DE3506805A1 - Photographic light-sensitive silver halide material - Google Patents

Abstract

A photographic light-sensitive silver halide material is described which contains a base on which there is at least one silver halide emulsion layer. The photographic light-sensitive material contains at least one compound suitable for forming a photographically useful group, or a precursor thereof, during the development processing, it being possible for a photographic function of the photographically useful group, or of the precursor thereof, to be varied by an intermolecular reaction. The photographic light-sensitive silver halide material has good storage stability and can lead to images of improved sharpness, in particular in areas of high frequencies, without a reduction in sensitivity and an increase in fogging.

Description

description

The invention relates to a silver halide photographic light-sensitive material, containing a new compound for photographic use, with a photographic useful group, the photographic function of which can be changed, d. H.

can be increased or decreased during development processing can.

Among those for use in silver halide photographic light-sensitive materials Suitable compounds are known various compounds which are photographically make useful group usable during development processing. An example is a group of photographic couplers that have one photographically useful Group of their coupling point when the coupler reacts with the oxidation products release of developing agent. An example of these connections is a DIR coupler, whose photographic functions are described in T. H. James, The Theory of the Photographic Process, 4th Edition, pp. 610-611 and 343 (The MacMillan Co., New York, 1977), etc .; there can be improved effects regarding sharpness, graininess, or color reproducibility. Also be in US Pat. No. 4,390,618 describes couplers which, upon reaction of the couplers with the Oxidation products of developing agents can release a compound that has a development accelerating function. In addition, the US PS 3,705,801 couplers described the a bleach inhibitor of theirs Can release the coupling site after the reaction of the coupler with the oxidation products of development funds. Couplers are also described in US Pat. No. 4,130,427, the one competing coupler from its coupling site after reaction of the coupler can release with the oxidation products of developing agents.

Numerous types of couplers are known, as described above, who can and they can release a photographically useful group can be used according to the various purposes of use. It has recently been to some extent possible, the release rate of a photographically useful group of couplers to control, or the diffusivity of a photographically usable released group to control. In particular, the time-controlled Groups as described in U.S. Patent 4,248,962 are exemplified. In these Compounds can adjust the timing of the photographically useful groups the reaction of the couplers with the oxidation products of developing agents without changing the properties of the photographically useful groups.

A group of compounds which are useful to be photographically to release useful group by alkaline hydrolysis at the time of development, is also known. For example, those described in U.S. Patents 4,350,752; 4,350 754 and 4,358,522, etc., decomposed by alkali, the Development time is available, and they set a development inhibitor, a dye, a developing agent, etc. free.

Another example are the compounds that are suitable for a photographically useful group by intramolecular displacement reaction to release, which however are not photographically useful group release as a result of suppression of the intramolecular displacement reaction, if they react with the oxidation products of developing agents before they enter into the shift reaction as described in U.S. Patent 3,980,479.

In contrast to the generation techniques described above Photographically useful groups are also known techniques which are characterized thereby are that photographically useful groups contribute their photographic functions of photographic development processing or subsequently lose. An example is a technique for color correction using colored couplers. That The principle of this technique is described in T. H. James, The Theory of the Photographic Process, 4th edition, pages 342 and 532-533 (The MacMillan Co., New York, 1977). In addition, they are DIR couplers that release a development inhibitor which gradually loses its inhibitory functions, in GB-PS 2,099 167 described. This technique is effective in clearing up the adverse pollution of processing solutions that occur when using development inhibitors, which have a high diffusibility to be photographically photosensitive Bringing materials to market with improved sharpness.

In the prior art as described above, photographic useful groups can be used at the time of development, or they lose theirs photographic functions at the time of development or later.

The characteristic that these compounds or techniques like them have usually been described above is that the photographic useful groups or the precursors thereof can have photographic functions or that they lead to compounds which have no photographic function monomolecular Reaction without reaction of the photographically useful groups or the precursors of which can be converted to one another. With these known compounds, in which the functions of the photographically useful groups by monomolecular Response are changed are the photographic functions and areas functions are limited, and thus photographic effects are limited. In particular, in the prior art, the areas of functions are photographic usable groups restricted to the area in which the center is a layer, to which the compounds are added.

In addition, there is a limitation in the prior art that the power of the photographic function depends on the concentration distribution of the photographically useful groups distributed in a first order relationship are determined. In addition, the prior art is as mentioned above photographic function is limited and can only be changed within its range will. In other words, the kind of the photographic function cannot be varied will. It is therefore expected that the properties of photographic photosensitive Materials can be improved exceptionally well when these limitations are lifted will.

In addition, with the type of connection described above, which releases a photographically useful group by alkaline hydrolysis, in most cases it can not be ruled out that these compounds of the hydrolysis reaction during storage of photographic light-sensitive materials using these Compounds contain, are subject, and therefore there are limitations on practical use.

To ensure the stability during storage of the photographic photosensitive To improve materials, it is therefore necessary that they be made hardly hydrolyzable which, however, lead to a delay in the release speed of the photographically useful group at the time of the development process. Because these known connections are so contradicting, they actually become used as photographic light-sensitive materials with severe restrictions.

Because of these limitations, the development works inhibiting properties both in areas with low frequency and in High frequency surfaces when couplers are used which one the development can release inhibiting group. Accordingly, there is a limitation regarding the improvement of sharpness using such Kupp-1er. aside from that the development-inhibiting groups are adjacent in high concentrations around the development points of silver halide, increasing the sensitivity is reduced considerably in some cases when couplers with a strong, the development inhibiting group can be used. It also leads at Couplers that can release a development accelerating group that excessively high concentration distribution of the development accelerating groups in the vicinity of development points of silver halide to an increase the fog density, which in some cases leads to a reduction in sensitivity leads.

It is therefore an object of the invention to provide a connection or a combination thereof, the distribution of photographically useful groups without the limitations described above.

Another object of the invention is to provide a photographic one light-sensitive material which further improves its photographic properties are made by incorporating a compound or a combination thereof that the Distribution of photographically useful groups excluding those described above Limit gen can bring about. ~ ~~ Other targets or objects of the invention will be apparent from the following more detailed description and examples.

These objects of the invention have been achieved by a photographic one silver halide light-sensitive material comprising a support on which at least one photosensitive silver halide emulsion layer is located, wherein the photographic light-sensitive material contains at least one compound, which is a photographically useful group or a precursor thereof to form during development processing, the photographic function the photographically useful group or the precursor thereof by an intermolecular one Response can be changed.

The invention is described in more detail below. The change of the photographic function addressed by the present invention means that Occurrence, increase, obliteration or decrease in function.

The photographically useful group includes a photographic dye Purposes or a precursor therefor, a development inhibitor, a development accelerator, a bleach inhibitor, a bleach accelerator, a developing agent, a Couplers (e.g., a color forming coupler, a competing coupler, a DIR coupler, etc.), a color-mixing preventing agent (e.g. an abbot for the oxidation product of a developing agent such as a hydroquinone, a sulfonamidophenol, etc.), a silver halide solvent, a fixing agent, a fogging agent, an anti-fogging agent, a chemical sensitizer, a hardener, * a p-aminophenol, a color fading preventing agent, a latent image preventing agent.

The following explains the reaction between molecules that the origin for the change in the photographic function in the invention Form connections.

The reactions undergone by the compounds of the invention can basically be illustrated by the following scheme. By The reactions illustrated in the following scheme are essentially reactions to produce the effects according to the invention. Of course it doesn't Problem when other side reactions may occur.

Scheme 1 A1 level (i) # B1 level (ii) A2> B2 level (iii) B1 + B2 # C In the above scheme, the compounds according to the invention are represented by A1 and A2. B1 and B2 represent compounds formed from Ag and A2 by the development processing reaction. C represents a connection made by the Reaction between B1 and B2 is formed. A1 and A2 can have the same connections or be different from one another and B1 and B2 can also be the same compounds or be different from each other.

The reaction formulas described above are used to to explain the invention in a fundamental sense, and there are numerous modifications possible.

For example, a modification is possible in which A1 and A2 are connected, to form a molecule. Another modification in which each stage, for example step (i) comprises two or more reaction processes to form B1 is possible. In addition, there may be a case where a preferred atmosphere for acceleration of the reaction between B1 and B2 in the step of forming C is present in the invention may be included. In short, the effect of the invention lies in that compounds (corresponding to B1 and B2) in the development process from compounds (corresponding to A1 and A2) are formed beforehand to be photographic photosensitive Materials have been joined and react with each other, creating another connection (according to C) can be formed.

The invention will be explained in more detail below with reference to the above Scheme described explained.

The reactions to form B1 and B2 from A1 and A2 include one Coupling reaction between a coupler and an oxidation product of a developing agent, an oxidation reaction between a reducing compound and an oxidation product a developing agent, a hydrolysis reaction with an alkali or an acid, a nucleophilic shift or

Displacement reaction or a nucleophilic addition reaction between a compound having an electrophilic functional group and a nucleophilic Agents such as sulfite ion, hydroxylamine, etc. contained in a developing solution etc., a reverse Michael addition reaction, a reverse Aldon condensation reaction, a bond cleavage reaction utilizing electron transfer from a Anion that is formed at the time of development, an intramolecular one nucleophiles Displacement or displacement reaction or an intramolecular nucleophilic addition reaction and a combination thereof, etc.

The intermolecular reaction between B1 and B2 involves a nucleophilic one Displacement or displacement reaction, a nucleophilic addition reaction, a Oxidation-reduction reaction, a coupling reaction, a cyclic addition reaction, a complex formation reaction via a hydrogen bond, a coordinate bond or batch transfer and a combination thereof, etc.

Each of the compounds represented by A1, A2, B1, B2, and C can be a to have a photographic function or not.

It is important to have at least one represented by B1, B2 and C Compounds a photographically useful group and that the photographic function of B1 or B2 is different from that of C.

The connections represented by A1 and A2 can be the same or to be different. If these compounds are different from each other, they can be incorporated in the same layer or in different layers. About that In addition, the compounds represented by A1 and A2 can be incorporated into any emulsion layer, an intermediate layer and a protective layer, etc. may be incorporated.

The compounds represented by A1, A2, B1, B2 and C can be diffusible or be non-diffusible. This can be selected depending on the purpose of use. The term that the compound is nondiffusible means that the compound does not diffuse significantly from a layer in which the compound is present, due to a diffusion-resistant group or adsorption to a medium in the general. The diffusion resistant group is an organic group that you molecule sufficiently large to make the compound essentially non-diffusible do.

The reactions to form B1 and B2 from A1 and A2 in the above The reaction scheme described can be divided into the following three cases: (1) Cases where the responses in the form of an image, according to the amount of exposure of photographic images progress, (2) cases where the response is indiscriminate progresses regardless of the exposure amount, and (3) cases where the Reaction that progresses fundamentally indiscriminately, and the reaction that proceeds in Image form advances, compete. The reaction between B1 and B2 can be basically also split into the same three cases.

Examples of the cases where the reaction progresses in the form of images, are generally cases in which remaining developing agent is developed Silver, a halide ion, and especially the oxidation product of a developing agent acts as a component of the reaction species. In particular, they include a coupling reaction with a coupler, an oxidation-reduction reaction with a reducing agent (such as a hydroquinone, etc.), etc. Most other organic chemical Responses are included in cases where the responses are indistinguishably independent progress of images. They also include cases where though the reactions to progress fundamentally indiscriminately, the progression of the reaction in the form of a picture is controlled, special cases where the above-described oxidation-reduction reaction or coupling reaction and other chemical reactions compete. Specific examples for such cases include the so-called Fields compounds, as in US Pat 3,980,479.

According to the invention, a reaction process is required in which the Function of the photographically useful group by reaction between molecules is changed with each other, for example the function is generated or the Function extinguished. This reaction process is represented by the reaction wherein B1 and B2 react with each other to form C as in the above reaction scheme described.

The reactions in which the photographically useful groups are generated are specifically illustrated below.

(1) Reaction in which a group of atoms (a functional group), which is supposed to have the fundamental photographic function: photographic useful groups generally have an atomic group that contains at least one Contains heteroatom that belongs to group VA or VIA of the periodic table and has two or three valences. Examples are in the case of a dye a chromophore such as an azo group, an azomethine group, etc., or an auxochrome, which controls a spectral absorption range, and in the case of an inhibitor one adsorbing group for silver halide such as a mercapto group, a triazolyl group etc. By protecting (blocking) the hetero atom included in such groups of atoms in the active form one obtains compounds which have no effect on the photographic Have properties.

If the reaction to eliminate the protecting group between two Molecules runs off, this corresponds to the present case of reaction (1). For example one of the two molecules is a precursor for a photographically useful group, and the other is a precursor for a reaction reagent for elimination the protecting group.

(2) Reaction in which a group of atoms is generated which is used for reinforcement of the photographic response is needed: A response in which the extent of the hydrophilic / hydrophobic properties of the molecule is changed, and a reaction, in which the degree of electron withdrawing / electron donating properties of a substituent is changed, etc.

corresponds to the present case of reaction (2).

For example, in the case of an inhibitor, a compound with little effect on photographic properties due to their strong hydrophilic properties sometimes associated with enhanced photographic properties Function can be converted by imparting a suitable hydrophobic property by changing a substituent.

This phenomenon can be exploited. In this case means the reaction between two molecules that a photographically useful group with strong hydrophilic properties, as one of the two molecules, and a reactant, containing a suitable hydrophobic substituent than other, with each other implemented, thereby connecting these connections together, and thus the inhibiting function is enhanced.

(3) reaction involving a compound having a photographic function is recorded at the desired and specific point: An example is one Reaction in which a compound that has a photographic function and a large one Has diffusivity, which has no essential photographic function, since it flows out into the developing solution, in connection with with low diffusivity is converted at the specific and desired location. The lowering of the diffusibility makes it photographically useful Group immobilized at the desired location and gives the photographic function in an effective way. The reactions to reduce diffusibility include for example a reaction in which a hydroquinone is converted into a quinone becomes, etc. In general, a reaction in which a water-soluble group is converted into a hydrophobic group, or a reaction in which a dye etc. is fixed by pickling etc. is included in the case of a reaction.

On the other hand, in contrast to the reactions described above Reactions in which a photographically useful group is its effective photographic Loses function, understood as reverse reactions of those described above will. In particular, a reaction comes into consideration in which a heteroatom, the represents the fundamental part for the occurrence of the photographic function, protected (blocked), a reaction in which photographic function is reduced is achieved by changing the degree of hydrophilic / hydrophobic properties, and a reaction in which the photographically useful group is drained by change diffusibility / non-diffusibility, etc.

In summary, it is understood that the reasons by which the various Objectives that are to be achieved according to the invention are achieved within the scope of the invention can be based on the essential principle as shown below. In the following, A1, A2, B1, B2 and C each represent the compound as in the above the reaction scheme described.

(1) When A1 and A2 are joined individually in different layers and one of B1 and B2 formed therefrom is diffusible, and that other being nondiffusible, the level of function may be more photographically useful Groups in the desired layer according to the information (for example the amount of exposure in image form) can be changed in the various layers. For example, this means that in a photosensitive, color photographic Material using a DIR coupler has the inhibiting effect, which as a Function of the DIR coupler is known, effectively and effectively controlled. This means that it is possible according to the invention to inhibit the interlayer without reinforcing inhibition in the layer itself, or in contrast to it only in the layer itself without inhibition in the intermediate layer.

(2) When A1 and A2 are put in the same layer and the diffusion rates (Diffusion areas) of B1 and B2, which are formed from them, are varied, the functional area of the photographically useful groups can be freely controlled. For example, it is assumed that B1 and B2 are each released by couplers, and B1 is a diffusible inhibitor and B2 is a nondiffusible deactivator for the inhibitor. At the time of development, B1 and B2 become through reactions with the oxidation products of developing agents formed in image areas, wherein the Oxidation products of the developing agent are generated. Because of the different Diffusivity of B1 and B2 diffuses B1 widely, whereas B2 diffuses narrowly Area diffuses. The compounds react with each other, and so do the inhibitors are deactivated.-However, this reaction takes place only around the central part in the pictures, due to the narrow concentration distribution from B2. as As a result, the inhibitors are deactivated all the more, the closer they get to it central part. This means that the inhibiting function does not work affects fine line images. This means that, based on CTF curves, the used to measure sharpness, the change of CTF in areas with high Frequency is decreased.

(3) The photographic functions of B1, B2 and C can be freely selected and the generation rates thereof can be freely controlled. For example, can they are selected so that B1 is a development accelerator and B2 is a development inhibitor and C is a compound that does not affect photographic properties affects. In such a case, if B1 and B2 are in the same layer generated by reactions with the oxidation products of developing agents, Dye clouds that are formed in various forms are controlled by Change in the diffusivity (functional surface) of every connection.

In addition, in another example, B1 and B2 have no effect on photographic properties, and C has a photographic function. For example, a type of reaction in which C may be a color fading preventive Is medium and is formed gradually after development, while B1 and B2 generated at the time of development. This means that the the color fading preventing agent can be made in good timing, when needed, for example under high temperature conditions and high humidity or when exposed to sunlight, whatever in the desired Concentration takes place.

(4) Since A1 and A2 can be joined individually in different layers, it is possible to use the opportunities of contact between B1 and B2, from A1 and A2 respectively can be formed during storage of photographic photosensitive Decrease materials. Hence, precursors become photographically useful groups realized with excellent storage stability.

This illustrates a case where C is caused by reaction between B1 and B2 are formed as a photographically useful group.

(5) Types of reactions in which B1 and B2 are formed from A1 and A2, respectively and which is formed from B1 and B2 can be freely selected. There is one Type of reaction that occurs in picture areas, a type of reaction that occurs in non-picture areas occurs and a type of reaction that occurs independently of images, as above described. Such a type of reaction can be selected depending on the purpose of use will.

The compounds that can be used in the present invention can can be represented by the following general formula (I): x - (CONT) n Y (I) wherein X represents an organic residue which is responsible for splitting off (CONT) -Y at the time of development suitable is; CONT represents a linking group that leads to the cleavage of Y after the cleavage of X is suitable, n is 0 or 1; and Y is an organic one Represents residue that can lose a photographic function, or a connection with photographic function can form by reacting with each other after the release.

The group represented by Y can be compared to the group with the same Structure to be implemented. Alternatively be two or more different types of connection represented by the general formula <1) are used, and two types of Y with structures different from each other, which are released by these compounds can be converted.

In the general formula <1> described above, X and CONT, CONT and Y or X and Y can be connected to another bond, the does not undergo a cleavage reaction with the formation of a cyclic structure, which in of the general formula (1) represented by X is specifically a group which undergo a coupling reaction with the oxidation product of a developing agent may, a group that has an oxidation-reduction reaction with the oxidation product of a developing agent, a group that undergoes a cleavage reaction in the presence of an acid or a base, or a combination thereof Group.

In addition, X can be a monomer, a compound of the bis type or be a polymer and can contain several groups - (CONT) n-Y in its molecule.

In the general formula (1) wherein X represents a group capable of coupling reaction with the oxidation product of a developing agent, it is preferred if the group is a coupler residue represented by the general formulas <A-1), (A- II), (A-111), (A-IV), (AV), (A-VI), (A-VII), (A-VIII), (A-IX), (AX) or (A- XI), which are described below. These couplers are preferred because of their high coupling rates.

In the general formulas described above, shows a free Bond attached to the coupling site, a site to which a group which is suitable for release by coupling, is bound. If R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 or R11 in the general terms described above Formulas contains a diffusion-resistant group, it is selected so that the Total number of carbon atoms included 8 to 32 and preferably 10 to 22. On the other hand, if it does not contain a diffusion-resistant group, the total number of carbon atoms involved is preferably not more than 15.

In the following, R1 to R ß m and p are described in the preceding 11 ' general formulas (A-I) to (A-XI) are explained.

In the general formula described above, R1 represents a aliphatic group, an aromatic group, an alkoxy group or a heterocyclic group Represents a group, and R2 and R3 each represent an aromatic group or a heterocyclic group Group.

The aliphatic group represented by R1 is preferably one aliphatic group with 1 to 22 carbon atoms and can have substituents or not and, moreover, may have a chain form or a cyclic form. Preferred substituents therefore include an alkoxy group, an aryloxy group, a Amino group, an acylamino group, a halogen atom, etc., each representing an or may have several other substituents.

Specific examples of aliphatic groups useful for R1 include an isopropyl group, an isobutyl group, a tert-butyl group, an isoamyl group, a tert-amyl group, an i, 1-dimethylbutyl group, a 1, 1 -dimethylhexyl group, a 1, 1 -diethylhexyl group, a dodecyl group, a Hexadecyl group, an octadecyl group, a cyclohexyl group, a 2-methoxy group isopropyl group, a 2-phenoxyisopropyl group, a 2-ptert-butylphenoxyisopropyl group, an α-aminoisopropyl group, an a- (diethylamino) isopropyl group, an a- (succinimido) isopropyl group, a a- (phthalimido) isopropyl group, an a- (benzenesulfonamido) isopropyl group, etc.

