JPH0567220B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to preventing fading and discoloration of dye images finally obtained by developing silver halide color photographic light-sensitive materials, particularly spirochroman-based discoloration prevention. This is related to drugs. (Prior Art) Color images obtained by photographically processing silver halide color photographic materials are generally azomethine dyes or indoaniline dyes formed by the reaction of an oxide of an aromatic primary amine developing agent with a coupler. Consists of. Color photographic images obtained in this way are not necessarily stable against light or moist heat;
Exposing to light for a long period of time or storing under high temperature and humidity can cause fading or discoloration of the pigmented image, resulting in deterioration of image quality. Such fading of the image is a fatal drawback to the recording material. As methods to eliminate these defects, proposals have been made to select and use couplers with low fading properties, to use anti-fading agents to prevent fading due to light, and to use ultraviolet absorbers to prevent image deterioration due to ultraviolet rays. ing. Among these, anti-fading agents have a great effect in preventing image deterioration, such as hydroquinones, hindered phenols, catechols, gallic acid esters, aminophenols, hindered amines,
and ethers or esters obtained by silylating, acylating, or alkylating the phenolic hydroxyl group of each of these compounds, as well as metal complexes (U.S. Patent No.
3935016, 3982944, 4254216, UK Patent No. 2066975, US Patent No. 3700455,
No. 4360589, No. 3457079, Special Publication No. 56-21144,
U.S. Patent No. 3336135, U.S. Patent No. 4268593, U.S. Patent No.
No. 4050938, No. 4241155, etc.) are known. Although these compounds have been recognized to be effective as agents for preventing fading and discoloration of dye images, they are insufficient to meet the demands of customers who are increasingly demanding high image quality, and they do not change the hue or change the color. However, it has not been able to exhibit an overall excellent effect for color photography because it causes fog, poor dispersion, or the formation of microcrystals after emulsion coating. On the other hand, it is known that tocopherols, which are natural antioxidants, are also useful as antifading agents for photography. Among these, α-tocopherol in particular is easily available, and the performance of many of them has been investigated. Compounds with chroman structures have been synthesized in an attempt to derive performance superior to natural tocopherols, and it is known that all of them have functions equivalent to or superior to tocopherols (U.S. Pat. No. 3,432,300, U.S. Pat. No. 3,574,627). No. 3573050, No. 4155765, No. 4264720, etc.). In addition to these, compounds with a chroman structure that forms a spiro ring (U.S. Patent No. 3764337, U.S. Patent No. 4174220)
number etc.). In this way, many compounds with a chroman structure have been synthesized starting from natural α-tocopherol and have been evaluated as antifading agents for photography. All of these have the effect of preventing fading, but as the times change, technology continues to improve.
The demand for image robustness has become even stronger, and the above-mentioned conventional techniques are now inadequate.
Further improvements are expected. (Problems to be Solved by the Invention) The purpose of the present invention is to prevent color images from discoloring for a long period of time.
An object of the present invention is to provide a color photographic material having a high degree of storage stability and in which yellow staining on a white background is significantly suppressed. Another object of the present invention is to provide a photographic antifading agent that is sufficiently effective in preventing fading and discoloration of color images without causing changes in hue or fogging. (Means for Solving the Problems) As a result of further studies on compounds having a chroma structure, the present inventors have incorporated at least one compound represented by the following general formula () into the photographic layer of a silver halide color photographic light-sensitive material. The present inventors have obtained the knowledge that the object of the present invention can be achieved by incorporating the present invention, and based on this finding, the present invention has been completed. General formula ()

