-tetrahydroxy-1,1'-spirobisindane compound used in the present invention,
The 4,4'-dihydroxy-1,1'-spirobisindane compound can be synthesized according to the method described in Chemistry and Industry, (1969) page 456. Further, 6,6'-hydroxy-2,2'-bisspirochroman compounds which are precursors of these compounds and compounds which substitute phenolic hydroxyl groups thereof are described in JP-B-49-20977 and JP-A-20327, respectively. It can be synthesized by the method described. The compounds of the present invention are 4,7, -Tetrahydroxy-1,1'-spirobisindane compound or 4,4'-dihydroxy-1,1'-spirobisindane compound can be synthesized by alkylating or esterifying by a conventional method.

Specific examples of synthesizing the compound are shown below, but other compounds can be synthesized by the same method.

Synthesis Example-1 6,6'-Dimethyl-3,3,3 ', 3'-tetramethyl-
4,7,4 ', 7'-Tetrapropyloxy-1,1'-
Synthesis of Spirobisindane (Compound No. 3) (1) 6,6'-Dimethyl-4,7,4 ', 7'-tetrahydroxy-3,3, -Synthesis of tetramethyl-1,1'-spirobisindane.

6,6'-dihydroxy-7,7'-dimethyl-4,
250 m of boron trifluoride diethyl ether complex was added to 36.8 g (0.1 mol) of 4,4 ', 4'-tetramethyl-2,2'-spirobischroman, and the mixture was stirred at an internal temperature of 70 ° C for 4 hours. The reaction solution was poured into ice water, and 100 m of ethyl acetate was added for extraction. The oil layer was washed with water, concentrated to dryness, and crystallized by adding n-hexane to give white crystals.

Yield 33.1 g Yield 90% (2) 6,6'-Dimethyl-3,3,3 ', 3'-tetramethyl-4,7,4', 7'-tetrapropyloxy-1,
Synthesis of 1'-Spirobisindane (Compound NO.-3) 6,6'-Dimethyl-4,7,4 ', 7'-tetrahydroxy-3,3,3', 3'-tetramethyl-1, 1 '
-Spirobisindane 33.1g (0.09mol) 150m
Dissolved in dimethylformamide, potassium carbonate 49.7g
(0.36 mol) was added and heated to 70 ° C. To this mixture
(n) Propyl bromide (55.4 g, 0.45 mol) was added dropwise.
The mixture was stirred at 70 ° C for 8 hours. The reaction solution was poured into ice water and extracted with 200 m of ethyl acetate. The oil layer was thoroughly washed with water, concentrated to dryness, and crystallized with methyl alcohol to obtain crude crystals. The crude crystals were recrystallized with methyl alcohol to obtain white crystals.

Melting point 75 ° C. Yield 35.9 g Yield 75% Elemental breakdown value C: 79.07% H: 9.09% Calculated value C: 78.91% H: 9.08% Synthesis example-2 6,6'-Dimethyl-3,3,3 ′, 3′-Tetramethyl-4,7,4 ′, 7′-tetrahexyloxy-1,
Synthesis of 1'-Spirobisindal (Compound NO.-13) 6,6'-Dimethyl-4,7,4 ', 7'-tetrahydroxy-3,3,3', 3'-tetramethyl-1 , 1 '
-Spirobisindane 18.4g (0.05mol) 100m
27.6g of potassium carbonate
(0.2 mol) was added and heated to 90 ° C. To this mixture (n)
Hexyl bromide (41.3 g, 0.25 mol) was added, and the mixture was stirred at 90 ° C. for 5 hours. The reaction solution was poured into ice water and ethyl acetate 200 was added.
extracted with m. The oil layer was washed thoroughly with water, concentrated, and separated by column chromatography to give a colorless oily substance.

