JPH012042A - Silver halide color photographic material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color photographic material that has excellent resistance to exposure to heat, heat, and humidity, and has little staining. This invention relates to silver halide color photographic materials.

(Prior art and its problems) Silver halide color photographic light-sensitive materials are subjected to imagewise GFT,
It is developed with an aromatic amine color developer, and a dye stage is formed by the reaction of the resulting oxidized developer with a dye image-forming coupler (hereinafter referred to as coupler). In color photographic materials, a combination of yellow coupler, cyan coupler and magenta coupler is usually used.

Generally, the quality of photographic images obtained with silver halide color photographic materials is not permanent, and deteriorates over time during storage. In particular, when color photographs are exposed to light for long periods of time or stored in high temperature and high humidity conditions, it is common for pigmented images to fade or discolor, and even the white background to discolor, resulting in image deterioration. Such image deterioration is a fatal drawback for recording materials. Many proposals have been made to eliminate these drawbacks. Among these, the most effective method is the use of anti-fading agents.

For example, hydroquinones, hindered phenol It,
) Copherols, p'mans, coumarans, and compounds in which the phenolic hydroxyl group of these compounds is etherified (US Pat.
JO, No. 144, No. 3 700.1411 Remaining No. 3
, 7t-1437, J, 4'J, JOO, J, 173,010, J/1,
British Patent No.

No. 044.971, No. 1. Jet, It-R, Japanese Patent Publication No. 11-304444, etc.) are known.

Although these compounds have been recognized to be effective as agents for preventing fading and changes in dye images, they cannot meet the demands of customers who are increasingly demanding high image quality because they produce undesirable components and change the hue. However, it has not been able to exhibit an overall excellent effect for color photography because it causes fogging, poor dispersion, or formation of microcrystals after emulsion coating.

Recently, it has been found that colored stains occur over time after processing due to processing solution components remaining in the photosensitive material after development. Among the components of the processing solution, the color developing agent in particular is greatly involved in the generation of colored stains. For the purpose of preventing such colored stains, US Pat. No. 44,444
No. 3.011, same #, 813, ri No. 11, Tokukai Sho!
Data air, aUS issue, same jter 229. ! ! The effectiveness of amine compounds such as No. 7 has been proposed.

Although these compounds were effective to some extent in preventing colored staining, they were still insufficient in terms of overall preservation of color photographs.

(Problems to be Solved by the Invention) As described above, when color photographs are viewed as long-term storage recording materials, their preservability is not sufficient, and there is a need to further improve their preservability.

Therefore, an object of the present invention is to provide a color photographic material in which the fastness of color images is significantly improved.

A first object of the present invention is to provide a color photographic light-sensitive material in which the occurrence of stain on a white background in uncolored areas is significantly prevented from occurring when exposed to light, heat, and humidity.

A third object of the present invention is to provide a color photographic material in which the generation of colored stains caused by processing solution components, particularly residual color developing agent, brought into the material after development is significantly prevented.

The first objective of the present invention is to reduce the amount of processing solution components such as a processing solution containing a large amount of water, a processing solution with a small amount of water washing, or a processing solution with no water washing, and a color developing solution that does not substantially contain benzyl or alcohol, carried into the photosensitive material. It is an object of the present invention to provide a color photographic material that has a remarkable effect of improving storage stability even when the composition of a processing solution is changed, such as a processing solution with a large amount of water or a processing solution that places a burden on background color development.

A third object of the present invention is to provide a color photographic material in which the color balance of the three colors yellow, magenta, and cyan dyes is maintained even during long-term storage, and the coloring of the white background is significantly reduced. be.

(Means for Solving the Problems) As a result of various studies, the present inventors unexpectedly found that at least one of the compounds represented by the following general formula (1), (It) or (III) and ( 1) A specific anti-fading agent represented by the following general formula CN) or (2) Copper, cobalt,
The above object can be achieved by containing at least one organometallic complex having nickel, palladium or platinum as a central metal and at least one organic ligand having a bidentate or higher conformation. I understand.

General formula (INR1(A-packed A represents a group that reacts with and leaves the aromatic amine developer, and A represents a group that reacts with an aromatic amine developer to form a chemical bond. n is /
Or 01&: represents. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or a sulfonyl group,
Y represents a group that promotes addition of an aromatic amine developer to the compound of general formula (II).

Here, Ro, X1Y, and R+2 or B may be bonded to each other to form a cyclic structure.

General formula (I[I) -Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group.

General formula (■) R3o-W-R3□ In the formula, '30 represents an aliphatic group, an aromatic group, or a heterocyclic group. R+3□ is a hydrogen atom or an aliphatic group. Here, 几, R and "34" may be the same or different and each represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyl group, or an aryloxy group.

W represents 10-1-S- or -to-. Here, kL35 represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, an oxyradical group, or a hydroxyl group.

R3゜ and R3□ may be combined with each other to form a J~7-membered ring, and , , and R3゜ or 几, □ may be combined with each other to form a J~7-membered ring. .

Among these, in terms of the effects of the present invention, - Formula (1)% (II)
The compound represented by n has a second-order reaction rate constant with p-anisidine measured by the method described in Application No. 4/-113 P/P, where 2(to"c) is i, op/mol-sec N/x
Compounds in the range of 10 g/mol@sec are preferred, while compounds represented by general formula (lli) have a
earson.

et al,,J,Am,Chem,Soc,,
Pa.

A group in which 31(/?4f)) is derived from a nucleophilic functional group of 3 or more is preferred.

The combined use of the compounds of the present invention can improve the prevention of deterioration of color images during long-term storage and the prevention of yellow stain on white backgrounds, and can also significantly prevent colored staining caused by processing solution components remaining in the photosensitive material after development. Ta. In particular, the degree of improvement in preventing deterioration of color images and preventing yellow stain on white backgrounds is remarkable and could not be expected from combinations of conventionally known antifading agents.

Among the compounds represented by formulas (1) to (IIl), the formula (
It is preferable to use the compound of formula (III) in combination with the compound of formula (III).

The winter wear of the compounds represented by general formulas (1), (n) and (III) will be explained in more detail.

The aliphatic group referred to in R, R2, B and 几 represents a linear, branched or cyclic alkyl group, alkenyl group or arginyl group, which may be further substituted with a substituent. The aromatic groups referred to in 几, R, B and R include carbocyclic aromatic groups (e.g. phenyl group, naphthyl group, etc.) and heterocyclic aromatic groups (e.g. furyl group, thienyl group, pyrazolyl group, pyridyl group, indolyl group, etc.), and may be a monocyclic system or a condensed ring system (eg, pentufuryl group, phenanthridinyl group, etc.).

Furthermore, these aromatic rings may have a substituent.

What is the heterocyclic group referred to in R, R2, B and R? A group having a cyclic structure of a J-membered ring to a 10-membered ring composed of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a hydrogen atom is preferable, and the heterocycle itself may be a saturated ring or an unsaturated ring. It may also be further substituted with a substituent (for example, a coumanyl group, a pyrrolidyl group, a pyrrolinyl group, a morpholinyl group, etc.).

-X in formula (1) is aromatic amine type 1! I Represents a group that reacts with a drug and leaves A, and is bonded to A via an oxygen atom, sulfur atom, or nitrogen atom (for example, 3-virazolyl group, JH-/, co, 4I-o-thadiazolin-!) −
An oxy group, an oxy group in aryl, a cy group in alk, a ruthio group in alk, an arylthio group, a 7 group in substituted N-O, etc.) t or /%t2 gun atom is preferable.

The person of general formula (1) represents a group that reacts with an aromatic amine developer to form a chemical group, and contains a group containing an atom of low electron density, such as -35, -s'i-. . X is a halogen atom and R
〃, n represents O. Here, L represents a single bond, an alkylene group, -('-e-s-s-N-tk...Y/ (for example, a carbonyl group, a sulfonyl group, a sulfinyl group, an oxycarbonyl group, a phosphonyl group, thiocarbonyl group, aminocarbonyl group, silyl group, etc.)
.

Y has the same meaning as Y in general formula (n), and Y/ has the same meaning as Y.

1(, / and R" may be the same or different and each represents -L12-.

Ro represents the same meaning as ru. R″′ is a hydrogen atom, an aliphatic group (e.g., methyl group, isobutyl group, t-butyl group, vinyl group, benzyl group, octate monocyl group, cyclohexyl group, etc.), aromatic group (e.g., phenyl group, pyridyl group, etc.) , naphthyl group, etc.), heterocycles (e.g. piperidinyl group, pyranyl group, furanyl group, chromanyl group, etc.), acyl groups (e.g. acetyl group, benzoyl group, and sulfonyl group (fat is methanesulfonyl group, benzenesulfonyl group, etc.) represents.

L', L" and L/" are -(J-, -8- and -N
- represents.

A divalent group represented by monoalkylene-- is preferred.

More preferred compounds among the compounds represented by formula (1) are general formulas Cl-8) and (1-b).

(I-C) and (1-d), and 2(10e'C) is 1x in the second-order reaction rate constant with p-anisidine.
io-1! ! /mol-sec~1xta-”, d/m
It is a compound that reacts in the ol-sec range.

In the R1-L ink CO-A r formula, R□ represents the same meaning as B in the general formula (1). Link represents a single link and 10-.

Ar represents an aromatic group. However, it reacts with aromatic amine developers and, as a result, is often a useful group as a reducing agent for photography, such as hydroquinone derivatives and catechol derivatives. Ra, Rh and Rc may be the same or different, and each represents a hydrogen atom to an aliphatic group, an aromatic group, a heterocycle,
alkoxy group, aryloxy group, heterocyclic oxy group,
Carboxyl group, alkylthio group, arylthio group, heterocyclic thio group, amine group, alkylamino group, acyl group, amino group, sulfonamide group, acyl group, sulfonyl group, alkoxycarbonyl group, sulfo group, hydroxy group, acyloxy group , represents a ureido group, a phrethane group, a carbamoyl group and a sulfamoyl group. Here, a and Rb or Rh and Rc may be joined together to form a j to 7-membered heterocycle, and this heterocycle may be further substituted with a substituent, or may be a spiro ring or a bicyclo ring. etc. may be fused with an aromatic ring. 2 and z2 are! ~7
! Represents a group of nonmetallic atoms necessary to form a member heterocycle, and this heterocycle may be further substituted with a substituent, form a spiro ring, bicyclo ring, etc., or be fused with an aromatic ring. good.

Among general formulas (1-a) to (I-d), especially - formula (1)
- In a), the second-order reaction rate constant with p-anisono is 2.
(IO"c) to /X10-"l/mol -@e~/
In order to adjust to the range of X10 J/mol-8ec, when At is a carbocyclic aromatic group, it can be adjusted by a substituent. At this time, although it depends on the type of group of 几,)i of each substituent
It is preferable that the sum of the σ values of imnett is O12 or more, and (
It is more preferable that it is 71 g or more, and even more preferable that it is Oo or more.