If R1, R2 or R3 represent an aromatic group (especially a phenyl group), it can have a substituent. Such an aryl group as a phenyl group etc., may be substituted with an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an aliphatic group Amino group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkylureido group, an alkyl-substituted succinimido group, etc., each having 32 or less carbon atoms contains, be. The alkyl group therein may include an alkyl group that is aromatic Contains group in its molecular chain, such as phenylene. In addition, a phenyl group, represented by R1, R2 or R3 may be substituted with an aryloxy group, one Aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group, an arylureido group, etc., the aryl group being each Group may be substituted with one or more alkyl groups, wherein the number of carbon atoms a total of 1 to 22.

In addition, a phenyl group represented by R1, R2 or R3 may have an amino group which substitutes an amino group with a lower alkyl group having 1 to 6 carbon atoms, a hydroxy group, a Carboxy group, a sulfo group, a nitro group, a cyano group, a thiocyano group or a halogen atom.

In addition, R1, R2 or R3 can represent a substituent -der is formed by condensation of a phenyl group and another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group, a tetrahydronaphthyl group, etc. These substituents may also have substituents themselves.

If R1 represents an alkoxy group, the alkyl radical thereof represents one straight or branched chain alkyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, an alkenyl group, a cyclic alkyl group or cyclic alkenyl group, each of which can be substituted with a halogen atom, an aryl group, an alkoxy group, etc.

If R1, R2 or R3 represents a heterocyclic group, is heterocyclic group on the carbon atom of the carbonyl group of the acyl radical or to the nitrogen atom of the amido radical of an α-acetylacetamido group through one of the carbon atoms forming the ring. Examples of such heterocyclic Rings include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, Pyridazine, Indolizine, Imidazole, Thiazole, Oxazole, Triazine, Thiadiazine, Oxazine, etc.

These rings can also have substituents in the individual rings exhibit.

In the above general formula, R5 denotes a straight-chain, branched chain alkyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms (e.g. a methyl group, an isopropyl group, a tert-butyl group, a hexyl group, a dodecyl group, etc.), an alkenyl group (e.g., an allyl group etc.), a cyclic alkyl group (e.g. a cyclopene acyl group, a cyclohexyl group, a norbornyl group, etc.), an aralkyl group (e.g. a benzyl group, a phenylethyl group etc.), a cyclic alkenyl group (e.g. a CyclopenXnylgruapet a cyclohexenyl group, etc.), etc., which groups may be substituted with a halogen atom, a nitro group, a cyano group, an aryl group, a Alkoxy group, an aryloxy group, a carboxy group, an alkylthiocarbonyl group, an arylthiocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a thiourethane group, a sulfonamido group, a heterocyclic group, an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an alkylthio group, an alkylamino group, a dialkylamino group, an anilino group, an N-arylanilino group, a N-alkylanilino group, an N-acylanilino group, a hydroxy group, a mercapto group etc.

R5 can also be an aryl group (e.g. a phenyl group, a a- or -naphthy1gruppe etc.). The aryl group can have one or more substituents to have. Specific examples of the substituents include an alkyl group, a Alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a sulfonamido group, a heterocyclic group, an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an alkylthio group or aralkylthio group, an alkylamino group, a dialkylamino group, an anilino group, an N-alkylanilino group, an N-arylanilino group, an N-acylanilino group, a hydroxy group, a mercapto group, etc. A more preferable one Group for R5 is one Phenyl group which is substituted with a Alkyl group, an alkoxy group, a halogen atom, etc. in at least one of o-positions as it causes coloring of the couplers present in the film layers remain, is prevented by light or heat.

In addition, R5 can be a heterocyclic group (e.g.

a 5-membered or 6-membered heterocyclic ring, which as Heteroatom contains a nitrogen atom, an oxygen atom or a sulfur atom, or a condensed ring thereof, specific examples being a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, an oxazolyl group, imidazolyl group, naphthoxazolyl group, etc.), heterocyclic Group substituted with one or more substituents as for those above defined aryl group, an aliphatic acyl group, an aromatic Acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group represent.

In the general formulas described above, R4 represents a Hydrogen atom, a straight or branched chain alkyl group of 1 to 32 Carbon atoms, preferably with 1 to 22 carbon atoms, an alkenyl group, a cyclic alkyl group, an aralkyl group, or cyclic alkenyl group (the may have one or more substituents as for that described above Substituents R5 defined), an aryl group or a heterocyclic group (the may also have one or more substituents, as for the one described above Substituents R5 defined), an alkoxycarbonyl group (e.g. a methoxycarbonyl group, an ethoxycarbonyl group, a stearyloxycarbonyl group, etc.), an aryloxycarbonyl group (e.g. a phenoxycarbonyl group, a naphthoxycarbonyl group, etc.), one Aralkyloxycarbonyl group (e.g. a benzyloxycarbonyl group, etc.), an alkoxy group (e.g. a methoxy group, an ethoxy group, a heptadecyloxy group, etc.), a Aryloxy group (e.g. a phenoxy group, a tolyloxy group, etc.), an alkylthio group (e.g. an ethylthio group, a dodecylthio group, etc.), an arylthio group (e.g. B. a phenylthio group, a «-naphthylthio group, etc.), a carboxy group, a Acylamino group (e.g. an acetylamino group, a 3-L (2, 4-di-tert-amylphenoxy) -acetamido? -benzamido group, etc.), a diacylamino group, an N-alkylacylamino group (e.g. an N-methylpropionamido group, etc.), an N-arylacylamino group (e.g. an N-phenylacetamido group, etc.), an ureido group (e.g. an ureido group, an N-arylureido group, an N-alkylureido group, etc.), a urethane group, a Thiourethane group, an arylamino group (e.g. a phenylamino group, an N-methylanilino group, a diphenylamino group, an N-acetylanilino group, a 2-chloro-5-tetradecanamidoanilino group etc.), an alkylamino group (e.g. an N-butylamino group, a methylamino group, a cyclohexylamino group, etc.), a cycloamino group (e.g. a piperidino group, a pyrrolidino group, etc.), a heterocyclic amino group (e.g. 4-pyridylamino group, a 2-benzoxazolylamino group, etc.), an alkylcarbonyl group (e.g. a methylcarbonyl group etc.), an arylcarbonyl group (e.g. a phenylcarbonyl group, etc.), a sulfonamido group (e.g. an alkylsulfonamido group, an arylsulfonamido group, etc.), a carbamoyl group (e.g. an ethylcarbamoyl group, a dimethylcarbamoyl group, an N-methylphenylcarbamoyl group, an N-phenylcarbamoyl group, etc.), a sulfamoyl group (e.g. an N-alkylsulfamoyl group, an N, N-dialkylsulfamoyl group, an N-arylsulfamoyl group, an N-alkyl-N-arylsulfamoyl group, an N, N-diarylsulfamoyl group, etc.), a cyano group, a hydroxy group, a Mercapto group, a halogen atom or a sulfo group.

In the general formulas described above, R6 represents a Hydrogen atom or a straight-chain or branched-chain alkyl group with 1 to 32 carbon atoms, preferably with 1 to 22 carbon atoms, an alkenyl group, a cyclic alkyl group, an aralkyl group or a cyclic alkenyl group, each of which may have one or more substituents, as described for the above Substituents R5 defined.

In addition, R6 can be an aryl group or a heterocyclic group mean, which may have one or more substituents, as above for the Substituents R5 defined.

In addition, R6 can be a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a sulfonamido group, an arylsulfonyl group, an alkylsulfonyl group, a Arylthio group, an alkylthio group, an alkylamino group, a dialkylamino group, an anilino group, an N-arylanilino group, an N-alkylanilino group, an N-acylanilino group, mean a hydroxyl group or a mercapto group.

In the general formulas described above, R7 and R8 are and Rg in each case a group which in conventional phenol or α-naphthol couplers from 4 equivalent type was used. Specifically, R7 means a hydrogen atom Halogen atom, an alkoxycarbonylamino group, an aliphatic hydrocarbon radical, an N-arylureido group, an acylamido group, an -O-R12 group or an -S-R12 group (wherein R12 is an aliphatic hydrocarbon radical). If two or more groups R7 are present in one molecule, they may be different from each other. the above-mentioned aliphatic hydrocarbon radicals include those having substituents exhibit. If these substituents include an aryl group, the aryl group may have one or more substituents as for the substituent described above R5 defined.

R8 and Rg each denote an aliphatic hydrocarbon radical, an aryl group or a heterocyclic group. Each of them can be a hydrogen atom be. The groups described above for R8 and Rg can also be certain Have substituents.

In addition, R8 and Rg can combine with each other and one nitrogen form containing heterocyclic nucleus.

In particular, the aliphatic hydrocarbon radicals described above include both saturated and unsaturated, each having a straight chain form, one branched chain form or a cyclic form. Preferred examples for this include an alkyl group (e.g. a methyl group, an ethyl group, a Propyl group, an isopropyl group, a butyl group, a tert-butyl group, a Isobutyl group, a dodecyl group, an octadecyl group, a cyclobutyl group, a cyclohexyl group, etc.) and an alkenyl group (e.g., an allyl group, a Octenyl group, etc.). The aryl group described above includes a phenyl group, a naphthyl group, etc. Examples of the heterocyclic group described above Group include a syridyl group, a quinolyl group, a thienyl group, a Piperidyl group, an imidazolyl group, etc. These aliphatic hydrocarbon radicals, Aryl groups and heterocyclic groups may each be substituted with one Halogen atom, a nitro group, a hydroxyl group, a carboxy group, a Amino group, a substituted amino group, a Sulfo group, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group Group, an alkoxy group, an aryloxy group, an arylthio group, an arylazo group, an acylamino group, a carbamoyl group, an ester group, an acyl group, an acyloxy group, a sulfonamido group, a sulfamoyl group, a sulfonyl group, a morpholino group, etc.

In the general formulas described above, t means one integer from 1 to 4, m means an integer from 1 to 3 and p means one integer from 1 to 5.

In the general formula described above, R10 represents a Arylcarbonyl group, an alkanoyl group, having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group with 2 to 32 carbon atoms, preferably with 2 to 22 carbon atoms, one Alkoxycarbonyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, or an aryloxycarbonyl group, each of which may be substituted. Examples for the substituents include an alkoxy group, an alkoxycarbonyl group, a Acylamino group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkylsuccinimido group, a halogen atom, a nitro group, a carboxy group, a nitrile group, an alkyl group, an aryl group, etc.

In the general formula described above, R11 represents Arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 32 carbon atoms, preferably 2 to 22 carbon atoms, an alkoxycarbonyl group with 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, an aryloxycarbonyl group, an alkanesulfonyl group with 1 to 32 carbon atoms, preferably preferably 1 to 22 carbon atoms, an arylsulfonyl group, an aryl group or a S-member or 6-membered heterocyclic group (containing as a heteroatom, a nitrogen atom, an oxygen atom or a sulfur atom, specific examples of which are a triazolyl group, an imidazolyl group, a phthalimido group, a succinimido group, a furyl group, a pyridyl group, a benzotriazolyl group, etc.

include), each having one or more substituents can as defined above for the substituent R10.

In the general formulas described above, a denotes free bond a site to which - (CONT) Y is bonded.

Specific examples of the coupler residues identified by the general Formulas (A-I) to (A-XI) shown include those in known literatures can be described as follows: U.S. Patents 3,874,948, 2,017,704, 2,113,330, 2,108,602, 2,296,306, 2,298,443, 2,728,658, 3,265,506, 3,841,880, and 3,933,501, U.S. Reissue Patent 30,211, French Patent 1,558,452, U.S. Patent 4,268,591, 4,336,327 and 4,266,019, European Patent 73,636 A1, U.S. Patents 3,926,634, 3,894,875, 3,733,335, 3,615,506, 3,907,571, 3,928,044, 3 926 436, 3 935 015, 3 926 634, 4 012 258, 4 009 035 and 4 012 258, GB-PS 1 325 363, U.S. Patents 3,772,002, 3,632,345, 3,958,993, 3,961,959, 4,095,984, 4,046,574, and 4,052 213, GB-PS 2,099,167, US-PS 4,427,767 and 4,333,999, etc.

In the general formula (I) wherein X represents a group capable of undergoing an oxidation-reduction reaction, it is preferred if the group is represented by the following general formula (AiXII): wherein R15 and R16 each represent a hydrogen atom or an organic radical, at least one group represented by R15 and R16 is - (CONT) -Y; Each is an integer from 1 to 4, when t represents 2 or more, the groups R15 and the groups R16 can be identical or different; R13 and R14 each represent a hydroxyl group or an amino group which may be substituted.

Specific examples of those represented by the general formula (A-XII) Groups include those described in known literature as follows U.S. Patents 3,639,417, 3,379,529, 3,620,746, 3,930,863, 4,144,071, 4,108,663 and 3,990,899 and Research Disclosure No. 18104, etc.

In the general formula (I), wherein X represents a group which - (CONT) -Y capable of releasing in the presence of an alkali include preferred examples for the following groups: an acyl group, a sulfonyl group, a carbamoyl group, an imidomethyl group as described in U.S. Patent 4,350,752, a methyl group, substituted with a uracil as described in US-PS 4,350,754, a group, suitable for cleavage by an intramolecular nucleophilic shift reaction, as described in U.S. Patent 4,358,522, a benzylidene group as described in U.S. Patent No. 4,358,522 U.S. Patent 4,382,119, a group using a reverse Michael reaction, as described in U.S. Patent No. 4,009,029, a group taking advantage an intramolecular nucleophilic shift reaction as described in US Pat US Pat. No. 4,310,612, a group suitable for splitting off using an electron transition, as described in U.S. Patents 3,674,478, 3,932,480 and 3,993,661, a group, suitable for cleavage using an electron transition, as described in U.S. Patent 4,335,200, and a group utilizing an intramolecular nucleophilic shift reaction as described in U.S. Patent 4,330,617, etc.

In the general formula (I), X can also represent a group which is suitable for splitting off the group different from X, or which is suitable is the cleavage reaction of the group different from X when competing with to prevent an oxidation-reduction reaction with a shift reaction.

Specific examples of such groups include a group such as described in U.S.P. 4,199,354, a group as described in U.S.P. 3 980,479, a BEND compound as described in U.S. Patent 4,139,379 and a group as described in JP-OS 130927/79, etc.

In addition, X in the general formula (I) can represent a coupler radical which is represented by the following general formulas (A-XIII), (A-XIV) or (A-XV): wherein R17 represents an organic radical; R18 denotes a hydrogen atom or a group which can be released on coupling; Nu represents an oxygen atom, a sulfur atom or an imino group which may be substituted and is suitable for forming a nucleophilic group by resonance of anions when the methine group adjacent thereto is converted into a carboxylic anion under alkaline conditions, E represents an electrophilic group; X1 represents a linking group for forming such a stereochemical configuration that the nucleophilic group (an oxygen anion in the general formula (A-XV)) and E are capable of undergoing an intramolecular shift reaction associated with ring formation; R7 and m each have the same meaning as defined for the general formula (A-VIII); and a free bond indicates the site to which - (CONT) -Y is bound.

The one represented by the general formula (A-XIV) or (A-XV) Coupler, no anion is formed in the nucleophilic group and thus none occurs intramolecular nucleophilic shift reaction when reacting with the oxidation product of a developing agent takes place. In contrast, in the remaining Coupler that does not react with the oxidation product of a developing agent is created, an anion in the nucleophilic group, and it goes an intramolecular one a nucleophilic shift reaction, whereby - (CONT) -Y is cleaved.

In the general formula (I), the linking group represented by CONT is shown to control the rate of cleavage of X or to control the diffusivity of the group represented by Y, which is bound to CONT, be used. According to the invention, the group represented by CONT can depending on used or not used for the intended purpose.

Specific examples of the connective represented by CONT Groups include a group that is useful in an intramolecular shift reaction to be cleaved after the release of X, as in US Pat. No. 4,248,962 and US Pat of Japanese Patent Laid-Open No. 56837/82, etc., a group suitable for electron transfer via a conjugate system as disclosed in GB-PS 2 072 363, JP-OS 154234/82 and 188035/82 etc.

described to be split off a methylenoxy group, as in U.S. Patent 4,146,396 and an oxycarbonyloxy group as disclosed in Japanese Patent Laid-Open 146828/76 etc. In addition, the group represented by CONT be a component that is suitable for reaction with the oxidation product of a Developing agent such as a coupler component as disclosed in Japanese Patent Laid-Open No. 111536/82 described.

In the general formula (I), the group represented by Y is a photographically useful group, a precursor of a photographically useful Group or a simple group that can be released, any of these is suitable for reaction between molecules. It's difficult to find a preferred one To determine the range of the rate or extent of the intermolecular reaction. this stems from the fact that the optimum range is within the development period or after the development depending on the intended use. For this Reasons it is meaningless to add substituents in examples described below Strictly limit reactions. In other words, the desired level of response can be can be adjusted by choosing the appropriate substituents. The ones described below Reactions are preferred examples of reactions between Y and Y. These reactions occur when the molecules and Y and Y have the same structure or different Have structures such as a photographically useful group and a Compound useful in deactivating the photographically useful group is. Y has at least one partial structure as described below. Such a one Partial structure is described below as a reactive group.

(1) Nucleophilic Shift Reaction One sulfur atom, one nitrogen atom or an oxygen atom is included as a nucleophile atom. The central atom an electrophilic group is a carbon atom, a sulfur atom or a phosphorus atom. An atom or group of atoms released from the electrophilic group, is a halogen atom (preferably a chlorine atom, a bromine atom and an iodine atom), a substituted oxygen atom, a substituted sulfur atom or a substituted one Nitrogen atom.

The intensity of the nucleophilic group and the ease of release can be varied depending on a combination of reaction species. However, basic examples are given in J. March, Advanced Organic Chemistry, 2. Edition, pages 321, 325 and 331 (McGraw-Hill Co., 1977).

(2) Nucleophilic addition reaction One sulfur atom, one nitrogen atom or an oxygen atom are included as a nucleophilic atom. An electrophile Group includes a multiple bond consisting of a carbon atom and a carbon atom consists of a multiple bond consisting of a carbon atom and a heteroatom consists, and a multiple bond consisting of a heteroatom and a heteroatom exists, etc.

(3) Coupling reaction An active methine group, an active methylene group or a phenolic hydroxy group are included as a coupling group (the free bond given in the general formulas (A-I) to (A-XI) is bonded to a hydrogen atom or an organic radical) .The other reaction component includes an aromatic primary amine and a hydrazine, etc.

(4) Oxidation-Reduction Reaction A reaction component is a Reducing agents, such as a hydroquinone (R15 and R16 in the general formula (A-XII) each represent a hydrogen atom or an organic radical), and the other Reaction component is an oxidizing agent or a reduced compound that is capable of forming an oxidized form.

Preferred examples of the photographically useful groups or Precursors thereof represented by Y include those represented by the general formulas given below are shown. In the following Examples, Y is bound to X- (CONT) n on a bond represented by L1, when Y is or may be a photographically useful group Y on X- (CONT) n at a suitable position that can be substituted other than with L1, when Y is a precursor of a photographically useful group. When L1 is a bond to connect to X- (CONT), it can be a reactive group be present at other sites that can be substituted. The atom that has the bond represented by L1, a reactive group (a nucleophilic Group). Furthermore, if Y is a precursor of a photographically useful one Group, the reactive partial structure (reactive group) is as in (1) above to (4) described are bound to the bond represented by L1. This means, that as a result of the reaction of the reactive group when Y is a photographic is a useful group, the function of which is changed, for example the Function strengthened or weakened, and if Y is a precursor of a photographic is useful group, the photographic function occurs.