[Formula] In the formula, R and R' may be the same or different, and each represents a hydrogen atom, an alkyl group (for example, methyl, ethyl, propyl, n-octyl, tert-
octyl, benzyl, hexadecyl), alkenyl groups (e.g. allyl, octenyl, oleyl),
an aryl group (e.g., phenyl, naphthyl), a heterocyclic group (e.g., tetrahydropyranyl, pyrimidyl), or R ₅ CO−, R ₆ SO ₂ −, or
R ₇ Represents a group represented by NHCO-. where R ₅ ,
R ₆ and R ₇ are each an alkyl group (e.g. methyl,
ethyl, n-propyl, n-butyl, n-actyl, tert-octyl, benzyl), alkenyl groups (e.g. allyl, octenyl, oleyl), aryl groups (e.g. phenyl, methoxyphenyl,
(naphthyl) or a heterocyclic group (eg, pyridyl, pyrimidyl). R ₁ and R′ ₁ may be the same or different, and each represents a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, bromine), an alkyl group (e.g., methyl, ethyl, n-butyl, benzyl), an alkenyl group. (e.g. allyl, hexenyl, octenyl), alkoxy groups (e.g. methoxy, ethoxy, benzyloxy), alkenoxy groups (e.g. 2-propenyloxy, hexenyloxy), aryloxy groups (e.g. phenyloxy, naphthyloxy), alkylthio groups (e.g. For example, ethylthio, butylthio), alkenylthio groups (e.g., 2-detenylthio, 2-pentenylthio), arylthio groups (e.g., phenylthio, naphthylthio), alkoxycarbonyl groups (e.g., methoxycarbonyl, butoxycarbonyl), alkylcarbonyl groups ( (e.g., acetyl, tetradecanoyl), hydroxy groups, alkylcarbonyloxy groups (e.g., acetylthioxy, tetradecanoyloxy), carbamoyl groups (e.g., N-ethylcarbamoyl, N-methyl-N-dodecylcarbamoyl), or It represents an acylamino group (eg, acetylamino, benzamino), and n represents an integer from 1 to 3. _R2
is a hydrogen atom, an alkyl group (e.g. methyl, ethyl, n-butyl, benzyl), an alkenyl group (e.g. 2-propenyl, hexenyl, octenyl), or an aryl group (e.g. phenyl, methoxyphenyl, chlorphenyl, naphthyl) represents. R ₃ and R ₄ are each a hydrogen atom, an alkyl group (e.g. methyl, ethyl, n-butyl), an alkenyl group (e.g. allyl, octenyl), an alkoxy group (e.g. methoxy, butoxy), an alkenoxy group (e.g. 2 -propenyloxy, hexenyloxy), aryloxy groups (e.g. phenyloxy, naphthyloxy), alkylthio groups (e.g. ethylthio, butylthio), alkenylthio groups (e.g. 2-butenylthio, 2-bentenylthio), or arylthio groups (e.g.
phenylthio, naphthylthio). However, R and R ₁ or R' and R' ₁ or n is 2
In the above cases, R ₁ 's or R ₁ ''s do not connect with each other to form a ring. Among the compounds represented by the general formula (), R ₂ ,
R ₃ and R ₄ are preferably groups selected from hydrogen atoms and alkyl groups, and more preferably R and R' are groups selected from hydrogen atoms and alkyl groups. . Further, R ₁ and R' ₁ are preferably a hydrogen atom, an alkyl group, an alkoxy group, or a hydroxy group, and n is preferably an integer of 1. The compound represented by the general formula () of the present invention has a structure similar to that of the spirochroman-based antifading agents described in US Pat. When the compound represented by the general formula () of the present invention is used in combination with the above-mentioned known anti-fading agent, its effect becomes even greater. Similarly, two or more of the compounds represented by the general formula () may be used in combination. The compound of general formula () used in the present invention differs depending on the type of coupler, but usually
Suitably, it is used in a range of 0.5 to 200 weight percent, preferably 2 to 150 weight percent. Representative examples of these compounds are shown below.
This does not limit the compounds used in the present invention.

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[ka]

