JPH07104447A - Direct positive color photographic material, color image forming method and color-proof forming method - Google Patents

Abstract

PURPOSE:To make the difference great in image concentration, and enhance a shelf life by letting both coupler emitting specified fogging agent or developing accelerator and redox compounds be included in either of a photosensitive layer or a non-photosensitive layer. CONSTITUTION:Let coupler emitting coupling agent or developing accelerator and redox compounds be included respectively at least in one out of a blue photosensitive layer, a green photosensitive layer, a red photosenstive layer and a non-photosensitive layer adjacent the aforesaid layers, which include in advance not-fogged internal latent image type silver halide particles and color image forming coupler. The aforesaid coupler is represented by a formula: Cp-(TIME)n-FA or a formula: BALL-Cp-(TIME)-FA, and redox compounds are represented by a formula: RED-(TIME)n-FA. In the formulas, Cp represents coupler residues formed by a coupling reaction with the oxidant of an aromatic first class amine developing main ingredient, BALL represents anti-diffusivity capable of being free from Cp, RED represents compound residues formed by an oxidation-reduction reaction with the oxidant of the aforesaid developing main ingredients, and FA represents coupling agent or developing accelerator.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a direct positive color photographic light-sensitive material utilizing an internal latent image type silver halide emulsion, a color image forming method using the same, and a color proof making, which makes it possible to directly obtain a positive image. Regarding the method.

[0002]

BACKGROUND OF THE INVENTION Photographic methods for obtaining direct positive images without the need for reversal processing steps or negative films are well known.
As a method for forming a positive image using a conventionally known direct positive color silver halide photographic light-sensitive material, there is a method using an internal latent image type silver halide emulsion which is not fogged in advance. This method is a method for directly obtaining a positive color image by subjecting a photographic light-sensitive material to image development, surface development after or after fog treatment. The internal latent image type silver halide photographic emulsion which has not been previously fogged is a type of halide having a photosensitive nucleus mainly inside the silver halide grain and a latent image is mainly formed inside the grain upon exposure. A silver photographic light sensitive emulsion. Various techniques have been known so far in this field. For example, US Pat. No. 2,592,250.
Nos. 2466957, 2497875, 25
No. 88982, No. 3317322, No. 3761266
Nos. 3,761,276, 3,796,577 and British Patent Nos. 1,115,363, 1,150,553, 10,
Those described in each specification of No. 11062 are the main ones. The formation mechanism of the direct positive image is explained as follows. That is, when imagewise exposure is performed, a so-called internal latent image is formed on the silver halide, and a fog treatment is then applied to cause a surface desensitizing action due to the internal latent image (that is, the halogen in the exposed portion is affected). Development nuclei (fog nuclei are not generated on the surface of silver halide), development nuclei are selectively generated only on the surface of unexposed silver halide,
Then, a normal surface development process is performed to form a photographic image (positive image) on the unexposed portion. The fog treatment method includes a so-called "optical fog method" for exposing the entire surface of the photosensitive layer and a "chemical fog method" for using a nucleating agent. Direct positive color silver halide photographic light-sensitive materials using internal latent image type silver halide emulsions which have not been previously fogged as described above have been accepted in recent years due to the simplicity of their processing steps, and color copying and color plate-making, It has been used for inspection of printing, preparation of color proof for adjustment, etc.

The working process of the color printed matter includes the steps of color-separating a color original and converting it into a halftone dot image to produce a transmission type halftone dot image. A printing plate is made from the obtained transmission type halftone image, but prior to this, the final printed matter (main printing)
There is a step of inspecting the state, characteristics, etc., and performing necessary calibration (color calibration). As a color proofing method, conventionally, a method of making a printing plate and making a test print has been used. However, in recent years, various color proofs have been produced for the purpose of speeding up the calibration process and reducing costs.
As a method for producing a color proof, a photopolymer, a diazo method, a surprint method using a photoadhesive polymer and the like, and an overlay method are known (for example, US Pat. No. 3,582,327, JP-A-56-50121).
7 and 59-97140). However, all of these methods require superposition and transfer of images, and also require superposition and transfer of a plurality of figures, and the process is complicated and requires a lot of time and cost. .. JP-A-56-104335 discloses that
A method for producing a color proof using a color photographic light-sensitive material has been disclosed, and this method has great advantages in terms of simplicity of process and low cost, and is also characterized by excellent tone reproducibility. The color proofing method using the above color photographic light-sensitive material uses a silver halide color photographic light-sensitive material of a coloring method having a continuous gradation, and a magenta (M) color, cyan (C) color, yellow ( This is a method in which each color of Y) and black (B) is sequentially contact-exposed so that a color negative is printed on a color paper, and then a designated color development processing is performed to obtain a color proof. This method has a feature that the process is simple and easy to automate as compared with the various methods described above. There are several possible silver halide color photographic light-sensitive materials that can be used in such color proofs. Among them, the transmission type black and white halftone image used in the production process of the color printed matter described above is often a positive type especially in Japan and Europe, and therefore, as a silver halide color photographic light-sensitive material for color proofing. Many positive-positive type photosensitive materials are used. Among them, the direct positive type color photographic light-sensitive material, of which the practical application technology has been rapidly advanced in recent years, has been noted as being most suitable for use in color proof because of the ease of processing.