(Development inhibitor) (Competing coupler, color-mixing preventive agent, developing agent, etc.) (Development agent or development accelerator) (Coupler) (Dye) L1 G8 - N = V8 - Gg (B-VII) (fogging agent) wherein V1, V2 and V3 each represent a nitrogen atom or a group of C-G3; V4 represents a group of N-G3, a sulfur atom or an oxygen atom; V5 denotes an oxygen atom or a group of N-G3, V6 denotes an oxygen atom or a group of N-G12, V8 denotes a nitrogen atom or a group of C-G13; G1 represents a substituent; G2 denotes a hydroxyl group or an amino group which may be substituted; G3 represents a hydrogen atom, an aromatic group or an aliphatic group; G4 denotes an aromatic group, G5 denotes a hydrogen atom or a group which can be liberated in the coupling reaction with the oxidation product of the developing agent when L1 is cleaved; G6 represents an alkoxy group, an aromatic amino group, an acylamino group, an aromatic group, an aliphatic group or a heterocyclic group; G7 represents an aromatic group, an aliphatic group, or a heterocyclic group; G8 represents a single bond or an atomic group to connect between III and the nitrogen atom containing an aromatic group, an aliphatic group or a heterocyclic group; Gg denotes an aliphatic group, an aromatic group or a heterocyclic group when V8 is a nitrogen atom, or can also denote an acyl group, a carbamoyl group, a sulfamoyl group, a nitro group, a cyano group, an alkoxycarbonyl group, a sulfinyl group or a sulfonyl group when V8 is a group of C-G13, G10 and G11 each represent a hydrogen atom, an aromatic group, an aliphatic group, an acyl group, a carbamoyl group, a sulfonyl group, a sulfamoyl group, an alkoxycarbonyl group or a sulfinyl group; G12 represents an aliphatic group, an aromatic group, a heterocyclic group or an amino group, or G12 may be bonded to G7 to form a cyclic structure (e.g. a pyrazole, etc.) when V6 is a group of N-G12; G13 is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, a carbamoyl group, a sulfamoyl group, a nitro group, a cyano group, an alkoxycarbonyl group, a sulfonyl group, or a sulfinyl group, or G13 at Gg to form a cyclic group Structure (e.g. a pyrazolone, etc.) may be bound; i and R7 each have the same meaning as defined in the general formula (A-VII); f is an integer from 0 to 4; g is an integer from 1 to 3; and h is an integer from 1 to 3.

Preferred examples of the simple group which can be released and which is represented by Y include those represented by the general formulas given below. In the examples below, L2 means a free bond which is bonded to X- (CONT) n and is a reactive group, bonded to other positions that can be substituted, or the atom having the bond represented by L2 forms a reactive group (in many cases a nucleophilic group).

2 9 V9 - Z2 (B-X) where Z1 denotes an organic radical which leads to Formation of a nitrogen-containing heterocyclic group together with the nitrogen atom is needed; Vg an oxygen atom, a sulfur atom, a nitrogen atom with a Hydrogen atom, a nitrogen atom with a substituent, a methylene group, represents a methine group having a substituent or a selenium atom; and Z2 one means organic residue.

In detail, the coupling-releasing groups are like them specific examples of the group represented by Y that can be released. A reactive one Group can be given at a suitable substitutable position of these as examples Connections exist. Examples of these are described in: U.S. Patent 4,269 936, 3 990 896, 4 022 620, 4 057 432, 3 973 968, 4 314 023, 4 046 575 and 4 304 845, GB-PS 1,529,573, DE-OS 2,454,741, U.S. Patents 4,072,525, 4,146 396, 4,115,121, 3,834,908, 4,237,217, 4,032,345, 4,040,836 and 4,241,168, JP Patent Publications Nos. 34937/77, 46453/78 and 10491/79, U.S. Patents 4,076,533, 3,737,316, 4,028,106, 4th 146 400, 4,186,019, 4,157,919, 4,189,321, 4,134,766, 4,326,024, 4,264,723, 4,310 619, 4 301 235, 4 351 897, 4 254 212, 4 228 233, 4 296 199, 4 296 200, 4 130 423, 3 447 928, 3 408 194, 3 733 201, 3 227 554, 3 419 391 and 3 214 437, DE-OS (OLS) No. 2 414 006, GB-PS 1 547 245, 2 006 755 and 2 038 808 etc.

The following are specific examples of those marked by X, CONT, or Y groups shown, without the invention being limited thereto.

Examples of the groups represented by X: In the following Formula indicates the + the position to the bond to - (CONT) -Y.

Examples of the coupler residues represented by the general formulas (AI) to (A-XI): (A - # /) Examples of the groups that can be split in the presence of an alkali.

(A - # #) CH3CO - * Examples of the groups that can compete between an oxidation-reduction reaction and a cleavage reaction: Examples of the coupler radicals represented by the general formulas (A-XIII) to (A-XV): Examples of the groups represented by Y: In the formulas below, the + means the point of attachment to X- (CONT) n and the character D means a reactive group (including a reactive atom).

Examples of the groups represented by the general formula (BI): Examples of the groups represented by the general formula (B-II): Examples of the groups represented by the general formula (B-III): Examples of the groups represented by the general formula (B-IV): Examples of the groups represented by the general formula (BV): Examples of the groups represented by the general formula (B-VI): Examples of the groups represented by the general formula (B-VII): Examples of the groups represented by the general formula (B-VIII): Examples of the groups represented by the general formula (B-IX) or (BX): Examples of the groups represented by CONT: In the formulas below, * means the position in relation to the bond to X, and the symbol * »means the position in relation to the bond to Y.

(C - /) * - OCH2 - ** So far the invention has been explained in more detail. The effects of the invention can be demonstrated well in the following cases No. 1 to No. 4.

Case # 1 A case where (1) a compound leading to release one releasable by reaction with the oxidation product of a developing agent Group is suitable and (2) wherein a compound which upon reaction with the oxidation product of a developing agent as a releasable group releases a compound which can react with the group released from the compound (1), below Formation of a development inhibitor that has a stronger function than the group, released from the compound (1) can be used together.

The two types of connection described above can be either in the same layer or in different layers and in any one Emulsion layer and intermediate layer are incorporated.

Preferred are the two types of compounds described above incorporated into the same emulsion layer. In addition, the two can types of compounds described above are dispersed as a mixture thereof, and the resulting dispersion can be added or they can be separated are dispersed, and the resulting dispersions can be in the form of a can be added to a separate dispersion.

In a preferred embodiment of the invention, a compound represented by the following general formula <11) and a compound represented by the general formula (III) described below combined used.

x - (CONT) n - AF - E (11) X - NU (III) wherein X is the same component as described in the general formula (I), namely a component those responsible for the release of (CONT) n-AF-E or NU after the reaction with the oxidation product a developing agent is suitable; n means 0 or 1, and when n means 1, CONT represents a component that is capable of releasing AF-E after CONT-AF-E was released from X; AF means a basic framework for developing a developing inhibiting function; E means a component that is exposed to attack by a nucleophile Group created in NU after NU is released from X, can be released can, and NU means a group that can generate a nucleophilic group after the release of X, and which is suitable for the formation of AF-NU, which is a development inhibitor Function in the reaction with AF-E results.

The component represented by X in the general formula (II) and the component represented by X in the general formula (III) may be the same or be different.

It can be supported by the theory described below that the combination of the compounds according to this case, according to the invention, the sharpness in particular can improve in areas with high spatial frequencies.

It is now assumed that an image made up of many parallel fine lines (A) and an image composed of lines held in parallel (B) is being photographed. If there are DIR couplers, will which produces development inhibitors in areas where development takes place, and thus the development is halted. In the case of the above Image (A) diffuse the development inhibitors from the area in which the development occurs, thereby reducing the amount of development inhibitors present in the development area is decreased.

On the other hand, in the above-described case of the image (B) a relatively large amount of the development inhibitors around the center of the Development around it, not from the area in which the development takes place, diffuse out, due to the large development area, assuming that the released development inhibitors have the same diffusibility in the case of the picture (A). As a result, the concentration of development inhibitors is in the case of the picture (B), larger than that in the case of the picture (A). Such facts will be for example in T. H. James, The Theory of the Photographic Process, 4th Edition, Pp. 609-610, The Macrillan Company (1977).

Accordingly, the degree of development inhibition in the case of the image (B), d. H. in the case of wide lines, larger than in the case of picture (A), i.e. with narrow lines. This means that the density of wider developed lines is lower is than the narrower lines. This phenomenon occurs two-dimensionally, and thus Images with large areas have low densities compared to images with small ones Surfaces on.

As a result of this phenomenon, the MTFc (chemical modulation transfer function, the definition of which is given on page 612, right column, last line and following of the above-mentioned book) gradually increases as the spatial frequency increases, as in the above-mentioned book Page 612 and the following are described ben. When determining an MTF value from MTFc and MTFo, the MTF value increases once when the spatial frequency increases and then decreases when the spatial frequency continues to increase, since MTFo rapidly decreases due to the light scattering phenomenon. Here, if the above-described phenomenon is increased, the tendency of the MTFc curve to rise in the region of high spatial frequency becomes larger, and thus the decrease in the MTF value due to light scattering can be reduced. Accordingly, the object of improving sharpness in areas having a relatively high spatial frequency can be achieved.

According to the invention, the effects of the invention can be obtained by amplifying the phenomenon that the smaller the development area, the greater the density that can be achieved by diffusion of the development inhibitors is formed.

The compound by that represented by the general formula (II) Compound released upon reaction with the oxidation product of a developing agent will, d. H. the compound represented by AF-E when n is 0, or the compounds represented by AF-E that are created after the cleavage of CONT, when n is 1, has no or weak development-inhibiting function. In addition, the compound which is derived from that represented by the general formula (III) compound represented in the reaction with the oxidation product of the developing agent is released, also no or a weak development-inhibiting function.

The groups released by the compounds diffuse, and the Differences in concentration of the released groups are dependent on the image areas generated. Such differences in concentration can be caused by the same Reason will be explained how above based on the development inhibitors described by DIR couplers.

According to this case of the present invention, the development inhibitor becomes only by the two molecular reactions (second order reaction) of two released groups are formed, each of which is released by the compounds. This reaction can be illustrated by the reaction equation below.

AF - E + NU -> AF - NU + E In reaction kinetics it is known that the extent of the reaction generally depends on the concentrations of the reagents in the second order reaction. In other words, the higher the concentration is, the greater the extent of the reaction or the reaction speed. the recorded properties of the compound according to the invention can through this Theory explained. In particular, the larger the image areas, the The greater the concentration of AF-E and NU as described above. The bigger the concentrations are so as to reduce the extent of the reaction to the second order reaction and thus the development inhibitors represented by AF-NU in be formed with a large extent of reaction or at a high reaction rate. From this it is understood that the concentration distribution of AF-NU at a distance from Development point stronger than either that of AF-E or that of NU. From this it follows an increased image density in images with small areas compared with Cases where common DIR couplers are used.

This shows that the increasing tendency of the above-described MTFc curve at high spatial frequencies is larger than that obtained with conventional DIR couplers is achieved and that the MTFc curve according to the invention higher than the usual DIR coupler, resulting in a higher MTF value even if both have the same inhibitory ability. Accordingly, the sharpness be improved in areas with high spatial frequencies.

In the general formula (II), the group represented by E is a group involved in the nucleophilic shift reaction by a nucleophile Attack by the group represented by NU, that by the group represented by the general Formula (III) represented compound on reaction with the oxidation product of a Developing agent is released, can be released. Preferred examples for the group represented by E include a halogen atom, an alkanesulfonyloxy group, an arylsulfonyloxy group, an aryloxy group, an acyloxy group and an alkoxy group. The alkyl radicals included in these groups represented by E can be straight-chain, branched-chain, cyclic, saturated or unsaturated, substituted or unsubstituted alkyl groups and contain 1 to 12, preferably 1 to 6 carbon atoms.

In the general formula (III) is the group represented by NU preferably a group formed by X on reaction with the oxidation product of a Developing agent can be released, and which has no such property as represented by AF-E in the general formula (II) Connection has. In particular, it is favorable if NU does not have such a group which have a nucleophilic shift reaction due to nucleophilic attack by NU, released from another molecule.

A particularly preferred group represented by NU is a group containing a sulfur atom, a nitrogen atom or an oxygen atom that the group is attached to X Specific examples of the preferred Groups include an arylthio group, a heterocyclic thio group, an aryloxy group, an alkoxy group, an alkylthio group, a benzotriazolyl group, a triazolyl group, an imidazolyl group, a benzimidazolyl group, an imidazolidinyl group, a Pyrazolyl group and an acylaminooxy group. In these preferred examples forms the sulfur atom, the nitrogen atom, or the oxygen atom bonded to X. is, a nucleophilic group after it is released from X.

In the general formula (II), E can be connected to the part AF by a connecting Group L3 be bonded, which is selected from a divalent organic radical (L3 is included in AF represented by the general formula (II)). In one In such a case it is favorable if AP'-L3-E (wherein AF 'the remainder of the distance of L3 and AF represents) can cause a nucleophilic shift reaction by nucleophilic attack of NU, that of that represented by the general formula (III) Compound is released, releasing E. The one represented by L3 linking group (included in the part of AF in general formula (II) includes the groups shown below. Any two or more groups, shown below can be attached to each other at an appropriate substitution site of which are bound as a whole to form L3. L3 is also on E bound to a suitable substitution site thereof.

Preferred examples of groups that form L3 include an alkyl group, an acylamino group, an aryl group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an alkanesulfonyl group, an alkylthio group, an alkanesulfoxo group and a Alkyl substituted ureido group, etc.

The alkyl radicals included in these groups represented by L. can be any straight chain, branched chain or cyclic, saturated or be and contain unsaturated, substituted or unsubstituted alkyl groups 1 to 10, preferably 1 to 5 carbon atoms.

Preferred examples of -L3-E include a halogenated alkyl group (e.g., a chloromethyl group, a bromoethyl group, etc.), an alkane or arylsulfonyloxyalkyl group, for example C4H9S020CH2CH2-, etc.), an aryloxyalkyl group (for example, etc.), etc.

The group represented by CONT in the general formula (II) has the same meaning as defined in the general formula (I) and represents a controlling group. This means that they are used for the purpose of controlling the Coupling rate or the control of the diffusivity (of a functional surface) can be used by AF-E. CONT may vary depending on the type of AF-E and the type of X used may or may not be used. A suitable CONT that can be selected depending on the X and AF-E to be used.

A basic development inhibitor motherboard that is created by AF represented in the general formula (II) is preferably nitrogen containing unsaturated heterocyclic group (the one on X- (CONT) n on the nitrogen atom of which is bonded) or a monocyclic or heterocyclic group with condensed Ring (which is bonded to X- <CONT) n on the sulfur atom thereof) etc. This nitrogen containing unsaturated heterocyclic group and heterocyclic Thio groups can contain one or more substituents and are preferred bonded to E through a substituent thereof.

Preferred examples of the nitrogen-containing unsaturated heterocyclic group and the heterocyclic thio group represented by AF in the general formula (II) can be represented by the general formulas <D-1) to (D-IX) described below . In the general formula described below, the asterisk (+) means the position to which the radical X- (CONT) n is attached thereto, and L3 has the same meaning as defined above.

wherein a substituent represented by X2 (included in the part of AF is included in the general formula (II)), a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkanamido group, an alkenamido group, an alkoxy group, a sulfonamido group, an aryl group or an alkylthio group means; Z3 is -O-, -S- or -NH; f1 is an integer from 1 to 2; and g1 is an integer from 1 to 6.

Specific examples of the compounds made by the general Formula (II) or (III) are listed below without that the invention is limited to this.

Examples of the compounds represented by the general formula (II): Examples of the compounds represented by the general formula (III): The compounds represented by general formula (II) or (III) according to the invention can be prepared using known procedures.

In particular, most of the connections are made by the general Formula (III) can be represented, known compounds, and they can be according to a synthetic route, for example as described in U.S. Patents 4,351,897, 4,264,723, 4,366,237, 4,246,396, 3,227,554, and 4,241,168, and so on.

Compounds represented by the general formula (II) can can be obtained by employing a synthetic route in which each Part one by one as shown below.

If n 1 means: X -> X-CONT -> X-CONT-AF -R X-CONT-AF-E If n 0 means: X -> X-AF -> X-AF-E in the reaction scheme above X, CONT, AF and E each have the same meaning as in the general formula (II) defined above, with the exception of the inclusion of the conversion of a functional Group, which shows the progression of each level.

Typical examples of synthetic methods for the compounds according to the invention are listed below.

Synthesis Example 1 Synthesis of Compound (II-1) A mixture of 35 g of 2-chloro-2-pivaloyl-N-L-2-chloro-5- (2,4-di-tert-amylphenoxybutanamido) -phen 16 g 5- (or 6 -) - aminobenzotriazole, 13 g potassium tert-butoxide and 100 ml N, N-dimethylformamide was stirred at 50 ° C. for 4 h. The reaction mixture was subjected to an after-treatment in the usual way Manner and then using a mixed solvent of ethyl acetate and hexane crystallizes to give 29 g of 2- [5- (or 6 -) - aminobenzotriazolyl] -2-pivaloyl-N- [2-chloro-5- (2,4-di-tert-amylphenoxybutanamido) phenyl ] acetamide.

A mixture of 29 g of the compound thus obtained, 3.9 g of chloroacetic acid and 8.5 g of N, N'-dicyclohexylcarbodiimide was 3 in acetonitrile at room temperature h implemented.

The N, N'-dicyclohexylurea formed as a by-product was through The filtration was removed and the filtrate was post-treated in the usual manner and then using a mixed solvent of ethyl acetate and hexane was crystallized to give 19 g of the desired compound (II-1).

Synthesis Example 2 Synthesis of Compound (II-5) A mixture of 53.1 g of 4-L 5- <or 6 -) - aminobenzotriazolyl] -3-methyl-1- (4-tetradecanamidophenyl) -5-pyrazolone and 18.6 g of 2-bromobutanoyl chloride was reacted in acetonitrile. The reaction mixture was subjected to post-treatment in the usual manner and then from a mixed solvent crystallized from acetonitrile and ether to give 11.8 g of the desired Compound (II-5).

Synthesis Example 3 Synthesis of Compound (11-25) 25.6 g of 3-dibutylamino-1- (4-tetradecanamidophenyl) -5-pyrazolone and 11.2 g of 2-amino-5-mercaptothiadiazole was dissolved in 200 ml of N, N-dimethylformamide. To the resulting solution, 16 g of bromine was added dropwise at 5 ° C. To 30 minutes of reaction, the reaction mixture was poured into 1 l of water and treated with 1 1 ethyl acetate extracted. The oil layer was washed with water, and the solvent was distilled off. The residue was made from a mixed solvent of ethyl acetate and hexane crystallized to give 19.3 g of 4- (2-aminothiadizole-5-thio) -3-dibutylamino-1- (4-tetradecanamidophenyl) - 5-pyrazolone.

The total amount of the compound thus obtained and 3 g of chloroacetic acid were mixed with 100 ml of N, N-dimethylformamide. The resulting solution became a solution added dropwise at room temperature, the 6.5 g of N, N'-dicyclohexylcarbodiimide, dissolved in 20 ml of acetonitrile. After 1 h of reaction, the N, N'-dicyclohexylurea, formed as a by-product is removed by filtration. The filtrate was Poured into 1 l of water and extracted with 1 l of ethyl acetate. The oil layer was separated and washed with dilute hydrochloric acid and then with water. The oil layer was separated and the solvent was distilled off. The residue was from a mixed solvent of acetonitrile and ethanol to yield 12.2 g of the desired compound (II-25) crystallized.

Case # 2 A case where compounds that are responsible for the release of a releasable group by reaction with the oxidation product of a developing agent are suitable and the groups released together to form a development inhibitor implemented, which has a stronger function than the released groups, be used.

The compounds used in this case can be represented by the following general formula (IV): X - <CONT) n - AF1 E1 (IV) where X represents the same component as described in general formula (I), namely a component, the (CONT) n-AF1-E1 after reaction with the oxidation product can release a developing agent; n means 0 or 1, and when n means 1, CONT represents a component that is suitable for the release of AF1-E1 after CONT-AF1-E1 is released from X; AF1 means a framework for achieving a development-inhibiting function and a component that is responsible for producing a nucleophilic groups after release of X or CONT is suitable; and E1 represents represent a group formed by intermolecular nucleophilic shift reaction between two molecules of AF1-E through an attack by a nucleophilic group present in AF1-E1 is generated, can be released.

In this case, two AF1-E1 molecules go through the nucleophilic shift reaction, to form AF1-AF1-E, which give a development inhibiting function can.

By the theory described in Case No. 1 above, support that the combination of the compounds according to the invention the sharpness in particular can improve in areas with high spatial frequencies.

The compound represented by the represented by the general formula (IV) Reaction with the oxidation product of the developing agent is released, d. H. the compound represented by AF1-E1 when n is 0 or that represented by AF1-E1 created connection, which is created after splitting off CONT, if n means 1, has no or a weak development-inhibiting function.

The groups released by the compounds diffuse and the Differences in concentration of the released groups AF1-E1 are dependent generated by the image surfaces. Such concentration differences can result from the the same reason as described above for the development inhibitors of the DIR couplers, explained.