[Chemical formula] The 2,2'-spirobischroman compound used in the present invention is manufactured by the Journal of the American Chemical Society (J.Amer.
Chem.Soc.), 72 3009 (1950). Synthesis examples of specific compounds are shown below, but other compounds can also be synthesized by similar methods. Synthesis example 1 6,6'-dimethoxy-7,4'-dimethyl-2,
Synthesis of 1,4-bis(2-hydroxy-4-methoxy-5-methyl)-1,4-pentadien-3-one, a synthetic intermediate for 2'-sprobischroman (compound No. 10) 2-hydroxy- 4-methoxy-5-methyl-
Dissolve 33.2 g (0.2 mol) of benzaldehyde in 100 ml of ethanol and dissolve 6 g (0.102 mol) of acetone.
was added and stirred at 20°C to 25°C. A solution of 16 g (0.4 mol) of sodium hydroxide dissolved in 25 ml of water was added dropwise to this over 30 minutes. After further stirring for 4 hours, the precipitated crystals were washed with 50 ml of cold ethanol to obtain 32.6 g of yellow crystals. (yield 82%) 6,6'-dimethoxy-7,7'-dimethyl-2,
Synthesis of 2'-spirobischroman Dissolve 32.6 g (0.082 mol) of 1,4-bis(2-hydroxy-4-methoxy-5-methyl)-1,4-pentadien-3-one in 150 ml of ethanol and add palladium/ 1.6 g of carbon was added, and hydrogenation was carried out under pressure of hydrogen gas at 25°C to 30°C in an autoclave. After the palladium/carbon was filtered off, the mixture was poured into 300 ml of ice water containing 15 ml (0.174 mol) of concentrated hydrochloric acid, and extracted with 300 ml of ethyl acetate. After washing twice with 200 ml of cold water, it was dried with anhydrous sodium sulfate. After filtering out Glauber's salt, 6 ml (0.1 mol) of acetic acid was added, and ethyl acetate was distilled off under reduced pressure at a bath temperature of 80°C to 90°C. 80 ml of acetonitrile was added to this for crystallization. When this crude crystal is recrystallized with 60 ml of acetonitrile, the melting point is 153℃~150℃.
21.2 g of colorless crystals were obtained. (Yield 76%) Elemental analysis values C: 74.04% H: 7.09% Calculated values C: 74.09% H: 7.12% Synthesis example 2 7,7'-dimethyl-6,6'-tetradecanoyloxy-2, 2′-spirobiscuman (compound no.
12) Synthesis of intermediate 1,4-bis(4-benzyloxy-2
Synthesis of -hydroxy-5-methyl)-1,4-pentadien-3-one 24.2 g (0.1 mol) of 4-benzyloxy-2-hydroxy-5-methyl-benzaldehyde was added to 100
ml of ethanol and 3 g of acetone (0.051
mol) was added and stirred at 20°C to 25°C. A solution of 8 g (0.2 mol) of sodium hydroxide dissolved in 16 ml of water was added dropwise to this over 30 minutes. After further stirring for 4 hours, the precipitated crystals were washed with 30 ml of cold ethanol to obtain 24.7 g of yellow crystals. (Yield 90%) 6,6'-dihydroxy-7,7'-dimethyl-
Synthesis of 2,2'-spirobischroman 1,4-bis(2-benzyloxy-2-hydroxy-5-methyl)-1,4-pentadiene-
24.7g (0.045mol) of 3-one in 250ml of ethanol
, add 1.2g of palladium/carbon,
Hydrogenation was carried out under pressure of hydrogen gas at 35°C to 40°C in an autoclave. After the palladium/carbon was filtered off, the mixture was immediately poured into 300 ml of ice water to which 17.2 ml (0.2 mol) of concentrated hydrochloric acid had been added, and extracted with 500 ml of diethyl ether. After washing with 200 ml of cold water, it was dried with anhydrous sodium sulfate. After filtering out the Glauber's salt, diethyl ether was distilled off under reduced pressure, and 100 ml of acetic acid was added and dissolved by heating.
Acetic acid was distilled off under reduced pressure at a bath temperature of 80°C to 90°C, solidified and ground by adding n-hexane, and filtered. Yield 9.8g
(Yield 70%) Synthesis of 7,7'-dimethyl-6,6'-tetradecanoyloxy-2,2'-spirobiscumane 6,6'-dihydroxy-7,7'-dimethyl-
2,2'-spirobischroman 5g (0.016 mol)
50ml of acetonitrile, 5ml of triethylamine
(0.036 mol was added and dissolved and stirred at 20°C to 25°C.
Add to this 7.9 g of tetradecanoyl chloride (0.032
mol) was added dropwise over 15 minutes. After stirring for an additional hour, the mixture was poured into 200 ml of ice water containing 1 ml of concentrated hydrochloric acid, and extracted with 100 ml of ethyl acetate. Add 200ml of cold water
After washing twice with water, it was dried with anhydrous sodium sulfate. After filtering out Glauber's salt, ethyl acetate was distilled off under reduced pressure, and the residue was purified by column chromatography. This was solidified and ground by adding n-hexane, and filtered. Yield 7.9g
(Yield 67%) Elemental analysis value C: 77.05% H: 9.89% Measured value C: 77.00% H: 9.90% The compound represented by the general formula () of the present invention is yellow covlar, magenta covlar, or cyan covlar. Can be used in combination. The couplers used in combination may be 4 equivalents or equivalents to silver ions, and
It may be in the form of a polymer or oligomer. Further, the couplers may be used alone or in combination of two or more. The general formulas of preferred couplers for use in the present invention are shown below. General formula ()

【formula】 General formula ()

【formula】 General formula ()

【formula】 General formula ()

【formula】 General formula ()

[Formula] (wherein R ₁ , R ₄ and R ₅ are each an aliphatic group,
represents an aromatic group, a heterocyclic group, an aromatic omino group or a heterocyclic amino group, R ₂ represents an aliphatic group, R ₃
and R ₆ are hydrogen atom, halogen atom,
represents an aliphatic group, an aliphatic oxy group, or an acylamino group; R ₇ and R ₉ represent a substituted or unsubstituted phenyl group; R ₈ represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic acyl group; _R10 represents a hydrogen atom or a substituent, Q represents a substituted or unsubstituted N-phenylcarbamoyl group, Za and Zb are methine, substituted methine, or =
N- represents Y ₁ , Y ₂ , Y ₃ , Y ₄ and Y ₅ , a hydrogen atom, or a group capable of leaving during a coupling reaction with an oxidized developing agent (hereinafter referred to as a leaving group). R ₂ in general formula () and general formula ()
and R ₃ and R ₅ and R ₆ may each form a 5-, 6-, or 7-membered ring. Furthermore, R ₁ , R ₂ , R ₃ or Y ₁ ; R ₄ , R ₅ , R ₆ or
_Y2 ; _R7 , _R8 , _R9 or _Y3 ; _R10 , Za, Zb or _Y4 ;
Q or Y ₅ may form a dimer or more multimer. The aliphatic group mentioned here refers to a linear, branched or cyclic alkyl, alkenyl or alkynyl group. Preferred examples of couplers represented by general formulas () and () are shown below. (C-1)

[ka] (C-2)

