JP2729690B2 - Silver halide color photographic materials - Google Patents

Description

Description: BACKGROUND OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and more particularly, to a compound having a high iodine emulsion and a compound capable of releasing an electron transfer agent in an imagewise manner. The present invention relates to a silver halide color photographic light-sensitive material which is hard, has excellent graininess, and has excellent storage stability and processing dependency.

[Conventional technology]

In recent years, silver halide light-sensitive materials, especially photographic light-sensitive materials, are ISO400 light-sensitive materials (SHG-
There is a demand for a light-sensitive material having high sensitivity and excellent granularity, as represented by 400), little change in photographic properties even when processed with various processing solutions, and excellent in storage stability of the light-sensitive material.

Recently, couplers that release an electron transfer agent in an image-wise manner for the purpose of compensating for the deterioration of granularity when standardized by gradation by a so-called DIR coupler have been disclosed in US Pat. No. 4,859,57.
No. 8, European Patent Publication No. 347,849, etc., but even with these compounds, the granularity was still unsatisfactory. Further, it has been revealed that the use of these compounds deteriorates the storability of the light-sensitive material, particularly the storability of the photographic performance with time from photographing to development, and increases the dependence of the photographic performance on the processing time.

[Problems to be solved by the invention]

The first object of the present invention is to provide a light-sensitive material having high sensitivity, high contrast and excellent granularity, and secondly, the storage stability over time, particularly the storage stability over time of photographic performance from photographing to development. Thirdly, it is to provide a light-sensitive material which has a small processing dependency and can shorten the processing time.

[Means for solving the problem]

These objects of the present invention have been achieved by the following light-sensitive materials.

In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer provided on a support, at least 40% by weight of silver halide grains in the emulsion layer has a silver iodide content of at least 7 mol%. Less than 30 mol% of particles,
A silver halide color photographic light-sensitive material, characterized in that at least one silver halide emulsion layer contains a compound represented by the following general formula (I).

In the general formula _{(I) A- (L) n} -ETA formula, A is by reaction with oxidized developer, - (L) _n -
L is a group that releases ETA, L represents a group that releases ETA after being cleaved from A, n represents 0, 1 or 2, and ETA is a compound that has been cleaved from A- (L) _n- Represents a group that functions as

 Hereinafter, the present invention will be described in detail.

A silver halide emulsion effective for use in the present invention is a silver halide emulsion containing silver iodide in an amount of 7 mol% to 30 mol%,
40% or more by weight based on all silver halide grains of the layer,
Preferably, the emulsion contains 60% or more, particularly preferably 80% or more.

The distribution of silver iodide in the grains may be uniform or non-uniform, but in the case of silver halide such as a double-structured grain as described later, the silver iodide Average of 7
It means that it is not less than 30 mol% and not more than mol%.

The silver iodide content of each silver halide grain is, for example, X
The measurement can be performed using a line microanalyzer, and by this method, the weight ratio of silver halide grains containing 4 mol% or more of silver iodide can be determined.

The upper limit of the iodine content of the high iodide silver halide emulsion effective for use in the present invention is determined by the solid solution limit value, and is about 40 mol%. Accordingly, the present invention provides a silver halide emulsion having a silver iodide content in the range of 7 mol% to 30 mol%,
More preferably, a silver halide emulsion having a silver iodide content in the range of 10 mol% to 25 mol% is used in combination with the compound represented by formula (I) of the present invention. When the silver iodide content is below the lower limit of the above range, the effect of improving graininess, which is the object of the present invention, is generally not remarkable. Conversely, if the upper limit is exceeded, the development progress is delayed, softening,
Alternatively, adverse effects such as poor desilvering tend to appear.

The high iodide silver halide emulsion of the present invention may be of any size. Preferably 0.2 to 3.0 μm,
More preferably, when a high iodide silver halide emulsion having a particle size of 0.5 to 2.0 μm is used in combination with the general formula (I) of the present invention, a color photographic light-sensitive material having excellent graininess, processing dependency and storage stability of a light-sensitive material can be obtained.

The high iodine emulsion used in the present invention can be prepared by various methods. That is, any of an acidic method, a neutral method, an ammonia method, and the like may be used, and a single-side mixing method, a double-mixing method, a combination thereof, and the like may be used as a method of reacting a soluble salt with a soluble halogen salt. One type of the double jet method is to maintain a constant pAg in the liquid phase in which silver halide is produced,
The double jet method can be used. As another form of the double jet method, a triple jet method (for example, a soluble silver salt, a soluble bromide salt, and a soluble iodide salt) in which soluble halides having different compositions are independently added can be used.
When a relatively large emulsion is prepared, it is preferable to use a silver halide solvent such as ammonia, a rhodanate, a thiourea or an amine (the above-mentioned James, p. 9). It is well known in the art to adjust the pH and pAg during grain formation to obtain favorable photographic properties, and it is preferable that the pH be changed in the range of 2 to 10 depending on the method of forming the grains.

The high iodine emulsion of the present invention is hexahedral, octahedral, dodecahedral,
It may have a regular crystal form such as a tetradecahedron, or a crystal form such as a sphere or a plate. The inside and the surface of the emulsion grains may have different halogen compositions, or may have a uniform halogen composition. Inside the particle (Co
(re part) is silver iodochlorobromide or silver iodobromide containing a high concentration of silver iodide, and the outside of the grain (shell part) is made of silver chloroiodobromide or silver iodobromide having a low silver iodide content. Kaisho 60-143331,
Double structure grains or multiple structure grains such as those described in JP-A-61-245151 are preferred as the emulsion of the present invention. The silver ratio of the Core part and the Shell part can be selected in a wide range, but is preferably 5/1 to 1/5.

In such a double structure grain or multiple structure grain, the object of the present invention is achieved in the case of silver halide in which the average value of the silver iodide content in the grain is 7 mol% or more. More specifically, the preferred silver iodide content of the Core portion is 15 mol% or more, and more preferably 25 mol%.
As described above, it is more preferable to select a value between 35 mol% and the limit value of silver iodobromide solid solution (see page 4 of James, supra). The silver iodide content of the shell part is preferably 5 mol% or less, and more preferably 3 mol% or less.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be allowed to coexist.

The emulsion is usually subjected to removal of soluble salts after precipitation or physical ripening, and as a means for this purpose, a known method of gelling gelatin, such as the Nudel washing method, may be used. Utilizing inorganic salts such as sodium sulfate, anionic surfactants, anionic polymers (eg, polystyrene sulfonic acid), or gelatin derivatives (eg, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) A sedimentation method (flocculation) may be used.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, see “Die Grundlagen de H. Frieser”
r Phtographischen Prozesse mit Silberhalogeniden "
(Akademische Verlagsgesellschaftt 1968) 675-734
The method described on page can be used.

That is, a sulfur sensitization method using a compound containing sulfur (e.g., thiosulfate, thioureas, mercapto compounds, rhodanines) which can react with active gelatin or silver; a reducing substance (e.g., stannous salt, Amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds) by reduction sensitization; noble metal compounds (for example, gold complex salts, Pt, I
Noble metal sensitization using a group VIII metal of the periodic table such as r or Pd) or a combination thereof can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles, for example, benzothiazolium salts, nitroimidazoles, nitrobayesimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines Thioketo compounds such as oxadolinthione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes and the like; Many compounds known as antifoggants or stabilizers, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide, and the like, can be added.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include:
Cyanine dye, merocyanine dye, complex cyanine dye,
Complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes are included. Particularly useful dyes are cyanine dyes,
It is a dye belonging to merocyanine dyes and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; Nucleus fused with an aromatic hydrocarbon ring, i.e., indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzene An imidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

In a merocyanine dye or a complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-
A 5- to 6-membered heterocyclic nucleus such as a 2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

Useful sensitizing dyes include, for example, German Patent 929,080
Nos., U.S. Pat.Nos. 2,231,658, 2,493,748, 2,503,77
No. 6, No. 2,519,001, No. 2,912,329, No. 3,656,959,
3,672,897, 3,694,217, 4,025,349, 4,0
46,572, UK Patent 1,242,588, JP-B-44-14030,
No. 52-24844 can be mentioned.

These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat.Nos. 2,688,545, 2,977,229, 3,397,060 and 3,5
22,052, 3,527,641, 3,617,293, 3,628,96
No. 4, 3,666,480, 3,672,898, 3,679,428,
3,703,377, 3,769,301, 3,814,609, 3,8
37,862, 4,026,707, British Patent 1,344,281, 1,
No. 507,803, JP-B-43-4936, JP-B-53-12,375, JP-A-5
Nos. 2-110,618 and 52-109,925.

Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, aminostil compounds substituted with a nitrogen-containing heterocyclic group (for example, those described in U.S. Pat. Nos. 2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensates (for example, those described in U.S. Pat. No. 3,743,510), Cadmium salts, azaindene compounds and the like may be included. US Patent
3,615,613, 3,615,641, 3,617,295, 3,63
The combinations described in 5,721 are particularly useful.

Hereinafter, the compound represented by formula (I) will be described in detail.

The electron transfer agent (electron transfer agent) constituting the present invention.
The compounds which release the agent are described below.

Preferably, a compound represented by the following general formula (I) is used.

Formula (I) A- (L) _n -ETA In the formula, A is a group that releases (L) _n -ETA by reaction with an oxidized developing agent, and L releases ETA after cleavage from A. N represents 0, 1 or 2, and ETA represents A-
(L) represents a group that functions as an electron transfer agent after cleavage from _n .

When n is 1 or more, a plurality of L represent the same or different, and (L) _n -ETA cleaved from A does not function as it is, and the bond between (L) _n and ETA is cleaved. E
The function of TA is substantially expressed.

A is preferably a coupler residue. That is, a group ((L) _n -ET
Any coupling group having A) can be used.

The group represented by ETA is preferably 1-aryl-
A 3-pyrazolidinone derivative is used. For example, U.S. Pat.Nos. 4,209,580, 4,463,081, 4471045, 4481287,
The compounds described in JP-A-62-123172 are known.

In the general formula (I), A preferably represents a coupler residue.

For example, a yellow coupler residue (for example, closed ketomethylene type), a magenta coupler residue (5-pyrazolone type, pyrazoloimidazole type, pyrazolotriazole type, etc.), a cyan coupler residue (phenol type, naphthol type, etc.), and none Color coupler residue (Indanone type,
Acetophenone type). Further, it may be a heterocyclic coupler residue described in US Pat. Nos. 4,315,070, 4,183,752, 3,961,959 or 4,171,223.

When A represents a coupler residue in the general formula (I), preferred examples of A are the following general formulas (Cp-1), (Cp-2),
(Cp-3), (Cp-4), (Cp-5), (Cp-6),
(Cp-7), (Cp-8), (Cp-9) or (Cp-1
It is a coupler residue represented by 0). These couplers are preferred because of their high coupling speed.

In the above formula, the free bond derived from the coupling position indicates the bonding position of the coupling-off group.

In the above formula, R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ ,
If R ₆₀ , R ₆₁ , R ₆₂ or R ₆₃ contains a diffusion-resistant group, it is selected such that the total number of carbon atoms is 8 to 40, preferably 10 to 30, otherwise the total number of carbon atoms is Is preferably 15 or less. In the case of bis-type, telomer-type or polymer-type couplers, any of the above substituents represents a divalent group, and connects repeating units and the like. In this case, the range of the carbon number may be out of the range.