With the compounds according to this case of the present invention become development inhibitors (AF1-AF1-E1) in the two-molecular reaction (reaction second order) of the released groups (AF1-E1) are formed.

This reaction can be represented by the one described below Reaction equation.

F1 1 E1 -> AF1 -AF1 - E1 + E1 It is a matter of course in the reaction kinetics, that the reaction rate generally depends on the concentrations of Reagents in the second order reaction is changed. In other words: The higher the concentration, the greater the rate of reaction. The excellent Properties of the compounds according to the invention in this case can be achieved by these Theory explained. In particular, the larger the image areas are, the more so greater the concentration of AF1 - E1, as described above. The bigger the The concentration of AF1 - E1, the greater the reaction rate of the reaction becomes second order, and thus the development inhibitors represented by AF1 - AF1 - E1, formed with a high reaction rate or high reaction rate will. Therefore, the concentration distribution of AF1 - AF1 - E1 increases more than that of AF1 - E1 This makes the image density in images with small areas larger than when using conventional DIR couplers.

This shows that the increasing tendency of the above-described MTFc curve at high spatial frequencies is larger than that obtained with conventional DIR couplers is obtained and that the MTFc curve of this case is higher according to the invention than the usual DIR coupler, resulting in a higher MTF value even if both have the same inhibiting power. Accordingly, the sharpness in areas can be improved with high spatial frequencies.

Has the group represented by X in the general formula (1V) the same meaning as defined in the general formula <1).

In the general formula <1V) can be used as a group represented by E1 and which is released from AF1 - E1, each group are generally used, which is released in the nucleophilic shift reaction.

Preferred examples of the group represented by E1 include a halogen atom, an alkanesulfonyloxy group, an arylsulfonyloxy group, an aryloxy group, an acyloxy group and an alkoxy group. The alkyl radicals included in this by E1 Groups shown may be straight-chain, branched-chain or cyclic, saturated or unsaturated, substituted or unsub- established Be alkyl groups and contain 1 to 12, preferably 1 to 6 carbon atoms.

The group represented by CONT in the general formula (IV) has the same meaning as defined in the general formula (I) and represents a controlling group.

This means that it can be used to control the extent of the coupling or to Control of diffusivity (a functional surface) used by AF1 - E1 will. CONT can be used or depending on the type of AF1-E1 being used Not used. A suitable CONT that can be used may vary depending on the X and AF1 - E1 can be selected.

In the general formula (IV), AF1 means a skeleton for achieving it the development inhibiting function which has a part, the silver halide can adsorb, and the part exhibits nucleophilic properties when released on. Preferred examples of the basic mother skeleton of the development inhibitor include a nitrogen-containing unsaturated heterocyclic group (belonging to X- (CONT) n- is bonded to the nitrogen atom thereof) or a heterocyclic thio group with monocyclic or condensed ring (the one on X- (CONT) on the sulfur atom thereof is bonded), etc. This nitrogen-containing heterocyclic group and heterocyclic Thio group can have one or more substituents and is preferred bonded to E1 through one of the substituents thereof.

Preferred examples of the nitrogen-containing unsaturated heterocyclic group and the heterocyclic thio group represented by AF1 in the general formula (IV) can be represented by the general formulas (E-1) to (E-IX) as described below. In the general formulas below, the asterisk (+) denotes the position to which the radical X- <CONT) n is bonded, and 114 denotes a divalent organic radical which is bonded to E1 and which is included in the part AF1 in of the general formula (IV) is included.

wherein a substituent represented by X3 (included in the part AF1 included in the general formula (IV)), a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkanamido group, an alkenamido group, an alkoxy group, a sulfonamido group, an aryl group or an alkylthio group is; Z4 has the meaning of -0-, -S- or -NH-; f2 is an integer from 1 to 2 means; and g2 is an integer from 1 to 6.

In general formulas (E-I) to (E-IX) includes that represented by L4 linking group (those included in the part AF1 in the general formula (IV) is) the groups shown below. Any two or more of the following Groups shown may join one another at an appropriate substitution point thereof be bound as a whole to form 114. L4 is also at E1 bound to a suitable substitution site thereof.

Preferred examples of groups that form L4 include an alkyl group, an alkanamido group, an aryl group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an alkanesulfonyl group, an alkylthio group, an alkanesulfinyl group and a Alkyl substituted ureido group, etc.

The alkyl radicals included in these groups represented by X3 or L4 can be straight-chain, branched-chain or cyclic, saturated or unsaturated, substituted or unsubstituted alkyl groups and contain 1 to 10, preferably 1 to 5 carbon atoms.

The most preferred group -L4-E1 in this case of the present invention is a group in which E1 represents a halogen atom and L4 has such a structure that there are 1 to 3 carbon atoms between the halogen atom represented by E1 and a carbonyl group or a sulfonyl group. Specific examples of this Specific examples of the compounds represented by the general formula (IV) are shown below, without the invention being limited thereto.

Those represented by the general formula (IV) according to the invention Connections can be made according to known resp.

usual methods are produced. In particular, they can get are made by a synthetic route in which each part is attached to one another as shown below is bound.

Case n 1 means: X + X-CONT + X-CONT-AF1 + X-C0NT-AF1-E1 If n 0 means: X + X-AF1 + X-AF1-E1 In the reaction scheme above, X, CONT, AF1 and E1 each have the same meaning as in the general formula (IV) above defined, with the exception of the inclusion of the conversion of a functional group, which indicates the progression of each stage.

Typical examples of the synthetic methods of the invention Connections are listed below.

Synthesis Example 4 Synthesis of Compound (IV-1) A mixture of 35 g of 2-chloro-2-pivaloyl-N- 2-chloro-5- (2,4-di-tert-amylphenoxybutanamido) phenyl] acetamide, 16 g of 5- (or 6 -) - aminobenzotriazole, 13 g of potassium tert-butoxide and 100 ml of N, N-dimethylformamide was stirred at 50 ° C. for 4 h. The reaction mixture was an aftertreatment in conventionally subjected and then using a mixed solvent crystallized from ethyl acetate and hexane to give 29 g of 2- 5- (or 6 -) - aminobenzotriazolyl) -2-pivaloyl-N- [2-chloro-5- (2,4-di-tert-amylphenoxybutanamido) phenyl ] acetamide.

A mixture of 29 g of the compound thus obtained, 3.9 g of chloroacetic acid and 8.5 g of N, N'-dicyclohexylcarbodiimide was 3 in acetonitrile at room temperature h implemented.

The N, N'-dicyclohexylurea formed as a by-product was through The filtration was removed and the filtrate was post-treated in the usual manner and then crystallized using a mixed solvent of ethyl acetate and hexane to give 19 g of the desired compound (IV-1).

Synthesis Example 5 Synthesis of Compound (IV-5) A mixture of 53.1 g of 4- [5- (or 6 -) - aminobenzotriazolyl-7-3-methyl-1- (4-tetradecanamidophenyl) -5-pyrazolone and 18.6 g of 2-bromobutanoyl chloride was reacted in acetonitrile. The reaction mixture was subjected to an after-treatment in the usual way and then off one Mixed solvent of acetonitrile and ether crystallizes to give 11.8 g of the desired compound (IV-5).

Synthesis Example 6 Synthesis of Compound (IV-25) 25.6 g of 3-dibutylamino-1- <4-tetradecanamidophenyl) -5-pyrazolone and 11.2 g of 2-amino-5-mercaptothiadiazole was dissolved in 200 ml of N, N-dimethylformamide. To the resulting solution were 16 g of bromine were added dropwise at 5 ° C. After reacting for 30 minutes, the reaction mixture became Poured into 1 l of water and extracted with 1 l of ethyl acetate. The oil layer was with Washed with water, and the solvent was distilled off. The residue was crystallized from a mixed solvent of ethyl acetate and hexane to give of 19.3 g 4- (2-aminothiadiazol-5-thio) -3-dibutylamino-1 - <4-tetradecanamidophenyl) -5-pyrazolone.

The total amount of the compound thus obtained and 3 g of chloroacetic acid were mixed with 100 ml of N, N-dimethylformamide. The resulting solution became a solution added dropwise at room temperature, the 6.5 g of N, N'-dicyclohexylcarbodiimide, dissolved in 20 ml of acetonitrile. After one hour of reaction, it became a by-product N, N '-dicyclohexylurea formed removed by filtration. The filtrate was Poured into 1 l of water and extracted with 1 l of ethyl acetate. The oil layer was separated and washed with dilute hydrochloric acid and then with water. The oil layer was separated and the solvent was distilled off. Of the The residue was crystallized from a mixed solvent of acetonitrile and ethanol to give 12.2 g of the desired compound (IV-25).

Case # 3 A case where at least one type of connection (a) as described below, and at least one type of compound (b), as described below is used.

(a) a compound useful in forming a development inhibitor upon reaction with the oxidation product of a developing agent.

(b) a compound capable of forming a compound upon reaction with the oxidation product of a developing agent, this compound being essentially the development inhibiting function of the development inhibitor upon reaction with this, can deactivate.

The two types of connection described above can be either incorporated in the same layer or in different layers and they can be incorporated into any emulsion layer and interlayer will. The two types of connection described above are preferably used in included the same emulsion layer.

According to a preferred embodiment of this case of the invention will provide a compound represented by the general formula (V) as follows and a general formula (VI) described below The connection shown is used in combination. The by the general formula (V) compounds shown fall into the category of compound (a) as above and the compounds represented by the general formula (VI) fall under the category of connection (b).

X - (CONT) - AF2 (V) X L5 E2 (VI) wherein X is the same component as described in the general formula (I), means, namely a component, suitable for the release of (CONT) 'AF2 or L5-E2 after reaction with the oxidation product a developing agent; n represents 0 or 1, and when n represents 1, represents CONT a component suitable for releasing AF2 after CONT-AF2 was released from X; AF2 means a development inhibitor and L5-E2 means a component that leads to an intermolecular, nucleophilic shift reaction with AF2 is suitable.

The component represented by X in the general formula (V) and the component represented by X in the general formula (VI) may be the same or be different.

If AF2 is released from CONT or X, an anion in AF2 and attacks L5-E2, releasing E2 from L5 to form L5-AF2 will. The 11 5-AF2 thus formed shows essentially no development-inhibiting effects Function.

It is believed that the improvement in sharpness, in particular in areas with high spatial frequencies according to this inventive case on the is based on the reason described below.

In general, when DIR couplers are present, they become inhibitors formed in exposed portions at the time of development, causing development is prevented. The development inhibitor can diffuse and form a concentration distribution of the development inhibitors, whereby, the higher the concentration of the development inhibitor, the closer it is it moves towards the center of the image, and when it is further away it becomes smaller. By this principle causes the edge effect and the sharpness can be improved (such as in T.H. James, The Theory of the Photographic Process, 4th Edition, Pp. 609-610, The Macmillan Company (1977)).

Assuming that couplers which are suitable are compounds (L5-E2 in the general formula (VI)) to release the with the released by the DIR couplers Development inhibitors react by deactivating the function of the development inhibitor, in addition to the DIR couplers are present, is the concentration distribution the development inhibitor different from that described above. before the explanation of such a change in the concentration distribution becomes one Reaction described in which the development inhibitors their inhibitory function lose. The reaction can be illustrated by the following reaction equation: AF2 + 115-E2 p 115-AF2 + E2 where AF2 and L5-E2 each have the same meaning as in the above general formulas (V) and (IV).

The development inhibitor represented by AF2 has an adsorbent Group for silver halide and a central atom of the group is a sulfur atom or a nitrogen atom. Such atoms can broadly be considered effective nucleophiles Central atoms act when they act as nucleophilic central atoms of the two-molecule nucleophilic shift reaction can be used.

In particular, the two-molecular nucleophilic shift reaction between AF2 and L5-E2 through the nucleophilic shift reaction carried out through a central atom which adsorbs silver halide included in AF2. There the L5-AF2 thus formed has no effect on silver halide. The fact, that such a reaction occurs at the time of development can make excellent properties according to the invention are expected to be explained.

Namely, it is believed that the reason why the present invention gives an excellent improvement in sharpness in areas with high spatial frequency, is in the concentration distribution of AF2 in the effective form. this will explained in more detail below.

As described above, AF2 and L5-E2 go the two-molecular, a nucleophilic shift reaction. This two-molecular reaction occurs more frequently in areas that are close to the silver halide particles that are developed (development center), where the concentrations of AF2 and L5-E2 are large. This changes the concentration distribution of 115-AF2, which has no development inhibiting function, is increased more than the concentration distribution of AF2 and L5-E2, and thus the concentration rate of 115-AF2 at the center / around larger than that of AF2.

This increases the concentration distribution of the development inhibitors in this case according to the invention at the development center relatively low and in the Environment around it is relatively high compared to the case where the connection, represented by the formula (V) is used alone.

The concentration distribution described above can improve the sharpness greatly improve in areas with high spatial frequencies compared to cases where common DIR couplers can be used; the reasons for this are explained below.

When common DIR couplers are used, more are development inhibitors at the development center, and therefore areas with high spatial frequencies, namely, fine lines, a considerable amount of the development inhibiting Subject to function. In contrast, in cases where the compound, which is represented by the general formula (V) and that by the general Formula (VI) shown compound can be used combined as the concentration the development inhibitors at the development centers decreases, in particular on surfaces with a high spatial frequency, namely fine lines, the active development inhibitor diffuse out of the lines and deactivated development inhibitors stay in the centers of the lines, thereby reducing the development inhibiting Function is caused. This increases the concentration of development inhibitors particularly low in fine lines, while the concentration of development inhibitors becomes relatively high. This corresponds to the fact that image densities on areas with high spatial frequencies where the development inhibiting function is small, stronger than in areas with low spatial frequencies, where the development-inhibiting Function strong, and therefore the image densities of areas with high spatial frequencies, where the densities can be assumed to be due to light scattering on silver halide particles are decreased, thereby improving the sharpness.

Since the above-described concentration distribution in which the The concentration of development inhibitors at the development center is low, while it is large in the environment, especially in cases where diffusibility occurs the compound suitable for deactivating the development-inhibiting function, that is formed from the compound (b) is less than that from the compound (a) resulting development inhibitor, such cases are special preferred. - -In the general formula (VI) can be used as a group represented by E2 and that is released by L5, any group known by nucleophiles can be used Shift reaction released can be used generally. Preferred Examples of the group represented by E2 include a halogen atom, an alkanesulfonyloxy group, an arylsulfonyloxy group, an aryloxy group, an acyloxy group and an alkoxy group. The alkyl radicals contained in these groups represented by E2 can be straight-chain, branched or cyclic, saturated or unsaturated, substituted or be unsubstituted alkyl groups and contain 1 to 12, preferably 1 to 6 carbon atoms.

In the general formula (VI), as a group represented by Lg any group can generally be used which is derived from X when reacted with the Oxidation product of a developing agent can be released. Preferred Examples of 115 include a group having a sulfur atom, a nitrogen atom or contains an oxygen atom through which the group is bonded to X, and in particular an arylthio group, a dioxoimidazolidinyl group, a heterocyclic thio group, an aryloxy group, an alkoxy group, an alkylthio group, a benzotriazolyl group, a dioxotriazolidinyl group, a triazolyl group, an imidazolyl group, a Benzimidazolyl group, an imidazolidinyl group, a pyrazolyl group or a Acylaminooxy group.

These releasable groups may contain one or more substituents and are preferably bonded to E2 through one of the substituents thereof. Preferred examples of the groups represented by L5 in the general formula (VI) can be represented by the following general formulas (FI) to (F-III). In the general formulas below, the asterisk ()) represents a position to which X is bonded thereto, and (D) g2 and W each represent a group included in the portion of L5 in the general formula (VI), and W means a divalent group attached to E2.

* - 2 - R - W - E2 (F-III) wherein a substituent represented by D a hydrogen atom, a halogen atom, an alkyl group, an acylamino group, a Alkoxy group, a sulfonamido group, an aryl group, an alkylthio group, a Cyano group, a nitro group, an alkoxycarbonyl group, a hydroxy group, a Carboxy group, a carbamoyl group linked to an alkyl group or an aryl group may be substituted, a sulfamoyl group with an alkyl group or a Aryl group may be substituted, an amino group with a Alkyl group or an aryl group, an arylthio group, a Ureido group substituted with an alkyl group or an aryl group may, an alkylsulfonyl group or an arylsulfonyl group, etc .; g2 means one integer from 1 to 3; W is a divalent group; T represents an organic The remainder to form a 5-membered or 6-membered nitrogen containing heterocyclic ring is required together with the nitrogen atom; Q means an oxygen atom or a sulfur atom; and R represents a substituted or unsubstituted alkylene group.

Examples of the substituents for the alkyl group represented by R include those as described for D.

Preferable examples of the divalent groups represented by W include the groups shown below. Any two or more of the following groups shown can be attached to one another at a suitable substitution point thereof be bound to form W as a whole. W is also at E2 at one suitable substitution site thereof bound.

Preferred examples of groups that form W include an alkyl group, an acylamino group, an aryl group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an alkanesulfonyl group, an alkylthio group, an alkanesulfoxo group and a Alkyl substituted ureido group, etc.

It is preferred if the total number of carbon atoms that included in L5-E2 range from 6 to 20.

Has the group represented by CONT in the general formula (V) has the same meaning as defined in general formula I and represents a controlling group. This means that they are for the purpose of control or regulation the coupling rate or the regulation of diffusibility (a functional surface) can be used by AF2. CONT can, depending on the type used or not used by AF2. A corresponding CONT to use can be selected depending on the X and AF2 used.

A basic backbone for the development inhibitor, the in the general formula (V) represented by AF2 is preferably one Nitrogen-containing unsaturated heterocyclic group (those at X- <CONT) n is bonded to the nitrogen atom thereof) or a heterocyclic thio group with monocyclic or fused ring (those on X- <CONT) n on the sulfur atom of which is bonded) etc. These nitrogen-containing unsaturated heterocyclic The group and heterocyclic thio group can contain one or more substituents.

Preferred examples of the nitrogen-containing unsaturated heterocyclic group and the heterocyclic thio group represented by AF2 in the general formula (V) can be represented by the general formulas <Gi) to (G-IX) described below. In the general formulas below, the asterisk (#) indicates a position to which the remainder of X- (CONT) is attached.

wherein a substituent represented by X4 is a hydrogen atom, a halogen atom, an alkyl group, an alkanamido group, an alkoxy group, a Sulfonamido group, an aryl group, an alkylthio group, an amino group, a N- (mono- or dialkyl) -amino group, an alkoxycarbonyl group, an acyloxy group, a carbamoyl group, an N- (mono- or dialkyl) -carbamoyl group, a nitro group, a cyano group, an alkanesulfonyl group, an aryloxy group, an ureido group, a sulfamoyl group, a hydroxy group, an anilino group, a heterocyclic group Group, a sulfonamido group or a carboxy group, etc .; one represented by X5 A substituent, a hydrogen atom, an alkyl group, a phenyl group or a heterocyclic group Group is; Z5 denotes -O-, -S- or -N-, in which x5 X5 has the same meaning as has defined above; f is an integer from 1 to 2, when f is 2, the groups X4 can be identical or different.

Those included in the substituents represented by X4 and X5 Alkyl radicals can be straight-chain, branched-chain or cyclic, saturated or be and contain unsaturated, substituted or unsubstituted alkyl groups 1 to 10, preferably 2 to 8 carbon atoms.

Specific examples of the compounds represented by the general formula (V) or (VI) are shown below without implying any limitation.

Those represented by the general formula (V) or (VI) according to the invention compounds shown can using known or customary methods getting produced. In particular, most of the connections are made by the general Formula (V) can be represented, known compounds and can be prepared are by a synthetic route, for example as described in GB-PS 2 099 167, 2,096,783 and 2,072,363, U.S. Patents 3,227,554, 3,639,417 and 4,063,950, etc.

Compounds represented by the general formula (VI), can basically be made by employing a synthetic route in which each part is connected in turn as shown below.

X 9 X - 115 -> - L5 E, have in the reaction scheme above X, 115 and E2 each have the same meaning as defined for the general formula (VI), with the exception that the conversion of a functional group is involved, which indicates the progression of each stage.

In the first stage, a method can be used in which X is halogenated and the halogenated compound with 115 in the presence of a base is reacted, or a method in which X has a hydroxyl group and on its active site is reacted with a halogenated compound of L5, etc.

Typical examples of Synthesemethofen for the invention Connections are listed below.

Synthesis Example 7 Synthesis of Compound (V-1) A mixture of 100 g of 2-bromo-2-pivaloyl-N-2-chloro-5- (2,4-di-tert-amylphenoxybutanamido) -phen 83.9 g 5- 5- (or 6 -) - phenoxycarbonylbenzotriazole, 49 ml triethylamine and 500 ml N, N-dimethylformamide was stirred at room temperature for 2 h. The reaction mixture was given an aftertreatment subjected in the usual manner to give 93 g of the desired compound (V-1).