[ka] (C-3)

[ka] (C-4)

【formula】 (C-5)

[ka] (C-6)

[ka] (C-7)

[ka] (C-8)

[ka] (C-9)

[ka] (C-10)

[ka] (C-11)

【formula】 (C-12)

[ka] (C-13)

[ka] (C-14)

[ka] (C-15)

[ka] (C-16)

[ka] (C-17)

[ka] (C-18)

[ka] (C-19)

[ka] (C-20)

[ka] (C-21)

[ka] (C-22)

[ka] (C-23)

[ka] (C-24)

[ka] (C-25)

[ka] (C-26)

[ka] (C-27)

[ka] (C-28)

[ka] (C-29)

[ka] (C-30)

[ka] (C-31)

[ka] (C-32)

[C] (C-33)

【formula】 (C-34)

[ka] x/y/z=50/20/30 (wt ratio) (C-35)

[ka] x/y=55/45 (wt ratio) (C-36)

[ka] x/y=60/40 (wt ratio) (C-37)

[ka] x/y=50/50 (wt ratio) (C-38)

[ka] x/y/z=55/40/5 (wt ratio) (C-39)

[ka] x/y=60/40 (wt ratio) (C-40)

[ka] x/7=50/50 (wt ratio) (C-41)

[ka] x/y=45/55 (wt ratio) (C-42)

[ka] x/y=50/50 (wt ratio) (C-43)

[ka] x/y/z=45/45/10 (wt ratio) (C-44)

[ka] x/y/z=50/20/30 (wt ratio) (C-45)

embedded image x/y=50/50 (wt ratio) Preferred specific examples of the couplers represented by the general formulas [] and [] are shown below. (M-1)

【formula】 (M-2)

[ka] (M-3)

[ka] (M-4)

[ka] (M-5)

[Formula] (M-6)

【formula】 (M-7)

【formula】 (M-8)

[ka] (M-9)

[ka] (M-10)

[ka] (M-11)

[ka] (M-12)

[ka] (M-13)

[ka] (M-14)

[ka] (M-15)

[ka] (M-16)

[ka] (M-17)

[ka] (M-18)

[ka] (M-19)

[ka] (M-20)

[ka] (M-21)

[ka] (M-22)

[ka] (M-23)

[ka] (M-24)

[ka] (M-25)

[ka] (M-26)

[ka] (M-27)

[ka] (M-28)

[ka] (M-29)

[ka] (M-30)

[ka] (M-31)

[ka] (M-32)

[ka] (M-33)

[ka] (M-34)

[ka] (M-35)

[ka] (M-36)

[ka] x/y/z=50/25/25 (wt ratio) (M-37)

[ka] x/y=50/50 (wt ratio) (M-38)

[ka] v/y/z=50/25/25 (wt ratio) (M-39)

[ka] /y=50/50 (wt ratio) (M-40)

[ka] x/y=40/60 (wt ratio) (M-41)

[ka] x/y=45/55 (wt ratio) (M-42)

[ka] v/y/z=50/45/5 (wt ratio) (M-43)

[ka] x/y=50/50 (wt ratio) (M-44)

[ka] x/y/z=45/50/5 (wt ratio) (M-45)

[ka] x/y=50/50 (wt ratio) (M-46)

[ka] x/y=50/50 (wt ratio) (M-47)

embedded image x/y=45/55 (wt ratio) Preferred specific examples of the coupler represented by the general formula [] are shown below. (Y-1)

[ka] (Y-2)

[ka] (Y-3)

[ka] (Y-4)

[ka] (Y-5)

[ka] (Y-6)

[ka] (Y-7)

[ka] (Y-8)

[ka] (Y-9)

[ka] (Y-10)

[ka] (Y-11)

[ka] (Y-12)

[ka] (Y-13)

[ka] (Y-14)

[ka] (Y-15)

[ka] (Y-16)

[ka] (Y-17)

[ka] (Y-18)

【formula】 (Y-19)

[ka] (Y-20)

[ka] (Y-21)

[ka] (Y-22)

[ka] (Y-23)

[ka] (Y-24)

[ka] (Y-25)

[ka] (Y-26)

[ka] (Y-27)

[ka] (Y-28)

[ka] (Y-29)

[ka] (Y-30)

[ka] (Y-31)

[ka] (Y-32)

[ka] (Y-33)

[ka] (Y-34)

[ka] (Y-35)

[ka] (Y-36)

[ka] (Y-37)

[ka] (Y-38)

[ka] (Y-39)

[ka] (Y-40)

[ka] x/y=50/55 (wt ratio) (Y-41)

[ka] x/y=45/55 (w+ratio) (Y-42)

[ka] x/y/z=50/45/5 (wt ratio) (Y-43)

[ka] x/y=50/50 (wt ratio) (Y-44)

[ka] x/y=50/50 (wt ratio) (Y-45)

[ka] x/y/z=55/40/5 (wt ratio) (Y-46)