The following R ₅₁ ~R _63, b, will be described in detail d and e. In the following, R ₄₁ represents an aliphatic group, an aromatic group or a heterocyclic group, R ₄₂ represents an aromatic group or a heterocyclic group,
R ₄₃ , R ₄₄ and R ₄₅ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

R ₅₁ has the same meaning as R ₄₁ . b represents 0 or 1. R ₅₂ and R ₅₃ each have the same meaning as R ₄₂ . R ₅₄
A group having the same meaning as R ₄₁ , Or an N≡C- group. R ₅₅ represents a group having the same meaning as R ₄₁ . R ₅₆ and R ₅₇ each have the same meaning as R ₄₃ , R ₄₁ S
Group, R ₄₃ O- group, Represents R ₅₈ represents a group having the same meaning as R ₄₁ . R ₅₉ is R ₄₁
A group with the same meaning as R ₄₁ O-group, R ₄₁ S-group, halogen atom, or Represents d represents 0 to 3. When d is plural, plural R _59s represent the same substituent or different substituents.
Further, each R ₅₉ may be linked to form a divalent group to form a cyclic structure. Examples of divalent groups for forming a cyclic structure include Is a typical example. Where f is 0 to 4
And g represents an integer of 0 to 2. R ₆₀ is R
Represents a group having the same meaning as ₄₁ . R ₆₁ is the same group as R ₄₁ ,
R ₆₂ is a group of the same meaning as R _41, R ₄₁ OCONH- group, R ₄₁ SO ₂ NH-
Group, R ₄₃ O-group, R ₄₁ S-group, halogen atom or Represents R ₆₃ is a group having the same meaning as R ₄₁ , R ₄₁ SO ₂ —, R ₄₃ OCO—, R ₄₃ O—SO ₂ —, halogen, nitro, cyano or R ₄₃ CO—. e represents an integer of 0 to 4. Each represent the same or different when there are a plurality of R ₆₂ or R _63.

In the above description, the aliphatic group is a saturated or unsaturated, linear or cyclic, linear or branched, substituted or unsubstituted aliphatic hydrocarbon group having 1 to 32, preferably 1 to 22 carbon atoms.
Representative examples include methyl, ethyl, propyl, isopropyl, butyl, (t) -butyl, (i) -butyl,
(T) -Amino, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 1,1,3,3-tetramethylbutyl, decyl, dodecyl, hexadecyl, or octadecyl.

The aromatic group is a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted naphthyl group.

The heterocyclic group is a substituted or unsubstituted, preferably 3- to 8-membered, heterocyclic group having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms, wherein the heteroatom is selected from a nitrogen atom, an oxygen atom or a sulfur atom. It is. Representative examples of heterocyclic groups include 2-pyridyl, 2-thienyl, 2-furyl, 1,3,
4-thiadiazol-2-yl, 2,4-dioxo-1,3-
Imidazolidine-5-yl, 1,2,4-triazole-2
-Yl or 1-pyrazolyl.

When the aliphatic hydrocarbon group, the aromatic group and the heterocyclic group have a substituent, typical substituents include a halogen atom, an R ₄₇ O-group, an R ₄₆ S- group, R ₄₆ COO—, R ₄₇ OSO ₂ —, cyano or nitro. Here, R ₄₆ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ₄₇ , R ₄₈ and R ₄₉ each represent an aliphatic group,
Represents an aromatic group, a heterocyclic group or a hydrogen atom. The meaning of the aliphatic group, the aromatic group or the heterocyclic group is the same as defined above.

Next, preferred ranges of R _{51 to} R ₆₃ , d and e will be described.

R ₅₁ is preferably an aliphatic group or an aromatic group. R ₅₂ , R ₅₃ and R ₅₅ are preferably aromatic groups. R ₅₄ is an R ₄₁ CONH- group, or Is preferred. R ₅₆ and R ₅₇ are an aliphatic group, an aromatic group, R ₄₁ O
-Or R ₄₁ S- groups are preferred. R ₅₃ is preferably an aliphatic group or an aromatic group. R ₅₉ in the general formula (Cp-6)
Is preferably a chlor atom, an aliphatic group or an R ₄₁ CONH— group. d is preferably 1 or 2. R ₆₀ is preferably an aromatic group. In the general formula (Cp-7), R ₅₉ is preferably an R ₄₁ CONH- group. In the general formula (Cp-7), d is preferably 1. R ₆₁ is preferably an aliphatic group or an aromatic group. In the general formula (Cp-8), e is preferably 0 or 1. R ₆₂ is preferably an R ₄₁ OCONH— group, an R ₄₁ CONH— group or an R ₄₁ SO ₂ NH— group, and the substitution position thereof is preferably the 5-position of the naphthol ring. In the general formula (Cp-9), R ₆₃ is R ₄₁ CONH
Group, R ₄₁ SO ₂ NH— group, Nitro or cyano groups are preferred.

In the general formula (Cp-10), R ₆₃ is R ₄₃ CCO— or R ₄₃ CO— groups are preferred.

As the group represented by L in the general formula (I), the following are preferred.

(1) Group utilizing cleavage reaction of hemiacetal The groups described in, for example, US Pat. No. 4,146,396, JP-A-60-249148 and JP-A-60-249149 are represented by the following general formula. Here, the symbol * represents the position of the compound represented by the general formula (I) that binds to A, and the symbol ** represents the position that binds to ETA.

Wherein W is an oxygen atom, a sulfur atom or Wherein R ₁₁ and R ₁₂ represent a hydrogen atom or a substituent, R ₁₃ represents a substituent, and t represents 1 or 2.
When t is 2, two Represents the same or different. R ₁₁ and R ₁₂
Each R ₁₅ but representative example of and R ₁₃ when a substituent is
Group, R ₁₅ CO- group, R ₁₅ SO ₂ -group, Is mentioned. Here, R ₁₅ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₁₆ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. R ₁₁ , R ₁₂ and R ₁₃ each represent a divalent group and are linked to form a cyclic structure. Specific examples of the group represented by formula (T-1) include the following groups.

(2) A group that causes a cleavage reaction by utilizing an intramolecular nucleophilic substitution reaction, for example, a timing group described in US Pat. No. 4,248,292. It can be represented by the following general formula.

Formula (T-2) * -Nu-Link-E-** wherein Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, E represents an electrophilic group, and Nu represents A group that can undergo a more nucleophilic attack to cleave the bond with the ** mark
Link represents a linking group that sterically links Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction. General formula (T
Specific examples of the group represented by -2) are as follows.

(3) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system.

For example, U.S. Pat.Nos. 4,409,323, 4,421,845, JP-A-57-188035, JP-A-58-98728, JP-A-58-209736, and 58
-209737, 58-209738 and the like, and is a group represented by the following formula (T-3).

In the formula, *, **, W, R ₁₁ , R ₁₂ and t are (T−
It has the same meaning as described in 1). However,
R ₁₁ and R ₁₂ may combine to form a benzene ring or a heterocyclic ring. Specific examples include the following groups.

(4) A group utilizing a cleavage reaction due to hydrolysis of an ester.

For example, the linking group described in West German Patent Publication No. 2,626,315 includes the following groups. In the formulas, * and ** have the same meaning as described for the general formula (T-1).

(5) A group that utilizes the cleavage reaction of imino ketal.

For example, it is a linking group described in US Pat. No. 4,546,073, and is a group represented by the following general formula.

In the formulas, *, ** and W have the same meaning as described in formula (T-1), and R ₁₄ has the same meaning as R ₁₃ . Specific examples of the group represented by Formula (T-6) include the following groups.

In the 1-aryl-3-pyrazolidinone derivative used in the present invention, the 4- and 5-positions may be substituted with alkyl, aryl, alkoxy, alkylthio, aryloxy or arylthio, etc., and the 1-aryl group is a benzene ring May be substituted by a substitutable group.

Preferred as the ETA used in the present invention are groups represented by the following general formula (II) or (III).

In the formula, * represents A- (L) _n represented in the general formula (I).
Represents a position where R ₁ , R ₂ , R ₃ and R ₄ are each independently alkyl, aryl, alkoxy, alkylthio,
Represents aryloxy or arylthio. R ₅ represents a group that can be substituted on a benzene ring, and m represents an integer of 0 to 6.

When R ₁ , R ₂ , R ₃ and R ₄ include an alkyl group moiety,
Preferably substituted or unsubstituted, chain-like, having 1 to 8 carbon atoms.
It is a branched or cyclic, saturated or unsaturated alkyl group. Examples of the substituent include a hydroxyl group, an alkoxy group (1 to 8 carbon atoms, for example, methoxy, ethoxy, butoxy), an acyloxy group (2 to 10 carbon atoms, for example, acetyloxy, butanoyloxy), an alkylthio group (carbon number 1 to 8, for example, methylthio, butylthio), an arylthio group (for 6 to 10 carbon atoms, for example, phenylthio), an aryloxy group (for 6 to 10 carbon atoms, for example, phenoxy, naphthoxy), and alkoxycarbonyl (2 to 10 carbon atoms, for example, methoxy) Carbonyl) or carbamoyl group (C 0
To 10, for example, unsubstituted carbamoyl and N-butylcarbamoyl).

When R ₁ , R ₂ , R ₃ and R ₄ include a moiety of an aryl group,
It is preferably a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. Examples of the substituent include a substituent for the alkyl group, a halogen atom (for example, chlor, fluorine, bromo), an acylamino group (for example, having 2 to 10 carbon atoms, for example, acetamido or benzamide), and an alkyl group (for having 1 carbon atom).
-8, for example methyl, butyl) or a carboxyl group.

Examples of R ₅ are examples of substituents for the aryl group. Preferred R _5, alkoxy group, a sulfonamido group, an acylamino group, a halogen atom or an alkyl group.

Compounds of the present invention, U.S. Pat.Nos. 4,859,578, 4,14
Nos. 6, 396, 4,248,962, 4,409,203 European Patent Publication Nos. 347,849A, 255,085A and JP-A-60-218
The compound can be synthesized according to the method described in No. 645 and the patent described therein.

These compounds are preferably added to the light-sensitive silver halide emulsion layer in the light-sensitive material or an adjacent layer thereof, and more preferably to the same layer as the emulsion of the present invention.
The total amount to the sensitive material in is 0.005~2.0g / m ^2, preferably from 0.05 to 1.0 g / m ^2, more preferably 0.1 to 0.6 g / m ²
It is. These compounds can be added in the same manner as in the usual coupler as described later.

It is preferable to add a compound represented by the following general formula (H) to the light-sensitive material of the present invention.

General formula (H) A- (L ₁ ) _v -B- (L ₂ ) _w -DI In the formula, A reacts with an oxidized developing agent and is (L ₁ ) _v -B- (L ₂ ) _w
Represents a group which cleaves -DI, L ₁ represents a linking group which cleaves the bond between B after cleavage bond with A, B reacts with oxidized developer to (L _{2) w} -DI Represents a cleaving group, L ₂
Represents a group that cleaves DI after cleavage of the bond with B;
Represents a development inhibitor, v and w each represent an integer of 0 to 2, and when they represent 2, two L ₁ and two L ₂ represent different or the same respectively.

Hereinafter, the compound represented by formula (H) will be described in detail.

The compound represented by the general formula (H) cleaves DI during development through the following reaction process.

In the formula, A, L ₁ , v, B, L ₂ , w and DI have the same meanings as described in the formula (H), and QDI represents an oxidized developing agent.

Further, A has the same meaning as A in the aforementioned general formula (I), and L ₁ and L ₂ have the same meanings as L in the general formula (I).

When A represents a residue that can be redox-reduced in the general formula (H), the general formula (H) is specifically represented by the Kendall-Pelz formula (P)
It is represented by

(P) A ₁ -P- (X = Y) _n -QA _{2 In the} formula, P and Q each independently represent an oxygen atom or a substituted or unsubstituted imino group, and at least n of X and Y one is _{- (L 1) v -B- (} L 2) represents a methine group having a _w -DI as a substituent, other X and Y represents a substituted or unsubstituted methine group or a nitrogen atom, n represents A ₁ and A ₂ each represent an integer of 1 to 3 (n X and n Y represent the same or different), and A ₁ and A ₂ each represent a hydrogen atom or a group which can be removed by an alkali. Here P, X, Y, Q, are also included if Izure or two substituents of A ₁ and A ₂ form a bivalent group and linked cyclic structure Te summer. For example, (X = Y) _n forms a benzene ring, a pyridine ring, and the like.