Synthesis Example 8 Synthesis of Compound (VI-1) A mixture of 50 g of 2-chloro-2-pivaloyl-N- 2-chloro-5- (2,4-di-tert-amylphenoxybutanamido) phenyl] acetamide, 13.9 g of 3-amino-1,2,4-triazole, 18.5 g of potassium tert-butoxide and dimethylformamide were used stirred at room temperature for 2 h. The reaction mixture was given an aftertreatment subjected in the usual manner to give 33 g of compound.

A mixture of 12 g of the compound thus obtained, 1.8 g of chloroacetic acid, 3.8 g of dicyclohexylcarbodiimide and 100 ml of acetonitrile were reacted for 2 hours. The as Urea formed by-product was removed by filtration and the filtrate was subjected to post-treatment in the usual manner to give 8.5 g of the desired compound (IV-1).

Case # 4 A case where (1) a compound that is about to be released a development accelerator upon reaction with the oxidation product of a developing agent is suitable, and (2) a compound to release a link by reaction with the oxidation product of a developing agent, the compound being which disable the development accelerating function of the development accelerator and which has a diffusibility greater than that of the development accelerator is to be used with each other.

The two types of connection described above can be either be incorporated into the same layer or into different layers, and they can be incorporated into any emulsion layer and intermediate layer. Preferably, the two types of connection described above become the same Emulsion layer incorporated. In addition, the above-described two kinds of compounds are dispersed as a mixture, and the resulting dispersion can be added or they can be dispersed separately, and the resulting Dispersions can be added in the form of separate dispersions.

According to a preferred embodiment of this case of the invention become a compound represented by the general formula (VII) below and a compound represented by the general formula (VIII) below used in combination.

x - <CONT) n - A (VII) 6 3 (VIII) wherein X is the same component as defined in the general formula (I), namely a component those for the release of (C0NT) nA or L6-E3 after reaction with the oxidation product a developing agent is suitable; L6 represents a group suitable for this is to make L6-E3 more diffusible than (CONT) n-A and which is suitable to L6-A to form which has essentially no photographic function, by intermolecular nucleophilic shift reaction with A by a nucleophile Attack of an anion generated in the released A; E3 represents a group which can be released from 116 by nucleophilic attack by A; A a Represents a group that forms part of a fogging agent or a development accelerating agent Agent contains in the molecule and is capable of an anion in the molecule thereof after release of X or CONT to form and nucleophilic attack by L6-E3; n Is 0 or 1, and when n is 1, CONT represents a component responsible for release of A after the release of CONT-A from X is suitable.

The component represented by X in the general formula (VII) and the component represented by X in the general formula (VIII) be the same or different. The component represented by CONT has the same Meaning as defined in the general formula (I).

In this case according to the invention, the measurement of the diffusibility in a gelatin layer or an emulsion layer with reference to the method, as in H. Iwano The Penetration Rate of Photographic Chemicals into Gelatin Layers and into Emulsion Layers under Development ", J. Phot. Sci. Vol 20, pages 135 bis 142 (1972). Practical measurements of diffusivity have been made carried out under conditions of color development, namely at pH 9 to 13, at a temperature of 20 to 50 ° C and in a swollen emulsion layer, which consists mainly of gelatin, in a solvent system which mainly consists of water.

The reason to improve the sharpness, especially in areas with high spatial frequency, by combining this case, the invention can be as follows be accepted.

The following is the image of a wide surface, like a curved one Line, and the image of a narrow area, considered as a fine line. When diffusible compounds are released from couplers, the diffusible ones begin Compounds to diffuse, and the concentration of diffusible compounds is smaller in a narrow area image than in a wide area image. This is because the diffusible compounds in the image have a wide area can remain, whereas a certain amount of the diffusible compounds run out of the image with a narrow area. The phenomenon occurs considerably with joints with high diffusibility.

Since the diffusibility of the compound to deactivate the development acceleration, that released from the compound represented by the general formula (VIII) is greater than that of the development accelerator, that of the general Formula (VII) represented compound is released, what for the present If the invention applies, the ratio of the compound to the deactivation is Development accelerator / development accelerator in the case of an image with a narrow Area less. So for a picture with a narrow area, the contribution is the connection to deactivate the development acceleration low, and the amount of active Development accelerator is large-As a result, the image progresses with narrower Area (areas with high spatial frequency) developing rapidly forward, and you achieves a high density. This means that a chemical modulation transfer function (MTFc) as described in T. H. James, The Theory of the Photographic Process, 4th Edition, page 612, The MacMillan Company (1977) larger in areas with tall Is spatial frequencies.

The display of a high MTFc value in areas with high spatial frequencies takes place through a decrease the degree of reduction of the MTF value in areas with high spatial frequencies due to light scattering. It will therefore assumed the MTF value in areas with high spatial frequencies in the inventive photographic light-sensitive material becomes higher in comparison with known ones photographic photosensitive materials.

In the general formula (VIII) can be used as a group represented by E3 and which is released from L6, any group can be used generally, which is suitable for release by nucleophilic shift reaction. Preferred Examples of the group represented by R3 include a halogen atom, an alkanesulfonyloxy group, an arylsulfonyloxy group, an aryloxy group, an acyloxy group, an alkoxy group. The alkyl radicals included in these groups represented by E3 can be straight-chain, branched or cyclic, saturated or unsaturated, substituted or be unsubstituted alkyl groups and contain 1 to 16, preferably 1 to 10 Carbon atoms.

In the general formula (VIII), can be used as a group represented by L6 any group generally used is that of X by reaction with the oxidation product a developing agent can be released.

Preferred examples of 11 include a group containing 6 a sulfur atom, contains a nitrogen atom or an oxygen atom through which the group is attached to X. is, and especially an arylthio group, a heterocyclic thio group, a Aryloxy group, an alkoxy group, an alkylthio group, a 2,4-dioxaimidazolidinyl group, a benzotriazolyl group, a triazolyl group, an imidazolyl group, an acyloxy group, a benzimidazolyl group, a 3,5-dioxotraizolidinyl group or an acylaminooxy group.

These releasable groups can have one or more substituents and are preferably bonded to E2 through one of the substituents thereof.

Preferred examples of the group represented by L6 in the general formula (VIII) can be represented by the following general formulas (HI) to (HV). In the general formula below, the asterisk (+) means a position to which X is bonded, and (X6) f4 and W1 each represent a group included in the part of L6 in the general formula (VIII) and W1 means a divalent group attached to E3.

wherein a substituent represented by X6 is a hydrogen atom, an alkyl group, an acylamino group, an alkoxy group, a sulfonamido group, an aryl group, an alkylthio group, a cyano group, a nitro group, a Alkoxycarbonyl group, a hydroxy group, a carboxy group, a carbamoyl group, which may be substituted with an alkyl group or an aryl group, a sulfamoyl group, which may be substituted with an alkyl group or an aryl group, an amino group, which may be substituted with an alkyl group or an aryl group, an arylthio group, an ureido group substituted with an alkyl group or an aryl group may be an alkylsulfonyl group or an arylsulfonyl group; f means an integer from 1 to 3; W1 represents a divalent group; Z3 means one organic residue that leads to the formation of a 5-membered or 6-membered nitrogen containing, heterocyclic ring is required together with the nitrogen atom; and X7 represents an alkylene group which is straight chain or branched chain cyclic, saturated or unsaturated, substituted or unsubstituted alkylene group can be.

Preferred examples of the divalent groups represented by W1 include the groups shown below. Any two or more of the Groups shown below can be joined to one another at a suitable site of substitution be bound, forming W1 as a whole. W1 is next to E3 to a suitable one Bound substitution site thereof.

Preferred examples of groups that form W1 include an alkyl group, an acylamino group, an aryl group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an alkanesulfonyl group, an alkyltrio group, an alkanesulfoxo group and a Alkyl substituted ureido group, etc.

The group represented by CONT in the general formula (VII) has the same meaning as defined in the general formula (I) and represents a controlling group. You can control a coupling rate or to Control of diffusivity (a functional surface) of A can be used. CONT may or may not be used depending on the type of A used be used. An appropriate CONT for use may vary depending on the X and A to be used are selected.

In the general formula (VII), the group represented by A contains a sulfur atom, a nitrogen atom or an oxygen atom through which the group is bound to X or CONT.

The group represented by A is released from X or CONT and undergoes a nucleophilic shift reaction with L, 3 on that described above Sulfur atom, nitrogen atom or oxygen atom, which is included (> qen, a, thereby forming A-L6.

More preferred groups represented by A include those represented by Thiourea, hydrazines, 3-pyrazolidones, rhodanines and thioamides, etc. derived are.

Particularly preferred examples of groups represented by A can by the general formula <J-I) or <J-II) as described below be elitist.

In the general formulas below, the asterisk (s) indicates a position in which the remainder X or CONT is attached.

wherein G is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group (e.g. a phenylene group etc.), a divalent substituted or unsubstituted heterocyclic group (for example a tetrazole ring, a thiadiazole ring, a thiadiazine ring, a thiazolriny, an oxadiazolriny, etc.), a divalent group, the one Ester bond, a thioether bond, an amido bond, a sulfonamido bond, contains a sulfone bond, an ether bond, etc. in an alkylene group, or represents a divalent group composed of two or more thereof; U1 and U2 each represent a hydrogen atom or a lower alkyl group and at least one of U1 and U2 represents a hydrogen atom; M means a formyl group, an acyl group, an alkylsulfonyl group, an aryl group, an arylsulfonyl group, an alkyl group, an alkyl group, a carbanioyl group or a sulfamoyl group; Z6 denotes an organic radical which leads to the formation of a 5-membered or 6-membered Nitrogen-containing heterocyclic ring together with the nitrogen atom is needed; and t means 0 or 1.

Specific examples of those represented by the general formula (VII) or (VIII) shown compounds are listed below, but without one To illustrate limitation of the invention.

Examples of the compounds represented by the general formula (VII): Examples of the compounds represented by the general formula (VIII): The compounds represented by the general formula (VII) or (VIII) according to the invention can be prepared by known or customary methods.

In particular, most of the by the general formula (VII) compounds shown are known compounds and can after a synthetic route, for example as described in GB-PS 2,097,140 and so on.

Compounds represented by the general formula (VIII) can, can be fundamentally obtained using a synthetic route, where each part is tied in turn as shown below.

X i X - L6 yX - 3 L3 In the above reaction scheme, each has of X, L6 and E3 have the same meaning as defined in general formula (VIII), however, the conversion of a functional group is involved, whereby the Progress of each stage is shown.

In the first stage, a method can be used in which X becomes halogenated, and the halogenated compound becomes with H-L6 in the presence reacted with a base, or a method in which X has a hydroxyl group on its active site, is reacted with a halogenated compound of L6, etc.

Typical examples of methods for the synthesis of the invention Connections are listed below.

Synthesis Example 9 Synthesis of Compound (VII-1) A mixture of 100 g of 2-bromo-2-pivaloyl-N- 2-chloro-5- (2,4-di-tert-amylphenoxybutanamido) -phenyl - / - acetamide, 55 g of 5-mercapto-1- 3- (4-formylhydrazinylphenylcarbamoyl) phenyl - / - tetrazole, 49 ml Triethylamine and 500 ml of N, N-dimethylformamide were passed at 20 ° C. for 2 h. The reaction mixture was subjected to post-treatment in the usual manner to give 93 g of the desired compound (VII-1).

Synthesis Example 10 Synthesis of Compound (VIII-1) A mixture of 50 g of 2-chloro-2-pivaloyl-N- / 2-chloro-5- (2,4-di-tert-amylphenoxybutanamido) -phenyl - / - acetamide, 13.9 g of 3-amino-1,2,4-triazole, 18.5 g of potassium tert-butoxide and ml of N, N-dimethylformamide was stirred at room temperature for 2 h. The reaction mixture was given an aftertreatment subjected in the usual manner to give 33 g of compound.

A mixture of 12 g of the compound thus obtained, 1.8 g of chloroacetic acid, 3.8 g of dicyclohexylcarbodiimide and 100 ml of acetonitrile were reacted for 2 hours. The received Urea by-product was removed by filtration and the filtrate became one Subjected after-treatment in the usual way, obtaining 8.5 g of the desired Compound (VIII-1).

The compounds according to the invention are preferably used in a light-sensitive Layer incorporated.

In the case of compound II and compound III, the compound V and the compound VI, or the compound VII and the compound VIII, becomes a Molar ratio of the two kinds of compounds in a range of 1/100 to 100/1 and preferably used from 1/20 to 10/1. The amount of compound IV, the compounds II and III, the compounds V and VI or the compounds VII and VIII, which are added is in the range of from 0.001 to 0.5 moles per mole of silver, and preferably from 0.001 to 0.01 moles per mole of silver.

It is a feature of the present invention that the intermolecular A reaction which may change the photographic function, in a hydrophilic colloid layer including a photosensitive layer of a photographic light-sensitive material.

The compounds according to the invention and couplers which are used according to the invention as described below can be used in photographic photosensitive Materials using various conventional or known dispersing methods be incorporated. Typical examples include a solid dispersing method, an alkali dispersion method, preferably a latex dispersion method, and more preferred an oil droplet-in-water type dispersing method. With the dispersion method of the oil-droplet-in-water type are compounds in either an organic Solvent with a high boiling point of 175 ° C or more, an auxiliary solvent having a low boiling point or a mixture thereof, and then becomes the solution finely in an aqueous medium such as water or an aqueous gelatin solution etc., in the presence of a surfactant, dispersed Specific Examples for the organic solvents with a high boiling point are given in U.S. Pat 2 322 027 etc.

A phase inversion can be associated with the preparation of the dispersion. In addition, dispersions are used for coating after removal or reduction the auxiliary solvent therein by distillation, pasta washing or ultrafiltration etc. used where appropriate.

Specific examples of the organic solvent with a high Boiling points include phthalic acid esters (e.g. dibutyl phthalate, dicyclohexyl phthalate, Di-2-ethylhexyl phthalate, didodecyl phthalate, etc.), phosphoric acid or phosphoric acid ester (for example triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, Tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, tributoxyethyl phosphate, Trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate, etc.), benzoic acid esters (e.g. 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl p-hydroxybenzoate, etc.), amides (e.g. diethyldodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or Phenols (e.g. isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic Carboxylic acid esters (for example dioctyl azelate, glycerol tributyrate, isostearyl lactate, Trioctyl citrate, etc.), aniline derivatives (e.g. N, N-dibutyl-2-butoxy-5-tert-octylaniline etc.), hydrocarbons (e.g. paraffin, dodecylbenzene, diisopropylnaphthalene etc.), etc. As auxiliary solvents, organic solvents having the boiling point from about 30 to about 160 ° C, etc. can be used. Typical examples of such Co-solvents include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, Cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, etc.

The procedures and effects of latex dispersion methods and specific Examples of latices for loading are given in US Pat. No. 4,199,363, DE-OSen 2 541 274 and 2,541 230, etc.

Various color couplers can be used in the present invention. The term color coupler as used herein means compounds that form of dyes by reaction with oxidation products of aromatic primary Amine developing agents are suitable. Typical examples of useful color couplers include compounds of the naphthol or phenol type, compounds of the pyrazolone or pyrazoloazole type and open-chain or heterocyclic compounds of the ketomethylene type. Specific examples of useful cyan, magenta and yellow couplers are given described in the patents contained in Research Disclosure, Item 17643, Vii-D (December 1978) and ibid., No. 18717 (November 1979).

It is preferred that these couplers be diffusion resistant thereby that they contain a ballast group or by polymerization. It is also preferred when the coupling position of this coupler instead of a hydrogen atom with a Group is substituted that can be released. In addition, couplers, which form colored dyes with diffusibility, colored couplers, non-color forming couplers or couplers which are development inhibitors or development accelerators together with the coupling reaction can be used.

Typical yellow couplers which can be used according to the invention are, for example acylacetamide type oil-protected couplers.

Specific examples thereof are described in U.S. Patent No. 2,407 210, 2,875,057 and 3,265,506, etc. In the present invention, preferred are 2-equivalent yellow couplers are used, and typical examples thereof include yellow couplers of the oxygen atom releasing type as described in U.S. Patents 3,408,194, 3,447,928, 3,933,501 and 4,401,752, etc. and yellow couplers from nitrogen atom-releasing Type as described in Japanese Patent Publication No. 10739/83, U.S. Patent No. 4,022 620 and 4,326,024, in Research Disclosure No. 18053 (April 1979), GB-PS 1 425 020, DE-OSes 2 219 917, 2 261 361, 2 329 587 and 2 433 812 etc. Α-Pivaloylacetanilide type couplers are known for the durability of the dyes formed and α-benzoylacetanilide type couplers are characterized by their good color-forming properties Characterized properties.

Examples of magenta couplers used in the present invention are oil-protected indazolone type couplers, cyanoacetyl type couplers and preferably 5-pyrazolone type couplers and pyrazoloazole type couplers such as pyrazolotriazoles. Among the 5-pyrazolone type couplers are those having an arylamino group or an acylamino group in their 3-position are substituted, due to the tone of the dyes formed and the extent or speed of color formation preferred. Typical examples of this are described in U.S. Patents 2,311,082, 2 343 703, 2 600 788, 2 908 573, 3 062 653, 3 152 896 and 3 936 015 etc. Couplers 2-equivalent 5-pyrazolone type are preferably used, and nitrogen atom-releasing ones Groups as described in US Pat. No. 4,310,619 and arylthio groups as described in US Pat U.S. Patent 4,351,897 are preferred as releasing groups. Furthermore are 5-pyrazolone type couplers with a ballast group, as in EP-PS 73,636 are advantageous because of their high color-forming reactivities.

Examples of pyrazoloazole type couplers include pyrazolobenzimidazoles, as described in US Pat. No. 3,369,897, and preferably PyrazoloL 1,2,4 7triazole, as described in U.S. Patent 3,725,067, pyrazolotetrazoles as described in Research Disclosure No. 24220 (June 1984) and pyrazolopyrazoles as described in Research Disclosure, No. 24230 (June 1984). Imidazopyrazoles as described in the JP patent application No. 23434/83 and pyrazole 1,5-b 7z 1,2,4 ~ / triazole as described in JP-PS 45512/83, are due to the lower yellow secondary absorption and light resistance the educated Dyes are particularly preferred. As according to the invention Usable cyan couplers can be exemplified by oil-protected naphthol type couplers and phenol type.

Typical examples thereof include naphthol type couplers as described in U.S. Patent 2,474,293, and preferably of the oxygen atom releasing type, are highly reactive 2-equivalent naphthol type couplers as described in U.S. Patents 4,052,212; 4,146,396, 4,228,233, and 4,296,200, etc. Specific examples of phenol type couplers are described in U.S. Patents 2,369,929, 2,423,730, 2,772,162, and 2,895,826, and so on.

Cyan couplers are resistant to heat, moisture and temperature preferably used according to the invention. Typical examples include cyan couplers phenol-type as described in U.S. Patent 3,772,002, 2,5-diacylamino substituted couplers Phenol type as described in U.S. Patents 2,772,162, 3,758,308, 4,126,396, 4,334 011 and 4 327 173, DE-OS 3 329 729 and JP patent application 42671/83 etc., and phenol type couplers having a phenylureido group in its 2-position, and an acylamino group at its 5-position as described in U.S. Patent 3,446 622, 4 333 999, 4 451 559 and 4 427 767 etc.

There can be two or more kinds of the above-described couplers be incorporated in the same layer as that used for photographic photosensitive Materials to meet required properties, or may be the same Connection can be joined in two or more different layers.

It is preferred to use colored couplers together in color photography photosensitive materials for photography to avoid unwanted absorptions to correct in shorter wavelength regions, which are formed in dyes from purple couplers and cyan couplers. Typical examples include yellow colored magenta couplers as described in JP Patent Publication 39413/82 etc., and purple colored cyan couplers as described in U.S. Patents 4,004,929 and 4,138,258, GB-PS 1,146,368, etc.

A black color forming coupler used to save silver used in X-ray photographic light-sensitive materials are used according to the invention. Specific examples of this are described in US-PS 4,126,461 and GB-PS 2 102 136 etc.

The color couplers described above may be in the form of biscouplers or polymeric couplers can be used. Typical examples of polymeric couplers are described in U.S. Patents 3,451,820 and 4,080,211, and so on.

Specific examples of magenta polymer couplers are given in GH-PS 2 102,173 and U.S. Patent 4,367,282, and so on.