[ka] x/y=60/40 (wt ratio) (Y-47)

[ka] x/y=50/50 (wt ratio) (Y-48)

[Chemical formula] x/y/z=60/30/10 (wt ratio) Other exemplary compounds or synthesis methods of couplers represented by the general formulas () to () are listed below. The cyan couplers represented by general formula () and general formula () can be synthesized by known methods. For example, the cyan coupler represented by the general formula () is synthesized by the method described in US Pat. Nos. 2,423,730 and 3,772,002. The cyan coupler represented by the general formula () is disclosed in U.S. Patent No. 2895826,
It is synthesized by the method described in 4333999, 4327173, etc. The magenta coupler represented by the general formula () is
No. 48-27930, No. 53-33846 and U.S. Pat.
It is synthesized by the method described in No. 3519429. The magenta coupler represented by the general formula (
It is synthesized by the method described in JP-A-59-171956 and JP-A-60-33552. The yellow coupler represented by the general formula () is disclosed in Japanese Patent Application Laid-Open No. 54-48541, Japanese Patent Publication No. 58-10739, U.S. Patent No. 4326024, and Research Disclosure.
It can be synthesized by the method described in No. 18053. The couplers used in the present invention are also colored couplers that have a color correction effect, or couplers that release a development inhibitor during development (so-called DIB).
It may also contain a coupler. The coupler may be one in which the product of the coupling reaction is colorless. As a colored coupler, for example, U.S. Patent No.
No. 3476560, No. 2521908, No. 3034892, Tokko Akira
No. 44-2016, No. 38-22335, No. 42-11304, No. 42-11304, No.
44-32461, JP-A-51-26034 specification, 5-
Specification No. 42121, West German Patent Application (OLS) 2418959
You can use those listed in the issue. As a DIR coupler, for example, U.S. Patent No.
No. 3227554, No. 3617291, No. 3701783, No. 3227554, No. 3617291, No. 3701783, No.
No. 3790384, No. 3632345, West German patent application (OLS)
No. 2414006, No. 2454301, No. 2454329, British Patent No. 953454, Japanese Patent Application Publication No. 1983-69624, No. 49-122335
Those described in Japanese Patent Publication No. 51-16141 can be used. In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development control agent during development; for example, U.S. Pat.
West German Patent Application (OLS) No. 2417914, Japanese Unexamined Patent Publication No. 1983-
Those described in No. 15271 and JP-A No. 539116 can be used. Among these, it is preferable to use it in combination with magenta couplers represented by the general formulas () and () in terms of the effects of the present invention. These couplers are generally added in an amount of 2 x 10 ^-3 mol to 5 x 10 ^-1 mol, preferably 1 x 10 ^-2 mol to 5 x 10 ^-1 mol, per mol of silver in the emulsion layer. In carrying out the present invention, the following known antifading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include, for example, U.S. Pat. No. 2,360,290, U.S. Pat.
2701197, 2704713, 2728659, 2701197, 2704713, 2728659,
No. 2732300, No. 2735765, No. 2710801, No. 2732300, No. 2735765, No. 2710801, No.
Hydroquinone derivatives described in No. 2816028, British Patent No. 1363921, etc., U.S. Patent No. 3457079,
Gallic acid derivatives described in U.S. Patent No. 3069626, etc., U.S. Pat.
p-alkoxyphenols described in US Pat. No. 20977 and US Pat. No. 52-6623, US Pat.
No. 3573050, No. 3574627, No. 3764337, JP-A-Sho
Examples include p-oxyphenol derivatives described in No. 52-35633, No. 52-14743, and No. 52-152225, and bisphenols described in U.S. Pat. Examples of methods for introducing the compound of the present invention (color image stabilizer) into the photographic layer of a color photosensitive material include:
It is also possible to dissolve the compound in a low-boiling organic solvent such as ethyl acetate or ethanol and directly add it to a mixed solution of a silver halide emulsion or coupler dispersion without emulsifying it. However, the compound of the present invention (color image stabilizer) is dissolved in a high boiling point solvent such as dibutyl phthalate, tricresyl phosphate, etc. together with the coupler, if necessary in the presence of a low boiling point auxiliary solvent, and is dissolved in an aqueous solution such as gelatin. It is desirable to add it to a silver halide emulsion as an emulsified dispersion in which oil droplets are dispersed in a protective colloid, or as an emulsified dispersion of only the color image stabilizer of the present invention together with a coupler dispersion. The photographic layer to which the compound of the present invention (color image stabilizer) is added includes coupler-containing silver halide light-sensitive emulsion layers (for example, red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, blue-sensitive silver halide emulsion layer). Emulsion layer), non-light-sensitive photographic auxiliary layer (e.g., protective layer, filter layer, intermediate layer, subbing layer, etc.), but in particular, the color image stabilizer of the present invention can be used in a magenta coupler-containing photographic layer. In other words, it is particularly effective for preventing fading and discoloration of magenta images. Typical examples of high-boiling organic solvents used for dispersing the color image stabilizer used in the present invention alone or together with couplers are butyl phthalate, dinonyl phthalate, butyl benzoate, diethylhexyl sebacate, butyl stearate, and dinonyl maleate. , tributyl citrate, tricresyl phosphate, dioctylbutyl phosphate, trihexyl phosphate, triotadecyl phosphate, etc. as described in US Pat. No. 3,676,137, diethyl succinate, dioctyl adipate,