- When adding compounds represented by formulas (1-a) to (I-b) during production of a sensitive material, the total carbon number of the compound itself is 13
The above is preferable, and the more the number, the more preferable.

In order to achieve the object of the present invention, the compound of the present invention is not preferably one that decomposes during development.

- Y in the formula (river) is an oxygen atom, an iodine atom, where 1 (
, R, and Ra are hydrogen atoms, aliphatic groups (e.g., methyl group, isopropyl group, t-butyl group, vinyl group, benzyl group, octadecyl group, cyclohexyl group, etc.), aromatic groups [e.g., phenyl group, pyridyl group, etc. , naphthyl group, etc.]
, heterocyclic group (e.g. piperidyl group, pyranyl group, furanyl group, /a manyl group, etc.), acyl group (e.g. acetyl group, benzoyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, benzenesulfonyl group, etc.) t-a I, R
and R6 may be bonded to each other to form a cyclic structure.

2 in general formula (I [ A nucleophilic group in which the atom is an oxygen atom, an iodine atom, or a nitrogen atom (for example, a benzenesulfinyl group, a -class amine, etc.) is preferable as a nucleophilic group.

- Among the compounds of formula (III), a particularly preferred compound can be represented by the following formula (III-1).

- Formula (I[Ia) where M is inorganic (e.g. L s % Na % Kx
Ca % Mg, etc.] or an atom or atomic group forming an organic salt (e.g. triethylamine, methylamine, ammonia, etc.) and where '15 and R□6 may be the same or different,
R, and □6, each representing a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, may be bonded to each other to form a j to 7-membered ring. R□7, R151% R2゜ and R2□ may be the same or different, and each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarmenyl group, a sulfonyl group, a frayed group, and a urethane group. Represents the basis. However, at least one of R15 and R16, and Ru. At least one of and R2□ is a hydrogen atom.几□ and R22 represent all hydrogen atoms, aliphatic groups, aromatic groups, or heterocyclic groups, R
1° further represents an alkylamino group, an arylamino group,
represents an alkoxy group, an aryloxy group, an acyl group, a dicarbonyl group in an alkyl group, and a dicarbonyl group in an ary=luo group, and at least one of the groups of 8□7.8□8% '111 is They may be bonded to each other to form a j-membered ring, or at least two groups of R2゜, 2□, and 几・2□ may be bonded to each other to form a j-7-membered ring. good. R23 represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group; R24 represents a hydrogen atom, an aliphatic group, an aromatic group, a halogen atom, an acyloxy group i, or a sulfonyl group; e"zs is hydrogen; An atom or a hydrolyzable group t-represents.

``10% 1'11% 121 13 and 14 may be the same or different, and each represents a hydrogen atom, an aliphatic 4 (
For example, methyl group, inozolobyl group, t-butyl group, vinyl group, benzyl group, octadecyl group, cyclohexyl group, aromatic group (e.g. phenyl group, pyridyl group, naphthyl group, etc.), heterocyclic group (e.g. biiridyl group, pyranyl group, furanyl group, riamanyl group, etc.], halogen atom (
For example, chloro atom, propentatom, etc.), -SR26-, cetyl group, benzoyl group, etc.), alkoxycarbonyl i&
(e.g., methoxycarbonyl group, methoxycarbonyl group, cyclohexylcarzenyl group, octyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, dicarbonyl group, etc.), Sulfonyl mC (for example, methanesulfonyl group, benzenesulfonyl group, etc.), sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group, ureido group, urethane group,
Carbamoyl group, sulfo group, carboxyl group, nitro group, cyano group, alkoyasalyl group (e.g., methoxy-midstyl group, imbutoxy-midstyl group, octyloxyxalyl group, penzoyloxygysaryl group, etc.), allylquiteryl group ( For example, phenoxygysaryl group, naphthoxyxalyl group, etc.), sulfonyloxy group (for example, methanesulfonyloxy group, benzenesulfonyloxy group, etc.),
``26)3, '(''26)2, '(''26)2
, -P((JR2,)3 and formyl group, where 几 and 几27 represent a hydrogen atom, an aliphatic group, an alkoxy group or an aromatic group.

Among these, -8(J□M group, Ha mm et
In terms of the effects of the present invention, it is preferable that the sum of the σ values is 0.3 or more.

Compounds represented by general formulas (1) to (Ill),
Preferred compounds for each individual general formula are as described above, but when looking at the compound as a whole, - formulas (1) and (■)
Compounds represented by are preferred.

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

(1-1) (I-2) CI-J) (I-Hiroshi) (1-j) (1-r) (I-2) (1-/1 (1-/1) (I-/ko)・ ”)018H!17 I (1-ti) (,1-ia) CI-/! r) 0 (I-/bu) (1-/7) <1-11) (Summer-)f) (1-Jo) (■-col) H3 (I-Here) (l-ko J) (■−λμ) (I-2ri (i-x6) (i-, 27) (I-kot) (1-J(7) (1-31) (1-Jx) (1-JJ) α (1-J4') α　　　　　　　　α (I-JJ) (1-Jr) (I-32) (1-4'1 (Summer -411) CO□C2H.

(■−μ2) (1-4’J) (■-Art u) (■-da J) (1-at) N (1-4’7) CO□C2H.

(l-referrer) (l--ta) Co, C2) 1゜ (1-j1) 8O□CH3 02NH2 (l-! 蓼) 803H-N(C2Hs)3 (1-jj) Go2G2) 1゜ (1-jj) (1-j7) 02CH3 (1-jlr) (i-JP) (l-buO) (■−≦7) α　　　　　　　　　α CI-jJ) α (1-44') CH.

Cl-41) Cf(.

(■-≦7) α tx-tr) (1-4ri) (I-7ko) (1-7j) (1-7F) α <1-40) (1-rt) (1-rλ) ( 1-tJ) CI-r-) <1-11) CI-rbu) (1-r7) O < ! -it>Cl-1ri) (II-/) (■-λ) (n-J) C)f =C)I-80-CH(n) 2 21113? (n-j) (■-ko) (Ill-J) (m-4') (m-3) (ill-4) (III-7) (m-1) (nl-ta) Cm-10) (m-/1) N (III-/ko) ([1-/J) (III-/da) (■-/j) (1-/4) 8υ
υ (■-蓼4c) (■-蓼り(■-弘t).

0 υ (In-Hiro7) (To”)COC)i3 (I-xi) Osu([[-!2) Cm-!J) (III-j≠) ([[-!ri([[- j7) ([11-jri) Cm-40) (III-bl) !1 (III-jJ) CL)ul !I'31 (III-43) I (■-4-) (In-47) (m-≦4) The synthesis method of these compounds is described in the patent application 1974-Kota!4c11.
Synthesized by the method described in No. 4/-47≠47, No. 4/-J44t/4, No. 4/-/rJWlY, No. 4/-/1Jt-0 or a method similar thereto. be able to.

The compound represented by general formula (IV) will be explained in more detail.

The aliphatic group, aromatic group and heterocyclic group represented by R3°, R3□ and R3 are as defined in general formulas (1) to (III).

几, □, R33 and R34 may be the same or different, and each represents an alkyl group (a chain, branched or cyclic alkyl group such as a methyl group, ethyl group, inofovir group, tert-butyl group, hensyl group). , octyl group, cyclohexyl group, hexadecyl group, etc.), alkenyl group (
(e.g., vinyl group, allyl group, etc.), aryl group (e.g., phenyl group, p-methylphenyl group, -monochlorophenyl group, 3-methoxyphenyl group, co-, ≠-dimethoxyphenyl group, ≠-hexadecyloxyphenyl group, 3-pentadecylphenyl group, μmm bromphenyl, naphthyl group, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, inopropyloxy group, cycloheyacyloxy group, be/zyloxy 7 group, hexadecyl group 7 group, methoxyethoxy group) groups), alkenoxy groups (e.g. alkoxy groups, etc.), aryloxy groups (e.g. phenoxy group, ≠-methoxyphenoxy group, 3-chlorophenoxy7 group, co-methylphenoxy group, co-1ert-butyl-Hiro-methylphenoxy group) , Hiro-hexadefluoroxyphenoxy group, naphthyloxy group, etc.) f.

-Among the compounds represented by the formula (M), preferred compounds can be represented by the following formulas (V-1) to (F/-f).

General formula (IV-1) L44 General formula (!V-b) 几44 General formula (IV-C1 几44 General formula (N-d) 几5G-0-R51 General formula (IV-1 Ri几 -8-几3, General formula (!V-f) In the formula, 几 and □ are hydrogen atoms, aliphatic groups, aromatic groups, "32
% R+33 and '34 represent t- with the same meaning as defined in general formula (IV).

几～几、6 may be the same or different from each other,
Each hydrogen atom, -W-33□, aliphatic group, aromatic group, heterocyclic group, diacylamino group, halogen atom, sulfonyl group, sulfinyl group, alkoxycarbonyl group,
It represents a hydroxycarbonyl group, a ureido group, a urethane group, a sulfamoyl group, a carbamoyl group, a cyano group, a nido a group, a carbonyloxy group, a sulfonylo group, a silyloxy group, and an imide group. Here-W-R3
□ represents the same meaning as defined in general formula (IV).

几, □ and R4□ may be combined with each other to form a J- to 7-membered ring. Further, substituents located at mutually ortho positions among R4□ to R46 may be combined to form a J- to 7-membered ring.

Alternatively, it may be combined with a group at the 6-position ortho to the 1-position to form a J- to 7-membered negative ring.

However, the j- to 7-membered ring defined here may be a monocyclic system, a condensed ring system, a spiro ring, or a big alicyclic ring, and the result of combining to form a ring is an alicyclic ring, an aromatic ring, a heterocyclic ring, It may be a heteroaromatic ring, and these may be further substituted with a substituent.

几'41 represents the same meaning as defined for 几 and 5 in the general formula (fV). Similarly to R4□, R'41 may be combined with R4□, □, or □ to form a j- to 7-membered ring in the same meaning as described above.

R6° represents an aliphatic group, a heterocyclic aromatic group, or a heterocyclic group; R51 represents a hydrogen atom, an aliphatic group, a heterocyclic aromatic group, or a heterocyclic group.

``35 is defined by the formula CIt1) and has the same meaning as 9 t-
represent.

R2O, 几6, maku, ``so'' and ru, may be combined with each other to form a j to 7-membered ring in the same meaning as described above.

Among the compounds represented by general formulas (fl/-1) to (IV-f), - formula (fl/-a) and (Iff'-
Those represented by f) are more preferable, and among these compounds, the following formulas (F/-al) to (IV-all
) and (IV-fl) are more preferred.

General formula (IV-11) 0几'41 General formula (lt/-R2) One formula CW-a3) General formula (■-a4) General formula (IV-ms) General formula (EV-as) General formula (fV -at) CO, 47 General formula (Pi-R8) General formula (IV-fl) In the formula, "41 to R4g represent the same meaning as defined in the general formula (fV-m),"几'4□ is R41 and B' ~R
' represents the same meaning as R4□ to R46, respectively.