In addition, couplers that can form diffuse dyes, can also be used to improve the graininess. Specific examples of such Types of magenta couplers are disclosed in U.S. Patent 4,366,237 and British Patent 2,125,570, etc. described, and those for yellow, magenta and cyan couplers are in EP-PS 96 873 and DE-OS 3,324,533, etc. are described.

The present invention can be applied to ordinary color photosensitive photosensitive photography Silver halide materials such as color negative films, color paper, color positive films, Color reversal films for slides, color reversal films for motion pictures, or color reversal films can be applied to television etc. However, it is particularly effective for color negative films and to use various color reversal films that have high sensitivity and require high quality images. They can also be used in color paper.

In the photographic light-sensitive materials according to the invention Ultraviolet rays absorbing agents can be incorporated to improve durability to improve the color images. When ultraviolet rays absorbent too an intermediate layer between a green-sensitive layer and a red-sensitive layer Layer can be joined together with means that mix colors prevent them from being dispersed. When ultraviolet ray absorbent too If a protective layer is added, another protective layer can be used as the outermost layer be piled on top. Matting agents can be used in this outermost protective layer be incorporated with a suitable particle size.

The ultraviolet ray absorbing agents described above can either be in organic solvents with a high boiling point, organic Solvents with a low boiling point or mixtures thereof and then dissolved in hydrophobic colloids in the same way as described above for couplers be dispersed. The ratio of high boiling point organic solvents and ultraviolet rays absorbing agents to be used no limitation, however, organic solvents with high Boiling points ranging from 0 to 300% based on the weight of the ultraviolet rays absorbent Funds used. It is preferred to use compounds that are at normal temperature are liquid, individually or together with or in a mixture.

The preservability of formed color images, especially cyan color images, especially the light resistance of cyan color images can be improved, when benzotriazole type ultraviolet rays absorbing agents together with the combinations of compounds according to the invention can be used. These ultraviolet rays absorbent Agent and cyan coupler can be dispersed with one another.

To the preservability of formed color images, in particular Enhancing yellow and purple images can have different anti-fading properties Organic type or metal complex type agents can also be used. Examples of organic-type fading preventive agents include hydroquinones, Gallic acid derivatives, p-alkoxyphenols, p-oxyphenols, etc. Suitable color image stabilizers, Stain preventing agents or antioxidants are referring to patents in Research Disclosure No. 17643, VII-I to VII-J. Beyond that metal complex type fading preventive agents in Research Disclosure, No. 15162 etc.

About the resistance to heat and light of yellow color images To improve, various compounds, for example phenols, hydroquinones, Hydroxychromans, hydroxycoumarans, hindered amines, alkyl ethers thereof, silyl ethers thereof or hydrolyzable precursor derivatives thereof, etc. can be used.

In the silver halide emulsion layer of the color photographic film of the present invention light-sensitive material can use various types of silver halide will. For example, silver chloride, silver bromide, silver chlorobromide, silver iodobromide or silver chloroiodobromide, etc. can be used. Silver iodobromide with a grade from 2 to 20 mol% of silver iodide and silver chlorobromide containing from 10 to 50 mole percent silver bromide is preferred. Crystal shape, crystal structure, particle size and particle size distribution, etc. of the silver halide particles are not subject to any Restriction. The crystals of silver halide can have normal structure and twin structure and they can be any hexahedral, octahedral or tetradecahedral be. In addition, tabular silver halide particles with a thickness of 0.5 ym or

Microns or less and a diameter of at least 0.6 µm or Microns and an average aspect ratio of 5 or more can be used.

Silver halide with a uniform crystal structure, silver halide with different composition in the inner part and in the outer parts, Layered silver halide, silver halide combined with silver halide with different composition of the epitaxial combination, or silver halide, composed of a mixture of different crystal forms can be used will. In addition, silver halide particles in which latent images are mainly are formed on the surface thereof, or those in which latent images are mainly formed inside.

The particle size of the silver halide can be varied, and it either fine grains of 0.1 μm or

Microns or less, or large grains up to 3 Fm or microns Diameters calculated from projected areas can be used. It can too monodisperse emulsions with a narrow distribution or polydisperse emulsions can be used with a wide distribution.

The silver halide particles can according to conventional or

named processes, which are usually based on the photographic Area to be used.

The silver halide emulsions can be prepared by a conventional chemical Awareness raising, d. H. a sulfur sensitization method, a noble metal sensitization method or a combination thereof. In addition, silver halide emulsions can be used according to the invention a spectral sensitivity in a desired wavelength range under the use of bestowed sensitizing dyes will. Examples of dyes which are advantageously used according to the invention, include methine dyes and styryl dyes such as cyanine dyes, hemicyanine dyes, Rhodacyanine dyes, or rhodanine dyes, merocyanine dyes, oxonol dyes, Hemioxonol dyes, etc. These dyes can be used individually or in combination of two or more of them can be used.

Any transparent support such as polyethylene terephthalate film can be used (or film) or a cellulose triacetate film (or film) etc. are used, and a reflective support as described below can be used as the support in the present invention be used. Reflective supports that are preferred include, for example Baryta coated paper, polyethylene coated paper, synthetic Polypropylene type paper, a transparent support on which a reflective Layer is located or used together with a reflective substance, for example a glass plate, a polyester film such as a polyethylene terephthalate film, a cellulose triacetate film or a cellulose nitrate film, etc., a polyamide film, a polycarbonate sheet, a polystyrene sheet, etc. Suitable supports may be suitable Way to be chosen depending on the purpose of use.

Blue-sensitive emulsions, green-sensitive emulsions and red-sensitive Emulsions which are used according to the invention are those which are spectrally sensitized so that they are color sensitive, methine dyes or other dyes be used. Examples of dyes that can be used include Cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes. Of these color substances are cyanine dyes, merocyanine dyes and complex merocyanine dyes are particularly useful.

In the color photographic light-sensitive materials of the present invention can be an auxiliary layer, such as an underlayer, an intermediate layer, a protective layer be present in addition to the build-up layers described above. About that In addition, a second ultraviolet ray absorbing layer can be sandwiched between a Red-sensitive silver halide emulsion layer and a green-sensitive Silver halide emulsion layer may be present. In such a Ultraviolet rays absorbing layers are preferably those described above Ultraviolet rays absorbing agents are used, but others can also be used known ultraviolet rays absorbing agents can be used.

Gelatin is advantageous as a binder or protective colloid for photographic emulsions are used, but other hydrophilic colloids can also be used be used.

For example, it is possible to use proteins such as gelatin derivatives, graft polymers of gelatin and other polymers, albumin or casein, etc., sucrose derivatives, such as cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose or cellulose sulfate etc., sodium alginate or starch of the 2 'vte etc., and synthetic hydrophilic High molecular weight substances such as homo- or copolymers, e.g. B. polyvinyl alcohol, Polyvinyl alcohol-partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, Polyacrylamine, polyvinylimidazole or polyvinylpyrazole, etc.

to use.

As gelatin can not only gelatin processed with lime, but also acid treated gelatin and enzyme treated gelatin as described in Bull. Soc. Sci.

Phot. Japan, No. 16, p. 30 (1966) can be used.

In addition, hydrolyzed or enzymatic products can also be used Decomposition products of gelatin can be used.

In the photographic light-sensitive material of the present invention can use the photographic emulsion layers and other hydrophilic colloid layers whitening or lightening agents, such as lightening agents of the stilbene type, triazine type, Contains oxazole type or coumarin type. You can use water-soluble and water-insoluble, lightening agents and can be used in the form of a dispersion. Specific examples of suitable brightening agents are described in U.S. Patents 2,632,701, 3,269,840 and 3,359,102, British Patents 852 075 and 1,319,763 and Research Disclosure, Volume 176, No. 17643, page 24, left column, lines 9 to 36, Brighteners (December 1978) etc.

In the photographic light-sensitive materials of the invention when dyes, ultraviolet rays absorbing agents and the like are included in the hydrophilic colloid layers are incorporated, these with cationic polymers etc. to be stained.

The photosensitive material according to the invention can be hydroquinone derivatives, Aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc. as color haze vczllin (1el-nde Funds included.

To the color photographic photosensitive according to the invention Material can contain various photographic additives known in the art are, for example, stabilizers, antifoggants, surface-active agents, Couplers other than those of the present invention, filter dyes, radiation inhibitors Agents, developing agents in addition to the compounds described above, if desired, can be added. Examples of such additives will in Research Disclosure, No. 17643 (December 1978).

In addition, silver halide emulsion layers or others can be used hydrophilic colloid layers, essentially light-insensitive, fine-grain silver halide emulsions, for example a silver chloride, silver bromide or silver chlorobromide emulsion with an average particle size of 0.20 μm or P or less, if appropriate can be added.

Color developing solutions used in the present invention are preferably alkaline aqueous solutions containing aromatic primary amine developing agents included as main components. Typical examples of the color developing agents include 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-S-hydroxyethylanilill, 3-methyl-4-alino-N-ethyl-N-0-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-ß-methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline, etc.

The color developing solutions can also contain pH buffering agents, such as sulfites, carbonates, borates and phosphates of alkali metals, etc., development inhibitors and antifoggants such as bromides, iodides or organic antifoggants, etc. contain. In addition, the color developing solutions can optionally also contain water softeners, Conservatives, tric Ilydr-oxyl; trnin, etc.

organic solvents such as benzyl alcohol, diethylene glycol, etc .; Development accelerators such as polyethylene glycol, quaternary ammonium salts, amines etc.; color forming couplers; competing couplers; haze-forming agents, such as Sodium borohydride, etc .; Auxiliary developing agents such as 1-phenyl-3-pyrazolidone, etc .; viscosity-imparting agents; polycarboxylic acid type chelating agents such as described in U.S. Patent 4,083,723; Antioxidants as described in DE-OS 2 622 950 and like. included.

After the color development, the photographic emulsion layer becomes usually subjected to bleach processing. This bleaching processing can be carried out at the same time can be done with a fixing process or it can be done independently will.

Bleaching agents that can be used include polyvalent compounds Metals, for example iron (III), cobalt (III), chromium (VI) and copper (II), peracids, Quinones and nitroso compounds. For example ferricyanides; Dichromates; organic Complex salts of iron (II11 or cobalt (III), for example complex salts of kninopolycarboxylic acids (e.g. ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanolacetic acid etc.) or organic acids (e.g.

Citric acid, tartaric acid, malic acid, etc.); Persulfates; Permanganates; Nitrosophenol, etc. can be used.

Of these compounds are potassium ferricyanide, iron (III) sodium ethylenediaminetetraacetate and ferric ammonium ethylenediaminetetraacetate are particularly valuable.

Ethylenediaminetetraacetic acid iron (III) complex salts are both useful in a stand-alone bleach solution as well as in a single bath bleach-fix solution.

After the color development or the bleach-fix processing step washing with water can be carried out.

Color development can be done at a suitable temperature in the range from 18 to 55 ° C. Preferably color development is at 30 ° C or higher and especially carried out at 35 ° C or higher. The one to develop required time ranges from about 1 minute to about 3.5 minutes, and the shorter Time is preferred. For continuous development processing, it is preferable to a renewal or addition of the processing solutions. Additions or

2 renewals from 160 ml to 330 ml per m2 and preferably 2 from 100 ml or less per m2 of the photographic materials to be processed can be applied. The concentration of benzyl alcohol in the developing solution is preferably 5 ml or less per liter thereof.

The bleach-fixing can be carried out in a suitable temperature range of 18 to 50 ° C and preferably at 30 ° C or higher. If that Bleach-fixing is carried out at 35 C or higher, it is possible to reduce the processing time to be shortened to a range of 1 minute or less and the amount to be added To reduce supplementation or renewal. The ones for washing with water after the color development or bleach-fix time is usually 3 minutes. It is also possible to washing with water using a stabilizing bath essentially to be omitted

The dyes formed are not only due to light, heat or Temperature decreases, but also through mold during storage. Because cyan color pictures especially spiked by mold, it is preferred to use anti-mold agents too use. Specific examples of anti-mold agents include 2-thiazolylbenzimidazoles, as described in JP-OS 157244/82. Mold anti-mold agents can be used in the photographic photosensitive materials incorporated or externally during development processing be added. Anti-mold agents can be included in the photographic materials while any suitable steps are incorporated, provided that the photographic Materials they contain after processing.

The following examples serve to further illustrate the invention, without restricting them.

Example 1 On a cellulose triacetate film support were Layers of the composition given below for the production of a multilayer applied color photographic light-sensitive material.

First layer: antihalation layer A gelatin layer, the black one Contains colloidal silver.

Second layer: intermediate layer A gelatin layer that is a dispersion of 2,5-di-tert-octyihydroquinone.

Third layer: a less sensitive red-sensitive emulsion layer A silver iodobromide emulsion (iodide content: 5 mol%), amount of silver coated: 1.6 g / m2 sensitizing 4.5 x 10 4 moles per mole of silver dye I sensitizing 1.5 x 10 4 moles per mole of silver Dye II Coupler EX-1 0.04 moles per mole of silver Coupler EX-3 0.003 moles per mole of silver Coupler EX-11 0.0006 moles per mole of silver Fourth Layer: Highly sensitive, red-sensitive emulsion layer A silver iodobromide emulsion (Iodide content: 10 mol%), amount of silver coated: 1.4 g / m2 of sensitizing agent 3 x 10 4 moles per mole of silver dye I sensitizer 1 x 10 4 moles per mole Silver dye II Coupler EX-1 0.002 moles per mole of silver coupler EX-2 0.02 moles per mole of silver Coupler EX-3 0.0016 moles per mole of silver Fifth layer: Intermediate layer The same layer as the second layer.

Sixth layer: Less sensitive, green-sensitive emulsion layer A silver iodobromide emulsion (iodide content: 4 mol%), amount of silver coated: 1.2 g / m2 sensitizer 5 x 10 4 mol per mol of silver dye III sensitizer 2 x 10 4 moles per mole of silver Dye IV Coupler EX-4 0.05 moles per mole of silver coupler EX-5 0.008 moles per mole of silver Coupler EX-9 0.0015 moles per mole of silver Seventh layer: Highly sensitive, green-sensitive emulsion layer A silver iodobromide emulsion (Iodide content: 8 mol%), amount of silver coated: 1.3 g / m2 of sensitizing agent 3 x 10 4 moles per mole of silver dye III sensitizer 1.2 x 10 4 moles per Silver Dye IV moles of Coupler EX-7 0.017 moles per mole of silver Coupler EX-6 0.003 Moles per mole of silver Coupler EX-10 0.0003 moles per mole of silver Eighth layer: Yellow Filter layer A gelatin layer containing yellow colloidal silver and one Dispersion of 2,5-di-tert-octylhydroquinone.

Ninth layer: low-sensitive blue-sensitive emulsion layer A silver iodobromide emulsion (iodide content: 6 mol%), amount of silver coated: 0.7 g / m2 Coupler EX-8 0.25 moles per mole of silver Coupler EX-9 0.015 moles per mole of silver Tenth layer: Highly sensitive blue-sensitive emulsion layer A silver iodobromide emulsion (Iodide content: 6 mol%), amount of silver coated: 0.6 g / m2 Coupler EX-8 0.06 Moles per mole of silver Eleventh layer: First protective layer containing a gelatin layer Silver iodobromide (iodine! Old 1 mol%, average particle size 0.07), coated Silver amount: 0.5 g / m 2 and a dispersion of the ultraviolet ray absorbent Using W -1.

Twelfth layer: Second protective layer containing a gelatin layer Polymethyl methacrylate particles (with a diameter of approx.

The gelatin hardener H-1 and a surfactant were used in each of the layers is incorporated in addition to the ingredients described above.

The sample thus prepared was named Sample 101.

Preparation of Samples 102 to 109 Samples 102 to 109 were produced in prepared in the same way as described for sample 1, with the exception that the coupler EX-9, the one in the poorly sensitive green-sensitive emulsion layer was replaced with the one in the table below I. connections shown.

The structures of the compounds used to make these samples are given below: H - / CH2 = CH - SO2 - CH2 - CONH - CH2 # CH2 = CH - SO2 - CH2 - CONH - CH2 Sensitizing dye I Sensitizing dye II Sensitizing dye III Sensitizing dye IV Samples 101 to 109 were subjected to exposure through a wedge to white light and then subjected to development processing at 38 ° C. after the following processing steps.

Processing stages Time 1. Color development 3 min and 15 s 2. Bleaching 6 min and 30 s 3. Wash with water 3 min and 15 s 4. Fixing 6 min and 30 s 5. Wash with water 3 min and 15 s 6. Stabilize 3 min and 15 s The composition any processing solution used in the processing described above is indicated below: Color developing solution 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 of 4- (N-ethyl-N-ß-hydroxyethylamino) -2-methylaniline sulfate, 4.5 g of water for preparation from 1 liter of bleach solution ammonium bromide 160.0 g aqueous ammonia (28 t) 25.0 ml Sodium ethylenediaminetetraacetato iron (III) 130.0 g of glacial acetic acid and 14.0 ml of water Preparation of 1 liter Fixing solution sodium tetrapolyphosphate 2.0 g sodium sulfite 4.0 g ammonium thiosulfate, aqueous solution (70%) 175.0 ml sodium bisulfite 4.6 g water for the preparation of 1 liter of stabilizing solution formalin 8.0 ml water to prepare 1 liter. The samples processed in this way showed almost the same sensitivity and gradation. The sharpness of the green-sensitive layers of these samples was below Evaluated using the usual MTF values. The results obtained are in the Table I below.

T a b e l l e I sample for the less sensitive- Added MTF values Green sensitivity amount +) lichen layer added 5 cycles / mm 50 cycles / mm set compound ++) 101 EX-9 1.0 1.13 0.22 (comparison) 102 (comparison) EX-10 1.0 1.03 0.23 103 (comparison) EX-9 + Ex-10 1.0 + 1.0 1.12 0.23 104 (according to the invention) (II-1) + (III-1) 2.0 + 4.0 1.14 0.38 105 (according to the invention) (II-4) + (III-2) 1.5 + 1.5 1.15 0.40 106 (according to the invention) (II-6) + (III-10) 1.0 + 1.0 1.14 0.37 107 (according to the invention) (II-7) + (III-3) 1.0 + 1.5 1.14 0.38 108 (according to the invention) (II-11) + (III-1) 2.0 + 4.0 1.13 0.36 109 (according to the invention) (II-25) + (III-8) 3.0 + 4.0 1.13 0.41 +) The amount added is listed as a molar ratio, the moles of the coupler EX-9 used in the example 101 were added, to be assumed as 1.

++) Instead of the EX-9 coupler, the less sensitive, green-sensitive one Layer added compound (s) From the results of the It can be seen from Table 1 that the MTF values are at 50 cycles / mm when used the combination of the compound represented by the general formula (II), and of the compound represented by the general formula according to the invention become extremely high compared with the case of using the usual combination of DIR couplers are.

Example 2 On a carrier made of cellulose triacetate foil or film layers of the same compositions as in Sample 101 of Ticigame became layers 1 to a multilayer, color photographic, photosensitive To manufacture material. This sample was named Sample 201.

Preparation of Samples 202 to 207 Samples 202 to 207 were produced in prepared in the same way as described for Example 201, but with the Coupler EX-9, the one in the less sensitive, green sensitive emulsion layer was changed to the compounds shown in Table II below became.

Samples 201 to; r; 2 () 7 were d ('g 1 ei ehen Kci l-nclichtung with white light and development processing as described in Example 1 subjected. The samples so processed showed almost the same sensitivity and gradation. The sharpness of the green-sensitive layers of this sample was under Evaluated using standard MTF values. The results obtained are in the following Table II listed.

T a b e l l e I I Sample For the less sensitive Added MTF value Green-sensitive layer amount +) 5 cycles / mm 50 cycles / mm added compound ++) 201 EX-9 1.0 1.14 0.23 (comparison) 202 (according to the invention) (IV-4) 1.5 1.10 0.32 203 (according to the invention) (IV-9) 2.0 1.11 0.35 204 (according to the invention) (IV-11) 2.0 1.10 0.35 205 (according to the invention) (IV-1) 2.0 1.15 0.37 206 (according to the invention) (IV-8) 1.0 1.12 0.35 207 (according to the invention) (IV-25) 1.5 1.12 0.37 +) The amount added is as a molar ratio given, the moles of coupler EX-9 added in sample 201 can be assumed to be 1.

++) Instead of the EX-9 coupler, the less sensitive, green-sensitive one Layer added compound (s) From the results of the Table II above shows that the MTF values in areas with relative high spatial frequencies, d. H. at 50 cycles / mm can be improved when using the Compound represented by the general formula (IV) according to the invention and the effects of these compounds are clear.