When P and Q represent a substituted or unsubstituted imino group, preferred is an imino group substituted with a sulfonyl group or an acyl group.

 At this time, P and Q are represented as follows.

Here, * indicates the position at which A ₁ or A ₂ is bonded.
* Mark - (represents one binds to the position of the free bonds of X = Y _n.

In the formula, the group represented by G is a linear or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted aliphatic hydrocarbon group having 1 to 32, preferably 1 to 22 carbon atoms (eg, methyl, Ethyl, benzyl, phenoxybutyl, isopropyl), a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms (eg, phenyl, 4-methylphenyl, 1-naphthyl, 4-dodecyloxyphenyl), a nitrogen atom as a hetero atom, sulfur 4 selected from atoms or oxygen atoms
Membered to 7-membered heterocyclic groups (eg, 1-phenyl-4
-Imidazolyl, 2-furyl, benzothienyl) or -OG '(G' has the same meaning as G) are preferred examples.

In the general formula (P), P and Q are preferably each independently an oxygen atom or a group represented by the general formula (N-1).

A group from which A ₁ and A ₂ can be removed by an alkali (hereinafter, referred to as
Preferred groups), for example, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, imidoyl, oxazolyl,
Sulfonyl hydrolyzable groups, U.S. Pat.No. 4,009,02
Precursor group of the type utilizing reverse Michael reaction described in No. 9, a precursor group of the type utilizing an anion generated after the ring cleavage reaction described in U.S. Pat.No. 4,310,612 as an intramolecular nucleophilic group, U.S. Pat.No.3,674,478 No. 3,932,480 or 3,993,661, a precursor group in which an anion described in No. 3,993,661 is electron-transferred through a conjugated system and thereby causes a cleavage reaction, by electron transfer of an anion reacted after ring cleavage described in U.S. Pat.No.4,335,200. Precursor groups that cause a cleavage reaction or U.S. Patent Nos. 4,363,865 and 4,41
No. 0,618, a precursor group utilizing an imidomethyl group.

Preferred in the general formula (P) is when P represents an oxygen atom and A2 represents a hydrogen atom.

More preferably, X and Y in the general formula (P)
Is a methine group having-(L ₁ ) _v -B- (L ₂ ) _w -DI as a substituent, other X and Y are substituted or unsubstituted methine groups.

Among the groups represented by the general formula (P), particularly preferred groups are represented by the following general formula (P1) or (P2).

In the formula, * indicates the position where-(L ₁ ) _v -B _1- (L ₂ ) _w -B ₂ is bonded, and P, Q, A ₁ and A ₂ are those described in the general formula (P). And R ₆₄ represents a substituent, and q represents an integer of 0.1 to 3. When q is 2 or more, two or more R ₆₄ may be the same or different, and when two R ₆₄ are substituents on adjacent carbons, they are linked to each other as a divalent group to form a cyclic structure. The case where it expresses is also included. In that case, it becomes a benzene condensed ring and becomes, for example, a ring structure of naphthalenes, benzonorbornenes, chromans, benzothiophenes, benzofurans, 2,3-dihydrobenzofurans, or indenes, and these have one or more substituents. May have. Examples of preferred substituents having a condensed group on these condensed rings, and R
Preferred examples of R _{64 when 64} does not form a condensed ring are those listed below. That is, R ₄₁ , a halogen atom, R ₄₃ O−, R ₄₃ S−, R ₄₃ (R ₄₄ ) NCO−, R ₄₃ OOC−, R ₄₃ SO
₂ −, R ₄₃ (R ₄₄ ) NSO ₂ −, R ₄₃ CON (R ₄₃ ) −, R ₄₁ SO ₂ N (R ₄₃ )
−, R ₄₃ CO−, R ₄₁ COO−, R ₄₁ SO−, nitro, R ₄₃ (R ₄₄ ) NC
ON (R ₄₅ ) −, cyano, R ₄₁ OCON (R ₄₃ ) −, R ₄₃ OSO ₂ −, R
_{43 (R 44) N-, R} 43 (R 44) NSO 2 N (R 45) -, or Is mentioned.

Here, R ₄₁ , R ₄₃ , R ₄₄ and R ₄₅ have the same meaning as described in the general formula (I).

In the general formulas (P1) and (P2), A ₁ and A ₂ preferably represent a hydrogen atom.

Preferred in the general formula (H) is a case where A represents a coupler residue for color development.

The group represented by B in the general formula (H) is a redox-reducible group capable of reducing an oxidized developing agent, or
A preferred example is a group which undergoes a coupling reaction with an oxidized developing agent to form a substantially colorless compound.

When the group represented by B represents a group capable of reducing an oxidized developing agent, it is preferably a group represented by the following formula (B).

Formula (B) * -P '- ( X' = Y ') in n'-Q'-A _2' formula, * mark represents the general formula (H) the point of attachment on the left side, A ₂ ', P ′, Q ′ and n ′ are represented by the general formula (P
It has the same meaning as A ₂ , P, Q and n described in 1), respectively. However, at least one of n 'X' and n 'Y' represents a methine group having (L ₂ ) _w -DI as a substituent, and the other X 'and Y' are substituted or unsubstituted methine. Represents a group or a nitrogen atom. here
The case where any two substituents of A ₂ ', P', Q ', X' and Y 'are combined with a divalent group to form a cyclic structure is also included. Such a ring structure is, for example, a benzene ring, an imidazole ring or a pyridine ring.

In the general formula (B), P 'preferably represents an oxygen atom, and Q' is preferably an oxygen atom or the following. Here mark * represents a bond that binds to an (X '= Y') n ', ** mark represents a bond that binds to an A _2.

In the formula, G represents the same meaning as described in the general formulas (N-1) and (N-2).

Q ′ is particularly preferably an oxygen atom or Is a group represented by

Representative examples of the group represented by B in formula (H) are shown below. In the following, the symbol * represents a position bonding to A- (L ₁ ) _n in the general formula (H). ** indicates (L ₂ ) _w −DI
Represents the bonding position of

Wherein R ₁₃ has the same meaning as R ₆₄ described above, R ₁₄ and R ₁₅ each have the same meaning as R ₄₁ described above, l is an integer of 0 to 2,
m represents an integer of 0 to 3, and a represents an integer of 0 or 1.

Specific examples of the case where B is eliminated to form a compound exhibiting a reducing action include, for example, U.S. Pat.
No., JP-A-61-102646, JP-A-61-107245, JP-A-61-113060
And the reducing agents described in JP-A Nos. 64-13547, 64-13548 and 64-73346.

When the group represented by B in the general formula (H) represents a group which forms a substantially colorless compound upon coupling reaction with an oxidized developing agent, for example, a phenol-type or naphthol-type coupler residue, a pyrazolone-type coupler include coupler residues of residue or indanone type, these are attached at an oxygen atom A- and (L _{1) v.} The coupler residue becomes a coupler after leaving from A- (L ₁ ) _v , and undergoes a coupling reaction with the oxidized developing agent. Here, a colored dye is usually formed, but if the dye has no diffusion-resistant group and the diffusivity is appropriately increased, the dye is eluted into the processing solution during the development processing, so that substantially no dye remains in the light-sensitive material. Alternatively, even if a colored dye is formed, if it is diffusible, it reacts with an alkali component (eg, hydroxyl ion, sulfite ion) in the developing solution at the time of development, and the dye is decomposed and turned colorless. No pigment remains in it. Preferably, the following are mentioned. In the following, * indicates a position where A- (L ₁ ) _v is bonded, and ** indicates a position where (L ₂ ) _w -DI is bonded.

In the formula, R ₁₃ , R ₁₄ and m have the same meanings as described above, and R ₁₆ has the same meaning as R ₄₃ described above.

The group represented by B ₁ in the general formula (H) is preferably
A- (L ₁ ) A group that reduces the oxidized developing agent after release from ( _v ).

The compound represented by the general formula (H) of the present invention includes a case where it is a polymer. That is, the following general formula (PI)
Is derived from the monomer compound represented by the general formula (P
A polymer having a repeating unit represented by the formula (II) or a non-color-forming monomer having at least one ethylene group and having no ability to couple with an oxidized form of an aromatic primary amine developing agent. It is a copolymer with more than one species.
Here, two or more monomers may be simultaneously polymerized.

In the formula, RR represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a chlorine atom, and A ₁₁ represents -CONH-, -NHCON
H -, - NHCOO -, - COO -, - SO 2 -, - CO -, - NHCO
_{-, - SO 2 NH -,} - NHSO 2 -, - OCO -, - OCONH -, - NH
-Or -O-, A ₁₂ represents -CONH- or -COO-, A ₁₃ represents an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group or an unsubstituted or substituted arylene group, The aralkylene group may be linear or branched.

QQ represents a compound residue represented by the general formula (H), and may be bonded at any position of A, L ₁ , B ₁ , B ₂ and L ₂ .

i, j and k represent 0 or 1, but i, j
And k cannot be 0 at the same time.

Here alkylene group represented by A _13, as the substituent of the aralkylene group or an arylene group aryl (e.g. phenyl), nitro, hydroxyl, cyano, sulfo, alkoxy (e.g. methoxy), aryloxy (e.g. phenoxy), acyloxy (e.g. Acetoxy), acylamino (eg, acetylamino), sulfonamide (eg, methanesulfonamide), sulfamoyl (eg, methylsulfamoyl), halogen atom (eg, fluorine, chlorine, bromine), carboxy, carbamoyl (eg, methylcarbamoyl), alkoxy Carbonyl (eg, methoxycarbonyl), sulfonyl (eg, methylsulfonyl). When two or more substituents are present, they may be the same or different.

Next, non-color-forming ethylene-like monomers that do not couple with the oxidation product of the aromatic primary amine developer are derived from acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid and these acrylic acids. Examples include esters or amides, methylenebisacrylamide, vinyl esters, acrylonitrile, aromatic vinyl compounds, maleic acid derivatives, and vinylpyridines. The non-color-forming ethylenically unsaturated monomer used here may be used in combination of two or more.

As the group represented by DI in the general formula (H), a conventionally known development inhibitor or the like is used. For example, a heterocyclic mercapto group, a 1-indazolyl group, or a triazolyl group is preferably used. Specifically, tetrazolylthio, thiadiazolylthio, oxadiazolylthio, triazolylthio, benzoxazolylthio, benzothiazolylthio, benzimidazolylthio, 1- (or 2-) benzotriazolyl Groups), 1,2,
Examples thereof include a 4-triazol-1- (or 4-) yl group and a 1-indazolyl group. When these have a substituent, examples of the substituent include an aliphatic group, an aromatic group, a heterocyclic group, And the substituents which may be possessed by the aromatic group.

The compound represented by the general formula (H) is disclosed in US Pat.
No. 1, No. 4770982, JP-A-63-284159, No. 60-203943
Or the method described in JP-A-63-23152.

Hereinafter, specific examples of the compound represented by the general formula (H) are shown, but are not limited thereto.

The compound represented by the general formula (H) is preferably added to a photosensitive silver halide emulsion layer or a layer adjacent to the photosensitive silver halide emulsion in the light-sensitive material, and the amount of the compound is 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol /.
m ² , preferably 3 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol / m ^{2, and} more preferably 1 × 10 ⁻⁵ to 2 × 10 ⁻⁴ mol / m ^2. As described below, the compound represented by the formula (1) can be added in the same manner as in a usual coupler.

In the present invention, it is preferable to use a cyan coupler represented by the general formula [C]. These couplers are
Only a small amount of high-boiling organic solvent used in combination is required, and as a result,
Since the amount of the binder can be reduced, high sensitivity and high contrast can be obtained, and the processing dependency is reduced. From this viewpoint, the amount of the high boiling organic solvent as described in JP-A-62-269958, that is, the amount of the high boiling organic solvent relative to the cyan coupler is 0.3 or less, more preferably 0.1 or less.