In this application, the direct positive type color photographic light-sensitive material is required to give an image with high contrast and to be capable of rapid processing. In silver halide color photographic light-sensitive materials, it is already known to use a compound which reacts with an oxidized product of a developing agent during development to release a fogging agent or a development accelerator.
5084, 59-170840, JP-A-2-2138.
38, 2-244041 and the like. In particular, hydroquinone compounds that release a fogging agent or a nucleation accelerator are particularly effective for increasing the maximum image density without increasing the minimum image density.
On the other hand, however, these compounds have a problem that the maximum image density is lowered by long-term storage, and further improvement has been desired.

[0005]

The object of the present invention is to provide a direct positive color photographic light-sensitive material having a high maximum image density, a low minimum image density, rapid processing and excellent storability, and a photographic light-sensitive material using the same. Another object of the present invention is to provide a conventional color image forming method and a color proof making method.

[0006]

Means for Solving the Problems As a result of intensive investigations by the present inventors for compounds suitable for the above-mentioned objects, the inventors have found that a fogging agent or a development accelerator represented by the following formula (I) or (II) is used. The present invention was completed by discovering that a light-sensitive material of the above purpose can be obtained by using a releasing coupler in combination with a fogging agent or a redox compound releasing a development accelerator represented by the following formula (III). did.

The present invention is directed to a support comprising a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer containing an internal latent image type silver halide grain not previously fogged and a color image-forming coupler, and a non-photosensitive layer adjacent thereto. A direct positive color photographic light-sensitive material provided with at least one photosensitive layer, at least one of the blue-sensitive layer, green-sensitive layer, red-sensitive layer and non-photosensitive layer is represented by the following formula (I) or (II) A coupler that releases a fogging agent or a development accelerator (hereinafter, FR coupler) and a redox compound (hereinafter, FR redox compound) that releases a fogging agent or a development accelerator represented by the following formula (III): It is a direct positive color photographic light-sensitive material characterized by containing.

The compounds represented by the following general formulas (I), (II) and (III) (hereinafter referred to as FR compounds) will be described in detail. (I) Cp- (TIME) _n -FA (II) BALL-Cp- (TIME) _n -FA (III) RED- (TIME) _n -FA In the above formula, Cp is an aromatic primary amine development. Represents a coupler residue capable of undergoing a coupling reaction with an oxidized form of a drug. B
ALL represents a diffusion-resistant group which can be separated from Cp by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. RED represents a compound residue capable of undergoing a redox reaction with an oxidized product of an aromatic primary amine developing agent. TIME
Represents a timing group that further releases FA after leaving Cp or RED by a coupling reaction. n represents 0 or 1, and FA is, when n is 0,
It is a group capable of leaving from Cp or RED by a coupling reaction, and a group capable of being released from TIME when n is 1 (in the case of the compound represented by (II) in the above formula,
FA does not have to leave Cp or TIME after the coupling reaction). Here, FA represents a so-called caplace agent or development accelerator that acts on silver halide grains during development to generate fog nuclei capable of initiating development. Examples of FA include a group that acts reductively on silver halide grains during development to produce fog nuclei or a group that acts on silver halide grains to produce silver sulfide nuclei which are fog nuclei that can initiate development. be able to.