Also, each substituent is bonded to each other in the same meaning as the general formula (mV-Jl)! ~ You may form a 7-membered ring. E
L6□ to R64 may be the same or different, and each represents a hydrogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.几. 3. 几. 6 may be the same or different, and each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an alkoxy group, an arylamino group, an argylthio group, an arylthio group, an alkylamino group, an acylamino group, -rj
Represents Thl. Here, E represents a group of nonmetallic atoms necessary to form a j to 7-membered ring.

R35 represents the same meaning as defined in general formula (IV-f). E is! Represents a group of nonmetallic atoms necessary to form a 7-membered ring.几71 to 几74 may be the same or different and represent a hydrogen atom and an alkyl group, respectively.

The Yoiki metal complex of the present invention will be explained in further detail.

The metal complex used in the present invention is steel, Kono? ruto, nickel,
It is an organometallic complex having radium or platinum as the central metal and at least one organic ligand having a λ-like conformation. Among these, nickel is particularly preferred as the central metal. Preferred atoms coordinating to the central metal are nitrogen atoms, sulfur atoms, oxygen atoms, and phosphorus atoms.

Particularly preferred structures of the organometallic complexes of the present invention are represented by general formulas (V-a) to (V-d).

- Numerical formula (V-a) General formula (V-b) General formula (V-C) General formula (V-d) In the formula, M is steel, cobalt, nickel, and platinum. represent. Rin,. and "go" may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or a hydroxyl group. Here, 几, . and electron may bond with each other, R8□・R,□ , ordinary,
3, B'81, 几'8□ and R' may be the same or different, and each represents a hydrogen atom, and the alkyl group represents an aryl group.

Here, FL82 and 几3, 几'8□ and 几'83 may be bonded to each other to form an aromatic ring or a j-r membered ring.

R84-几85, R'84 and R'8. may be the same or different, and each represents an alkyl group, an aryl group, an alkylthio group, an arylthio group, an alkoxy group, an arylamino group, an alkylamino group, or an arylamino group.几〜R%R′〜B/,. may be the same or different and each represents a hydrogen atom, an alkyl group or an aryl group.

Here, R, 6 and R, 7, R,. and Ro. , Rt'8° and R'87 or R'8. and 几′. At least one of them is bonded to each other to form an aromatic ring or! ~r-membered ring may be formed. X represents a compound that can coordinate with M * A 1 , A 2 % A'□ and A/2 may be the same or different, and each represents an oxygen atom, a sulfur atom, -NR,, -, hydroxyl group, alkoxy group, alkylthio group or alkyl group, aryl group, hydroxyl group te represents an alkoxy group, 几, 2 and "93 may be the same or different and each represents a hydrogen atom or an alkyl groupe A 3 % A'3 represents an oxygen atom, a sulfur atom or -NH-.

The compounds of the present invention are specifically illustrated below, but are not limited thereto.

-t -J CH3 -a person-j person-4 A-ta OCR2C)1,C)12Co□C2H.

People-IO , person-// A-/2 A-73 A-/4 Person-7! QC8H,,,”) A-/J A-/7 -1Jr A-/ri CH3 (JCl(3 person-22 A-1 Hiroshi H People! person-2 Person-ko7 A-kot -JI Person-3J C,1(,,(1) A-J Ri A-Hiro O -a l A-Octopus -a3 A-a μ A-Buddha! A-≠2 People-μ7 λ−≠l A-≠ri A-j/ A-j co -zs Person-J- A-j! -zy Person-11 A-zuri CH3CH.

A-6/ A-47 A-≦Hiroshi A-6! A-7bu A-bu 7 A-Otori -7O A-7/ person-73 A-7 reference A-71 A-7≦ person-77 -7F A-7ri A-1/ A -4λ ni-13 Human-t4A NH04H, (nJ A-r A-r7 CH3 A-fp.

person-f/ -yi 123 CH3 A-5F≠ -yj A-ta Otsu CH23CH2QC□4H2, (n) -P7 A-ta r CH3 human data 2 A-io.

A-10/ A-10 -104c Person-101 -toa -to7 -toy H3 -1Of A-/10 People -／／／ A-//ko A-//J A-//Hiroshi A-//J l-13 A-//4 A-//7 -1/r -7ly A-/J17 A-/2/ person-l here A-/λ3 A-/J Hiromu CR3 A-/2! A-121m A-/core A-/Kol 2M.

A-/Jri QC4H, (n) CH8 A-/JO A-/J/ A-/3 A-/JJ A-/J# A-/Jj A-/34 people-/17 A-139 A -74tO A-/Reference/A-/4L Ko5C8H17(n) A-/III H3 A-/Guru-14t1 Person-74c4 C8H! ? (S-74t7 A-/Gr A-/4AP H3CH3 A-/!O A-/J/ (rl) C, Hl, QC8H,, (n) A-tsko('') C, H, 30CH2CH2QC, H13(n)A
-/! ! ('')C,,H,,8Cj42CH2QC,H.

A-/! Hiro(”)C□2H2,80)12CH12SC□2H25
(n) A-/11 "lcl 2H,, UCH2CH2UG, 2H2B" 人-/It A-/17 A-/11 A-/lriA-/buO A-ノ41 A-#J -riC, H.

-H3 A-t6 蓼 A-/buj A-/44 A-/47 CH.

^-141 90- A-/4P A-/7/ These compounds are described in U.S. Patent No. 33341Jj, 3μ3
-300, same 3! tJoso, 3J7μt core, 1-cho 37004TJJ, 376443J7, 3101A, 3yr? Sanko issue, same μ co! 4L
Ko 16, same 4Lλ7ri? ri No. 0, English [i1轡 License/34
A7! it issue, xotirrr issue, same JOtG4P7
No. 7, 20774 Ajjt4ij, % Gansho jr---〇! Core issue, Tokukai Akira! Call lj2 here! No. 13-/
No. 7722, No. 7722, No. 0JJ7, No. ta-i4cz
sJo issue, same! ! -63ko No. 1, same! ! -2100 (4
No. Jl-2≠74! / issue, same! Day 10! Jf number,
Same tcoat t7j36, special public showμr-JItco! It can be synthesized by the method described in No. J4C-lco No. 337, and nine methods analogous thereto.

If the compound of the present invention has a low molecular weight or is easily soluble in water, it may be added to the processing solution and incorporated into the photosensitive material during the development process. Preferably, it is added to the photosensitive material at the stage of aesthetically shaping the photosensitive material. The latter method is usually performed by dissolving a high-boiling point solvent (oil) alone with a boiling point of iyo@C or higher, a low-boiling point solvent alone, or a mixed solvent of the oil and a low-boiling point solvent at atmospheric pressure, and then adding gelatin or the like to this solution. The compound of the present invention, which is emulsified and dispersed in an aqueous hydrophilic colloid solution, is preferably soluble in a high-boiling organic solvent.

There is no particular restriction on the particle size of the emulsified dispersion particles, but 0.0
! μ~0. ! μ is preferable, and 0. From the viewpoint of the effect of the present invention, it is preferable that the non-inventive compound is co-emulsified with the coupler. In this case, the oil/coupler ratio is preferably 0.00 to 1.0% by weight. Preferably it is 0.

Further, the proportion of the compound of the present invention is from 10''-2 to 10 moles per 7 moles of coupler, preferably J×
10-" to 3 moles.

Specific examples of the oil include phthalic acid algyl esters (digityl phthalate, dioctyl phthalate, diisodecyl phthalate, dimethoxyethyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, etc.). phate, dioctyl butyl phosphate, monophenyl-p-1-f tylphenyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (PI such as octyl benzoate), alkyl amides (e.g. diethyl laurylamide, (diethyl laurylamide), fatty esters (e.g. dibutoxyethyl succinate, diethyl azelate, dioctyl sepacate), trimesic acid esters (e.g. tributyl trimesate), compounds containing an Evo-cyclocyclic ring (e.g. US patent! Compounds described in J$0,417), phenols (for example, C3H11 (Cl2Hff
il$(SUU5H11tt) C t3 CH3 Ethers (eg, phenol, diethylene glycol monophenyl ether) can be mentioned. Examples of low boiling point solvents used as replenishing solvents include organic solvents having a boiling point of about 30@C to /jO@c at atmospheric pressure, such as lower alkyl acetates such as ethyl acetate, isoprobyl acetate, and ethyl acetate, ethyl ethyl acetate, and
Methanol, ethanol, -class phthyl alcohol, cyclohexanol, alzole fluoride, mityl inzotyl ketone, β-ethyl acetate methyl seasolzoacetate acetone, methyl acetone, acetonitrile, dioxane, dimethyl formamide, Dimethyl sulfoxide, chloroform, cyclohekate, etc. can be mentioned.

In addition, instead of the high-boiling point VIFiAI@ medium, not only oil-based solutions of additives such as couplers (including those that are solid at room temperature such as wax), but also latex polymers can be used, or couplers and color mixing inhibitors can be used. and ultraviolet absorbers, etc.
The additive itself may be an oil medium.

Latex polymers include acrylic acid, methacrylic acid, and its esters (e.g., methyl acrylate, ethyl acrylate, butyl methacrylate, etc.), acrylamide, methacrylate, vinyl esters (e.g., vinyl acetate, vinyl f-robionate, etc.), acrylonitrile, and styrene. , divinylbenzene, vinyl alkyl ether (911, t&-f vinyl ethyl ether), maleic acid ester (fl, t hamaric acid methyl ester 9N-vinyl-2-pyrrolidone, N-vinylpyridine, co-vinylpyridine, etc.) A latex polymer produced using one or more of these monomers is used.

Examples of surfactants used when dispersing a solution of the compound of the present invention alone or together with a coupler in an aqueous protective colloid solution include saponin, alkylsul-7-sodium ocuccinate, alkyl-benzenesul-7-sodium succinate, etc. can be mentioned.

The compounds of this invention can be used in combination with yellow couplers, magenta couplers, or cyan couplers. Among them, it is paired with a magenta coupler.

When used in combination, it is particularly preferable in terms of the effects of the present invention.

The Kabutsu used in combination may be equivalent to or equivalent to the scissors ion, and may be in the form of a polymer or oligomer. Further, the couplers used in combination may be used alone or in a mixture of one or more types.

The general formulas of preferred couplers for use in the present invention are shown below.

1st trial (C-Summer) H General formula (C-11H General formula CM-1) General formula (M-fl) - Monna (Y) (In the formula, 几□, RU, and R6 are each fat family group,
represents an aromatic group, a dicyclic group, an aromatic amino group, or a heterocyclic amino group, 几2 represents an aliphatic group, and EL3〉 and 几 each represent a hydrogen atom, a hydrogen atom, an aliphatic group, or an aliphatic oxy group. Represents a group or acylamino group, and ru and ′ are hydrogen atoms or 几.

is synonymous with , and 几 and 几 are substituted or not Wi.
R represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, RlG represents a hydrogen atom or a substituent, and Q represents a substituted or unsubstituted phenyl group. represents a phenylcarbamoyl group, Za and zb are methine, substituted methine, or +:+l
lN-1-represented by Y, Y2, Y3, Y4 and Y5
Is it water JA atom or current? A group capable of leaving l1t (hereinafter abbreviated as a leaving group) during a coupling reaction with an oxidized form of a potential drug.