In the formula (C), R ₁ is -CONR ₄ R ₅ , -SO ₂ NR ₄ R ₅ , -NHC
_{OR 4, -NHCOOR 6, -NHSO 2} R 6, -NHCONR 4 R 5 or -NHSO
₂ NR ₄ R ₅ , R ₂ is a group that can be substituted on a naphthalene ring, 1 is 0
R ₃ represents a substituent; X represents a hydrogen atom or a group which can be eliminated by a coupling reaction with an oxidized aromatic primary amine developer. However, R ₄ and
R ₅ may be the same or different and each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₆ represents an alkyl group, an aryl group or a heterocyclic group. When 1 is plural, R ₂ may be the same or different, and may combine with each other to form a ring. R ₂ and R ₃ , or R ₃ and X may be bonded to each other to form a ring. Further, a dimer or a multimer of R ₁ , R ₂ , R ₃ or X bonded to each other via a divalent or divalent or higher valent group may be formed.

Hereinafter, each substituent in the formula [C] will be described in detail.

R ₁ is -CONR ₄ R ₅ , -SO ₂ NR ₄ R ₅ , -NHCOR ₄ , -NHCOOR ₆ ,
-NHSO ₂ R _6, represents -NHCONR ₄ R ₅ or -NHSO ₂ NR ₄ R _5,
R ₄ , R ₅ and R ₆ each independently represent an alkyl group having 1 to 30 carbon atoms (hereinafter referred to as C number), an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 2 to 30 carbon atoms. R ₄ and R ₅ may also be a hydrogen atom.

R ₂ represents a group (including an atom; the same applies hereinafter) which can be substituted on a naphthalene ring, and a halogen atom (F, Cl,
Br, I), hydroxyl group, carboxyl group, amino group, sulfo group, cyano group, alkyl group, aryl group, heterocyclic group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group,
Acyloxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, sulfamoylamino group,
Examples include an alkoxycarbonylamino group, a nitro group, and an imide group. Examples of the case where l = 2 include a dioxymethylene group and a trimethylene group. (R ₂ ) l has a C number of 0 to 30.

R ₃ represents a substituent, and is preferably represented by the following formula [C-1].

Formula [C-1] R ₇ (Y) _m − In Formula [C-1], Y is NH, CO or SO.
₂ , m is an integer of 0 or 1, R ₇ is a hydrogen atom, C number 1
An alkyl group having up to 30; an aryl group having 6 to 30 carbon atoms;
30 heterocyclic groups, -COR ₈ , It represents a -SO ₂ OR ₁₀ or -SO ₂ R _10, respectively. here
R ₈ , R ₉ and R ₁₀ have the same meanings as R ₄ , R ₅ and R ₆ , respectively.

In R ₁ or R ₇ , R ₄ and R ₅ and R ₈ and R ₉ may be bonded to each other to form a nitrogen-containing heterocyclic ring (for example, a pyrrolidine ring, a piperidine ring, or a morpholine ring).

X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized form of an aromatic primary amine developing agent (a leaving group; including a leaving atom; the same applies hereinafter); a halogen atom, a typical example of the leaving group; A thiocyanate group; a heterocyclic group having 1 to 30 carbon atoms and having a nitrogen atom and bonded to a coupling active site (for example, a succinimide group, a phthalimide group, a pyrazolyl group, a hydantoinyl group, or a 2-benzotriazolyl group). . Here, R ₁₁ has the same meaning as R ₆ .

In the above, the alkyl group may be linear, branched or cyclic, and may contain a substituent (for example, a halogen atom, a hydroxyl group, an aryl group, a heterocyclic group, an alkoxy group) even if it contains an unsaturated bond. , An aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an acyloxy group, an acyl group), and typical examples include methyl, isopropyl, isobutyl, t-butyl, 2-ethylhexyl, and cyclohexyl. , N-dodecyl, n-hexadecyl, 2-
Methoxyethyl, benzyl, trifluoromethyl, 3-
Dodecyloxypropyl, 3- (2,4-di-t-pentylphenoxy) propyl.

Further, even when the aryl group is a condensed ring (for example, a naphthyl group), a substituent (for example, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a cyano group,
Acyl group, alkoxycarbonyl group, albonamide group, sulfonamide group, carbamoyl group, fluamoyl group, alkylsulfonyl group, arylsulfonyl group)
May be represented by phenyl, tolyl,
Examples include pentafluorophenyl, 2-chlorophenyl, 4-hydroxyphenyl, 4-cyanophenyl, 2-tetradecyloxyphenyl, 2-chloro-5-dodecyloxyphenyl, and 4-t-butylphenyl.

The heterocyclic group is a 3- to 8-membered monocyclic or condensed-ring heterocyclic group containing at least one heteroatom of O, N, S, P, Se, Te in the ring, and has a substituent (for example, Halogen atom, carboxyl group, hydroxyl group, nitro group, alkyl group,
An aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group). , 4-pyridyl, 2-furyl, 4-thienyl, benzotriazol-1-yl,
5-phenyltetrazol-1-yl, 5-methylthio-1,3,4-thiadiazol-2-yl, 5-methyl-1,
There is 3,4-oxadiazol-2-yl.

 Preferred examples of the substituent in the present invention are described below.

R ₁ is preferably -CONR ₄ R ₅ or -SO ₂ NR ₄ R ₅ ,
Specific examples include carbamoyl, Nn-butylcarbamoyl, Nn-dodecylcarbamoyl, N- (3-n-dodecyloxypropyl) carbamoyl, N-cyclohexylcarbamoyl, N- [3- (2,4-di-t -Pentylphenoxy) propyl] carbamoyl, N-hexadecylcarbamoyl, N- [4- (2,4-di-t-pentylphenoxy) butyl] carbamoyl, N- (3-dodecyloxy-2-methyl) Propyl) carbamoyl, N-
[3- (4-t-octylphenoxy) propyl] carbamoyl, N-hexadecyl-N-methylcarbamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N- [4- (2,4-di-t -Pentylphenoxy)
[Butyl] sulfamoyl. R ₁ is particularly preferably-
CONR ₄ R ₅ .

As R ₂ and l, l = 0, that is, unsubstituted one is most preferred, and then l = 1 is preferred. R ₂ is preferably a halogen atom, an alkyl group (eg, methyl, isopropyl,
t-butyl, cyclopentyl), a carbonamide group (eg, acetamido, pivalinamide, trifluoroacetamido, benzamide), a sulfonamide (eg, methanesulfonamide, toluenesulfonamide) or a cyano group.

R ₃ is preferably m = 0 in the formula [C-1];
More preferably, R ₇ is —COR ₈ [for example, formyl, acetyl, trifluoroacetyl, 2-ethylhexanoyl, pivaloyl, benzoyl, pentafluorobenzoyl, 4- (2,4-di-t-pentylphenoxy) butanoyl ], -COOR ₁₀ [for example, methoxycarbonyl, ethoxycarbonyl, isobutoxycarbonyl, 2-ethylhexyloxycarbonyl, n- dodecyloxycarbonyl, 2-methoxyethoxy carbonyl] or -SO ₂ R ₁₀
[For example, methylsulfonyl, n-butylsulfonyl, n
-Hexadecylsulfonyl, phenylsulfonyl, p-
Tolylsulfonyl, p-chlorophenylsulfonyl, trifluoromethylsulfonyl], and particularly preferably
R ₇ is —COOR ₁₀ .

X is preferably a hydrogen atom, a halogen atom, -OR ₁₁ [eg, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy, 2- (2-hydroxyethoxy) ethoxy,
2-methylsulfonylethoxy, ethoxycarbonylmethoxy, carboxymethoxy, 3-carboxypropoxy, N- (2-methoxyethyl) carbamoylmethoxy, 1-carboxytridecyloxy, 2-methanesulfonamidoethoxy, 2- (carboxymethylthio) ethoxy And alkoxy groups such as 2- (1-carboxytridecylthio) ethoxy, for example 4-cyanophenoxy, 4-carboxyphenoxy, 4-methoxyphenoxy, 4-t-octylphenoxy, 4-nitrophenoxy, 4- (3-carboxypropanamide) phenoxy, an aryloxy group such as a 4-acetamidophenoxy group] or -SR ₁₁ [for example, carboxymethylthio,
2-carboxymethylthio, 2-methoxyethylthio,
Alkylthio groups such as ethoxycarbonylmethylthio, 2,3-dihydroxypropylthio, 2- (N, N-dimethylamino) ethylthio, for example, 4-carboxyphenylthio, 4-methoxyphenylthio, 4- (3-carboxy Arylthio groups such as propanamide) phenylthio], and particularly preferably a hydrogen atom, a chlorine atom, an alkoxy group or an alkylthio group.

The coupler represented by the general formula (C) has substituents R ₁ , R ₂ ,
A dimer or higher multimer linked to each other via a divalent or divalent or higher valent group at R ₃ or X may be formed. In this case, the number of carbon atoms may not be within the range specified for each substituent.

When the coupler represented by the general formula [C] forms a polymer, an addition-polymerizable ethylenically unsaturated compound having a cyan dye-forming coupler residue (a homo- or copolymer of a cyan-color-forming monomer is a typical example. A polymer derived from the monomer compound represented by the general formula (PI) described in the aforementioned general formula (H) and having a repeating unit represented by the general formula (P-II), or an aromatic compound It is a copolymer of at least one non-color-forming monomer having at least one ethylene group and having no ability to couple with an oxidized form of a primary amine developing agent, provided that the compound represented by the general formula (P-
In I) and the general formula (P-II), QQ represents the general formula [C]
Represents a cyan coupler residue obtained by removing one hydrogen atom from R ₁ , R ₂ , R ₃ or X of the compound represented by the formula: Specific examples of each substituent in the formula [C] and the cyan coupler represented by the formula [C] are shown below.

R ₁ example R ₂ example Example of R ₃ NH− Example of X Other couplers Where A is Represents a cyclohexyl group, Is a cyclopentyl group, and -C ₈ H _17-t is Represents

Other specific examples of the cyan coupler represented by the formula [C] and / or methods for synthesizing these compounds are described in, for example, U.S. Pat. No. 4,690,889, JP-A-60-237448 and JP-A-61-153640.
No. 61-145557, No. 63-208042, No. 64-31159, and West German Patent No. 3823049A.

The cyan coupler represented by the formula (C) is described in JP-A-62-2.
As described in 69958, it is preferable to use a small amount of a high-boiling organic solvent for dispersion in order to further improve sharpness and desilverability.

Specifically, a high-boiling organic solvent is used in a weight ratio of 0.3 or less, more preferably 0.1 or less, to the cyan coupler represented by the formula [C].

The total amount of the cyan coupler represented by the formula [C] is at least 30 mol%, preferably at least 50 mol%, more preferably at least 70 mol%, further preferably at least 90 mol% of the total cyan coupler.

The cyan coupler represented by the formula [C] is preferably used in combination of two or more kinds. When the same color-sensitive layer is divided into two or more layers having different sensitivities, a 2-equivalent cyan coupler is added to the highest sensitivity layer. It is preferable to use a 4-equivalent cyan coupler in the lowest sensitivity layer. It is preferable to use one or both of them in the same color-sensitive layer other than the above.

It is particularly preferable to use a benzoylacetanilide-based yellow coupler represented by the following general formula [A] in the light-sensitive material of the present invention. Since the yellow coupler represented by the general formula [A] has a high ε, the thickness of the photographic layer can be reduced, and as a result, a higher sensitivity and higher contrast can be obtained.
Processing dependency is also reduced.