Preferred groups for FA include groups having adsorptivity for silver halide grains and can be represented as follows. AD- (L) _m -X AD represents a group having adsorptivity to silver halide, L represents a divalent group, and m represents 0 or 1.
X represents a reducing group or a group capable of acting on silver halide to form silver sulfide. However, when X is the latter, it may also have the function of AD, and in this case, AD- (L) _m- is not always necessary. When FA is a group represented by AD- (L) _m -X, TIM
The position of binding to E, Cp or RED is AD- (L) _m
It may be any position in -X. In the general formula (I), −
(TIME) _n -FA binds to the coupling position of Cp, and the bond is cleaved during the coupling reaction. In the general formula (II), BALL is bonded to the coupling position of Cp, and the bond is cleaved during the coupling reaction. Further, since-(TIME) _n -FA is bonded to the non-coupling position of Cp, the bond is not immediately cleaved by the coupling. In the general formula (III),-(TIME) _n -FA is bonded to a position where RED can be released from RED by a redox reaction with an oxidized aromatic primary amine developer or a subsequent reaction thereof.
On the other hand, the group represented by TIME may be a trivalent group in the case of the general formula (I). That is, one of the trivalent bonds binds to FA, one of the remaining two bonds to the coupling position of Cp, and the other one binds to the uncoupling position of Cp. . The compound having such a structure is characterized in that, at the time of the coupling reaction with the aromatic primary amine developing agent, the bond with TIME that is bonded to the coupling site is cut off, but the compound is bonded to the non-coupling site. The bond with the existing TIME is not cleaved, and the cleaved bond portion (anion) of the TIME cleaves the bond with FA by intramolecular electron transfer of TIME and / or intramolecular nucleophilic substitution reaction to form FA. It can be released. Therefore, in the case of such compounds,
In addition to being a trivalent group, it is necessary to have a structure capable of releasing FA by intramolecular electron transfer and / or intramolecular nucleophilic substitution reaction.

In the following, the general formulas (I), (II) and (III)
Will be described in more detail. In formula (I), the coupler residue represented by Cp has a partial structure of a non-color forming coupler and a black color forming coupler in addition to the yellow, magenta and cyan couplers described below. Typical examples of the yellow coupler among the couplers are U.S. Pat. Nos. 2875057, 2407210, and 32655.
No. 06, No. 2298443, No. 3048194, No. 3447928 and the like. Among the yellow couplers, acylacetamide derivatives such as benzoylacetanilide and pivaloylacetanilide are preferable. Therefore, the yellow coupler residue (Cp)
Those represented by the following general formulas (Ia) and (IIa) are preferable.

[0011]

[Chemical 2]

In addition, * represents the bonding position of FA group or TIME group (the same applies to the following general formula (XVa)). Here, R ¹ represents a non-diffusible group having 8 to 32 carbon atoms, and R ² and R ³ are each independently a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a non-diffusible group having 8 to 32 carbon atoms. Represents a diffusible group. p is an integer of 1 to 4,
q represents an integer of 1 to 5. When p and q are 2 or more, R ² and R ³ may be the same or different from each other.

Typical examples of magenta couplers are shown in US Pat. Nos. 2,600,788, 2,369,489 and 234.
No. 3703, No. 2311082, No. 3152896
No. 35, 194529, 3062653, 29.
No. 08573, Japanese Patent Publication No. 47-27411,
JP-A-59-171956 and 59-162548.
No. 60-33552, No. 60-43659, No. 60-172982, and the like.
Of the magenta couplers, pyrazolone or pyrazoloazoles (pyrazolopyrazole, pyrazoloimidazole, pyrazolotriazole, pyrazolotetrazole, etc.)
Is preferred. Therefore, the magenta coupler residue (C
As p), those represented by the following general formulas (IIIa), (IVa) and (Va) are preferable.

[0014]

[Chemical 3]

Here, R ¹¹ represents a diffusion resistant group having 8 to 32 carbon atoms, and R ¹² represents a halogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group or a substituted phenyl group. Z represents a nonmetallic atom group necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring), The substituent may be a diffusion resistant group.

Typical examples of cyan couplers are US Pat. Nos. 2,772,162, 2,895,826 and 3,0028.
No. 36, No. 3034892, No. 2474293, No. 2423730, No. 2367531, and No. 30.
No. 41236, JP-A-56-99341,
57-155538, 57-204545, 58-189154, and 59-31953,
58-118643, 58-187928, 58-213748, U.S. Pat. No. 4,333,399.
No. 9 specification and the like. Of those cyan couplers, phenols or naphthols are preferable. Therefore, as the cyan coupler residue (Cp), those represented by the following general formulas (VIa), (VIIa), (VIIIa) and (IXa) are preferable.