General formula (C-1> and - crest hole (c-n, I in +
t2 and f: R3 and R6 may each form 31 or a 7-membered ring.

Furthermore, Ru□, R2, Ru, or Y□; , 几3, kL,
My father is Y2. R, ・R,, R9 or Y3: 10% Za,
Zb or Y4: Q or Y may form a comer or higher multimer.

The fat t mentioned here! The term radical refers to a linear, branched or cyclic alkyl, alkenyl or arginyl radical.

Preferred specific examples of couplers represented by (C-1) and (C-TI) are shown below.

(C-1) α (C-co) α (C-3) α (C-≠) (C-j) α (C-t) (C-7) (C-ta) α (C-10) (C-/J) (C-ta) α (e-/J) (C-/4) <c-ty) α (C-)l) (t) C, Hl.

(C-/ri) (C-co0) (C-co1) (C-22) OH (C-23) (t (C-coU) (C-2ri(t)C5H, □ (C -, 2tan (C-24b) (C-27) (C-kot) α (C-3o) (C-J1) (C-jko) (C-JJ) (C-31) α (C -Jri (c-sr) α x/y/s error 10/ko0 (Wt (c-iri) α X/y-xJJ7 reference I (wt ratio) (C-SO) /JO・/, - 4・/・0 ratio) .w*kk,)
(G-#1) x/y day J O / J O (wt ratio) (C-Hiroko) α x / y / z = s j j / μ0 / j (
Ratio of w ] X / y = to7 〇 (C-pipi) Preferred embodiments fIl of couplers represented by crest holes (M-1) and CM-II) are shown.

α (M-ko) α (M-4)　　　　(.

QC)i3 (M-2)ct (M-/r) CH3 CII’S Me0 (M-J1) C, H Yu, (S (M-ko J) (M-Koda) C8H17 (S (M-coj) C8H,, (1) α i1-Jj)’ M-Jlr) し、h17ttJ (M-□,).

(M-Reference) α (wt ratio) (M-Reference)) α (M-μm) (M-413) CI(3 (M-≠l) x/y=France!/11 (wt ratio) M-≠ri j
1 ratio) tbi-4! t) x/ytsuj O/j O (wt ratio) CM-g2no x / y == zo / z O (ratio of Iv) (M-17) (ratio of w) Below, - Monana ( Preferred specific examples of the coupler represented by Y) are shown below.

(Y-1) (Y-co) N (Y-J) (y-4L) α (Y-j) (Y-4) (Y-7) α (yr) (Y-2) Nl( su2ci-t3 (Y-10) Heku1 Yutaka (Y-/ko) otnt (Y-/It) (Y-/z) α (Y-/≦nα COυ11 (Y-/7) α (Y- /r) et(GO(3M Cl2H*B (Y-/ri) (Y-10) α (JL:2ti, L, ;21-1°(Y-co1
) (Y-12) (Y-23) α H (Y-kol) α (Y-2ri(Y-kot) t ni l-13 (Y-J7) α (Y-+2t) CυOH ( Y-J P ) (Y-3o) α (Y-Jl) (Y-Jko) (J (Y-31) (Y-Jl) (y-3z) (Y-34) (Y-J7) ( JH (Y-31) (Y-JIP) (Y-da0) (Y-u/ ) (wt ratio) (Y-Zancon (Y-$7) X/Y/1mjO/
Other exemplary compounds of couplers represented by the general formula from (C-1) to (Y)'t List the literature describing the synthesis method.

Cyan couplers represented by the general formula (C-1) and -Momona (C-[1) can be synthesized by known methods, for example -
The cyan coupler represented by the hole (C-1) is US 4e.
i=ff@J, 4'ko J, 7JO No. J, 77
It is synthesized by the method described in, for example, No. 2,002. −Monka<
The cyan coupler represented by c-n) is disclosed in U.S. Patent No. 1.
ltej, tko1shu Dodaihiro, 333. Tatata, same number, JJ7. It is synthesized by the method described in No./77.

- Magenta coupler that is made in Monana CM-1), Jikai Sho Guday 7440 Koku, same day 74COλ1,
It is synthesized by Kihori's method in Jiko-r-27f JO, JJ-JJrut, and US Patent J, j/f, #2f. - The magenta coupler represented by the pattern hole (M-II) is disclosed in Japanese Patent Application Publication No. ShojP-/12jgr and US Patent No. gj #7, respectively. , No. 047, JP-A-Shojter/7/
,the law of nature! It is synthesized by the method described in JP-A-40-33,112 and the like.

The yellow coupler represented by the general formula (Y) is
#-ul! 41/-q, Tokko Akira! r-107JP, U.S. Pat. No. 3-B, No. 0244 and
lr:x-')-'r-(R,,D,) No. 11033.

These turnips are generally 1 mol of chlorine in the emulsion layer x 70 mols! x no 0 mol, preferably 1 x 10 mol to j X / 0-'' mol is added.

The compound of the present invention has the general formula (C-1), (CM- on C-n)
From the viewpoint of the effects of the present invention, it is preferable to use it in combination with a coupler represented by 1) and CM-n), and in particular, it is preferable to use it in combination with a coupler represented by
It is more preferable to use it in combination with magenta couplers M-1) and CM-1).

-ff Among the compounds represented by formula CM-11), Za
When used in combination with a magenta coupler in which is -N co, zb is substituted methylene, and Y4 is a chloro atom, -Momonana (1-1
Among the compounds represented by , the compound in which zl forms a birazoline ring has a relatively small effect on improving the light fastness of magenta dye compared to other compounds.

In the photosensitive material produced using the present invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc.
They may be mordanted with cationic polymers and the like.

The light-sensitive material produced using the present invention may contain a hydrocquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, or the like as a color antifoggant.

The photosensitive material used in the present invention may contain a UV absorber in the hydrophilic colloid layer.For example, a benzotriazole compound substituted with an aryl group (US Pat. No. 33,794') % l-
Thiazolidone compounds (e.g. U.S. Grant J, J/4T,
7rihiro issue, same J, J! Ko.

At1), benzophenone compounds (e.g., those described in JP-A No. 27-27), cinnamate ester compounds am (e.g., U.S. Patent No. 3,7or, rot, J, 707.J7#) ), butadiene compounds (e.g., those described in U.S. Pat.

Oh! , Coco P), or benzoxidol compounds (e.g., U.S. Pat. No. 3,700,
) can be used. Ultraviolet absorbing couplers (eg, α-naphthol cyan dye-forming couplers), ultraviolet absorbing polymers, and the like may be used, and these ultraviolet absorbers may be mordanted in certain layers.

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

As the binder or protective cocoid that can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is preferably used.
However, other hydrophilic colloids can also be used alone or with gelatin.

In the present invention, the gelatin may be lime-fed gelatin or acid-treated gelatin. The details of the method for producing gelatin are described in Arthur Weiss's book, Error Chemistry of Gelatin (Academic Press, first published in 1999).

The photographic emulsion layer of the photographic light-sensitive material used in the present invention contains a
Any of silver silver, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used as the silver gunkide.

The average grain size of silver halide grains in photographic emulsions (the grain size is the grain diameter in the case of spherical or approximately spherical grains, and the average length in the case of cubic grains, expressed as an average based on the projected area) is particularly important. No, but preferably λμ or less.

The grain size may be narrow or wide, but it is preferable to use a monodispersed emulsion with a fluctuation rate of 11% or less.

The silver halide grains in the photographic emulsion layer may have a regular crystalline structure such as a cube or hexagonal, or may have an irregular crystalline structure such as a ring or a plate. It is preferable to use normal crystal emulsions, which may consist of a mixture of grains of various crystal forms.

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

The silver halide grains may have different phases inside and in Table IZ. Further, the particles may be particles in which the particles are mainly formed on the surface, or may be particles in which the particles are mainly formed inside the particles.

The formation of silver halide grains occurs during the physical ripening process. A complex salt or the like may also be present.

Silver halide emulsions are usually chemically sensitized.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing capri in the manufacturing process of the light-sensitive material, during storage, or during photographic processing, or for the purpose of stabilizing photographic performance. can. That is, azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzidazoles, and lye! o Benzimidazole,
Glomobenzidazoles, mercaptothiazoles, mercaptobe/zothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole a (in %/-phenyl-!-mercagut) tetrazole, etc.), mercaptopyrimidines, mercaptotriazines, etc.: For example, thioketo compounds such as triazaindone; azaindenes, such as triazaindenes, tetraazainde: /a (% with derhydrochlorination (/, J, J Heat.

7) Tetraazaindene), hantaazaindenes: benzenethiosulfonic acid, benzenesulfinic acid,
A number of compounds known as anti-capriagents or stabilizers can be added, such as benzene sulfof-6 amides and the like.

The invention is also applicable to multilayer, multicolor photographic materials having a spectral sensitivity of at least λX on the support. The multilayer multicolor photographic material has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer on a suitable support. these! The order of - can be arbitrarily selected as necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion /11 contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. You can also take it.

The supports used in the present invention are usually cellulose nitrate films, cellulose acetate films, cellulose acetate glylate films, cellulose acetate pcubionate films, polystyrene films, polyethylene terephthalate films, polycarbonate films, which are used in photographic materials. In addition, there are laminates of these materials, thin glass films, paper, etc. Paraita or α-olefin polymers, especially polyethylene,
Polymers of α-oletuin having co-10 carbon atoms, such as polyolefin, ethylene butene copolymer, etc. T-cross cloth or laminated paper, surface T-roughening as shown in Tokuko Sho-7-/Rioarg This improves the adhesion with other polymeric substances and also gives good results to supports such as plastic films. Also % UV rays
1- You can also use it.

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 colored and transparent.

Opaque supports include paper-like, naturally opaque materials, as well as
Transparent film with dyes, titanium oxide, and other substances added to it, or is it a transparent film? It also includes glass films surface-treated by the method shown in No. 011, as well as paper or plastic films made completely light-shielding by adding carbon black, dyes, etc. The support is usually provided with an undercoat. 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.