Yield 31.5 g Yield 90% Elemental fragmentation value C: 80.58% H: 10.38% Calculated value C: 80.52% H: 10.35% Synthesis example-3 6,7,6 ', 7'-tetrahexyloxy-4,4 ′-
Synthesis of dihydroxy-3,3,3 ', 3'-tetramethylspirobisindane (Compound NO.-11) 6,7,6', 7'-Tetrahexy-4,4,4 ', 4'
-Tetramethylbis-2,2'-spirochroman 30g
(0.042 mol) boron trifluoride diethyl ether complex 10
0 m was added, and the mixture was stirred at an internal temperature of 50 ° C. for 5 hours. The reaction solution was poured into ice water and 100 m of ethyl acetate was added for extraction.
The oil layer was washed thoroughly with water, concentrated, and separated by column chromatography to give a colorless oily substance.

Yield 18.5 g Yield 61.7% Elemental breakdown value C: 76.31% H: 10.26% Calculated value C: 76.23, H: 10.24% The compound represented by the general formula (I) of the present invention is a known compound having a similar chemical structure. , U.S. Pat. No. 4,360,58
5,6,5 ', 6'-tetraalkoxy-1, described in No. 9,
It is superior to 1'-spiroindanes, 6,6'-dihydroxy-2,2'-spirobischromans described in JP-A-3,764,337 and ethers thereof.

The compound used in the present invention varies depending on the kind of the coupler used in combination, but is about 0.5 to 200 relative to the coupler.
% By weight, preferably in the range of about 2-150% by weight (mol%
It is appropriate to use the range shown in ().
If the amount is less than this range, the effect of preventing discoloration and coloring of the white background is so small that it is not suitable for practical use. On the other hand, if the amount is too large, the progress of development may be hindered and the color density may be lowered.

The compounds used in the present invention may be used alone or in combination of two or more kinds. Further, the above-mentioned known anti-fading agent or color image stabilizer can be used in combination.

The compound used in the present invention is effective in preventing fading of color images of yellow, cyan and magenta and preventing yellow stain on a white background. In particular, it is excellent in preventing fading of magenta images and preventing yellow stain on a white background.

Examples of magenta dye-forming couplers include pyrazoloazole couplers such as 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, pyrazolopyrazole couplers, pyrazolotetrazole couplers, cyanoacetylcoumarone couplers, and open-chain acyl couplers. There are acetonitrile couplers and the like, but as the magenta coupler to be combined with the compound represented by the general formula (I) of the present invention, the following general formulas (II), (III),
Alternatively, the coupler represented by (IV) gives particularly good results.

General formula (II) In the formula, R ₁ represents an anilino group, an acylamino group, or a ureido group, X ₁ , X ₂ and X ₃ are a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, an aryloxy group,
Acylamino group, carbamoyl group, sulfamoyl group,
It represents a sulfonyl group or a cyano group. X ₁ , X ₂ and X ₃ may be the same or different. R ₂ represents a hydrogen atom or a group capable of splitting off during the coupling reaction with the oxidation product of the aromatic primary amine developing agent.

General formula (III) In the formula, R ₁ and R ₂ represent the group defined in the general formula (II),
R ₃ represents a hydrogen atom, an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, an aryl group or a heterocyclic group.

General formula (IV) In the formula, R ₂ represents a group defined by the general formula (II), and R ₄ represents a hydrogen atom or a substituent. Za, Zh and Zc are methine, substituted methine, methylene, substituted methylene, = N-, or Represents Here, R ₅ represents a hydrogen atom or a substituent.
Of the Za-Zb bond and the Zb-Zc bond, one represents a double bond and the other represents a single bond.

Further, R ₄ or R ₂ may form a dimer or higher multimer, and when Za, Zb, or Zc is a substituted methine, the substituted methine may form a dimer or higher dimer. You may.

It may be a polymerizable vinyl monomer having a structure represented by the general formulas (II), (III) and (IV), and may be a homopolymer thereof or a copolymer with a non-color forming vinyl monomer.