[0017]

[Chemical 4]

Here, R ²¹ represents a diffusion resistant group having 8 to 32 carbon atoms, R ²² represents a halogen atom, a lower alkyl group or a lower alkoxy group, and r represents an integer of 1 to 3. r
When is 2 or more, R ^{22 s} may be the same or different.

Cp may be a so-called colorless coupler. Typical examples of colorless couplers are described in US Pat. Nos. 3,912,513 and 4,048,67,
It is described in JP-A No. 52-152721.
Representative examples of these non-color-forming coupler residues have skeletons represented by the following general formulas (Xa), (XIa) and (XIIa).

[0020]

[Chemical 5]

Here, R ³¹ represents a diffusion resistant group having 8 to ³² carbon atoms, and R ³² represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group.

[0022]

[Chemical 6]

Here, R ³¹ represents a diffusion resistant group having 8 to 32 carbon atoms, and V represents an oxygen atom, a sulfur atom or --N.
Represents an (R ³³ ) -group. R ³³ is a hydrogen atom or has 1 carbon atom
Represents an alkyl group of 32.

[0024]

[Chemical 7]

Here, R ⁴¹ and R ⁴² are each independently an alkoxycarbonyl group, aminocarbonyl group, acyl group, alkoxysulfonyl group, alkoxysulfinyl group, sulfamoyl group, sulfinamoyl group, sulfonyl group, sulfinyl group, cyano group, It represents an ammonium mill group, a nitrogen-containing heterocycle bonded by a nitrogen atom, and the like.
R ⁴¹ and R ⁴² may combine to form a 5- or 6-membered ring.

In addition to the above, Cp may be a color-forming coupler residue that develops black color by reacting with an oxidized product of a developing agent. Examples of those couplers include US Pat.
939231, 2181944, 233310.
No. 6, 4126461, West German patent (OL
S) 2644194 and 2650764. Specifically, those coupler residues are represented by the following general formulas (XIIIa), (XIVa) and (XVa)
It is represented by.

[0027]

[Chemical 8]

Here, R ⁵¹ is an alkyl group having 3 to 20 carbon atoms or a phenyl group (wherein the phenyl group is substituted with a hydroxyl group, a halogen atom, an amino group, an alkyl group having 1 to 20 carbon atoms or an alkoxy group). Represents). R ⁵² and R ⁵³ are each independently a hydrogen atom, a halogen atom,
It represents an alkyl group or an alkenyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ⁵⁴ represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or another monovalent organic group, and r represents an integer of 1 to 3. When r is 2 or more, R ⁵⁴ may be the same as or different from each other.

The Cp represented by the above general formulas (Ia) to (XVa) may form a dimer or higher multimer at a portion other than the coupling site, and may be bound to the polymer at that portion. You may have.

In the general formula (II), the coupler residue represented by Cp has the structure represented by the above general formulas (Ia) to (XVa), and BALL is bound to the * mark, and the other residues are One is bound to-(TIME) _n -FA.

In the general formula (II), the nondiffusible group represented by BALL is a polymer having a size and shape giving non-diffusivity to the coupler and having a plurality of leaving groups linked to each other. It may have an alkyl group and / or an aryl group that imparts non-diffusibility. In the latter case, the total number of carbon atoms in the alkyl group and / or aryl group is preferably about 8 to 32. B
ALL has a group for bonding to the coupling position of Cp, and typical examples thereof include -O- and -S.
-, - N = N -, - OCO -, - OSO 2 -, and is -N constituting the hetero ring =.

In the general formula (III), the group represented by RED has a skeleton of hydroquinone, catechol, o-aminophenol or p-aminophenol, and is an oxidized product of an aromatic primary amine developer and a redox compound. React and subsequently undergo alkaline hydrolysis to-(TIME) _n -F
Group A (in the following general formulas (XVIa) to (XXIa), this is referred to as “F
R "is abbreviated).

Specific examples thereof are represented by general formulas (XVIa) to (XXI
Shown in a).

[0034]

[Chemical 9]

[0035]

[Chemical 10]

In the above formula, R ⁶¹ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group,
Aryloxy group, alkylthio group, arylthio group,
Cyano group, alkoxycarbonyl group, carbamoyl group,
It represents a sulfamoyl group, a carboxyl group, a sulfo group, a sulfonyl group, an acyl group, a carbonamido group, a sulfonamide group or a heterocyclic group, r represents an integer of 1 to 3, and p represents an integer of 1 to 4. When p and r are 2 or more, R ⁶¹ may be the same as or different from each other, and two in the vic-position are bonded to each other to form a benzene ring or a 5- to 7-membered heterocycle. It may be formed. R ⁶² is an alkyl group, an aryl group, an acyl group, a carbamoyl group,
Represents a sulfonyl group or a sulfamoyl group. T ¹ represents a hydrogen atom or a group capable of splitting off upon hydrolysis under alkaline conditions. When two T ^1's are present in the molecule, they may be different from each other. Representative examples of T ¹ include a hydrogen atom, an acyl group, a sulfonyl group, an alkoxycarbonyl group, a carbamoyl group and an oxalyl group.