The cuff-sensitive material applicable to the production of the color photographic apparatus of the present invention is preferably a conventional color-sensitive material, particularly a color-sensitive material for printing, and US Pat.
．． J! No. 0, same 3. Ko27゜11/No. J, J Core,
No. 134 and U.S. Provisional Publication Patent No. υS, BJj/, 47J, etc., color photographic methods, especially color diffusion transfer photographic materials, may be applied. In order to obtain this, a post-exposure photographic development process is required. Color photographic processing basically includes color development; bleaching; and constant polishing. The two steps of bleaching and fixing may be completed in one process, or a combination such as color development, first fixing, and bleach-fixing may be used. Currently (P4t is used in the processing process as necessary)
Various techniques such as i-hard ffl bath, neutralization tower, first development (black and white development), image stabilization bath, and water washing are combined. ...The 4th degree is often more than it 'C. The symbol often used is θ'c-to °C1. Recently, 3o'c to 60
°C range.

The color developing solution is an aqueous alkaline solution containing an aromatic/class amine color developer and having a pH of r or higher, preferably 2 to 1λ.

After the fixing or bleaching process, a "washing process" is usually carried out, but instead of the washing process, a simple processing method such as a so-called "stabilization process" is performed instead of a thorough washing process. You can also use

Preferred examples of aromatic primary amine thread developers Fip Mill-
Typical examples of phenylenediamine derivatives are shown below.
It is not limited to these.

D-NO N,N-)Ethyl-p-phenylenediamine D-44-Puminoj-diethylaminotoluene D-J Coamino-5-(N-ethyl-N-lacrylamino)toluene D-French p-(N-ethyl-N -(β-hydroxyethyl)aminoaniline D-j λ-methyl-gu[N-ethyl-N-(β
-hydroxyethyl)aminoaniline D-jN-ethyl-N-(β-methanesulfonamidoethyl]-3-methyl-Hiroshi-aminoaniline D-7N-(λ-amino!-diethylaminophenylethyl)methanesulfonamide D- IN, N-dimethyl-p-phenylenediamine D-P ≠-amino-3-methyl-N-ethyl-N
-methoxyethylanili/D-704A-amino-3-methyl-N-7ethyl-N
-ethylanili in β-ethyl/D-tts-amino-3-methyl-N-ethyl-N-β
-Butoxyetheraniline These p-phenylenediamine derivatives may also be converted into sulfates, hydrochlorides, sulfites, p-toluenesulfonates, and the like. The above-mentioned compounds are listed under US ff2. /ri J, 0/j issue, same λ, 11 pieces.

λ4t/issue, same co! 64, 27/issue, same co! 2-2
3tgu issue, 3,634. ri No. 10, same J.

It is described in Buri-t, No. 323, etc. The fecal dose of the aromatic-grade amine visual agent is approximately
t ~ about -〇? , (preferably at a concentration of about 0.3t to about 1Of).

As is well known, the color solution used in the present invention may contain hydroxylamines.

The processing temperature of the color printing liquid in the present invention is 3o'c
-7o'c is preferred, more preferably 33°C-≠2
It is °C. The replenishment amount is J Ovrl per m2 of photosensitive material.
N2000 td, preferably 304~l! 00flL
It is l. From the viewpoint of reducing the amount of waste liquid, it is preferable that the amount of these replenishments be small.

In addition, when benzyl alcohol is contained in the color developing solution, it is preferably 0/11 or less ~ O sat/ll.
The following are more preferred. 9 color development is preferable in the case of benzyl alcohol additive-free (the time is preferably within 30 seconds, more preferably 70 seconds or more and within 30 seconds. The most preferable is Buddha!Sho IJ knee 2) This is the case within minutes.

Example l Cyan coupler (e-t) t3. or dibutyl phthalate 10. ≠a/, dissolve in 30 lft of ethyl acetate, and add this solution to sodium dodecylbenzenesulfonate/1. Gelatin solution 700 containing gelatin 101
fK was added to obtain a fine emulsified dispersion.

The total amount of this emulsified dispersion was added with 100 tK of silver chlorobromide emulsion (containing Br jo mol I Ag4. -Triazi/sodium salt 10xlt-
In addition, so that the amount of coated silver was 2!0 fNl/mK,
A sample was prepared by coating on a paper support laminated with polyethylene on both sides, and providing a gelatin layer on top of this coating layer. This is called class A.

After preparing samples with the combinations shown in Table 1, these samples were treated with looocoM, 8. Give a wedge of Sadamitsu, and then process it at night as shown below.

Current sales benzyl alcohol /j rttl
Diethylenetriamine J vinegar @ jpK13r
09ufN a 2
SO2jr Na s COs J Ot
Cyanine sulfate in human a? Hiro-a (
No-no-methyl-N-β-(methanesulfonamide) Ethylaniline-J/CoH,30,-H,Ou,jt Make 1000d with water p1410. / Bleach-fix ammonium thiosulfate (70wt width) / JOdN Maro 28
03 z fNa(Fe
(EDTA)) go fBDTA
≠? pH 1, r Treatment process iM degree Time boundary Image Liquid JJ@CJ minutes 30 seconds bleach constant 5! ＃Liquid jJ@c /min 30 seconds water
(9! λr~, is"Ci min) After forming the dye image in this way and determining the photographic characteristics of each sample, 4AOO nm! An aS collection filter was attached to the front, and a color fading test was performed for 7 days using a xenon tester (Hikariko 00,000 Lux).Measurements were made using a Fuji Jiji 3 meter, and the color fading was measured at the initial concentration of 1.2 before the test. The changes in density of the parts were determined.Furthermore, the discoloration and deterioration due to heat was also measured after being left at a high temperature of 100°C for 7 days.These results are shown in Table 1.

Example 2 Silver chlorobromide emulsion and pure silver platinum emulsion 10100f (
A, 3tfr: Contains) hsJM other than weird data? Samples with the combinations shown in Table 4 were prepared using IJ/ and similar materials.

3. to these samples. A query exposure of oooc, M, and 8 was given, and the treatment was performed with the following treatment solution.

water t
oo Godiethylenetrianepentaacetic acid J, Ofpotassium bromide 0. Jf Potassium carbonate J09N-ethyl-N-
(β-Methanesulfonamidoethyl) -! Monomethyl-l-aminoanili 7, sulfate J, it Sodium IJite /, 7? Whitening agent (Hiroshi, Buddha)
-diaminostilbene system) /, Add water and pH at 10001 dKUH
The same solution used in Example 1 was prepared and had a pH of 10.

Processing process Time Temperature Color phenomenon 1 phenomenon 4t! seconds it"c bleached foot end at second Js@c water wash to second!j "c photographic properties of the obtained color image・'! No. 11 constant trowel, light fastness test) + and heat fastness test similar to those in Example 1 were conducted.

The results are shown in Table 2.

Example 3 Magenta coupler (M-1) #, Bu? Add and dissolve tricresyl phosphate u, ty, ff [ethyl/jd, dodecylbenzenesulfone at sodium/ls
A mechanically fine emulsified dispersion was prepared by adding 100 ml of gelatin aqueous solution containing 10 ft of gelatin.

The entire amount of this emulsified dispersion was mixed with silver chlorobromide emulsion 1009 (Brj
04: %, Ag4. Contains JP, W) K is added and used as a hardening agent. Reference-dihydroxy-1-crocou8-)
Add 10 ral of riazin sodium salt just before application,
It was coated on a paper support coated with polyethylene on both sides so that the amount of coated iron was JIrOIIq/m2.

A sample was prepared by providing a gelatin layer as a protective layer on top of this coating layer.

This is designated as sample C.

Similarly, prepare samples of the combinations shown in Table 3.

These samples thus prepared were exposed and processed according to the method described in Example 1K. “The photographic properties of these samples were measured, and then a Fujifilm ultraviolet absorption filter that cuts out short wavelengths of less than 100 nm was attached to the front of each sample, and a firefly light fading tester (/, 10,000 Lux) was applied to each sample. We tested the light fastness by exposing it to light for three months.The results are shown in Part 3.

Example 4 Maze 7fi Kaklar CM-33)/J, If is tricresyl phosphate 13. rM, ethyl acetate/! gelatin water containing gold and dissolved sodium dodecylbenzenesulfonate 19% gelatin fflH10o
A mechanically fine emulsified dispersion can be added to g.

Sample 1) was prepared in the same manner as in Example 3 by adding the total amount of silver chloride to a pure silver chloride emulsion 100/(including λgA, jt1-).

Samples were prepared using the combinations shown in Table 4c below, and a fluorescent lamp fading test was conducted in the same manner as in Example 3. The result is the 4th c.
Shown in the table.

Example 5 Iza-coupler (Y-33) 10.7f with 1.0% dibutyl phthalate. tml, ethyl acetate-jd was added and dissolved by heating, and this solution was mixed with an aqueous solution containing 700 tfc@ of sodium dodecylbenzenesulfonate/f and 10 t of gelatin.
and mechanical stirring was applied to obtain a fine emulsified dispersion.

The entire amount of this emulsified dispersion was mixed into a silver chlorobromide emulsion (Brl
Omosp%, Ag4, Ift'') and 2.Derdihydroxy-bu-k aa-8, which is used as a hardening agent.
-) Add 10al of riazin sodium salt just before application,
A sample was prepared by coating on a paper support whose both sides were laminated with polyethylene so that the coated silver amount was J j OIf / Wi, and 111t of gelatin was provided on the upper layer of this coated layer. This is designated as sample E.

Similarly, samples of the combinations shown in Table 1 were prepared, and these samples were exposed and processed as described in Example 1 to obtain color images, their photographic properties were measured, and then a fluorescent light fading test was performed. The lightfastness of these samples was tested in a tester (1,000 lux). At this time, attach the previous UV filter to the front of the sample and remove it for about a month.

On the other hand, to evaluate the wet heat fastness,
After being left for trial @ meeting under forced conditions, and after 3 periods of menstruation, the color image! Measure the change once (Doxt, j) to be sure. 3rd result
Shown in the table.

From the results of Examples/-j, the general formula (1,1
When the compound represented by ~(Ill) and the general formula (II1) or the organometallic complex of the present invention are used in combination, the sample has the following formula: - formula (
1) The combination of the compounds represented by (Ill) to (Ill) or the compounds or organometallic complexes represented by the formula (IV) has a remarkable effect of improving the fastness to heat or moist heat.

Example 6 On a paper support laminated on both sides with polyethylene, the 7th layer (bottom layer) to the 71st layer (top 11th layer) with the composition of A-
A color photographic material was prepared by sequential coating.

The spectral sensitizing dyes used in each emulsion layer are as follows.

Blue-sensitive emulsion layer: (Addition of 10-' mol of Xico-X per 1 mol of silver halide.) Green-sensitive emulsion layer: (OH,), 803Na (Addition of 9 mol of JXlo''' per 1 mol of silver halide.) Red-sensitive emulsion layer: (Ha) Addition of 7, jX10-'7 per mole of silver saponide. (a) Solvent (s s o C, Hl 90h P=0<b) Color mixing inhibitor CH (l of solvent Conil mixture (weight ratio) (d) Ultraviolet absorber C, H, (suCH, C) 1. Cot) C,) i,

/:j:Jfi compound (molar ratio (e) solvent (f) color image stabilizer C4H, (SCH) The following dyes were used as anti-irradiation dyes in each emulsion layer.