Next, examples of magenta couplers, coupler monomers and polymer couplers for obtaining magenta polymer couplers useful in the present invention will be shown, but the present invention is not limited thereto.

n- (1) n- (2) n- (3) n- (4) n- (5) n- (6) n- (7) n- (8) n- (9) n- (10) n- (11) n- (12) n- (13) n- (14) n- (15) n- (16) n- (17) n- (18) n- (19) n- (20) n- (21) n- (22) n- (23) n- (24) n- (25) n- (26) n- (27) n- (28) n- (29) n- (30) n- (31) n- (32) n- (33) n- (34) n- (35) n- (36) n- (37) n- (38) n- (39) n- (40) n- (41) n- (42) n- (43) n- (44) n- (45) n- (46) n- (47) n- (48) n- (49) n- (50) n- (51) n- (52) n- (53) n- (54) n- (55) n- (56) n- (57) n- (58) The couplers and the like can be used in combination of two or more kinds in the same layer in order to satisfy the characteristics required for the light-sensitive material, and it is of course possible to add the same compound to two or more different layers.

The compound of the present invention can be introduced into the light-sensitive material by a known method alone or simultaneously with a magenta coupler and the like, and examples thereof include solid dispersion method, alkali dispersion method, preferably latex dispersion method, more preferably oil-in-water dispersion method. It can be mentioned as a typical example. In the oil-in-water dispersion method, after dissolving in either a single liquid of a high boiling organic solvent having a boiling point of 175 ° C. or higher and a so-called auxiliary solvent having a low boiling point or a mixed liquid of both, water or gelatin is added in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous solution. Examples of high boiling point organic solvents are described in US Pat. No. 2,322,027 and the like. The dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, rinsing with water or ultrafiltration, and then used for coating.

Specific examples of the high boiling point organic solvent include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate,
Di-2-ethylhexyl phthalate, decyl phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl) Phosphate, tridecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2
-Ethylhexylphenylphosphonate, etc.), benzoates (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecane amide, N-tetradecylpyrrolidone, etc.), alcohols or Phenols (isostearyl alcohol,
2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate, etc., aniline derivatives (N,
N-dibutyl-2-butoxy-5-tert-octylaniline and the like), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene and the like) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexane, 2- Examples include ethoxyethyl acetate and dimethylformamide.

The process of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230. It is described in.

The photographic photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (for example, those described in US Pat. No. 3,533,794), 4-thiazolidone compounds (for example, US Pat.
14, 794 and 3,352,681), benzophenone compounds (for example, JP-A-46-27).
No. 84), cinnamic acid ester compounds (for example, US Pat. Nos. 3,705,805 and 3,707,37).
No. 5), a butadiene compound (for example, those described in US Pat. No. 4,045,229), or a benzooxide compound (for example, US Pat. No. 3,700,
No. 455) can be used. Further, U.S. Pat. No. 3,499,762 and JP-A-54-48
Those described in No. 535 can also be used. An ultraviolet absorbing coupler (for example, an α-naphthol-based cyan dye forming coupler), an ultraviolet absorbing polymer, or the like may be used. These UV absorbers may be mordanted in a specific layer.

Any silver halide of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. A preferred silver halide is silver iodobromide or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is about 2 mol%
To about 25 mol% silver iodobromide.

The silver halide grains in the photographic emulsion may be so-called Regular grains having regular crystal bodies such as cubes, octahedra and tetradecahedrons, and those having irregular crystal shapes such as spheres, It may have a crystal defect such as a twin plane or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.1 micron or less, or large grains having a projected area diameter of up to about 10 microns, whether it is a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. Good.

The silver halide photographic emulsion which can be used in the present invention can be produced by a known method. Dice Closure (RD), NO.17643 (December 1978), 22
Pp. 23, "I. Emul-sion preparation and
types) ”and ibid., No. 18716 (11 November 1979)
Mon.), page 648.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Glafkides.Chimi).
e et Physique Photographique Paul Montel. 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press, Inc. (G.
F.Duffin.Photographic Emulsion Chemistry (Focal Pre
ss. 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Forcal Press (VL Zelikman et al. Makin.
g and Coating Photographic Emul-sion. Focal Press.1
964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good. Method of forming grains in the presence of excess silver ion (so-called reverse mixing method)
Can be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion composed of the above-mentioned regular grains can be obtained by controlling pAg and pH during grain formation. For details, see, for example, Photograph. Science and Engineering (Photographic Science and Engine
ering) Volume 6, 159-165 (1962); Journal of Photographic Science (Journal o)
f Photographic Science), Volume 12, pp. 242-251 (19
64), U.S. Pat. No. 3,655,394 and British Patent No. 1,413,748.