3-Ethylbiphenyl, "Improved Photographic Dye Image Stabilizer", Product Licensing Index Vol. 83, pp. 26-29 (March 1971)
These include liquid dye stabilizers listed in Japan). Examples of low-boiling organic solvents used as co-solvents along with high-boiling organic solvents include ethyl acetate, butyl acetate, ethyl propionate, ethyl formate, butyl formate, nitroethane, carbon tetrachloride, chloroform, hexane, cyclohexane, ethylene glycol, Examples include acetone, ethanol, dimethylformamide, dioxane, etc., but benzene, toluene, xylene, etc. can also be added to these solvents. Examples of surfactants used in dispersing a solution of the color image stabilizer used in the present invention alone or together with a coupler in an aqueous protective colloid solution include sabonin, sodium alkylsulfosuccinate, and alkylbenzenesulfon. Examples of hydrophilic protective colloids include gelatin (either coal gelatin or acid-treated gelatin). , sazein, carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, styrene-maleic anhydride copolymer, condensate of styrene-maleic anhydride copolymer and polyvinyl alcohol, polyacrylate, ethyl cellulose, etc. It is not limited to these. The supports used in the present invention are usually cellulose nitrate films, cellulose acetate films, cellulose acetate butyrate films, cellulose acetate propionate films, polystyrene films, polyethylene terephthalate films, which are used in photographic materials.
Examples include polycarbonate film, other laminates thereof, thin glass film, paper, etc. Paper coated or laminated with baryta or α-olefin polymers, especially polymers of α-olefins having 2 to 10 carbon atoms, such as polyethylene, polypropylene, ethylene butene copolymers, etc.
Supports such as plastic films whose surfaces are roughened to improve adhesion to other polymeric substances as shown in No. 19068 also give good results. These supports are selected to be transparent or opaque depending on the purpose of the photosensitive material. It is also possible to add dyes or pigments to make it transparent. Opaque supports include those that are inherently opaque such as paper, transparent films that have dyes or pigments such as titanium oxide added to them, or those that have been surface-treated by the method described in Japanese Patent Publication No. 19068/1983. It also includes plastic film, and also paper or plastic film that has been made completely light-shielding by adding carbon black, dye, etc. The support is usually provided with an undercoat layer. In order to further improve adhesion, the surface of the support may be subjected to preliminary treatment such as corona discharge, ultraviolet irradiation, flame treatment, etc. When carrying out the present invention, it is of course possible to provide an ultraviolet absorbing layer on the upper surface of the photographic light-sensitive emulsion layer, which is an image forming layer, to be more effective against discoloration and fading caused by light. Yes, it is preferable. Furthermore, the present invention is not limited by the types of commonly used color processing agents, such as color developers, bleaching agents, fixing agents, etc. In particular, the present invention can be advantageously applied to silver-blind color photosensitive materials described in US Pat. No. 3,902,905 and the like. In addition, West German patent OLS181390, Japanese Patent Application Publication No. 1972-9728, Japanese Patent Publication No. 1973
There are no restrictions on the type of intensifying agent used in the color intensifying treatment described in No. 14625. Color photosensitive materials to which the present invention can be applied include ordinary color photosensitive materials, especially color photosensitive materials for printing, but also U.S. Pat.
No. 3227551, No. 3227552 and US Provisional Publication Patent US,
It may also be a color photographic method, particularly a color diffusion transfer photographic method, as described in No. B351673. The color photographic material of the present invention also requires color photographic development treatment after exposure in order to obtain a dye image. Color photographic processing basically includes color development; bleaching; and fixing steps. In some cases, two steps can be completed in one treatment. Alternatively, a combination of color development, first fixing, and bleach-fixing is also possible. In the development process, a pre-hardening bath, neutralization bath, first development (black and white development), image stabilization bath,
Various processes such as washing with water are combined. Processing temperature is 18℃
More often than not. Especially often used is 20℃
~60°C, and recently in the range of 30°C to 60°C. The color developing solution is an alkaline aqueous solution containing an aromatic primary amine color developing agent and having a pH of 8 or more, preferably 9 to 12. Examples of the color developing agent include 4-amino N,N-diethylaniline, 3-amino
Methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-hydroxyethylaniline,
4-amino-3-methyl-N-ethyl-N-β-
Methanesulfamide ethylaniline, 4-amino-N,N-dimethylaniline, 4-amino-3-
Methoxy-N,N-diethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, 4-amino-3-methoxy-N
-ethyl-N-β-methoxyethylaniline, 4
-Amino-3-β-methanesulfamide ethyl-
Preferred representative examples include N,N-diethylaniline and salts thereof (eg, sulfate, hydrochloride, sulfite, p-toluenesulfonate, etc.). Others: U.S. Patent No. 2193015, U.S. Patent No. 2592364
No. 48-64933 or L.F.A. Meson, Photographic Processing Chemistry (published by Focal Press in 1966)
[LFAMason, Photographic Processing
226 in Chemistry (Focal Press, London, 1966)