Green-sensitive emulsion 15.

Red-sensitive emulsion No. 1: A sample was prepared by combining a coupler and the compound 5 of the present invention as shown in Table 6.

After exposing these samples through an optical wedge,
Color development was performed according to the following method.

Treatment process (JJ@C) The components of each treatment solution are 1. -Ill below.

Color development Hanawa 7 liquid benzyl alcohol l Koi diethylene glycol! dpotassium carbonate
Ko! ? sodium chloride
□・/f Sodium bromide
0. ! f anhydrous sodium sulfite
xt human cuquidylamine (iil!! salt
KO2 Fluorescent brightener /fN
-Ethyl-N-β-meta/sulfonamidoethyl-3-methyl-≠-aminoaniline sulfate.

Add water to bring it to tll, then add 77 CI of Na (JH and adjust to pH 10°).

Bleach-fixing solution Ammonium thilate / Co μ, Jt Sodium metabisulfite / J, Jt Anhydrous sodium sulfite 2.7? EDTA ferrous ammonium salt 4j? Color development I drops liquid
100dpH 6.7-4. Water was added to match R, and l processing solution was processed using a normal roller transport H1m image processing machine with normal replenishment, and the composition of the processing solution was almost at equilibrium. What has been achieved t-
used.

After measuring and determining the reflection densities of cyan, yellow, and magenta using Fuji-style self-recording, I tested each of these samples for 3θ days with a fluorescent light tester (illuminance / , 10,000 lux). K going 9.

The results are shown in Table 6.

As a result, it can be seen from Table 1 that the combination of the compounds of the present invention has a remarkable effect of improving light fastness even in the heavy l-coated samples.

Example 7 A photographic material (Sample G) as shown below
It was created.

The following +
From the 4th layer! A color photographic light-sensitive material was prepared by multilayer coating of fIt-9, and on the polyethylene fabric side, Chiku/White was applied as a white yt family, and a trace amount of group Wt- was applied.
Contains as a backcolor dye.

(Photosensitivity 111 Composition) The components are shown below in units of 97 m'',
For halogen (silver), the coating amount is shown in terms of a.

No. 771 (Anti-Halley 717 layer) Black colloidal silver ・−・σ, at gelatin ・−・−−0,2 No. 27 + 11 (
N-hole silver iodobromide emulsion spectrally sensitized with red sensitizing dyes (4 to 5 and 4) (low-sensitivity red-sensitive skin)
) ・---Silver 0. /J gelatin
・°41° I-O cyan coupler (bone 3) @・-・
・0. JO anti-fading agent (buttock 2)...0. /
! Coupler solvent (buttock 12 and ÷1)...Fist 00.01 3rd
# (high-sensitivity red-sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dyes (buttock 6 and back 4) (iodide @r, o molar concentration, average grain size 0.7
μ) ...Silver 0.10 gelatin
・-@@-0,! 0 Cyan Kagura (Tatami 3) ・@Holly-
-0,10 anti-fading agent (忰2) ...0.0
2 Kabuku solvent (buttocks 12 and 1) ---0,02 No. a
+1 (Middle layer) Iecuco 04) 'Silver @""0.02 Gelatin
・・1.0c color mixing prevention agent (bone 11
)...a, or color mixing inhibitor r6 medium (41
10) ----a, /4 polymer latex (buttock 6)
...o, 4c.

Third layer (low-sensitivity green-sensitive layer) Spectrally sensitized with a green sensitizing dye (bud 9) and sub-silver iodobromide emulsion (
Silver iodide 2.3 mol%, average grain size 0. μμ)
・Fist・III Silver O9-〇 Gelatin
....-0,70 magenta coupler (blue 8) @-Ki・kai O, aO turnip 2-solvent (矀15) ......O
0≦O 41st (+Gi sensitivity green sensitive layer) Silver iodobromide emulsion spectrally sensitized with green f'J sensitive dye (screen 9) (3.3 molar silver iodide, average grain size O02μ)
-・・・Silver 0. λO gelatin
-----0,70 Maze/Takabura (÷8)・-・
・・004LO coupler solvent (+15) -----
-0, tO 7th layer (yellow filter/yellow colloid)"&1...0.20 Gelatin -/, 00 color mixture prevention agent (豐11)...0.0 ≦Color mixing prevention bathing agent (tatami 10) - O0λ Hirodai - 1st layer (low a positive feeling)
C--) Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye (appetizer 13) (silver iodide 2.3 mol%, average grain size O0jμ)
・Fist e... Money 0. /j gelatin ・
...00SO yellow coupler (yellow 12) ...
0.20 coupler solvent (appetizer 15) ・Excellent・-@0.0
! 1st Ifn (high-sensitivity evening-sensing layer) Silver iodobromide emulsion spectrally sensitized with W color sensitizing dye (axe 13) (silver iodide 2.3 mol%, average grain size /, 4 Lμ)
... Zeng Feng O, Ko0 1st (Bat ultraviolet rays - anti-absorption layer gelatin 1., -/, IO ultraviolet absorption? II (Nihon 16) ...... i,.

Ultraviolet absorber solvent (bone IS) ・・・0.30 Color mixing prevention agent (+14) ・・・・・・o, or 1st/layer (hotan layer) Gelatin ・・1・ 1.0 used here The compounds are as follows: tatami 1 dioctyl phthalate tatami 2 co(cohydroxy-j-aec-butyl-
t-butylphenyl) benzotriazole 3 Co [α-(co, 4A-di-t-amylphenol Φsynbutanamide) - Hiro, bu- diku ef C! -j-ethylphenol tatami 4!
r,j'-dichloro-J,J/-di(3-sulfobutyl)-terethylthiacarbocyanine Na salt tatami 5 triethylammonium-3-[co 12-(
J-(J-sulfobutyl) Nat (l, code d) thiazoline-λ -ylidenemethyl)-/-butenyl) -3-naphtho ('t code) thiazolino] pro/kaise sulfonate + S polyethyl acrylate tatami 7 phosphoric acid Trioctyl ester tatami 8M-33 9! , j'-diphenyl-terethyl-J.

3'-Disulfodemipyruoxacarbocyanine Na salt - 1G Phosphorus flll-o-cresyl ester 1) 11
J, μm di-t-octylhydroquinone 12 α-piparoyl-α- [(ko, 4cm geod
f'No/-benzil-! -Ethoxyhydantoin-3
-il) -Coke aet-! -(α-2,≠-dioxo1-amylphenoxy]butamino]acetanilide tatami 13 triethylammonium 3-[co(3-benzylrhodanine-z-i+)f7)-3-benzosilinyl]2'lopane Sulfonate bones! 4 Ko, Gauge 5eC-Octyl Hydro Medium Non-tatami! 5 Phosphoric acid trinonyl ester + 16z-/Roruko (cohydroxy-J-t-zotyl-j-1-octyl) phenylbenztriazole As shown in Table 7, the third layer and the third layer of sample G +1- of the present invention Other samples were prepared in the same manner as Sample G except for the addition of compounds.

The sample thus obtained was exposed to light through an optical quench, and then color developed according to the processing method described below.

[Processing process] 1st development (black and white development) Jl, "C/min/J seconds water
Wash JJr'C/min JO seconds anti@exposure 1o
oLux or more 7 minutes or more color present Jr.”
C2 minutes/j seconds water washing Jr”0
441 seconds Bleach fixing JroC minutes oo seconds Water washing ir"c minutes/J seconds [Processing R composition] 1st developer Nitri a-N,N,N-)rimethylenephosphonic acid pentatrichum salt 0.4f Diethylenetriaminepentaacetic acid/pentasodium salt Hiroshi, ay potassium sulfite 10. Of potassium thiocyanate /, JP potassium carbonate
JJ, Ot Hyde cI! ? Non-monosulfonate potassium 2! r,Ofdiethylene glycol/1.0dl-phenyl-hydroxymethyl-dermethyl-J-pyrazolidone 2. Of Potassium Bromide 0・! V diiopotassium
j, 01119 add water
ig (pH?, 70) Benzyl alcohol /j, 0ptl diethylene glycol /co, 0rd3.6-cythia/, 1-medium ctanediol 0. J? Nitori et
-N, N, N-) Rimethylene phosphone beak/pentatrichum salt o, jt diethylene triad/pentaacetic acid/pentatrichum salt co, ot sodium sulfite co, Of potassium carbonate
Ko! t, Of human eldP dylamine sulfate J, Of N-ethyl-N-(β-methanesulfonado ζ-doethyl)-J -methyl-l-aelectronoaniline sulfate J, Of potassium bromide o, Jr potassium chloride
/ Add O”f water
l1l (pH 10,140) Bleach-fix solution Komel Kabuto-/,! , 4A- triazole /, Of ethylenediaminetetraacetic acid disodium dihydrate j, Of ethycinediaminetetraacetic acid Fe (II) - ammonium hydrate ro, ot Sodium sulfite JJ, Of Sodium thiosulfate (700f/l liquid) /60.0p11 Ice vinegar iRj, Oal Add water /E(p)i
j, jO) Next, t'LK of each of the above-mentioned photosensitive materials that have been developed.
After measuring the magenta reflection density (stain) of the non-image area,
The magenta reflection density K (stain) of the non-111f 1 part was measured in the same way again when it was left at 10°C, 70°C, under H0 for 3 days, and when it was left at room temperature for t0 days. ft, *f47! ! shows the increase in stain from 1 hour after treatment.

To evaluate the light fastness, after measuring the magenta reflection density Wtt using a Fuji type self-recording density needle, each of these samples was tested with a fluorescent lamp tester (illuminance 1,000 lux) for 3
0 day fading test 2 lines Natsu Nen.

The results are also shown in Table 7.

As a result, the combination of the compounds of the present invention is extremely effective in preventing coloration (magenta) staining over time after processing.
Moreover, the effect of improving the light fastness of the magenta dye is remarkable.

Example 8 On a paper support laminated on both sides with polyethylene, @ / u # 1 from the next bar! Created nine color photographic materials for JgI.

The polyethylene coating side of the first layer contains titanium white as a white pigment and a trace amount of ultramarine t-tin dye.

(Photosensitive J11# composition) The components and f/rn” are shown below in units of 9 coatings tt-
For silver halide, the coating amount is shown in terms of silver. An example of the emulsion\A splitting method excluding the first U layer is shown below.

Aqueous solution of potassium and silver nitrate to beautify the IA back of the emulsion, A g 1 mol per mole 0
．． J? Do not stir vigorously in an aqueous gelatin solution to which 3,4L-dimethyl-/J-thiazoline-corchion has been added. @C was added simultaneously over a period of about 2 Q minutes to obtain a monodisperse silver bromide emulsion with an average grain size of about 0 and an octahedron of 4 co μm. To this emulsion, 94 my of sodium thiosulfate per mole of silver and 7119 of chlorauric acid (salt water salt) were added.
Chemical sensitization treatment was carried out by heating for 20 minutes at 90°C.