The monodisperse emulsion is a silver halide grain having an average grain diameter of more than about 0.1 micron, of which at least about 9
Emulsions such that 5% by weight are within ± 40% of the average grain diameter are typical. Emulsions having an average grain diameter of about 0.25 to 2 microns and having at least about 95% by weight or at least about 95% by number silver halide grains within the average grain diameter ± 20% can be used in the present invention. . A method for producing such an emulsion is described in US Pat. No. 3,574,628,
No. 3,655,394 and British Patent No. 1,41
No. 3,748. In addition, JP-A-48-86
00, 51-39027, 51-83097.
No. 53-137133, No. 54-48521,
54-99419, 58-37635, 58.
Monodisperse emulsions such as those described in JP-A-49938 can also be preferably used in the present invention.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering.
(Gutoff, Photographic Science and Engineering), Vol. 14, pp. 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, 4; , 439,520 and British Patent 2,112,157, and the like. When tabular grains are used, there are advantages such as improvement of color sensitization efficiency, improvement of graininess and increase of sharpness by a sensitizing dye, which is cited in US Pat. No. 4,434,226 cited above. In detail.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are described in British Patent 1,027,1
46, U.S. Pat. Nos. 3,505,068 and 4,44
No. 4,877 and Japanese Patent Application No. 58-248469. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halides such as silver rhodanide and lead oxide. These emulsion grains are described in U.S. Pat. Nos. 4,094,684, 4,142,900,
No. 4,459,353, British Patent No. 2,038,79.
No. 2, U.S. Pat. Nos. 4,349,622 and 4,39.
5,478, 4,433,501, 4,46
No. 3,087, No. 3,656,962, No. 3,85
2,067, JP-A-59-162540 and the like.

Also, a mixture of particles having various crystal forms may be used.

The emulsion of the present invention is usually used after physical ripening, chemical ripening and spectral sensitization. The additives used in such a process are Research Disclosure No. 176.
43 and No. 18716, and the corresponding parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above-mentioned two Research Disclosures, and the locations described in the table below are shown.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure mentioned above.
(RD) No. 17643, VII-C to G. As the dye-forming coupler, a coupler that gives the three primary colors of the subtractive method (that is, yellow, magenta, and cyan) by color development is important, and has a resistance to diffusion.
Specific examples of 4-equivalent or 2-equivalent couplers are described in RD176 above.
In addition to the couplers described in the patents described in paragraphs 43, VII-C and D, the following can be preferably used in the present invention.

A typical example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. The specific fee is US Patent No. 2,
No. 407,210, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat. Nos. 3,408,194 and 3,447,928 are preferred.
No. 3,933,501 and No. 4,022.
No. 620 and other yellow couplers of oxygen atom elimination type or Japanese Patent Publication No. 58-10739, U.S. Pat. Nos. 4,401,752, 4,326,024, R
D18053 (April 1979), British Patent No. 1,42
No. 5,020, West German Application Publication No. 2,219,917,
Typical examples thereof include nitrogen atom releasing yellow couplers described in Nos. 2,261,361, 2,329,587 and 2,433,812. The α-pivaloyl acetanilide type coupler is excellent in the fastness of the color forming dye, especially the light fastness, while
The benzoylacetanilide coupler provides high color density.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion resistant naphthol-type and phenol-type wappers, and the naphthol-type couplers described in US Pat. No. 2,474,293, preferably US Pat. 052
No. 212, No. 4,146, 396, No. 4,22
Typical examples are the oxygen atom desorption type two-equivalent naphthol couplers described in JP-A-8,233 and JP-A-4,296,200. Further, specific examples of the phenol-based coupler are described in US Pat. Nos. 2,369,929 and 2,8.
01,171, 2,772,162, 2,
No. 895,826. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, of which typical examples are US Pat. No. 3,773.
2,002,162, US Pat. Nos. 2,772,162 and 3,7, which are described in US Pat. No. 2,002, with a phenolic cyan coupler having an ethyl group or higher alkyl group at the meta position of the phenol nucleus.
58,308, 4,126,396, 4,
334,011, 4,327,173, West German Patent Publication No. 3,329,729 and European Patent No. 12
2,5-diacylamino-substituted phenol-based couplers described in US Pat. No. 1,365, and US Pat. No. 3,44.
No. 6,622, No. 4,333,999, No. 4,4
51,559 and 4,427,767, etc., and has a phenylureido group at the 2-position and 5-
Examples thereof include phenol couplers having an acylamino group at the position.