It is also written on pages 229 and 229. Color developers 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. can. Specific examples of antifoggants include potassium bromide, potassium iodide, nitrobenzimidazoles described in U.S. Pat. -Mercaptotetrazole, U.S. Patent Nos. 3,113,864, 3,342,596,
Compounds described in No. 3295976, No. 3615522, No. 3597199, etc., thiosulfonyl compounds described in British Patent No. 972211, or phenazine-N-oxides as described in Japanese Patent Publication No. 46-41675, scientific photographs These include fog suppressants listed in the Handbook, Volume 2, pages 29 to 47. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, It may also contain a fogging agent such as sodium borohydride, an auxiliary developer such as 1-phenyl-3-pyrazolidone, a tackifying agent, and the like. In addition, when the color developer contains benzyl alcohol, it is preferably 2.0 ml or less, and 0.5 ml/
The following are more preferred. Preferably, no benzyl alcohol is added. Color development time is 2
The time is preferably within minutes and 30 seconds, and more preferably between 30 seconds and 2 minutes and 30 seconds. The most preferable time is 45 seconds or more and 2 minutes or less. The color photosensitive material of the present invention is subjected to ordinary color development processing, but the following color intensification color development processing can also be applied. For example, US patent
No. 3674490, No. 3761265, West German patent application (OLS)
No. 2056360, JP-A-47-6338, JP-A-47-10538
No., JP-A-52-13335, JP-A No. 52-13334, JP-A No. 52-
13336, etc., and West German Patent Application (OLS) No. 2226770, JP-A-Sho.
No. 48-9728, No. 48-9729, JP-A-51-6026,
No. 51-94822, No. 51-133023, No. 52-7728,
52-11034, etc., as well as the method using cobalt complex salts described in JP-B No. 52-14625, JP-A-51-
No. 99022, No. 51-103430, etc., using chlorous acid. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Bleach agents include iron (), cobalt (), chromium (), and copper ().
Compounds of polyvalent metals such as, peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron () or cobalt (), aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid, or citric acid, Complex salts of organic acids such as tartaric acid and malic acid; persulfates and permanganates;
Nitrosophenols and the like can be used.
Of these, potassium ferricyanide, sodium ferric ethylenediaminetetraacetate, and ammonium ferric ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron() complex salts are useful in both stand-alone bleach solutions and single bath bleach-fix solutions. Bleach or bleach-fix solution is a U.S. patent
Various additives can be added, including the bleaching accelerators described in Japanese Patent Publication No. 3042520, Japanese Patent Publication No. 3241966, Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 45-8836, etc. (Effects of the Invention) The silver halide color photographic light-sensitive material of the present invention does not discolor color images for a long period of time, significantly suppresses yellow staining on white backgrounds, and has a high degree of storage stability. In the color photographic light-sensitive material of the present invention, the antifading agent has a sufficient effect in preventing fading and discoloration of color images without causing a change in hue or fogging. (Example) The present invention will be described below based on specific examples, but is not limited thereto. Example 1 10 g of magenta coupler M-1 was dissolved in 20 ml of tricresyl phosphate and 20 ml of ethyl acetate, and this solution was added to 80 g of a gelatin solution containing 8 ml of a 1% aqueous solution of sodium dodecylbenzenesulfonate.
It was emulsified and dispersed. Next, this emulsified dispersion was mixed with 145 g (containing 7 g of Ag) of a green-sensitive silver chlorobromide emulsion (Br 50 mol%), sodium dodecylbenzenesulfonate was added as a coating aid, and paper was laminated on both sides with polyethylene. Coated on a support. The coupler application amount was set at 400 mg/m ² . A gelatin protective layer (gelatin 1 g/m ² ) was applied on top of this layer to prepare sample A. When making the above emulsified dispersion using the same method, Table 1
Magenta coupler M-17 or M- as shown in
A combination of 23 or M-31 and a compound of the general formula () of the present invention or a comparative compound as an antifading agent was prepared. The compound of general formula () and the comparative compound were added in an amount of 50 mol% based on the coupler used.
Samples B to T were prepared by applying the same method as sample A except for changing the anti-fading agent. These samples were exposed to light at 1000 lux for 1 second and treated with the following processing solution. Developer solution Benzyl alcohol 15ml Diethylenetriamine pentaacetic acid 5g KBr 0.4g Na ₂ SO ₃ 5g Na ₂ CO ₃ 30g Hydroxamine sulfate 2g 4-amino-3-methyl-N-ethyl-N-β-
(Methanesulfonamide)ethylaniline・3/
2H ₂ SO ₄・H ₂ O 4.5g Make up to 1000ml with water PH10.1 Bleach-fix ammonium thiosulfate (70wt%) 150ml Na ₂ SO ₃ 5g Na (Fe (EDTA)) 40g EDTA 4g Make up to 1000ml with water PH6. 8 Processing process Temperature Time Developing solution 33°C 3 minutes 30 seconds Bleach-fixing solution 33°C 1 minute 30 seconds Washing 28°C - 35°C 3 minutes Each sample with a dye image formed in this way
Attach a Fujifilm ultraviolet absorption filter that cuts out wavelengths below 400 nm, and use a xenon tester (illuminance
200,000 lux) for 6 days. Measurements were performed using a Macbeth densitometer RD-514 model (Status AA filter), and changes in concentration at the initial concentration of 2.0 were measured. The results are shown in Table 1.