Using the thus obtained silver bromide grains as a core, they were further grown in the same precipitation environment as the first time, to finally obtain a monodisperse core/shell silver bromide emulsion with an average grain size of approximately 0.7 μm and an octahedron. The coefficient of variation for zero particle size is approximately 10%.

1 mole of this emulsion is added to the emulsion. ! Add sodium thiosulfate from Ki and/or chloroauric acid (sulfur salt) from jH9 and incubate at 10°C for 4 hours.
Chemical sensitization was carried out by heating for 0 minutes to obtain an internal silver halide emulsion.

g/layer (antihalation layer) Black colloidal silver...0. IO gelatin ・--/, JO 3rd layer (intermediate layer) Gelatin... 0.70 3rd layer (low sensitivity red sensitivity 11l) Spectral sensitized with red sensitizing dye (ExS-/, ko, 3) Iron bromide (average particle size 0.3μ, size distribution R, octahedral) spectrally sensitized with red sensitizing dye (Exa-/, CotJ) Size 0.-jr, size distribution 1
0≦, octahedron) Medium ・ ・ o, i.

Gelatin /, 00 Cyan Kagura (ExC-1) ・ ・ Buddha 0. 74! Cyan coupler (BxC-J) ・ ・ ・ O# 07 Antifading agent (Cpd-J, J, u, /1* amount) 0.1 Cocoupler dispersion medium (Cpd-j) ・ ・ *-0, DJ Coupler solvent (801 mer), Ko, J equivalent n...
0,01 1st layer (high sensitivity red sensitive layer) Silver chlorobromide (average grain size 0.7jμ, size distribution 10
Attack, octahedron) '0, /J Gelatin /, 00 Cyan Kagura (BxC-1) 1 ・ ・ o, 2°7 Ankagura (BxC-J) 0. 10 Antifading agent (CL such as Cpd-, Z, J, L, /lr) 0
, /j coupler dispersion medium (Cpd-ri0, 03 coupler solvent (801V-/#J, j etc.)...
0, / 0th j fil (intermediate I-) gelatin /, 00 color mixing prevention I
), MCCpd-7)'--- o, or color mixing inhibitor solvent (8o1mer" tz ) □ ・ ・ ・
0,/t Polymer latex (Cpd-jr) ・ ・ ・ 0. 10 6th layer (low sensitivity green sensitive layer) Spectral sensitization with green sensitizing dye (Exa-J, a) Silver nonabromide (average grain size 0.Jrtss grain size division r rumor, octahedron),・ ・ -o, oa Beautified silver spectrally sensitized with green sensitizing dyes (Exa-J, u) (average particle size O, aZμ, particle size distribution rumored to be 10, octahedral) # -・o, o4゜gelatin ...@ o, t.

Magenta coupler (ExM-1) ・--a, 10 Coupler dispersion medium (Cpd-7) -0
,0-2 coupler solvent (8o1v-pi-6 equivalents)・”
0.11 7th layer (high sensitivity red-sensitive layer) Silver bromide (
Average particle size O0Pμ, particle size distribution 10 times, octahedral) 0.10 Gelatin 0.10 Magenta coupler (ExM-1) @--a, 10 Coupler dispersion medium (cpa-j) - - 0, 0! Coupler solvent (8o 1 v-u, 44*) a, /j r# (intermediate layer - same as third layer 'd layer' (yellow filter layer) Yaku colloidal silver...-0,20 gelatin
... No, o.

Color mixing prevention agent (Cpd-7)... o, o Color mixing prevention agent B medium (Sol v-da, j, etc.) 0, No J Polymer latex (Cpd-r) 0, 10 701N 3rd layer The same 1/1 m (low-sensitivity sensitizing layer) Silver bromide (
Average particle size 0.33μ, particle size distribution lr%, 7
μ-hedron) 0.07! Color sensitizing dye (silver bromide (J
P average particle size O, US μ, particle size distribution 10 width, i
4c-hedron) 0.10 Gelatin 0.30 Yellow coupler (ExY-1) e＠War-0,20 Anti-stinting agent (Cpd-7) 0.00/ Anti-fading agent (Cpd-4)... 0.10 Coupler dispersion medium (Cpd-1) O, aS Coupler solvent (Solv-co) 0, 03 @/U nom (, %* Degree 1 - Sensitivity J dimension 1) Blue sensitizing dye (Exa-j, 4 ) sensitized silver bromide (average grain size 7.2 μ, grain size distribution io rumor, 14c hedron) O, Co! Gelatin 1.00 ye a
-Coupler (ExY-1) ---t), @.

Anti-fading agent (Cpd-7) φ・, 0.002 Anti-fading agent (cpa-a)...a, 10 Coupler dispersion medium (Cpd-7) 0,0! Coupler solvent (Solv-J) 0. 10 73rd layer (ultraviolet absorption layer) Gelatin i, s.

Ultraviolet #lI absorber (Cpd-/, J, P, etc.) 7.00 Color mixing prevention + h Qi 11 (Cpd-4, to equivalent) o, o
t-min@medium (Cpd-j) Ultraviolet a absorber solvent (8o1v-/, 2 equivalents) 0,/
j Anti-irradiation dye (Cpd-//, /2 equivalent)
0.02 anti-irradiation dye n (CPd-/J, /4ζ etc. 11L)
- Life 0.02th i u4 (protection) Fine grain silver chlorobromide (silver chloride P7 mol%, average size 0.λ
μ) 0.1! modified popal
0.02 gelatin
/,! 0 gelatin hardener (H-1) book...
0. /7 Furthermore, each photosensitive layer contains (N-I-
? ) was used as a nucleation accelerator in an amount of (ExZS-/)t-/0-29% based on the amount of silver halide coated.

Each layer contains alkanol XC (Du) as an emulsification dispersion aid.
Pont) and alkylbenzene sulfone sodium, succinic acid ester and hydrogen as coating aids, +1V
1a gefa CF-/JO (manufactured by Dainippon Ink Co., Ltd.) was used. The halogenated colloidal silver-containing layer contains (Cpd-1!) as a stabilizer.

/4. /7) was used, and this sample was designated as sample number H.

The compounds used in the examples are shown below.

Sample H except that additives were added to the @ layer and the seventh layer of sample H.
In the same manner as above, samples of the combinations shown in the table were prepared.

H-/ 1, +2-bis(vinylsulfonylacetamido)ethane (N-1-F) C1-1,CmiC1(・α04- C(ExZ8-1) Exa-/ (OH,)3S03H x8-2 Exa -j Exa-a Sυ3H Cpd-/ C,H,(suCpa-J C,)l,(suCpa-J Cpa-kyuu, it,(ri C41(.(suCpa-j CONH04H,(su( n-70ON1000) Cpa-1 Cpa-7 OH Cpar-r Polyethyl acrylate Cpd-P (JH Cpd-// cpct-/ koCpd-/J Cpd-i≠ Cpd-/j H cpct-/6 H Cpd- t7 Cpd-/r ExC-/ α t; Phthalate Sol Mer- Tricresyl phosphate olv-j Dibutyl phthalate olv-4 Trioctyl phosphate olv-7 Dioctyl sepacate treatment process Human bleach fixing -3 seconds Jr@C Water Wash ■
4 cJ seconds st@c Water Wash■ aj seconds Jr"C The washing water replenishment method was a so-called countercurrent replenishment method in which the washing bath (■) was replenished and the overflow ?a of the washing bath (■) was led to the washing bath (■).

[Color development sales]

Diethylenetriaminepentaacetic acid fRO, jfl- and ethylidene/9 I-diphosphonic acid o, st diethylene glycol r, oIP benzyl alcohol l co, Of sodium bromide
0.7f sodium sulfite
ko, otN, N-diethylhuman o+cylamino J, jf triethylene cyano (/, 4C-diazabicyclo [ko, ko.

Cocooctane) J, jfJ-methyl-thin-amino-N-ethyl-N-(β-methanesulfonade ζ-doethyl)-aniline t, op potassium carbonate! 0. Of firefly whitening agent (
xf Reuben 43/, Of adding pure water
toooo, 1p)l
10.109H was prepared with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution]

Mother liquor thiog & acid ammoecium / 10f sodium bisulfite ta,ot ethylenediamine 40 NR iron(III) ansonitum cohydrate
Of pure water t-■
Then, adjust the toied pH to 7,0 with aqueous ammonia or hydrochloric acid.

[Washing water]

Pure water was used.

Here, pure water is water in which all cations other than hydrogen ions and all anions other than hydroxide ions in tap water are removed by ion exchange treatment to a concentration of ttppm or less.

Sample 1 thus obtained was exposed to light through an optical wedge and developed in processing [A]. After measuring the magenta reflection of each of these samples with a Fuji self-recording densitometer,
A 0-day fading test was conducted using a fluorescent light tester (illuminance/10,000 lux).

The results are shown in Table r.

This result is almost the same as that of Example t, that is, it can be seen that the degree of light fastness improvement effect due to the combination of the compounds of the present invention is significantly large despite the difference in the layer structure of the light-sensitive materials.

(Effects of the Invention) According to the present invention, a color photograph with excellent fastness of the color image 11R can be obtained. In particular, when the color photographic light-sensitive material of the present invention is used, three dyes: yellow dye, maze/red dye, and cyan dye, can be used.
The color no-lance is maintained even during long-term storage,
Moreover, a color photograph with significantly less coloring on the white background can be obtained.

Patent Applicant: Fuji Photo Film Co., Ltd. July 2019 Issue No. 2, Title of Invention: Silver chloride color photographic material 3, Person performing correction 8! Contact information Fuji Photo Film Co., Ltd. Tokyo Head Office 1lt5F, 2-26-30 Nishi-Azabu, Minato-ku, Tokyo 106, (406) 2537 Table Date of amendment order Voluntary & subject of amendment Name of amendment Details of amendment (No changes to the contents) will be submitted.

Procedural amendment 1. Display of incident 1986 Fugan No. 111!34
No. 11 No. 2, Title of the invention Silver halide color photographic light-sensitive material 3, Relationship with the amended case Hinoki License Applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Contact Address 2-26 Nishi-Azabu, Minato-ku, Tokyo 106 No. 30 No. 4, Subject of amendment All statements in the "Scope of Claims" column and "Detailed Description of the Invention" column 5 of the specification, and the "Scope of Claims" section of the description of the contents of the amendment Correct as expected.

The statement in the "Detailed Description of the Invention" section of the specification is amended as follows.

l) Page 7, line 7 After "Improved Nine" Insert ``Color photo and how to get it''.

2) Page 7, line l/ K after “Prevented Nine” Insert "color photo and get it" 3) Page 7/j to line 16 K after "prevented" Insert "Power 2 - Photo and how to get it".

4) Page 7, line 76 After "Power 2 - Photographic Light-sensitive Materials" "And the method for producing the color photograph" Insert.