In order to correct the unwanted absorption of chromophores, it is desirable to use a colored coupler in combination with the color sensitive material for photography to perform masking. Yellow coloring magenta couplers described in U.S. Pat. No. 4,163,670 and Japanese Patent Publication No. 57-39413 or U.S. Pat. No. 4,004,929.
No. 4,138,258 and British Patent No. 1,1.
Typical examples are magenta color forming cyan couplers described in JP-A No. 46,368. Other colored couplers are described in RD17643, paragraphs VII-G above.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such couplers are
U.S. Pat. No. 4,366,237 and British Patent No. 2,
Specific examples of magenta couplers are disclosed in 125,570, European Patent No. 96,570 and West German Patent Application Publication 3,23.
No. 4,533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are found in US Pat. No. 3,451,82.
0 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Patent No. 4,367,
282.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is RD17643, VI described above.
The couplers of the patents described in paragraphs I-F are useful.

A preferred combination with the present invention is JP-A-57-
No. 151944, a developer inactivating type; U.S. Pat. No. 4,248,962 and JP-A-57-154234.
Timing type represented by the Japanese Patent No. 59-39653
No. 57-151944, JP-A No. 58-217932 and JP-A Nos.
Developer inactivating DIR couplers described in Japanese Patent Application Nos. 59-75474, 59-82214, 59-82214 and 59-90438, and Japanese Patent Application No. 59-75438.
It is a reactive DIR coupler described in JP-A-39653 and the like.

The light-sensitive material of the present invention can use a coupler which releases a nucleating agent or a development accelerator or a precursor thereof imagewise during development. Specific examples of such compounds are:
British Patent Nos. 2,097,140 and 2,131,1
88. A coupler which releases a nucleating agent having an adsorbing action on silver halide is particularly preferable, and specific examples thereof are described in JP-A-59-157638 and JP-A-59-170840.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D. No. 17643, page 28, and No. 18716, page 647, right column to page 648, left column.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD, N
28-29 of O.17643 and ibid., NO.18716.
No. 651, left column to right column, can be developed by the usual method.

The color photographic light-sensitive material of the present invention is usually subjected to washing treatment or stabilizing treatment after development, bleach-fixing or fixing treatment.

In the water washing step, it is general to carry out countercurrent water washing of two or more tanks to save water. A typical example of the stabilizing treatment is a multistage countercurrent stabilizing treatment as described in JP-A-57-8543 instead of the water washing step. 2-9 in the case of this step
A countercurrent bath in the bath is required. Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, various buffers (eg borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia mono) for adjusting the concentrated pH (eg pH 3 to 8). Representative examples thereof include carboxylic acid, dicarboxylic acid, polycarboxylic acid and the like) and formalin. In addition, water softener (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericide (benzisothiazolinone, irithiazolone, 4-thiazolinebenzimidazole), if necessary. , Halogenated phenols, etc.),
Various additives such as a surfactant, a fluorescent brightening agent and a hardener may be used, and two or more kinds of the same or different target compounds may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjuster after the treatment.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. The present invention also provides Research Disclosure 17123 (197).
It can also be applied to a black-and-white light-sensitive material using a mixture of three-color couplers described in July, 8).

(Example) Hereinafter, the present invention will be described based on specific examples, but the present invention is not limited thereto.

Example 1 Magenta coupler, 1- (2,4,6-trichlorophenyl) -3-{(2-chloro-5-tetradecanamido) anilino} -2-pyrazolin-5-one 10 g was tricresyl phosphate. 20m, and ethyl acetate 2
Gelatin solution 8 containing 1% sodium dodecylbenzenesulfonate aqueous solution 8m
It was emulsified and dispersed in 0 g.