In the general formula [A], M and Q are groups (including atoms) substitutable on a benzene ring, L is a hydrogen atom, a halogen atom or an aliphatic oxy group, m is an integer of 0 to 5, and n is 0
And X represents a group capable of leaving by a coupling reaction with an oxidized aromatic primary amine developer. However, when m is plural, (M) _m may be the same or different, and when n is plural, (Q) _n may be the same or different. M, Q, L or X may be a divalent to tetravalent linking group to form a dimer or tetramer of a yellow coupler represented by the general formula [A].

Examples of M and Q include a halogen atom (fluorine, chlorine,
Bromine), an aliphatic group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an aliphatic oxy group having 1 to 20 carbon atoms, an aromatic oxy group having 6 to 20 carbon atoms, and 2 to 24 carbon atoms A carbonamide group having 0 to 20 carbon atoms, a carbamoyl group having 1 to 24 carbon atoms, a sulfamoyl group having 0 to 20 carbon atoms, and 2 carbon atoms
~ 20 acyloxy group, C2-20 aliphatic oxycarbonyl group, C2-24 substituted amino group, C1 ~ 1
24 aliphatic thio groups, ureido group having 0 to 20 carbon atoms, sulfamoylamino group having 0 to 20 carbon atoms, cyano group, 2 carbon atoms
~ 20 aliphatic oxycarbonylamino groups, 4-20 carbon atoms
Imide group, an aliphatic sulfonyl group having 1 to 20 carbon atoms, an aromatic sulfonyl group having 6 to 20 carbon atoms, a heterocyclic group having 1 to 20 carbon atoms, and the like. L is a hydrogen atom, a halogen atom (fluorine, chlorine, bromine) or an aliphatic oxy group having 1 to 24 carbon atoms. X is a group capable of leaving by a coupling reaction with an oxidized aromatic primary amine developer, and is represented by the following general formulas [B], [C] and [D].

In the general formula [B], R 'is an aromatic group having 2 to 30 carbon atoms, a heterocyclic group having 1 to 28 carbon atoms, an acyl group having 2 to 28 carbon atoms, an aliphatic sulfonyl group having 1 to 24 carbon atoms or a carbon atom. Number 6
To 24 aromatic sulfonyl groups.

In the general formula [C], R ″ represents an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or a heterocyclic group having 1 to 28 carbon atoms.

In the general formula [D], Y represents a nonmetallic atom group necessary for forming a 5- to 7-membered heterocyclic ring of a single ring or a condensed ring with Q. Examples of heterocycles formed by Q and Y include pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, tetraazaindene, succinimide, phthalimide Saccharin, oxazolidine-2,4-dione, imidazolidine-2,4-dione, thiazolidine-2,4-dione, urazole, parabanic acid, maleimide, 2-pyridone,
-Pyridone, 6-pyridazone, 6-pyrimidone, 2-pyrazone, 1,3,5-triazin-2-one, 1,2,4-triazin-6-one, 1,3,4-triazin-6-one , 2-
Oxazolone, 2-thiazolone, 2-imidazolone, 3
-Isoxazolone, 5-tetrazolone, 1,2,4-triazo-5-one and the like, which may be substituted, as examples of the substituent, a halogen atom, a hydroxy group,
Nitro group, cyano group, hydroxy group, aliphatic group, aromatic group, heterocyclic group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic oxycarbonyl group,
Examples include a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a ureido group, a sulfamoylamino group, an aliphatic oxycarbonylamino group, and a substituted amino group.

In the present invention, the aliphatic group represents a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, which may be substituted. Examples of the aliphatic group include methyl, ethyl, isopropyl, n-butyl, t-butyl, t-amyl, n-hexyl, cyclohexyl, n-
Octyl, 2-ethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, 2-hexyldecyl, n-octadecyl, allyl, benzyl, phenethyl, undecenyl, octadecenyl, trifluoromethyl, chloroethyl, cyanoethyl, -(Ethoxycarbonyl) ethyl, methoxyethyl, butoxyethyl, 3-dodecyloxypropyl, phenoxyethyl and the like. In the present invention, the heterocyclic group is a substituted or unsubstituted monocyclic or condensed-ring heterocyclic group. 2-furyl, 2-thienyl, 2-pyridyl, 3-pyridyl, 4-
Pyridyl, 2-quinolyl, oxazol-2-yl, thiazol-2-yl, benzoxazol-2-yl,
Benzothiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-oxadiazol-2-yl and the like. In the present invention, the aromatic group is a substituted or unsubstituted monocyclic or condensed-ring aryl group, and examples thereof include phenyl, tolyl, 4-chlorophenyl, 4-methoxyphenyl, 1-naphthyl, 2-naphthyl and 4-naphthyl. t-butylphenoxy and the like.

Next, examples of preferred substituents in the coupler represented by formula (A) preferably used in the present invention will be described.
M is preferably an aliphatic group (methyl, ethyl, n-propyl, t-butyl, etc.), an aliphatic oxy group (methoxy, ethoxy, n-butoxy, n-dodecyloxy, etc.), a halogen atom (fluorine, chlorine, Bromine), a carbonamide group (acetamide, n-butanamide, n-tetradecaneamide, benzamide, etc.) or a sulfonamide group (methylsulfonamide), n-butylsulfonamide, n-octylsulfonamide, n-dodecylsulfonamide,
Toluenesulfonamide). L is preferably a chlorine atom or an aliphatic oxy group (methoxy, ethoxy, methoxyethoxy, n-octyloxy, 2-ethylhexyloxy, n-tetradecyloxy, etc.).

Q is preferably an aliphatic oxycarbonyl group (methoxycarbonyl, ethoxycarbonyl, n-butoxycarbonyl, n-hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, 1- (ethoxycarbonyl) ethyl, in addition to the substituents mentioned above in M. Oxycarbonyl, 3-dodecyloxypropyloxycarbonyl, n
-Decyloxycarbonyl, n-dodecyloxycarbonyl, phenethyloxycarbonyl and the like or a carbamoyl group (dimethylcarbamoyl, dibutylcarbamoyl, dihexylcarbamoyl, di-2-ethylhexylcarbamoyl, n-dodecylcarbamoyl and the like).
m is preferably 0 to 2, and n is preferably 0 to 2. X is preferably a group (4-methoxycarbonylphenoxy) wherein R 'is an aromatic group in the general formula [B].
-Methylsulfonylphenoxy, 4-cyanophenoxy, 4-dimethylsulfamoylphenoxy, 2-acetamido-4-ethoxycarbonylphenoxy, 4-ethoxycarbonyl-2-methylsulfonamidophenoxy, etc.) or general It is a group represented by the formula [D], and among the latter, a group represented by the following general formula [E] is more preferable.

In the general formula [E], V represents a substituted or unsubstituted methylene group or a substituted or unsubstituted imino group, and W represents an oxygen atom, a sulfur atom, a substituted or unsubstituted methylene group or an unsubstituted imino group. However, when V is an imino group, W is neither an oxygen atom nor a sulfur atom. Examples of the group represented by the general formula [E] include succinimide, phthalimide, 1-methyl-imidazolidin-2,4-dione-3-yl, 1-benzyl-imidazolidin-2,4
-Dion-3-yl, 5-ethoxy-1-methylimidazolidin-2,4-dione-3-yl, 5-methoxy-1
-Methylimidazolidin-2,4-dione-3-yl, 5,5
-Dimethyloxazolidin-2,4-dione-3-yl,
Thiazolidine-2,4-dione-3-yl, 1-benzyl-2-phenyltriazolidine-3,5-dione-4-yl, 1-n-propyl-2-phenyltriazolidine-
Examples include 3,5-dione-4-yl, 5-ethoxy-1-benzyl-imidazolidin-2,4-dione-3-yl and the like.

The yellow coupler represented by the general formula [A] may have any of the substituents M, Q, L or X be a divalent to tetravalent linking group to form a dimeric or tetrameric yellow coupler. , A monomer or a dimer. Here, when the yellow coupler represented by the general formula [A] is a dimer to a tetramer, the carbon number ranges described above for M, Q, L or X do not apply.

Specific examples of the yellow coupler represented by the general formula [A] used in the present invention are shown below, but the coupler used in the present invention is not limited thereto.

The yellow coupler preferably used in the present invention is synthesized by a conventionally known method. For example, U.S. Pat.Nos. 3,227,554, 3,408,194, 3,415,652,
No. 3,447,928, No. 4,401,752, British Patent 1,040,710, JP-A-47-26133, No. 47-37736, No. 48-733147, No. 48-
94432, 48-68834, 48-68835, 48-68836
No. 50-34232, No. 51-50734, No. 51-102636, No. 5
5-598, 55-161239, 56-95237, 56-161543
No. 56-153343, No. 59-174839, and No. 60-35730.

The above-mentioned yellow coupler is synthesized by a conventionally known method. For example, U.S. Patent Nos. 3,227,554 and 3,408,194,
No. 3,415,652, No. 3447,928, No. 4,401,752, UK patent
No. 1,040,710, JP-A-47-26133, JP-A-47-37736, JP-A-48-
733147, 48-94432, 48-68834, 48-68835
No. 48-68836, No. 50-34232, No. 51-50734, No. 51
-102636, 55-598, 55-161239, 56-95237
No. 56-161543, No. 56-153343, No. 59-174839 and No. 60-35730.

For the green-sensitive layer of the silver halide color photographic light-sensitive material of the present invention, use of a polymer coupler obtained from a monomer represented by the following general formula (PA) makes it possible to obtain high contrast and high sensitivity and to reduce processing dependence. It is more preferable from the viewpoint of reducing the number.

Wherein, R ₁₂₁ represents a hydrogen atom, 1 to 4 alkyl groups or chlorine atoms,-D-is -COO -, - CONR ₁₂₂ -,
Or a substituted or unsubstituted phenyl group,
- represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, -F- is -CONR ₁₂₂ -,
_{-NR 122 CONR 122 -, - NR} 122 COO -, - NR 122 CO -, - OCO
_{NR 122 -, - NR 122 -} , - COO -, - OCO -, - CO -, - O
_{-, S -, - SO 2} -, - NR 122 SO 2 - or -SO ₂ NR _122,
Represents-. R ₁₂₂ represents a hydrogen atom or a substituted or unsubstituted aliphatic or aryl group. When two or more _R122s are present in the same molecule, they may be the same or different.
p, q, and r represent 0 or 1. Where p, q, r
Are never 0 at the same time.

T is a coupler residue of a magenta coupler represented by the following general formula (PB) (any part of Ar, X, and _R133 ;
(Bonded to DEF of the general formula (PA)).

In the formula, Ar is a well-known type of substituent at the 1-position of the 2-pyrazolin-5-one coupler, for example, an alkyl group, a substituted alkyl group (eg, haloalkyl such as fluoroalkyl, cyanoalkyl, benzylalkyl, etc.), substituted or unsubstituted. A heterocyclic group (for example, 4-pyridyl, 2-thiazoyl), a substituted or unsubstituted aryl group (an alkyl group (for example, methyl or ethyl) or an alkoxy group (for example, methoxy or ethoxy as a substituent of the heterocyclic group or the aryl group) ), Aryloxy groups (eg phenyloxy),
Alkoxycarbonyl group (eg, methoxycarbonyl), acylamino group (eg, acetylamino), carbamoyl group, alkylcarbamoyl group (eg, methylcarbamoyl, ethylcarbonyl), dialkylcarbamoyl group (eg, dimethylcarbamoyl), arylcarbamoyl group (eg, phenylcarbamoyl) Alkylsulfonyl group (eg, methylsulfonyl), arylsulfonyl group (eg, phenylsulfonyl), alkylsulfonamide group (eg, methanesulfonamide), arylsulfonamide group (eg, phenylsulfonamide), sulfamoyl group, alkylsulfamoyl Group (eg, ethylsulfamoyl), dialkylsulfamoyl (eg, dimethylsulfamoyl), alkylthio (eg, methylthio) , An arylthio group (e.g. phenylthio), a cyano group, a nitro group, a halogen atom (e.g. fluorine, chlorine, bromine, etc.), with different connexion may be the same as when the substituents are two or more.