Example 3 On a carrier made of cellulose triacetate foil or film layers and compositions were coated as indicated below, to prepare a multilayer color photographic light-sensitive material.

First layer: anti-halo coating A gelatin layer, the black one Contains colloidal silver.

Second layer: intermediate layer A gelatin layer that is a dispersion of 2,5-di-tert-octylhydroquinone.

Third layer: Less sensitive, red-sensitive emulsion layer A silver iodobromide emulsion (iodide content: 5 mol%), coated amounts of silver: 1.6 g / m2 sensitizing dye I '4.5 x 10 4 mol per mol of silver sensitizer Dye II '1.5 x 10 4 moles per mole of silver Coupler EX-1' 0.03 moles per mole of silver Coupler EX-3 '0.003 moles per mole of silver Fourth layer: Highly sensitive, Red-sensitive emulsion schi cit A silver iodobromide emulsion (iodine content: 10 mol%), Amount of silver coated: 1.4 g / m2 Sensitizing dye I '3 x 10 4 mol per mole of silver sensitizing dye II '1 x 10 moles per mole of silver coupler EX-1 '0.002 moles per mole of silver Coupler EX-2' 0.02 moles per mole of silver Coupler EX-3 ' 0.0016 mol per mol of silver Fifth layer: Intermediate layer The same as the second Layer Sixth layer: Less sensitive, green-sensitive emulsion layer A silver iodobromide emulsion (iodide content: 4 mol%), amount of silver coated: 1.2 g / m2 sensitizing dye III '5 x 10 moles per mole of silver sensitizing agent Dye IV '2 x 10 4 moles per mole of silver Coupler EX-4' 0.05 moles per mole of silver Coupler EX-5 '0.008 mol per mol of silver Compound (V-17) 0.0015 mol per mol of silver Seventh layer: highly sensitive, green-sensitive emulsion layer A silver iodobromide emulsion (Iodide content: 8 mol%), amount of silver coated: 1.3 g / m2 of sensitizing agent Dye III '3 x 10 4 moles per mole of silver Sensitizing Dye IV' 1,2 x 10 4 moles per mole of silver Coupler EX-7 '0.017 mole per mole of silver Coupler EX-6 '0.003 moles per mole of silver Eighth layer: Yellow filter layer A gelatin layer, containing yellow colloidal silver and a dispersion of 2,5-di-tert-octylhydroquinone.

Ninth layer: Less sensitive, blue-sensitive emulsion layer A silver iodobromide emulsion (iodide content: 6 mol%), amount of silver coated: 0.7 g / m2 Coupler EX-8 '0.25 mol per mol of silver Compound (V-17) 0.015 mol per mol Silver Tenth Layer: 11-hole sensitive, blue-sensitive emulsion layer one Silver iodobromide emulsion (iodide content: 6 moles of coated silver amount: 0.6 g / m2 Coupler EX-8 '0.06 moles per mole of silver Eleventh layer: First protective layer A gelatin layer, containing silver iodobromide (iodide content: 1 mol%, average particle size: 0.07), coated amount of silver: 0.5 g / m 2, and a dispersion of the ultravioet ray absorbent Using UV-1 '.

Twelfth layer: Second protective layer containing a gelatin layer Polymethyl methacrylate particles (with a diameter of approx.

The gelatin hardener 11-1 'and a surface active agent were used incorporated into each of the layers in addition to the components described above.

The sample thus prepared was named Sample 301.

Preparation of Samples 302 to 309 Samples 302 to 309 were produced in manufactured in the same way as described for sample 301, but with an exchange of the compound (V-17) in the less sensitive, green-sensitive emulsion layer was used for the compounds shown in Table III below.

The structures of the compounds used to make these samples are listed below: Samples 301 to 309 were subjected to the same wedge exposure to white light and development processing as described in Example 1. The samples so processed showed almost the same sensitivity and gradation. The sharpness of the green-sensitive layer of these samples was evaluated using conventional MTF values. The results are given in Table III below.

T a b e l l e I I I Sample for the less sensitive, MTF value green-sensitive Layer added 5 cycles / mm 50 cycles / mm added compound ++) amount +) 301 (V-17) 4.0 1.02 0.24 (comparison) 302 (V-17) + (VI-2) 3.0 + 6.0 1.11 0.38 (according to the invention) 303 (V-9) 4.0 1.04 0.27 (comparison) 304 (V-9) + (VI-1) 3.0 + 6.0 1.10 0.36 (according to the invention) 305 (V-2) + (VI-1) 3.0 + 6.0 1.10 0.38 (according to the invention) 306 (V-6) + (VI-8) 3.0 + 6.0 1.15 0.40 (according to the invention) 307 (V-1) + (VI-14) 3.0 + 6.0 1.13 0.35 (according to the invention) 308 (V-4) + (VI-5) 3.0 + 6.0 1.15 0.40 (according to the invention) 309 (V-12) + (VI-15) 3.0 + 6.0 1.18 0.41 (according to the invention) +) The amount added stating a molar ratio indicated, being the moles of the compound (V-17) that were added in sample 301 should be assumed to be 4.0.

++) Instead of the link (V-17) to the less sensitive, green-sensitive Layer added compound (s) From the above Results shown in Table III, it is understood that not only the increase in MPF values in the areas with low spatial frequencies, but also the increase the MTF values in areas with high spatial frequencies in the case of using the combination the compound represented by the general formula (V) and that represented by the general Formula (VI) represented compound compared with the comparisons very high and that the effects of these compounds were clearly shown.

Example 4 On a carrier made of cellulose triacetate foil or film became layers of the same compositions as in sample 101 of the example 1 coated to form a multilayer color photographic photosensitive To manufacture material. This sample was named Sample 401.

Preparation of Samples 402 to 410 Samples 402 to 410 were produced in manufactured in the same way as described for sample 401, but with an exchange of the coupler EX-9, which is in the less sensitive, green-sensitive emulsion layer was used against the compounds shown in Table IV below.

Samples 401-410 underwent the same wedge exposure with white Light and development processing as described in Example 1 was subjected. The samples so processed showed almost the same sensitivity and gradation. The sharpness of the green-sensitive layers of these samples was measured using normal MTF values. The results obtained are in the following Table IV listed.

T a b e l l e I V sample For the less sensitive, added MTF value Green-sensitive layer amount +) 5 cycles / mm 50 cycles / mm added compound ++) 401 EX-9 1 1.15 0.22 (comparison) 402 (comparison) EX-10 3 1.06 0.23 403 (req. according to) (IV-7) + (VIII-5) + EX-9 1 + 5 + 1 1.14 0.34 404 (required according to) (VII-8) + (VIII-5) + EX-9 1 + 5 + 1 1.15 0.35 405 (req. Acc.) (VII-15) + (VIII-1) + EX-9 1 + 5 + 1 1.16 0.32 406 (req. according to) (VII-16) + (VIII-5) + EX-9 1 + 5 + 1 1.14 0.35 407 (required according to) (VII-14) + (VIII-2) + EX-9 1 + 5 + 1 1.14 0.33 408 (req. Acc.) (VII-20) + (VIII-9) + EX-9 1 + 5 + 1 1.15 0.34 409 (req. according to) (VII-20) + (VIII-9) 1 + 5 1.13 0.32 410 (required according to) (VII-21) + (VIII-15) 1 + 5 1.13 0.33 Notes to Table IV +) The amount is given with a Molar ratio given, being the moles of coupler EX-9 found in sample 401 was added, can be assumed to be 1.

++) Instead of the EX-9 coupler, the less sensitive, green-sensitive one Layer added compound (s) From the results in the table above IV it can be seen that the MTF values in areas with high spatial frequencies, i. at 50 cycles / mm in the samples according to the invention are very high, and that the effects the combination of the compound represented by the general formula (VII) and of the compound represented by the general formula (VIII) is clearly demonstrated became.

Claims (76)