Next, this emulsified dispersion was mixed with 145 g of a green-sensitive silver chlorobromide emulsion (Br50 mol%) (containing 7 g of Ag), sodium dodecylbenzenesulfonate was added as a coating aid, and both sides were laminated with polyethylene. Applied on top.

The coupler coating amount was set to 400 mg / m ² .

A gelatin protective layer (gelatin 1 g / m ² ) was coated on this layer to prepare Sample A.

In a similar manner, combinations of magenta couplers with compounds of general formula (I) of the invention and comparative compounds were prepared as shown in Table 1 in making the above emulsions. The compounds of the general formula (I) and the comparative compound were added in an amount of 50 mol% with respect to the coupler used, and Samples B to J were prepared in the same manner as Sample A except for changing the coupler and the inhibitor.

These samples were exposed at 1000 lux for 1 second and processed with the following processing solutions.

Developer Benzyl alcohol 15m diethylenetriaminepentaacetic acid _{5g KBr 0.4g Na 2 SO 3 5g} Na 2 CO 3 30g hydroxylamine sulfate 2 g 4-amino-3-methyl -N- ethyl -N-beta-(methanesulfonic Ruhon'amido) Echiruaniri down - 3 / 2H ₂ SO ₄ · H ₂ O 4.5g Water to 1000m pH 10.1 Bleach-fixer Ammonium thiosulfate (70wt%) 150m Na ₂ SO ₃ 5g Na [Fe (EDTA)] 40g EDTA 4g Water to 1000m pH6.8 Treatment process Temperature Time Developer 33 ° C. 3 minutes 30 seconds Bleach fixing plate 33 ° C. 1 minute 30 seconds Washing 28-35 ° C. 3 minutes Fuji Film cutting 400 nm or less on each sample on which a dye image is formed in this way A UV absorbing filter was attached and a fading test was performed for 5 days with a xenon tester (illuminance: 200,000 lux). Measurement is Macbeth densitometer RD-51
Performed with Type 4 (Status AA filter), initial density 2.0
The change in the density of the density part of was measured. The results are shown in Table 1.

Comparative compound (a) Comparative compound (b) Comparative compound (c) From these results, it can be seen that the sample of the present invention shows a better improvement in light fastness than the case of using a known structurally similar anti-fading agent.

Example 2 Using the exemplified compound n- (25) as the magenta coupler, a coating composition for the third layer having the composition shown in Table 3 was prepared according to the method of the sample A of Example 1, and further contained this third layer. Multilayer samples as shown in Table 3 were prepared. On the other hand, multilayer samples L to O containing the anti-fading agent of the present invention and the comparative compound as shown in Table 2 in the third layer were prepared according to the above samples.

These samples were exposed as described in Example 1,
Treated. The color-developing dye image of each sample thus obtained was exposed to a fluorescent lamp fading device (15,000 lux) for 4 weeks, and a fading test was performed to measure the change in the density of the initial density of 1.0. The results are shown in Table 2.

Comparative compound (d) Comparative compound (e) From the results shown in the above table, it can be seen that the compound of the present invention has a remarkable effect of improving color image fastness even in the case of a sample coated with multiple layers.

[Effects of the Invention] As is clear from the above results, the color photographic material of the present invention can provide a color image with extremely excellent light fastness.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material comprising at least one compound represented by the following general formula (I). General formula (I) In the formula, R ₁ and R ₂ represent a hydrogen atom, an aliphatic group, a heterocyclic group, a R ₇ CO— group, a R ₈ SO ₂ — group or a R ₉ NHCO— group, and R ₃
Represents a hydrogen atom or an aliphatic group, R ₄ represents a hydrogen atom, an aliphatic group or an aliphatic oxy group, R ₅ and R ₆ represent a hydrogen atom, an aliphatic group or an aryl group,
R ₇ , R ₈ and R ₉ represent an aliphatic group, an aryl group or a heterocyclic group, R ₃ and R ₄ may be closed, and the above aliphatic group, aryl group and heterocyclic group are Both may have a substituent. However, R ₁ and R ₂ are not hydrogen atoms at the same time, and R ₁ and R ₄ are not ring-closed.