Particularly preferred substituents include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a cyano group. ]. R ₂₃ represents an unsubstituted or substituted anilino group, an acylamino group (eg, alkylcarbonamide, phenylcarbonamide, alkoxycarbonamide, phenyloxycarbonamide), a ureido group (eg, alkylureido, phenylureido), and a sulfonamide group. These substituents include a halogen atom (eg, fluorine, chlorine, bromine, etc.), a linear or branched alkyl group (eg, methyl, t-butyl, octyl, tetradecyl), and an alkoxy group (eg, methoxy, ethoxy, 2-ethylhexyloxy, tetradecyloxy), acylamino group (for example, acetamido,
Benzamide, butanamide, octaneamide, tetradecaneamide, α- (2,4-di-tert-amylphenoxy) acetamide, α- (2,4-di-tert-amylphenoxy) butylamide, α- (3-pentadecylphenoxy) ) Hexaneamide, α- (4-hydroxy-3-te
(rt-butylphenoxy) tetradecaneamide, 2-oxo-pyrrolidin-1-yl, 2-oxo-5-tetradecylpyrrolidin-1-yl, N-methyl-tetradecanamido), sulfonamide group (for example, methanesulfonamide, benzene Sulfonamide, ethylsulfonamide, p-toluenesulfonamide, octanesulfonamide, p-dodecylbenzenesulfonamide, N-methyl-tetradecanesulfonamide), sulfamoyl group (for example, sulfamoyl, N-methylsulfamoyl, N-ethyl) Sulfamoyl, N, N-dimethylsulfamoyl, N, N-dihexylsulfamoyl, N-hexadecylsulfamoyl, N- [3- (dodecyloxy) -propyl] sulfamoyl, N- [4- ( 2,4-
Di-tert-amylphenoxy) butyl] sulfamoyl, N-methyl-N-tetradecylsulfamoyl),
Carbamoyl group (for example, N-methylcarbamoyl, N
-Butylcarbamoyl, N-octadecylcarbamoyl, N- [4- (2,4-di-tert-amylphenoxy)
Butyl] carbamoyl, N-methyl-N-tetradecylcarbamoyl), diacylamino group (N-succinimide, N-phthalimide, 2,5-dioxo-1-oxazolidinyl, 3-dodecyl-2,5-dioxo-1-hydantoinyl , 3- (N-acetyl-N-dodecylamino)
Succinimide), an alkoxycarbonyl group (for example,
Methoxycarbonyl, tetradecyloxycarbonyl,
Benzyloxycarbonyl), alkoxysulfonyl groups (eg, methoxysulfonyl, butoxysulfonyl,
Octyloxysulfonyl, tetradecyloxysulfonyl), aryloxysulfonyl groups (eg, phenoxysulfonyl, p-methylphenoxysulfonyl),
2,4-di-tert-amylphenoxysulfonyl), alkanesulfonyl group (for example, methanesulfonyl, ethanesulfonyl, octanesulfonyl, 2-ethylhexylsulfonyl, hexadecanesulfonyl), arylsulfonyl group (for example, benzenesulfonyl, 4- Nonylbenzenesulfonyl), an alkylthio group (eg, methylthio, ethylthio, hexylthio, benzylthio, tetradecylthio, 2- (2,4-di-tert-amylphenoxy) ethylthio), an arylthio group (eg, phenylthio, p-tolylthio), Alkyloxycarbonylamino groups (eg, methoxycarbonylamino, ethyloxycarbonylamino, benzyloxycarbonylamino, hexadecyloxycarbonylamino), alkylureido groups (eg, N Methylureido, N, N- dimethylureido, N- methyl -N- dodecyl ureido, N
-Hexadecylureide, N, N-dioctadecylureide), acyl group (for example, acetyl, benzoyl, octadecanoyl, p-dodecanamidobenzoyl), nitro group, carboxyl group, sulfo group, hydroxy group or trichloromethyl group Can be mentioned.

However, among the above substituents, those defined as alkyl groups have 1 to 36 carbon atoms, and those defined as aryl groups have 6 to 38 carbon atoms.

Z represents a hydrogen atom, a halogen atom (for example, chlorine or bromine) or a coupling-off group linked by an oxygen atom (for example, acetoxy, propanoyloxy, benzoyloxy,
Ethoxy oxaloyloxy, pyrvinyloxy, cinnamoyloxy, phenoxy, 4-cyanophenoxyl, 4-titaniumsulfonamidophenoxy, α-naphthoxy, 4-cyanoxyl, 4-methanesulfonamide-
Phenoxy, α-naphthoxy, 3-pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy,
-Cyanoethoxy, benzyloxy, 2-phenethyloxy, 2-phenoxy-ethoxy, 5-phenyltetrazolyloxy, 2-benzothiazolyloxy), a coupling-off group linked by a nitrogen atom (for example, JP-A-59-59) 994
No. 37), specifically, benzenesulfonamide, N-ethyltoluenesulfonamide, heptafluorobutanamide, 2,3,4,5,6-pentafluorobenzamide, octanesulfonamide, p- Cyanophenylureido, N, N-diethylsulfamoylamino, 1-piperidyl, 5,5-dimethyl-2,4-dioxo-
3-oxazolidinyl, 1-benzyl-5-ethoxy-
3-hydantoinyl, 2-oxo-1,2-dihydro-1
-Pyridinyl, imidazolyl, pyrazolyl, 3,5-diethyl-1,2,4-triazol-1-yl, 5- or 6
-Bromo-benzotriazol-1-yl, 5-methyl-1,2,3,4-triazol-1-yl group, benzimidazolyl), coupling-off groups linked by sulfur atoms (e.g. phenylthio, 2-carboxyphenyl) Lucio,
2-methoxy-5-octylphenylthio, 4-methanesulfonylphenylthio, 4-octanesulfonamidophenylthio, benzylthio, 2-cyanoethylthio,
5-phenyl-2,3,4,5-tetrazolylthio, 2-benzothiazolyl).

Preferred is a coupling-off group linked by a nitrogen atom, and particularly preferred is a pyrazolyl group.

E represents an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group, or a phenylene group;
The alkylene group may be linear or branched. Examples of the alkylene group include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene groups such as benzylidene, and phenylene groups such as p-phenylene, m-phenylene and methylphenylene. and so on.

Examples of the substituent of the alkylene group, aralkylene group or phenylene group represented by E include an aryl group (eg, phenyl) nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (eg, methoxy), an aryloxy group (eg, phenoxy), Acyloxy groups (eg, acetoxy), acylamino groups (eg, acetylamino), sulfonamide groups (eg, methanesulfonamide), sulfamoyl groups (eg, methylsulfamoyl), halogen atoms (eg, fluorine, chlorine, bromine), carboxy groups, Examples include a carbamoyl group (eg, methylcarbamoyl), an alkoxycarbonyl group (eg, methoxycarbonyl), a sulfonyl group (eg, methylsulfonyl), and the like.
When two or more substituents are present, they may be the same or different.

Next, examples of non-color-forming ethylene-like monomers which do not couple with the oxidized aromatic primary amine developer which can be copolymerized with the coupler monomer represented by the general formula (PA) include, for example, acrylates and methacrylic esters. Examples include acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, acrylamides, methacrylamides, vinyl ethers, styrenes and the like.

More specific examples of these monomers are shown below. As acrylic acid esters, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2- Ethylhexyl acrylate, acetoxyethyl acrylate, phenyl acrylate, 2-methoxy acrylate, 2-ethoxy acrylate, 2-
(2-methoxyethoxy) ethyl acrylate and the like. Examples of the methacrylate include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, and the like. Crotonic acid esters include butyl crotonate, hexyl crotonate and the like. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, and vinyl benzoate. Examples of the maleic acid diester include diethyl maleate, dimethyl maleate, dibutyl maleate and the like. Examples of the fumaric acid diester include diethyl fumarate, dimethyl fumarate, dibutyl fumarate, and the like. Examples of the itaconic acid diester include diethyl itaconate, dimethyl itaconate, and dibutyl itaconate. Acrylamides include acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide,
n-butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, 2-methoxyethylacrylamide, dimethylacrylamide, diethylacrylamide, phenylacrylamide and the like. Examples of the methacrylamides include methyl methacrylamide, ethyl methacrylamide, n-butyl methacrylamide, tert-butyl methacrylamide, 2-methoxy methacrylamide, dimethyl methacrylamide, and diethyl methacrylamide. As vinyl ethers, methyl vinyl ether, butyl vinyl ether,
Hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether and the like can be mentioned. As styrenes, styrene, methyl styrene,
Dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, chloromethylstyrene, methoxystyrene, butoxystyrene,
Acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl vinyl benzoate,
2-methylstyrene and the like.

Examples of other monomers include allyl compounds (eg, allyl acetate), vinyl ketones (eg, methyl vinyl ketone), vinyl heterocyclic compounds (eg, vinyl pyridine),
Glycidyl esters (eg, glycidyl acrylate), unsaturated nitriles (eg, acrylonitrile),
Acrylic acid, methacrylic acid, itaconic acid, maleic acid,
Monoalkyl itaconate (eg, monomethyl itaconate), monoalkyl maleate (eg, monomethyl maleate), citraconic acid, vinylsulfonic acid, acryloyloxyalkylsulfonic acid (eg, acryloyloxymethylsulfonic acid), acrylamidoalkylsulfonic acid (eg, 2-acrylamido-2-methylethanesulfone) and the like. These acids may be salts of alkali metals (eg, Na, K) or ammonium ions.

Among these monomers, preferably used comonomers include acrylates, methacrylates, styrenes, maleates, acrylamides, and methacrylamides.

These monomers may be used in combination of two or more. When two or more kinds are used in combination, for example, n-butyl acrylate and styrene, n-butyl acrylate and butyl styrene, t-butyl methacrylamide and n-butyl acrylate, and the like are exemplified.

The general formula (P
The proportion of the colored portion corresponding to B) is usually preferably from 5 to 80% by weight, but from the viewpoint of color reproduction and stability, from 30 to 80% by weight.
70% by weight is preferred. In this case, the equivalent molecular weight (gram number of the polymer containing one mole of the monomer coupler) is about 250 to 4.0.
00, but not limited to this.

The polymer coupler used in the present invention is added to a silver halide emulsion layer or a layer adjacent thereto.

The magenta polymer coupler is based on the coupler monomer.
005 mol to 0.5 mol, preferably 0.03 to 0.25 mol is added.

The coating amount of the case of using the magenta polymer coupler in a non-photosensitive ^{layer, 0.01g / m 2 ~1.0g / m} 2, preferably 0.1 g /
The range is from m ^{2 to} 0.5 g / m ² .

The polymer coupler used in the present invention may be prepared by emulsifying and dispersing a lipophilic polymer coupler obtained by polymerization of a monomer coupler in an organic solvent in the form of a latex in an aqueous gelatin solution as described above. Alternatively, it may be made directly by an emulsion polymerization method.

A method of emulsifying and dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution is described in U.S. Pat.
No. 820, U.S. Pat.
The methods described in 3,370,952 and EP 341,088A2 can be used.

Synthesis of the above magenta polymer coupler is a polymerization initiator,
As polymerization solvents JP-A-56-5543, JP-A-57-94752, JP-A-57-176038, JP-A-57-204038, JP-A-58-28745, JP-A-58-10738, JP-A-58-10738 42044, using compounds described in JP-A-58-145944.

The polymerization temperature must be set in relation to the molecular weight of the polymer to be formed, the type of the initiator, and the like.
Although it is possible to raise the temperature up to or higher, the polymerization is usually carried out in the range of 30 to 100 ° C.

Next, specific examples of the magenta polymer coupler that can be used in the present invention will be described, but the present invention is not limited thereto.