Silver halide photographic light-sensitive material. Claims 1. Silver halide photographic light-sensitive material containing a A support having at least one silver halide emulsion layer thereon, wherein the photographic, light-sensitive material contains at least one compound, those for forming a photographically useful group or a precursor thereof during development processing is suitable having a photographic function the photographically useful group or the precursor thereof by an intermolecular one Response can be changed. 2. Silver halide photographic light-sensitive material according to Claim 1 wherein the compound is represented by the following general Formula 1): x - (CONT) n Y <1) where X is an organic radical means that is suitable for splitting off (CONT) n - Y at the time of development is; CONT represents a linking group necessary for the cleavage of Y after cleavage of X is suitable; n is 0 or 1; and Y represents an organic radical which is liable to lose a photographic function or a connection with to form photographic function in reacting with each other after release. 3. Silver halide photographic light-sensitive material according to Claim 2, wherein the group represented by X is a group undergoing a coupling reaction can enter into with the oxidation product of a developing agent, a group, an oxidation-reduction reaction with the oxidation product of a developing agent can enter into a group capable of a cleavage reaction in the presence to enter into an acid or a base or a group composed thereof is. 4. The silver halide photographic light-sensitive material of claim 3 or 2, wherein X represents a coupler group represented by the following general formula (AI) or (A-II): wherein R1 represents an aliphatic group, an aromatic group, an alkoxy group or a heterocyclic group; and R2 and R3 each represent an aromatic group or a heterocyclic group. 5. Silver halide photographic light-sensitive material according to Claim 4, wherein the aliphatic group represented by R1 is an alkyl group which may be substituted with a substituent selected from an alkoxy group, an aryloxy group, an amino group, an acylamino group and a halogen atom. 6. Silver halide photographic light-sensitive material according to Claim 4, wherein the aromatic group represented by R1, R2 or R3 is Phenyl group which may be substituted with a substituent is selected from an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an aliphatic amido group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkylureido group, an alkyl-substituted group Succinimido group each containing 32 or fewer carbon atoms, an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, a Arylsulfamoyl group, an arylsulfonamido group, an arylureido group, a Amino group, a hydroxyl group, a carboxy group, a sulfo group, a Nitro group, a cyano group, a thiocyano group and a halogen atom. 7. Silver halide photographic light-sensitive material according to Claim 4, 5 or 6, wherein the aromatic group represented by R1, R2 or R3 is, a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, is a coumaranyl group or a tetrahydronaphthyl group. 8. Silver halide photographic light-sensitive material according to Claim 4, 5, 6 or 7, wherein the alkoxy group represented by R1 is an alkoxy group in which the alkyl portion has a straight or branched chain alkyl group 1 to 32 carbon atoms, an alkenyl group, a cyclic alkyl group or represents a cyclic alkenyl group, each of which is represented by a substituent, selected from a halogen atom, an aryl group and an alkoxy group can be. 9. Silver halide photographic light-sensitive material according to any one of claims 4 to 8, wherein the heterocyclic represented by R1, R2 or R3 Group is a group derived from a saturated hetero ring of thiophene, Furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolidine, Imidazole, thiazole, oxazole, triazine, thiadiazole and oxazine. 10. The silver halide photographic light-sensitive material of claim 3, wherein X represents a coupler residue represented by the following general formulas (A-III), (A-IV), (AV) or (A-VI): wherein R5 represents a straight or branched chain alkyl group having 1 to 32 carbon atoms, an alkenyl group, a cyclic alkyl group, an aralkyl group or a cyclic alkenyl group, each of which may be substituted with a substituent selected from a halogen atom, a nitro group, a cyano group, an aryl group , an alkoxy group, an aryloxy group, a carboxy group, an alkylthiocarbonyl group, an arylthiocarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a sulfiamido group, a sulfoethano group, a urethiouro group heterocyclic group, an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an alkylthio group, an alkylamino group, a dialkylamino group, an anilino group, an N-arylanilino group, an N-alkylanilino group, an N- Acylanilino group, a hydroxy group and a mercapto group; an aryl group which may be substituted with a substituent selected from an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group , an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a sulfonamido group, a heterocyclic group, an arylsulfonyl group, an alkylsulfonyl group, an arylsulfonyl group, an arylsulfonyl group, an a dialkylamino group, an anilino group, an N-alkylanilino group, an N-arylanilino group, an N-acylanilino group, a hydroxy group and a mercapto group; a heterocyclic group which may be substituted with a substituent selected from the substituents as defined for the above-described aryl group; an aliphatic acyl group; an aromatic acyl group; Alkylsulfonyl group; an arylsulfonyl group; an alkylcarbamoyl group; an arylcarbamoyl group; an alkylthiocarbamoyl group; or represents an arylthiocarbamoyl group; R4 is a hydrogen atom; a straight or branched chain alkyl group having 1 to 32 carbon atoms, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, an aryl group or a heterocyclic group, each of which may be substituted with a substituent selected from the substituents such as these Groups of R5 each defined; an alkoxycarbonyl group; an aryloxycarbonyl group; an aralkyloxycarbonyl group; an alkoxy group; an aryloxy group; an alkylthio group; an arylthio group; a carboxy group; an acylamino group; a diacylamino group; an N-alkylacylamino group; an N-arylacylamino group; an ureido group; a urethane group; a thiourethane group; an arylamino group; an alkylamino group; a cycloamino group; a heterocyclic amino group; an alkylcarbonyl group; an arylcarbonyl group; a sulfonamido group; a carbamoyl group; a sulfamoyl group; a cyano group; a hydroxy group; a mercapto group; a halogen atom; or represents a sulfo group; and R6 is a hydrogen atom; a straight or branched chain alkyl group having 1 to 32 carbon atoms, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, an aryl group, or a heterocyclic group, each of which may be substituted with a substituent selected from the substituents such as these Group of R5 defined in each case; a cyano group; an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, an alkyl sulfone group, an alkyl arylamido group , an arylthio group, an alkylthio group, an alkylamino group, a dialkylamino group, an anilino group, an N-arylanilino group, an N-alkylanilino group, an N-acylanilino group, a hydroxy group or a mercapto group. 11. Silver halide photographic light-sensitive material according to Claim 10 or one of the other preceding claims, wherein R5 is a phenyl group means substituted with an alkyl group, an alkoxy group or a Halogen atom, in at least one of the o-positions. 12. The silver halide photographic light-sensitive material as claimed in claim 3 or any preceding claim, wherein X represents a coupler radical represented by the following general formulas (A-VII), (A-VIII), (A-IX) or (AX): wherein R7 represents a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, an aliphatic hydrocarbon radical, an N-arylureido group, an acylamino group, a group -O-R12 or a group -S-R12 (where R12 represents an aliphatic hydrocarbon radical); R8 and Rg each represent an aliphatic hydrocarbon radical, an aryl group, or a heterocyclic group, wherein one of R8 and R9 may be hydrogen or R8 and R9 may be combined to form a nitrogen-containing heterocyclic ring; 2 is an integer from 1 to 4; m is an integer from 1 to 3; and p is an integer from 1 to 5. 13. Silver halide photographic light-sensitive material according to Claim 12, wherein the aliphatic hydrocarbon group, the aryl group or the heterocyclic group represented by R7, R8 or Rg may be substituted can with a substituent selected from a halogen atom, a nitro group, a hydroxyl group, a carboxy group, an amino group, a substituted one Amino group, a sulfo group, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an arylthio group, an arylazo group, an acylamino group, a carbamoyl group, an ester group, an acyl group, an acyloxy group, a sulfonamido group, a sulfamoyl group, a sulfonyl group, and a morpholino group. 14. The silver halide photographic light-sensitive material of claim 3, wherein X represents a coupler residue represented by the following general formula (A-XI): wherein R10 is an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 32 carbon atoms, an alkoxycarbonyl group having 1 to 32 carbon atoms, or an aryloxycarbonyl group, each of which may be substituted with a substituent selected from an alkoxy group, an alkoxycarbonyl group, an acylamino group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkylsuccinimido group, a halogen atom, a nitro group, a carboxy group, a nitrile group, an alkyl group and an aryl group; and R11 an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, an arylcarbamoyl group; an alkanecarbamoyl group having 2 to 32 carbon atoms; an alkoxycarbonyl group having 1 to 32 carbon atoms; represents an aryloxycarbonyl group, an alkanesulfonyl group having 1 to 32 carbon atoms, an arylsulfonyl group, an aryl group, or an S-membered or 6-membered heterocyclic group, each of which may be substituted with a substituent selected from the substituents defined for R10. 15. The silver halide photographic light-sensitive material of claim 3, wherein X represents a group represented by the following general formula (A-XII): wherein R15 and R16 each represent a hydrogen atom or an organic radical, at least one of the groups represented by R15 and R16 being - (CONT) -Y; t is an integer from 1 to 4 if f is 2 or more, the R15 radicals and R16 radicals can be identical or different; R13 and R14 each represent a hydroxyl group or an amino group which may be substituted. 16. Silver halide photographic light-sensitive material according to Claim 3 or any of the remaining preceding claims, wherein X is a group represents which - <CONT) n can release in the presence of an alkali. 17. Silver halide photographic light-sensitive material according to Claim 3 or any of the other preceding claims, wherein X is a group represents which is suitable for splitting off the group different from X, or which is suitable for the cleavage reaction of the group different from X. the competition of an oxidation-reduction reaction with a shift reaction to prevent. 18. The silver halide photographic light-sensitive material as claimed in claim 3 or any preceding claim, wherein X represents a coupler radical represented by the following general formulas (A-XIII), (A-XIV) or (A-XV): wherein R17 is an organic radical; R18 denotes a hydrogen atom or a group which can be released on coupling; Nu represents an oxygen atom, a sulfur atom or an imino group which may be substituted and which is capable of forming a nucleophilic group by resonance of anions when the methine group adjacent thereto is converted into a carbon anion under alkaline conditions; E represents an electrophilic group, X1 represents a linking group for forming such a stereochemical configuration that the nucleophilic group (an oxygen anion in the general formula (A-XV)) and E are suitable for an intramolecular, nucleophilic shift reaction resulting from ring formation is accompanied to enter; R7 and m each have the same meaning as in the general formula (A-VIII) as claimed in claim 12. 19. Silver halide photographic light-sensitive material according to Claim 2 or any of the other preceding claims, wherein the CONT linking group shown is a group capable of initiating a cleavage reaction to enter into an intramolecular shift reaction after the release of X, a Group capable of cleavage upon electron transfer via a conjugated To enter into a system, a methylenoxy group or an oxycarbonyloxy group. 20. Silver halide photographic light-sensitive material according to Claim 2 or one of the other preceding claims, wherein the CONT connecting group shown is a component which is suitable for the reaction with the oxidation product of a developing agent. 21. Silver halide photographic light-sensitive material according to Claim 2 or any of the remaining preceding claims, wherein that represented by Y Group a photographically useful group, a precursor to a photographically is a useful group or a simple group suitable for release, and each of which is suitable for reaction between molecules. 22. The silver halide photographic light-sensitive material according to claim 21, wherein the photographically useful group or the precursor thereof represented by Y is a group represented by the following general formulas (BI), (B-II), (B-III), (B-IV), (BV), (B-VI), (B-VII) or (B-VIII) wherein V1, V2 and V3 each represent a nitrogen atom or a group of C-G3; V4 represents a group of N-G3, a sulfur atom or an oxygen atom; V5 represents an oxygen atom or a group of N-G3; V6 represents an oxygen atom or a group of N-G12; V8 represents a nitrogen atom or a group from C-G13; G1 represents a substituent; G2 denotes a hydroxyl group or an amino group which may be substituted; G3 represents a hydrogen atom, an aromatic group or an aliphatic group; G4 represents an aromatic group; G5 represents a hydrogen atom or a group capable of coupling reaction with the oxidation product of a developing agent when L1 is split off; G6 represents an alkoxy group, an aromatic amino group, an acylamino group, an aromatic group, an aliphatic group or a heterocyclic group; G7 represents an aromatic group, an aliphatic group, or a heterocyclic group; G8 represents a single bond or an atomic group for connecting L1 and the nitrogen atom, which contains an aromatic group, an aliphatic group or a heterocyclic group; Gg denotes an aliphatic group, an aromatic group or a heterocyclic group when V8 is a nitrogen atom, or in addition it can represent an acyl group, a carbamoyl group, a sulfamoyl group, a nitro group, a cyano group, an alkoxycarbonyl group, a sulfinyl group or a sulfonyl group when V8 is a group of C-G13; G and G11 each represent a hydrogen atom, an aromatic group, an aliphatic group, an acyl group, a carbamoyl group, a sulfonyl group, a sulfamoyl group, an alkoxycarbonyl group, or a sulfinyl group; G12 represents an aliphatic group, an aromatic group, a heterocyclic group or an amino group, or G12 may be linked to G7 to form a cyclic structure when V6 is a group of N-G12; G13 represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, a carbamoyl group, a sulfamoyl group, a nitro group, a cyano group, an alkoxycarbonyl group, a sulfonyl group or a sulfinyl group, or G13 may be bonded to G9, to form a cyclic structure; £ and R7 each have the same meaning as defined in the general formula (AVIl) as claimed in claim 12, f is an integer from 0 to 4; g is an integer from 1 to 3 and h is an integer from 1 to 3. 23. The silver halide photographic light-sensitive material according to claim 21 or any preceding claim, wherein the simple group which can be released represented by Y is a group represented by the following general formula (B-IX) or (BX): wherein Z1 represents an organic residue required to form a nitrogen-containing heterocyclic group together with the nitrogen atom; V9 represents an oxygen atom, a sulfur atom, a nitrogen atom with a hydrogen atom, a nitrogen atom with a substituent, a methylene group, a methine group with a substituent or a selenium atom; and Z2 is an organic residue. 24. Silver halide photographic light-sensitive material according to Claim 1 or any of the remaining preceding claims, wherein the photographic, photosensitive material (1) a compound capable of releasing a through Reaction with the oxidation product of a developing agent-releasable group is suitable, and (2) contains a compound which upon reaction with the oxidation product of a developing agent as a releasable group releases a compound which can react with the group released from compound (1) to form a development inhibitor that has a stronger function than that of the compound (1) released group. 25. Silver halide photographic light-sensitive material according to Claim 24, wherein both the compound (1) and the compound (2) in the same silver halide emulsion layer are present. 26. Silver halide photographic light-sensitive material according to Claim 1 or one of the other preceding claims, which has a compound, represented by the following general formula (II) and a compound by the following general formula (III): x - (CONT) n - AF - E (11) X - NU (III) where X represents a component which is suitable, (CONT) n-AF-E or To release NU upon reaction with the oxidation product of a developing agent; n is 0 or 1; and when n represents 1, CONT represents a component which is capable of releasing AF-E after CONT-AF-E is released from X; AF on Basic skeleton to achieve a development inhibiting Function represents; E means a component that is released in the event of an attack a nucleophilic group formed in NU after NU of X is released; and NU represents a group suitable to be a nucleophile To form group after the release of X and is suitable to form AF-NU, the developed a development inhibiting function upon reaction with AF-E. 27. Silver halide photographic light-sensitive material according to Claim 26, wherein the component represented by X in the general formula (III) may be the same or different from one another. 28. Silver halide photographic light-sensitive material according to Claim 26, wherein the component represented by E in the general formula (II) is a group that is apt to be released in the nucleophilic shift reaction to become by entering into a nucleophilic attack by the one represented by NU Group released from that represented by the general formula (III) Compound when reacting with the oxidation product of a developing agent. 29. Silver halide photographic light-sensitive material according to Claim 28, wherein E is a halogen atom, an alkanesulfonyloxy group, an arylsulfonyloxy group, represents an aryloxy group, an acyloxy group or an alkoxy group. 30. Silver halide photographic light-sensitive material according to Claim 26 or one of the remaining preceding claims, wherein the by NU in the general formula (III) shown group does not have a group which has a nucleophilic shift reaction by a nucleophilic attack by a other NU molecule can enter. 31. Silver halide photographic light-sensitive material according to Claim 26 or one of the remaining preceding claims, wherein the by NU represented group is a group containing a sulfur atom, a nitrogen atom or contains an oxygen atom through which the group is attached to X. 32. Silver halide photographic light-sensitive material according to Claim 31, wherein NU represents a group selected from an arylthio group, a heterocyclic thio group, an aryloxy group, an alkoxy group, a Alkylthio group, a benzotriazolyl group, a triazolyl group, an imidazolyl group, a benzimidazolyl group, an imidazolidinyl group, a pyrazolyl group and an acylaminooxy group. 33. Silver halide photographic light-sensitive material according to Claim 26 or any of the other preceding claims, wherein the AF-E component represented in the general formula (II) is a group by -AF'-L3-E, where AF 'means the remainder to remove L3 from AF and L3 represents a divalent organic linking group. 34. Silver halide photographic light-sensitive material according to Claim 33, wherein L3 represents a divalent group derived from an alkyl group, an acylamino group, an aryl group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an alkanesulfonyl group, an alkylthio group, an alkanesulfoxo group, an alkyl substituted ureido group or a combination of two or more of that. 35. Silver halide photographic light-sensitive material according to Claim 33, wherein -L3-E is a halogenated alkyl group, an alkyl or arylsulfonyloxyalkyl group or represents an aryloxyalkyl group. 36. Silver halide photographic light-sensitive material according to Claim 26 or any of the other preceding claims, wherein the CONT in the general formula (II) represented a component having a component Function to regulate the coupling rate or the diffusibility of AF-E is. 37. Silver halide photographic light-sensitive material according to Claim 26 or one of the other preceding claims, wherein the basic skeleton the development inhibitor represented by AF in the general formula (II) is a nitrogen-containing unsaturated heterocyclic group attached to the Part of X- (CONT) - is bonded to the nitrogen atom thereof, or a heterocyclic one Thio group with a monocyclic or fused ring attached to the part of X- (CONT) n is bonded to the sulfur atom thereof. 38. The silver halide photographic light-sensitive material of claim 37, wherein AF is a group represented by the following general formulas (DI) to (D-IX): wherein the asterisk (*) indicates a position to which the portion of COUP- (CONT) n is attached thereto; L3 represents a divalent organic linking group; X2 represents a substituent selected from a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkanamido group, an alkenamido group, an alkoxy group, a sulfonamido group, an aryl group and an alkylthio group; Z3 is -O-, -S- or -NH-, f1 is an integer from 1 to 2; and gl represents an integer from 1 to 6. 39. Silver halide photographic light-sensitive material according to Claim 1 or one of the remaining preceding claims, which contains compounds which are suitable, a releasable group by reaction with the oxidation product of a developing agent, and the released groups with each other react to form a development inhibitor with a stronger function than those of the released groups. 40. Silver halide photographic light-sensitive material according to Claim 39, wherein the compound is represented by the following general Formula (IV) X - (CONT) - AF1 - E1 (IV) wherein X is the same component as in FIG general Formula (I) is described, namely a component which is suitable (CONT) nAF1 -E1 after reacting with the oxidation product of a To release developing agent; n is 0 or 1, and when n is 1, CONT represents a component suitable for the release of AF1-E1 after CONT-AF1-E1 is released from X; AF a basic skeleton to achieve a die Development-inhibiting function and represents a component that is suitable to generate a nucleophilic group after the release of X or CONT; and E1 represents a group that is capable of being caused by intermolecular, nucleophilic shift reaction between two molecules of AF1-E1 through attack by a nucleophilic group, generated in AF1-E1 to be released. 41. Silver halide photographic light-sensitive material according to Claim 40, wherein E1 is a halogen atom, an alkanesulfonyloxy group, an arylsulfonyloxy group, represents an aryloxy group, an acyloxy group or an alkoxy group. 42. Silver halide photographic light-sensitive material according to Claim 40, wherein the component represented by CONT in the general formula (IV) a component having a function of regulating the coupling rate or the diffusibility from AF1-E1. 43. Silver halide photographic light-sensitive material according to Claim 40, wherein the basic skeleton of the development inhibitor represented by AF1 in the general formula (IV), a nitrogen-containing, unsaturated, heterocyclic Is a group bonded to the part X- (CONT) - on the nitrogen atom thereof, or a heterocyclic thio group with a monocyclic or condensed ring, the is bonded to the part of X- (CONT) n on the sulfur atom thereof. 44. The silver halide photographic light-sensitive material of claim 43, wherein AF1 is a group represented by the following general formulas (EI) to (E-IX): wherein the asterisk (F) indicates the position to which the portion of X- (CONT) n is attached; L4 represents a divalent organic linking group, X3 represents a substituent selected from a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkanamido group, an alkenamido group, an alkoxy group, a sulfonamido group, an aryl group and an alkylthio group; Z4 is -O-, -S- or -NH-, f2 is an integer from 1 to 2; and g2 is an integer from 1 to 6. 45. Silver halide photographic light-sensitive material according to Claim 44, wherein L4 represents a divalent group derived from an alkyl group, an alkanamido group, an aryl group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an alkanesulfonyl group, an alkylthio group, an alkanesulfoxo group, a Alkyl substituted ureido group or a combination of two or more of that. 46. Silver halide photographic light-sensitive material according to Claim 44, wherein -L4-E1 represents a group in which E1 is a halogen atom and L4 has a structure such that 1 to 3 carbon atoms between the through E1 represented halogen atom and a carbonyl group or a sulfonyl group available. 47. Silver halide photographic light-sensitive material according to Claim 1 or one of the other preceding claims, the at least one Kind of compounds (a), as described below, and at least one kind of Compounds (b) as described below comprises: a) a Compound suitable for forming a development inhibitor by reaction with the oxidation product of a developing agent; b) a connection suitable for Formation of a compound by reaction with the oxidation product of a developing agent, and wherein said compound essentially has a development inhibiting function of the development inhibitor can deactivate by reacting with it. 48. Silver halide photographic light-sensitive material according to Claim 47, wherein both compound a) and compound b) in the same Silver halide emulsion layer are present. 49. Silver halide photographic light-sensitive material according to Claim 47 or 48 including a compound represented by the following general formula (V) and a compound represented by the following general Formula (VI) X - (CONT) - AF2 (V) 5 2 (VI) wherein X is the same component as in of the general formula (I), namely a component, is suitable for the release of (CONT) -AF n 2 or L5-E2 after the reaction with the oxidation product a developing agent; n is 0 or 1, and when n is 1, CONT is one Represents component that is suitable for the release of AF2 after CONT-AF2 of X is released; AF2 represents a development inhibitor; and L5 -E2 a component represents suitable for the intermolecular nucleophilic shift reaction with AF2 is. 50. Silver halide photographic light-sensitive material according to Claim 49, wherein the component represented by X in the formula (V) and the component represented by X in formula (VI) may be the same or different can. 51. Silver halide photographic light-sensitive material according to Claim 47, 48, 49 or 50, wherein the diffusibility of the compound used for Deactivation of the development inhibiting function resulting from the compound b) is less than that of the development inhibitor that is formed from the compound a) is formed. 52. Silver halide photographic light-sensitive material according to Claim 49, 50 or 51, wherein E2 is a halogen atom, an alkanesulfonyloxy group, an arylsulfonyloxy group, an aryloxy group, an acyloxy group or an alkoxy group represents. 53. Silver halide photographic light-sensitive material according to Claims 49 to 52, wherein L5 represents a group containing a sulfur atom, a nitrogen atom or contains an oxygen atom through which the group is attached to X. 54. Silver halide photographic light-sensitive material according to Claim 52 or 53, wherein the group represented by L5 is an arylthio group, a dioxoimidazolidinyl group, a heterocyclic thio group, an aryloxy group, an alkoxy group, an alkylthio group, a benzotriazolyl group, a deoxotriazolidinyl group, a triazolyl group, an imidazolyl group, a benzimidazolyl group, an imidazolidinyl group, represents a pyrazolyl group or an acylaminooxy group. 55. The silver halide photographic light-sensitive material of claim 52, 53 or 54, wherein the group represented by L5 is a group represented by the following general formulas (FI), (F-II) or (F-III): * - Q - R - W - E2 (F-III) wherein the asterisk (*) indicates the position X is attached to it; a substituent represented by D is a hydrogen atom, a halogen atom, an alkyl group, an acylamino group, an alkoxy group, a sulfonamido group, an aryl group, an alkylthio group, a cyano group, a nitro group, an alkoxycarbonyl group, a hydroxy group, a carboxy group, a carbamoyl group, which with a An alkyl group or an aryl group, a sulfamoyl group which may be substituted with an alkyl group or an aryl group, an amino group which may be substituted with an alkyl group or an aryl group, an arylthio group, an ureido group which is substituted with an alkyl group or an aryl group may be an alkylsulfonyl group or an arylsulfonyl group, etc .; g2 represents an integer from 1 to 3; W represents a divalent group; T represents an organic radical required to form a 5-membered or 6-membered nitrogen-containing heterocyclic ring together with the nitrogen atom; Q represents an oxygen atom or a sulfur atom; and R is a substituted or unsubstituted alkylene group. 56. Silver halide photographic light-sensitive material according to Claim 54 or 55, wherein W represents a divalent group which is derived from an alkyl group, an acylamino group, an aryl group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an alkanesulfonyl group, an alkylthio group, an alkanesulfoxo group, an alkyl substituted ureido group or a combination of two or more of that. 57. Silver halide photographic light-sensitive material according to Claim 49 or any of the remaining preceding claims, wherein the total number of the carbon atoms included in L5-E2 is in the range from 6 to 20. 58. Silver halide photographic light-sensitive material according to Claim 49 or any of the other preceding claims, wherein the CONT The component shown in the general formula (V) is a component having the function to control the coupling rate or diffusibility of AF-E. 59. Silver halide photographic light-sensitive material according to Claim 49 or one of the other preceding claims, wherein the basic skeleton of the development inhibitor represented by AF2 in the general formula (V) is a nitrogen-containing unsaturated heterocyclic group attached to the Part of X- (CONT) n is bonded to the nitrogen atom thereof, or a heterocyclic one Thio group with a monocyclic or fused ring attached to the part of X- (CONT) n is bonded to the sulfur atom thereof. 60. The silver halide photographic light-sensitive material according to claim 58 or 59, wherein AF2 is a group represented by the following general formulas (GI) to (G-IX) wherein the asterisk (+) indicates the position to which the portion of X- (CONT) n is attached thereto; a substituent represented by X4 is a hydrogen atom, a halogen atom, an alkyl group, an alkanamido group, an alkoxy group, a sulfonamido group, an aryl group, an alkylthio group, an amino group, an N- (mono- or dialkyl) -carbamoyl group, a nitro group, a cyano group, is an alkanesulfonyl group, an aryloxy group, a ureido group, a sulfamoyl group, a hydroxy group, an anilino group, a heterocyclic group, a sulfenamido group or a carboxy group, etc .; a substituent represented by X5 is a hydrogen atom, an alkyl group, a phenyl group or a heterocyclic group; Z5 represents -O-, -S- or -N-, x5 wherein X5 has the same meaning as defined above; f3 denotes an integer from 1 to 2; if f3 denotes 2, the radicals X4 can be identical or different. 61. Silver halide photographic light-sensitive material according to Claim 1 or any of the remaining preceding claims which (1) is a compound contains which is capable of a development accelerator upon reaction with the To release oxidation product of a developing agent, and (2) used at the same time contains a compound capable of being compounded by reaction with the oxidation product to release a developing agent, the compound being the development accelerating Function of the development accelerator can deactivate and a greater diffusivity than that of the development accelerator. 62. Silver halide photographic light-sensitive material according to Claim 60 or 61, wherein both the compound (1) and the compound (2) are present in the same silver halide emulsion layer. 63. Silver halide photographic light-sensitive material according to Claim 60, 61 or 62 which has a compound represented by the following general Formula (VII) and a compound represented by the following general formula (VIII) contains: X - (CONT) n - A (VII) 6 3 (VIII) where X is the same component as defined in the general formula (I), namely a component which is suitable, (CONT) n-A or L6-E3 after reacting with the oxidation product of a To release developing agent; L6 represents a group that is appropriate to L6-E3 to make more diffusible than (CONT) n-A and which is suitable to form L6-A, that essentially has no photographic function in the case of intermolecular nucleophiles Shift reaction with A through nucleophilic attack by an anion that is released in the A is generated to enter; E3 is a group lost by L6 by nucleophilic attack can be released from A; A is a group that is part of an obfuscation agent ttel s or a development accelerator reducing agent in that Molecule contains and is capable of an anion in the molecule after release to generate from X or CONT, and to attack L6-E3 nucleophilically; n means 0 or 1 and, if n is 1, CONT is a compound capable of releasing A, after CONT-A is released from X. 64. Silver halide photographic light-sensitive material according to Claim 62 or 63, wherein the component represented by X in formula (VII) and the component represented by X in the formula (VIII) is the same or different could be. 65. Silver halide photographic light-sensitive material according to Claim 62, 63 or 64, wherein E3 is a halogen atom, an alkanesulfonyloxy group, an arylsulfonyloxy group, an aryloxy group, an acyloxy group or an alkoxy group represents. 66. Silver halide photographic light-sensitive material according to Claim 63 or any of the remaining preceding claims, wherein 116 is a group represents containing a sulfur atom, a nitrogen atom or an oxygen atom, through which the group is attached to X 67. Silver halide photographic light-sensitive material according to Claim 65 or 66, wherein the group represented by 116 is an arylthio group, a heterocyclic thio group, an aryloxy group, an alkoxy group, an alkylthio group, a 2,4-dioxoimidazolidinyl group, a benzotriazolyl group, a triazolyl group, an imidazolyl group, an acyloxy group, a benzimidazolyl group, a 3,5-dioxotriazolidinyl group, represents an imidazolidinyl group, a pyrazolyl group or an acylaminooxy group. 68. The silver halide photographic light-sensitive material of claim 66 or any preceding claim, wherein the group represented by L6 is a group represented by the following general formulas (HI) to (HV): * - 0 - X7 - Wl E3 (H-III) * - S - X7 - W1 E E3 (HV) wherein the asterisk (+) indicates the position to which X is attached; a substituent represented by X6 is a hydrogen atom, an alkyl group, an acylamino group, an alkoxy group, a sulfonamido group, an aryl group, an alkylthio group, a cyano group, a nitro group, an alkoxycarbonyl group, a hydroxy group, a carboxy group, a carbamoyl group, represented by an alkyl group or a Aryl group may be substituted, a sulfamoyl group which may be substituted by an alkyl group or an aryl group, an amino group which may be substituted by an alkyl group or an aryl group, an arylthio group, an ureido group which may be substituted by an alkyl group or an aryl group, represents an alkylsulfonyl group or an arylsulfonyl group; f represents an integer from 1 to 3; W1 represents a divalent group; Z3 represents an organic radical suitable for forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring together with the nitrogen atom; and X7 is an alkylene group which can be any straight, branched, or cyclic saturated or unsaturated, substituted or unsubstituted alkylene group. 69. Silver halide photographic light-sensitive material according to Claim 68 or any of the other preceding claims, wherein W1 is a divalent Represents a group derived from an alkyl group, an acylamino group, an aryl group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, an alkanesulfonyl group, an alkylthio group, an alkanesulfoxo group, an alkyl-substituted ureido group or a combination of two or more thereof. 70. Silver halide photographic light-sensitive material according to Claim 63 or any of the other preceding claims, wherein the CONT in the general formula (VII) component represented a component with the Function to regulate the coupling rate or the diffusibility of A is. 71. Silver halide photographic light-sensitive material according to Claim 63 or any of the remaining preceding claims, wherein the one represented by A. Group is a group containing a sulfur atom, a nitrogen atom or an oxygen atom by which the group is attached to X or CONT. 72. Silver halide photographic light-sensitive material according to Claim 71 or any one of the remaining preceding claims, wherein that represented by A. Group is a group formed by a thiourea, a hydrazine, a 3-pyrazolidone, is derived from a rhodanine or a thioamide. 73. A silver halide photographic light-sensitive material as claimed in claim 71 or any preceding claim, wherein the group A is a group represented by the following general formula (JI) or (J-II): wherein the asterisk (+) indicates the position to which X- (CONT) n is attached; G is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a divalent substituted or unsubstituted heterocyclic group, a divalent group containing an ester bond, a thioether bond, an amido bond, a sulfonamido bond, a sulfone bond or an ether bond in an alkylene group, or a represents a divalent group composed of two or more thereof, U1 and U2 each represent a hydrogen atom or a lower alkyl group, and at least one of U1 and U2 represents a hydrogen atom, M represents a formyl group, an acyl group, an alkylsulfonyl group, an aryl group, an arylsulfonyl group , represents an alkyl group, an alkoxycarbonyl group, a carbamoyl group or a sulfamoyl group; Z6 denotes an organic radical which is required to form a 5-membered or 6-membered nitrogen-containing heterocyclic ring together with the nitrogen atom; and t is 0 or 1. 74. Silver halide photographic light-sensitive material according to Claim 1 or one of the other preceding claims, which also has a contains a color-forming coupler which is capable of causing a dye in the reaction in the oxidation product of a developing agent. 75. Silver halide photographic light-sensitive material according to Claim 73 or 74 in which the color-forming coupler is a 2-equivalent coupler. 76. Silver halide photographic light-sensitive material according to Claim 73, 74, 75 or one of the other preceding claims, the at least a red sensitive silver halide emulsion layer which at least contains a cyan color-forming coupler, at least one green-sensitive silver halide emulsion layer, the at least one purple or Magenta color image-forming coupler contains and at least one blue-sensitive Silver halide emulsion layer containing at least one yellow color image-forming coupler contains, has.