5) Set the number on the 3rd line of the page. After "remarkable" Insert ``Color photo and how to get it''.

6) Page 1, line 3 After “color photographic materials” "And method for producing limb color photographs" Insert.

7) Number of pages to rows "Photosensitive material" Delete.

8) The page/r line "Contains" t "use" and correct it.

9) 1st line on page 1 After "Wakatsuki." Attachment ■ Insert.

1o) It page j~ is the line “Shigansho 4/-/II Ri/Ri No.” t [European Application Publication (EP) O, Co., Ltd.

6t AJJ and correct it.

U) "Derived from a nucleophilic functional group" t in the 1st/@/J~/line is corrected to "A nucleophilic functional group or derived from it." , 12) After "preferred" on page 1, line 1, insert K "Examples of j or more nucleophilic functional groups are amino groups, mercapto groups, sulfinic acid groups, etc." .

la) First page, first line After “What is a heterocyclic group?” "As a bone nucleation atom" Insert all.

14)! /Page ko, line O to page 13, line 1, ``, sulfur atom M9 is a hydrogen atom'' t ``M9 is a sulfur atom'' Corrected.

15) Page 13 Hiroyuki "Kumaniru" t "Cromanil" and correct it.

16) Page 1j λ~3rd line After “heterocycle” "Ki" Insert.

17) Page 17, line 3 “It can’t be.”t “It will never happen.” and correct it.

18) Page 17! row After “heterocycle” "Ki" Insert.

19) "Group, amino group...sulfony" on page 17, line t-2? “Ki,
Amino group, alkylamino group, acyl group, sulfonamide group, sulfony group.”

zo) Page 1r, line 3 "Anisono" t "Aningin" and correct it.

21) Page 11r, line 1/ r (1-a) ~ (1-b) jt-r(1)J and correct it.

22) First page visit "Heterocyclic group" "Non-aromatic heterocyclic group" and correct it.

23) 10th line from the bottom of page 20 After rMgJ ",ammonia" Insert all.

24) Page 20, second line from the bottom ",ammonia" Delete.

25) Page 27! row “R15 and RtaJk "R17 and R18" and correct it.

26) Line io of page λ "-8R26-Jk r-8-R26J and correct it.

27) Page 23, rows 1 to 3, "Ru group, ...... Bency" 2 "Ru group, nitro group, cyano group, alkoxyoxalyl group (e.g. methoxyoxalyl, isobutoxyoxalyl, "Octyloxyoxalyl, benzii," he corrected.

28) Page 56 ([1-/A) [S "5O2Na 1” and correct it.

29) Refer to page 1-line 6 of page 1 for "a method according to these..."
so, o4cth issue, same 0,2! j, 7th No. 2, same 0,211. Atko Aλ No., Hinoki Kaisho tλ-2 Kota 14c
The method described in item z shall be amended as follows.

30) Insert "R47 represents an aliphatic group and an aromatic group represents a heterocyclic group" after "may be formed." in the second line from the bottom of page 76.

31) No. ioz page A-7j " and correct it.

32) Page 107 A-IJ [ and correct it.

33) No. ior page A-11f) r　NHC4Hg(n) ↓　　　　　Jk and correct it.

34) 73rd≠page/line "Compound" t Correct it to "compound or organometallic complex of formula (fV)".

35) "In this case" in the IOth line of pages i and iz is amended to read, "Although the use of oil is not essential in the present invention, its use is preferable, and in this case."

36) Page i3z // line "o, oo~ko, 0"t "2.0 or less" and correct it.

37) No. 13! Page 72nd line After "The percentage is" "Each" Insert.

3B) On page 131/line 4C, after "is.""The molar ratio of group (1) and group (2) is preferably in the range of o, i to 10. When these are added to the treatment liquid, the amount of each addition is preferably 10-5 to 7 mol/l.'' is inserted.

39) 1st page 1 A-/cot r　/NHTOz　-J　k r, NH30x-J and correct it.

4G) Page t3r // line After "acrylic acid" k "," Insert.

41) 1st page ≠ page 3~ After “Created.” "Additives listed in Table 1 should be added to the silver chlorobromide emulsion layer." Insert.

42) Correct the reference table on the 1st copy op page as shown in the attached sheet ◎.

43) 21st page, line λQ "0, after 4cOJ "(As solid content of latex)" Insert.

44) After the chemical structural formula on page 1 EXS-j,
Insert "S-6".

45) No. λao page Ex, 5-4A ” and correct it.

46) No. 24t page Cpd-A 1--C, O- 0jk 1--C-0- 0” and correct it.

47) Second! /page Table 1 is corrected as shown in Attachment 0.

4B) No. 13 Insert attachment [F].

Attachment ■ 2. Claims Formulas (1) and (11) are combined with at least one compound represented by (IIN) and +1) an organic antifading agent represented by the following formula (IV). (2) The steel, cobalt, nickel, or e-radium container must contain platinum as the central metal, and at least one organic metal complex having at least one organic ligand having a co-located or higher conformation. tCharacteristic color respect・General formula (1) %Formula% General formula (n)Formula?, R1.R2 each represents an aliphatic group, an aromatic group, or a heterocyclic group.X is aromatic at pHr or below A represents a group that reacts with an aromatic amine developer to form a chemical bond. n represents l or 0. B represents a hydrogen atom or an aliphatic group. , represents an aromatic group, a heterocyclic group, an acyl group or a sulfonyl group, and Y
represents a group that promotes the addition of an aromatic amine developer to the compound of general formula (n).

Here, R1 and X. Y and R2 or B may be bonded to each other to form a cyclic structure.

General formula (III) -Z In the formula, R represents an aliphatic group, and aromatic group represents a heterocyclic group. 2 represents a nucleophilic group. 2 represents a group that decomposes in the light-sensitive material to release a nucleophilic group.

-Formula (IV) 131) -W-R a 1 In the formula, R30 represents an aliphatic group, and aromatic group 9 represents a heterocyclic group. R31 represents a hydrogen atom or an aliphatic group. Here, R32 #I'Laa and R34 may be the same or different, and each represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an alkenoxy group, and 9 represents an aryloxy group. W is 10. -S-Mayu is expressed as 1N-.

Here, R3S represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, or an oxy radical group;

1'Lao and R31 may be bonded to each other to form a j~7-membered ring, and R3!6 and l'Lso may be bonded to Rat to form a j~7-membered ring. Good too.

2) The compound represented by formulas (1) and (n) has a second-order reaction rate constant of 2(r(7
'C) is/, 01/rnol-sec~/. o×lO
t/mol sec, Z of the compound represented by formula (TI) is Pe
arson's nucleophilic "CH3I value is a group derived from a nucleophilic functional group of 3 or more and is an optical material.

A method of manufacturing color photographs in which a silver halide photographic base material having a layer is imagewise exposed, followed by at least color development, bleaching and fixing.

Attachment ■ That is, the present invention relates to the color photograph described below, a refined silver halide color photographic light-sensitive material obtained therefrom, and its power 2.
- A method of manufacturing photographs.

1) Yellow IIIIgI-forming dye-containing layer, magenta image-forming dye-containing layer and cyan a in any order on the support.
m image-forming dye-containing layer, and optionally/on the support.
17'? - is the following formula (1) in multiple photographic constituent layers,
(II) is then combined with at least one of the compounds represented by (I[); C1) an organic antifading agent represented by the following formula (■); or (2) a metal with copper, cobalt, nickel, noradium or platinum as the center. and contains at least one organometallic complex having at least one organic ligand having a bidentate or higher conformation.
? Cool paper as a sign □True.

2) A yellow image-forming silver halide emulsion layer, a magenta painter-correcting silver halide emulsion layer, and a cyan image-forming silver halide emulsion layer are provided on the support in any order, and any color on the support is /17t has the following in multiple photographic constituent layers -
Formulas (I) and (II) are at least one compound represented by (II); C1) an organic antifading agent represented by formula (IV); (2) copper, cobalt; , nickel, and noradium contain at least one of the organometallic complexes having platinum as the central metal and at least one organic ligand having a bidentate or more conformation. Silver chemical color photographic material.

3) Acupuncture-like exposure of a silver halide photographic substrate material having a yellow image forming silver halide emulsion layer, a magenta image forming silver halide emulsion layer and a cyan image forming silver halide emulsion layer on a support in any order. After that, at least the color development is carried out by the photographic processing of bleaching, fixing (t7't is bleach-fixing), and washing (or stabilization).1 In the method for producing color photographs, the following formula (1) (I[) or (III)
At least one of the compounds represented by: and (l) an organic antifading agent represented by the following formula (■) or (2)
Copper, cobalt, nickel, and radium are photographically processed in the presence of at least one organometallic complex having platinum as the center and at least one organic ligand having a λ-plate conformation. I decided to give it! A method of manufacturing color photographs.

Attachment [F] A-/73 (CHs)2N-OC12H25 A-/7th edition ((n) Cs H,,) 8 NOH person-/71 A-/74 A-/77 A-/71 A-/7P person - 1tO person-/1/ A-/IF

Claims (1)

[Scope of Claims] 1) at least one compound represented by the following general formula (I), (II) or (III); and (1) the following general formula (
Among the organic antifading agents represented by IV) or (2) organometallic complexes having copper, cobalt, nickel, palladium, or platinum as a central metal and at least one organic ligand having a bidentate or higher conformation. A silver halide color photographic material containing at least one of the following. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ -General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_2 are aliphatic groups, aromatic groups,
Or represents a heterocyclic group. X represents a group that reacts with an aromatic amine developer and leaves at pH 8 or lower, and A represents a group that reacts with the aromatic amine developer to form a chemical bond. n
represents 1 or 0. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or a sulfonyl group,
Y represents a group that promotes addition of an aromatic amine developer to the compound of general formula (II). Here, R_1 and X, Y and R_2, or B may be bonded to each other to form a cyclic structure. General formula (III) R-Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group. General formula (IV) R_3_0-W-R_3_1 In the formula, R_3_0 represents an aliphatic group, an aromatic group or a heterocyclic group. R_3_1 represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or ▲a numerical formula, a chemical formula, a table, etc.▼. where R_3_2, R_3_3 and R_3_
4 may be the same or different, and each represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenoxy group, or an aryloxy group. W is -O
Represents -, -S- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Here, R_3_5 is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group,
Represents an oxy radical group or a hydroxyl group. R_3_0 and R_3_1 may be combined with each other to form a 5- to 7-membered ring, or R_3_5 and R_3_0 or R
_3_1 may be combined with each other to form a 5- to 7-membered ring. 2) The compounds represented by the general formulas (I) and (II) have a second-order reaction rate constant k_2(8
0℃) is 1.0l/mol・sec~1.0×10^-
It is a compound in the range of ^5l/mol・sec, and Z of the compound represented by the general formula (III) is Pear
The silver halide color photographic light-sensitive material according to claim (1), which is a group derived from a nucleophilic functional group having a nucleophilicity^nCH_3I value of 5 or more.