(Subscript numbers represent molar ratios.) The light-sensitive material of the present invention comprises at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer of a silver halide emulsion layer on a support.
The number of layers and the order of the silver halide emulsion layer and the non-photosensitive layer are not particularly limited as long as the layers are provided. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, generally, The arrangement is such that a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

Non-light-sensitive layers such as various intermediate layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer, JP-A-61-43748, JP-A-59-113438,
No. 59-113440, No. 61-20037, couplers as described in the specification of No. 61-20038, and may contain a DIR compound, etc., and contain a color mixing inhibitor as usually used. Is also good.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045.
No. 2 of the high-speed emulsion layer and the low-speed emulsion layer
A layer configuration can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also, JP-A-57-112751, 62-20
As described in JP-A Nos. 0350, 62-206541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL) or BH / BL /
They can be installed in the order of GL / GH / RH / RL or BH / BL / GH / GL / RL / RH.

Also, as described in Japanese Patent Publication No. 55-34932,
From the farthest side from the support, blue light-sensitive layers / GH / RH / GL / RL can be arranged in this order. JP-A-56-25738, 62
As described in -63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

Also, as described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the less sensitive silver halide emulsion layer, and the lower layer is more sensitive than the middle layer. An arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and three layers having different sensitivities are sequentially reduced in sensitivity toward a support, may be mentioned. Even when such a three-layer structure having different sensitivities is used, Japanese Patent Application Laid-Open No.
As described in the specification of JP-A No. 464, a medium-speed emulsion layer / a high-speed emulsion layer / a low-speed emulsion layer may be arranged in the same color-sensitive layer from the side away from the support.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.

The arrangement may be changed as described above even in the case of four or more layers.

No. 4,663,271 to improve color reproduction
No. 4,705,744, 4,707,436, JP-A-62-160
A donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layers such as BL, GL, and RL described in the specifications of JP-A Nos. 448 and 63-89850 is disposed adjacent to or close to the main photosensitive layer. Is preferred.

As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

Preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 25 mol% silver iodide.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may be one having regular crystals such as tetradecahedron, one having irregular crystal forms such as spherical or plate-like, one having crystal defects such as twin planes, or a complex form thereof.

The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion that can be used in the present invention is described in, for example, Research Disclosure (RD) No. 17643 (1978).
December, p. 22-23, "I. Emulsion preparatio
n and types) ”, No. 18716 (November 1979), p.648,
No. 307105 (November 1989), pp. 863-865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P.
Glafkides, Chemie et Phisique Photographique, Paul M
ontel, 1967), Duffin, "Photographic Emulsion Chemistry", Focal Press (GFDuffin, Photographic Emulsion Che)
mistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsion" by Zelikuman et al., Focal Press (VLZeli)
kmanet al., Making and Coating Photographic Emulsio
n, Focal Press, 1964).

Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineerin.
g), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4,434,2
No. 26, 4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,157 can be easily prepared.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, may have a layered structure, and even if silver halides having different compositions are joined by epitaxial junction. Also, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is Research Disclosure No. 1
No. 7643, No. 18716, and No. 307105, and the relevant portions are summarized in the table below. In the present invention,
It is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably 0.5 to 10 mol% of silver iodide
It contains.

The fine grain silver halide preferably has an average grain size (average value of the circle equivalent diameter of the projected area) of 0.01 to 0.5 μm, and 0.02 to 0.2 μm.
μm is more preferred.

Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, before adding this to the coating solution, a triazole-based, azaindene-based,
It is preferable to add a known stabilizer such as a benzothiazolium-based or mercapto-based compound or a zinc compound.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table.

Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Patent Nos. 4,411,987 and 4,435,503
It is preferable to add a compound capable of being fixed by reacting with formaldehyde described in (1) to the photosensitive material.

Various color couplers can be used in the present invention, and specific examples thereof are described in the aforementioned Research Disclosure.
No. 17643, VII-C to G, and No. 307105, VII-C to G
The patent is described in US Pat.

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Pat.
Preferred are those described in 968, 4,314,023, 4,511,649, EP 249,473A, and the like.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
Nos. 619 and 4,351,897, European Patent No. 73,636, U.S. Patent Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552
No., Research Disclosure No.24230 (June 1984)
Mon), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730
No. 55-118034, No. 60-185951, U.S. Pat.
No. 630, No. 4,540,654, No. 4,556,630, International Publication W
Those described in, for example, No. 088/04795 are particularly preferred.

Cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No. 249,453
A, U.S. Pat.Nos. 3,446,622, 4,333,999,
No. 4,775,616, No. 4,451,559, No. 4,427,767, No. 4,690,889, No. 4,254,212, No. 4,296,199,
Those described in JP-A-61-42658 are preferred.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,409,320, No. 4,576,910, British Patent 2,10
2,137, EP 341,188A and the like.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533.

Colored couplers for correcting unwanted absorption of coloring dyes are described in Research Disclosure No. 17643, VII-
Section G, Section VII-G of No. 307105, U.S. Pat.No. 4,163,670,
JP-B-57-39413, U.S. Pat.No. 4,004,929, U.S. Pat.
No. 8,258, British Patent No. 1,146,368 are preferred. Further, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181 and a dye that can form a dye by reacting with a developing agent described in U.S. Pat.No.4,777,120 It is also preferable to use a coupler having a precursor group as a leaving group.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD 17643, Sections VII-F and No. 307105, Patents described in Sections VII-F and
-151944, 57-154234, 60-184248, 63-3734
No. 6, No. 63-37350, U.S. Pat.No. 4,248,962, No. 4,782,01
Those described in No. 2 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include UK Patent Nos. 2,097,140 and 2,1
Preferred are those described in JP-A-31-188, JP-A-59-157638 and JP-A-59-170840.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427 and the like, multi-equivalent couplers described in U.S. Pat.Nos. 4,283,472, 4,338,393, and 4,310,618. , JP 60-18
No. 5950, DIR redox compound releasing couplers described in JP-A-62-24252, etc., DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, European Patent Nos. 173,302A, 313,30
A coupler that releases a dye that recolors after detachment described in No. 8A,
RD No. 11449, 24241, bleaching accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in U.S. Pat.No. 4,555,477, etc., and leuco dyes described in JP-A-63-75747. Emitting coupler, U.S. Pat.No. 4,774,18
Couplers that emit the fluorescent dye described in No. 1 are exemplified.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc., phosphoric acid or phosphonic acid ester (Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-
2-ethylhexylphenylphosphonate, etc.), benzoates (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N, N-diethyllaurylamide) , N-tetradecylpyrrolidone), alcohols or phenols (isostearyl alcohol, 2,4-di-tert)
-Amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl- 2-butoxy-5-ter
t-octylaniline, etc.), and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-hexane. Ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

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

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747, JP-A-62-272248, and JP-A-
1-80941 1,2-benzisothiazolin-3-one, n-butyl, p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- (4-thiazolyl It is preferable to add various preservatives or fungicides such as benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers.

Suitable supports that can be used in the present invention include, for example, those described above.
No. 17643, page 28, No. 18716, page 647 right column to page 648 left column, and No. 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and particularly preferably 16 μm or less. The film swelling speed T _1/2
Is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling speed T _1/2 can be measured according to a method known in the art. For example, A
Photographic Science and Engineering (Photogr.Sci.En) by A. Green
g.), 19 vol., No. 2, by using the type of Swellometer described (swelling meter) pp 124-129, can be measured, T _1/2 is 30 ° C. in a color developing solution, 3 minutes 15 90% of the maximum swelling film thickness reached after the second treatment is defined as the saturated film thickness, and defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T1 _{/ 2} can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is 15
0-400% is preferred. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness−film thickness) /
It can be calculated according to the film thickness.

The color photographic light-sensitive material according to the present invention is described in RD.
Development can be carried out by the usual methods described on pages 28 to 29 of 17643, No. 18716, left column to right column of 651, and No. 307105, pages 880 to 881.

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-.
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred. These compounds can be used in combination of two or more depending on the purpose.

Color developing solutions include pH buffers such as alkali metal carbonates, borates or phosphates, chlorides, bromides,
It generally contains a development inhibitor or an antifoggant such as an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. Also, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexyl Njiamin tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo -N, N, N-trimethylenephosphonic acid, ethylenediamine -N, N, N, N-tetramethylene phosphonic acid,
Ethylenediamine-di (o-hydroxyphenylacetic acid)
And their salts can be mentioned as typical examples.

When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 l or less per square meter of the light-sensitive material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air.

The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below.

That is, The above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, 63-216050 can be mentioned. The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing processing before bleach-fixing processing or bleaching processing after bleach-fixing processing can be arbitrarily performed according to the purpose.
As the bleaching agent, for example, compounds of a polyvalent metal such as iron (III), peracids, quinones, and nitro compounds are used. Representative bleaching agents include organic complex salts of iron (III) such as aminoamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid. Polycarboxylic acids or complex acids such as citric acid, tartaric acid and malic acid can be used. Among these, iron aminopolycarboxylates (II) including iron (III) complex salts of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate
I) Complex salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution.
The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but the processing can be carried out at a lower pH for speeding up the processing.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and 2,059,98.
No. 8, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418
Nos. 53-72623, 53-95630, 53-95631, 53
-104232, 53-124424, 53-141623, 53-2842
No. 6, Research Disclosure No. 17129 (1978
A compound having a mercapto group or a disulfide group described in, for example, July, 1983; a thiazolidine derivative described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832,
Nos. 53-32735, U.S. Pat. No. 3,706,561; thiourea derivatives; West German Patent No. 1,127,715, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966,410, 2,748,430
No. 45-883
Polyamine compound described in No. 6; Other JP-A-49-40,943
Nos. 49-59,644, 53-94,927, 54-35,727,
Compounds described in JP-A Nos. 55-26,506 and 58-163,940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable in view of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858 and West German Patent No. 1,2
Compounds described in JP-A-90,812 and JP-A-53-95,630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids have an acid dissociation constant (pka) of 2
And acetic acid, propionic acid and the like.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, a large amount of iodides, and the like. In particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative for fixer and bleach-fixer,
Sulfites, bisulfites, carbonyl bisulfite adducts or the sulfinic acid compounds described in EP-A-294769A are preferred. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution. The total time of the desilvering step is preferably shorter as long as the desilvering failure does not occur. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferred temperature range, the desilvering speed is improved,
In addition, the occurrence of stain after processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening stirring,
JP-A-62-183460 describes a method of impinging a jet of a processing solution on an emulsion surface of a light-sensitive material, JP-A-62-183461, a method of increasing a stirring effect by using a rotating means, There are a method of moving the photosensitive material while bringing the emulsion surface in contact with the provided wiper blade to make the emulsion surface turbulent, thereby improving the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is disclosed in
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 60-191257, 60-191258 and 60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8,542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Bactericidal and Fungicide Chemistry" (19
1986) Sankyo Publishing, Sanitary Technology Society, “Sterilization and sterilization of microorganisms,
A fungicide described in "Encyclopedia of Fungicides" (1986), "Encyclopedia of Fungicides and Antifungal Agents" (1986) edited by the Industrial Technology Association and the Japan Society of Antifungals and Fungi can also be used.

In the processing of the light-sensitive material of the present invention, the pH of the washing water is from 4 to
9, preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but in general, 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Unexamined Patent Application Publication No.
Known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can all be used.

Further, after the water washing treatment, a stabilization treatment may be further carried out. As an example, a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography, is exemplified. be able to. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline-based compounds described in U.S. Pat. The metal salt complex described,
Urethane compounds described in JP-A-53-135628 can be exemplified.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-1154.
No. 38, etc.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to.

The silver halide light-sensitive material of the present invention is disclosed in U.S. Pat.
No. 500,626, JP-A-60-133449, 59-218443, 61-
It can also be applied to the photothermographic materials described in 238056, European Patent 210,660A2 and the like.