【table】

[Table] Example 2 Using M-25 as a magenta coupler, a coating composition for the third layer having the composition shown in Table 3 was prepared according to the method for Sample A of Example 1, and a coating composition containing the third layer was prepared. A multilayer sample like No. 3 was prepared. On the other hand, according to the above samples, multilayer samples b to
Five types of f were produced. These samples were exposed and processed in the same manner as in Example 1. The color image of each sample thus obtained was exposed to light using a fluorescent lamp bleacher (15,000 lux) four times for a fading test, and changes in density at the initial density of 1.0 were measured. The results are shown in Table 2. From these results, it was confirmed that the compound of the present invention has a remarkable effect on preventing photofading of color images. In addition, these samples are separately prepared with Blue−Green−Red.
When three-color separation exposure was applied, the same processing as in Example 1 was performed, and the magenta hues were compared, it was found that samples b to d gave hues with excellent chroma that were exactly the same as sample a. It was found that the addition of the compound of the present invention did not affect the hue in any way.

【table】

【table】

【table】

[Table] Example 3 The magenta coupler in Sample A of Example 1 was replaced with cyan coupler C-1, and the green-sensitive silver chlorobromide emulsion was replaced with a red-sensitive silver chlorobromide emulsion (Br 50 mol%). Sample g was prepared in the same manner as in Example 1 except for this. A sample in which 50 mol% of the color image stabilizer was added to the coupler was prepared in the same manner. Exposure and development were performed in the same manner as in Example 1. In order to check the light resistance of each sample that had formed a dye image in this way, we attached a Fujifilm ultraviolet absorption filter that cuts out wavelengths of 400 nm or less, and after 500 hours of exposure with a xenon tester (illumination intensity of 100,000 lux), the initial density was 2.0. The residual rate of dye after exposure is expressed as a percentage. In addition, in order to examine heat resistance, the dye residual rate at an initial concentration of 2.0 when stored in the dark at 100°C for 100 hours was expressed as a percentage.

[Table] Example 4 The magenta coupler in Sample A of Example 1 was replaced with yellow coupler Y-35, and the green-sensitive silver chlorobromide emulsion was replaced with a blue-sensitive silver chlorobromide emulsion (br 80 mol%). Sample 1 was prepared in the same manner as in Example 1 except for the following. A sample in which 50 mol% of the color image stabilizer was added to the coupler was also prepared in the same manner. Exposure and development were performed in the same manner as in Example 1. In order to examine the light resistance, the dye was exposed for 200 hours using a xenon tester in the same manner as in Example 3, and the residual rate of the dye after exposure at an emission density of 2.0 was expressed as a percentage. In addition, to examine heat resistance, the samples were stored in the dark at 100°C for 500 hours, and the dye residual rate at an initial concentration of 2.0 was expressed as a percentage. The results are shown in Table 5.

[Table] As can be seen from the results of Examples 1 to 4, the general formula () of the present invention was compared with known similar compounds.
The compound represented by has an excellent anti-fading effect on all cyan, magenta and yellow color images. Furthermore, it can be seen that especially for cyan and yellow color images, the effect of not only light fastness but also heat fastness is excellent.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material containing at least one compound represented by the following general formula (). [Formula] (In the formula, R and R' may be the same or different, and each is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an R ₅ CO- group,
R ₆ SO ₂ - group or R ₇ NHCO- group, R ₁ and R ₁ ' may be the same or different, and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenoxy group, It represents an aryloxy group, an alkylthio group, an alkenylthio group, an arylthio group, an alkoxycarbonyl group, an alkylcarbonyl group, a hydroxy group, an alkylcarbonyloxy group, a carbamoyl group, or an acylamino group, and n represents an integer from 1 to 3.
However, R ₅ , R ₆ and R ₇ each represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. R ₂ represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, and R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkenoxy group, an aryloxy group, an alkylthio group, an alkenylthio group, Or represents an arylthio group. Further, R and R ₁ , R' and R ₁ ', or R 1 and R ₁ when n is 2 or more, or R ₁ ' do not bond to each other to form a ring. )