(Examples) Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1 Sample 101, which is a multilayer color photosensitive material, was prepared by coating each layer having the composition shown below on a subbed cellulose triacetate film support.

(Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First layer; antihalation layer Black colloidal silver ... silver 0.18 gelatin ... 0.40 Second layer; intermediate layer 2,5-di-t-pentadecylhydroquinone ... 0.18 EX-1 ... 0.07 EX-3 ... 0.02 EX -12 ... 0.002 U-1 ... 0.06 U-2 ... 0.08 U-3 ... 0.10 HBS-1 ... 0.10 HBS-2 ... 0.02 Gelatin ... 1.04 Third layer (first red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (3.5 mol% of silver iodide, average particle size 0.22 μ, coefficient of variation relating to particle size 0.16) ... silver 0.25 sensitizing dye I ... 6.9 x 10 ^-5 sensitizing dye II ... 1.8 x 10 ^-5 sensitizing dye III ... 3.1 × 10 ^-4 sensitizing dye IV 4.0 × 10 ^-5 Preferred cyan coupler of the present invention (C-8) 0.150 EX-10 0.020 Gelatin 0.45 4th layer (second red-sensitive emulsion layer) Tabular iodine odor halide emulsion (silver iodide 3.2 mol%, average particle diameter 0.50Myu, average aspect ratio 5.5, average thickness 0.15 micron) ... silver 0.70 sensitizing dye IX ... 5.1 × 10 ^-5 sensitizing dye II ... 1.4 × 10 ^-5 Sensitive dye III ... 2.3 × 10 ^-4 Sensitizing dye ^{IV ... 3.0 × 10 -5 EX-} 2 ... 0.100 Preferred cyan couplers of the present invention the general formula of (C-8) ... 0.300 EX -3 ... 0.012 present invention (H) Compound (5): 0.015 Gelatin: 1.30 Fifth layer (third red-sensitive emulsion layer) Emulsion A: Silver 1.80 Sensitizing dye IX 5.4 × ^10-5 Sensitizing dye II 1.4 × ^10-5 Sensitizing dye III 2.4 × ^10-4 sensitizing dye IV 3.1 × ^10-5 EX-10 0.007 Preferred cyan coupler of the present invention (C-8) 0.030 EX-3 0.045 EX-4 0.040 Preferred cyan coupler of the present invention (C-34) ) ... 0.080 HBS-1 ... 0.22 HBS-2 ... 0.10 Gelatin ... 1.63 6th layer (intermediate layer) EX-5 ... 0.040 HBS-1 ... 0.020 Gelatin ... 0.80 7th layer (first green-sensitive emulsion layer) Tabular iodine silver bromide emulsion (silver iodide 2.4 mol%, average particle diameter 0.30Myu, average aspect ratio 6.0, average thickness 0.08 microns) ... 0.40 sensitized silver dye V ... 3.0 × 10 ^-5 sensitizing dye VI ... 1.0 × 10 ^{- 4} Sensitizing dye V II 3.8 × 10 ^-4 EX-6 0.100 Preferred polymer coupler (P-13) of the present invention 0.200 EX-1 0.021 EX-7 0.030 EX-8 0.025 HBS-1 0.100 HBS-11 0.10 Gelatin: 0.75 Eighth layer (second green-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (3.5 mol% of silver iodide, average particle diameter: 0.40 µ, variation coefficient of particle diameter: 0.17) Silver: 0.80 Sensitizing dye V: 2.1 × 10 ^-5 sensitizing dye VI ... 7.0 × 10 ^-5 sensitizing dye VII ... 2.6 × 10 ^-4 Preferred polymer coupler (P-13) of the present invention ... 0.180 EX-8 ... 0.010 EX-1 ... 0.008 EX- 7 ... 0.012 HBS-1 ... 0.160 HBS-11 ... 0.008 Gelatin ... 1.10 9th layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (3.3 mol% silver iodide, average grain size 0.70)
μ) Silver 1.2 Sensitizing dye V 3.5 × 10 ^-5 Sensitizing dye VI 8.0 × 10 ^-5 Sensitizing dye VII 3.0 × 10 ^-4 EX-6… 0.065 EX-11… 0.030 EX-1… 0.025 HBS-1 ... 0.25 EX-10 ... 0.010 Gelatin ... 1.10 10th layer (yellow filter layer) Yellow colloidal silver ... silver 0.05 EX-5 ... 0.08 HBS-1 ... 0.03 Gelatin ... 0.50 11th layer (first blue sensitive emulsion layer) ) Tabular silver iodobromide emulsion (2.5 mol% silver iodide, average particle size 0.30 μm, average aspect ratio 7.3, average thickness 0.07) ... silver 0.24 sensitizing dye VIII 3.5 x 10 ^-4 Preferred yellow coupler of the present invention ( Y-1) 0.85 EX-8 0.059 HBS-1 0.28 Gelatin 1.50 12th layer (second blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (2.7 mol% silver iodide, average grain size 0.35 µm) , compounds of the preferred couplers of the variation coefficient 0.18) ... silver 0.45 sensitizing dye VIII ... 2.1 × 10 ^-4 present invention relates to a particle size (formula Y-1) ... 0.20 present invention (H) (5 ... 0.015 HBS-1 ... 0.03 Gelatin ... 0.45 13th layer (third blue-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 3.5 mol%, average particle diameter 0.95
μ) Silver 0.77 Sensitizing dye VIII 2.2 × 10 ^-4 Preferred coupler (Y-1) of the present invention 0.20 EX-9 0.005 Compound (5) of the general formula (H) of the present invention 0.005 HBS-1 0.07 Gelatin… 0.69 14th layer (first protective layer) Silver iodobromide emulsion (2 mol% of silver iodide, average particle size 0.07
μ) Silver 0.5 U-4 0.11 U-5 0.17 HBS-1 0.90 Gelatin 0.60 15th layer (second protective layer) Polymethyl acrylate particles (approximately 1.5 μm in diameter) 0.54 S-1 0.15 S -2 ... 0.05 Gelatin ... 0.72 In addition to the above components, gelatin hardener H-1, surfactant, benzisothiazolone (average 200 ppm based on gelatin), n-butyl-p-hydroxybenzoate (equal average) 500 ppm) and phenoxyethanol (average
1000 ppm) was added.

(Samples 102 to 106) Samples 102 to 106 were prepared by replacing Emulsion A in the fifth layer of Sample 101 with Emulsions BF.

(Samples 107 to 118) Compounds (I-2) and (I-6) represented by the general formula (I) of the present invention were added to the fifth layer of Samples 101 to 106, respectively, in a thickness of 0.5%.
Samples 107 to 112 and 113 to 118 were prepared by adding 20 g / m ² .

Emulsions A to F were prepared according to the method for preparing Emulsion 2 of Example 1 of JP-A-1-269935. Table 1 summarizes this.

These samples were subjected to red imagewise exposure and color development described below. The concentration of the treated sample was measured with a red filter. The obtained photographic performance data was converted to RM indicating granularity.
The results are shown in Table 2 together with the S value (aperture having a diameter of 48 μ).

After the same exposure, the film was left standing at 40 ° C. and a relative humidity of 70% for 10 days, developed, and evaluated for photographic performance.

 The development treatment used here was performed at 38 ° C. under the following conditions.

1. Color development: 3 minutes 15 seconds or 2 minutes 35 seconds 2. Bleaching 6 minutes 30 seconds 3. Rinse 3 minutes 15 seconds 4. Fixed 6 Min 30 sec 5. Rinse ... 3 min 15 sec 6. Stable 3 min 15 sec The composition of the processing solution used for each process is as follows.

Color developer Sodium nitrilotriacetate 1.0 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide 1.4 g Hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-β-hydroxyethylamino) -2-methyl-aniline sulfate Salt 4.5g Add water 1 Bleaching solution Ammonium bromide 160.0g Ammonia water (28%) 25.0ml Sodium ethylenediamine-tetraacetate 130g Glacial acetic acid 14ml Add water 1 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite 4.6g Add water 1 Stabilizer Formalin 8.0ml Add water 1 Here the relative sensitivity is the logarithm of the reciprocal of the exposure that gives a density of (fog + 0.2) The values were expressed as relative values when the value of Sample 101 after development for 2 minutes and 35 seconds was set to 0.

Gamma is a gradient of a straight line connecting points of (fog + 0.2) and (fog + 1.0), and indicates a gradient of density with respect to log (exposure amount).

As is evident from Table 2, the sample of the present invention has high sensitivity and high contrast, little dependence of photographic performance on processing time, little increase in fog even when exposed to high-temperature and high-humidity conditions before development after exposure, and It can be seen that the decrease in sensitivity is small.

Compound used in Example 1 Example 2 Compounds (I-5) and (I-11) of the present invention were added to the ninth and thirteenth layers of Sample 105 of JP-A-1-14849, respectively, for 0.20.
Samples 201 and 202 were prepared by adding g / m ² .

These samples were subjected to white imagewise exposure, and the following color development was performed to evaluate photographic performance. Gamma and relative sensitivity were determined by the method of Example 1.

Table 3 shows that the sample of the present invention has high sensitivity and high contrast.

In the color development processing, the following processing was performed at 38 ° C. by an automatic developing machine.

Color development 3 minutes 15 seconds Bleaching 1 minute Bleaching and fixing 3 minutes 15 seconds Rinse 40 seconds Rinse 1 minute Stable 40 seconds Dry (50 ° C) 1 minute 15 seconds In the above process, rinsing is countercurrent water The washing method was adopted. Next, the composition of each processing solution will be described.

The replenishment amount of each processing solution was 1200 ml for color development per 1 m ² of the color photographic material, and 800 ml for all others including washing with water. The pre-bath carry-amount to the washing step was color light-sensitive material 1 m ² per 50 ml.

<< Bleaching solution >> Common mother liquor and replenisher Ferric ammonium ethylenediaminetetraacetate 120.0 g Disodium ethylenediaminetetraacetate 10.0 g Ammonium nitrate 10.0 g Ammonium bromide 100.0 g Bleaching accelerator 5 × 10 ^-3 mol Add ammonia water and pH 6.3 Add water 1.0l << Bleach-fixing solution >> Common for mother liquor and replenisher Ferric ammonium salt of ethylenediaminetetraacetic acid 50.0g Disodium salt of ethylenediaminetetraacetic acid 5.0g Sodium sulfite 12.0g Aqueous solution of ammonium thiosulfate (70 %) 240ml Add ammonia water, pH 7.3 Add water 1 《Washing water》 Calcium ion 32mg / l, Magnesium ion 7.3mg /
l is passed through a column filled with H-form strongly acidic cation exchange resin and OH-form strongly basic anion exchange resin,
1.2 mg / l calcium ion, 0.4 mg / l magnesium ion
Sodium isocyanurate dichloride in water treated in 1
20 mg was used per addition.

<< Stabilizing solution >> Formalin (37% w / v) 2.0ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3g Ethylenediaminetetraacetic acid disodium salt 0.05g Add water 1 pH 5.8 << Dry >> The drying temperature was 50 ° C.

Claims (1)

(57) [Claims] 1. A silver halide color photographic light-sensitive material comprising at least one silver halide emulsion layer provided on a support, wherein at least 40% by weight of silver halide grains in said emulsion layer are:
The grains are occupied by grains having a silver iodide content of 7 mol% or more and 30 mol% or less, and in at least one silver halide emulsion layer,
A silver halide color photographic light-sensitive material comprising a compound represented by the following general formula (I). In the general formula _{(I) A- (L) n} -ETA formula, A is by reaction with oxidized developer, - (L) _n -ET
L is a group that releases A, L represents a group that releases ETA after cleavage from A, n represents 0, 1 or 2, and ETA
Represents a group which functions as an electron transfer agent after being cleaved from A- (L) _n- .