The timing group represented by TIME is described in US Pat. No. 4,248,962 and JP-A-57-56.
As described in Japanese Patent No. 837, etc., the compound is released from Cp or RED by a coupling reaction or a redox reaction, and then FA is released by an intramolecular substitution reaction, British Patent 20
72363A, JP-A-57-154234, 57.
No. 188035, No. 56-114946, No. 57-
56837, 58-209736, 58-20
No. 9737, No. 58-209738, No. 58-209
Nos. 740 and 58-98728, which release FA by electron transfer through a conjugated system, and oxidation of aromatic primary amine developers as disclosed in JP-A-57-111536. Examples thereof include those that are coupling components capable of releasing FA by a coupling reaction with the body. These reactions may be carried out in one step or in multiple steps.

Further, as described above, a trivalent TIME which binds to the coupling site and the non-coupling site and FA is also preferable (an example of incorporation into a yellow coupler is disclosed in JP-A-58-209740). Have been described).

When FA is a group containing AD- (L) _m -X, AD may be directly bonded to the carbon atom at the coupling position, or either L or X may be eliminated by the coupling reaction. If possible, these may be bonded to the coupling carbon. What is known as a so-called 2-equivalent leaving group may be interposed between the coupling carbon and AD. These 2-equivalent leaving groups include an alkoxy group (eg methoxy), an aryloxy group (eg phenoxy), an alkylthio group (eg ethylthio), an arylthio group (eg phenylthio), a heterocyclic oxy group (eg tetrazolyloxy), Heterocyclic thio groups (eg pyridylthio), heterocyclic groups (eg hydantoinyl, pyrazolyl, triazolyl, benzotriazolyl). In addition, those described in British Patent Publication No. 2011391 can be used as FA.

The group capable of adsorbing to silver halide represented by AD is a nitrogen-containing heterocycle having a dissociable hydrogen atom (pyrrole, imidazole, pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole, benzotriazole). , Uracil, tetraazaindene, imidazotetrazole, pyrazolotriazole, pentaazaindene, etc.), a heterocycle having at least one nitrogen atom and another heteroatom (oxygen atom, sulfur atom, selenium atom, etc.) in the ring ( Oxazoles, thiazoles, thiazolines, thiazolidines, thiadiazoles, benzothiazoles, benzoxazoles, benzselenazoles, etc.), mercapto group-containing heterocycles (2-mercaptobenzthiazole, 2-mercaptopyrimidine, 2-mercaptobenzoxy). Sol, 1-phenyl-5-mercaptotetrazole, etc.), quaternary salt (quaternary salt of tertiary amine, pyridine, quinoline, benzthiazole, benzimidazole, benzoxazole, etc.), thiophenols, alkylthiols (cysteine, etc.) ), And = NC
Examples thereof include compounds having an S- partial structure (for example, thiourea, dithiocarbamate, thioamide, rhodanine, thiazolidinethione, thiohydantoin, thiobarbituric acid).

[0041] As the divalent linking group represented by L in the FA alkylene, alkenylene, phenylene, naphthylene, -O -, - S -, - SO -, - SO 2 -, - N = N
-, Carbonyl, amide, thioamide, sulfonamide, ureido, thioureido, heterocycle and the like. If one of the divalent linking groups forming L is a group capable of being cleaved by the action of a component (eg, hydroxide ion, hydroxylamine, sulfite ion, etc.) in the developer, the fogging effect can be controlled. It can also be deactivated.

The group represented by X is a reducing compound (hydrazine, hydrazide, hydrazone, hydroquinone, catechol, p-aminophenol, p-phenylenediamine, 1-phenyl-3-pyrazolidinone, enamine, aldehyde, polyamine, acetylene. , Aminoborane, tetrazolium salts, quaternary salts such as ethylenebispyridinium salts, etc.) or compounds capable of forming silver sulfide during development (eg, thiourea, thioamide, dithiocarbamate, rhodanine, thiohydantoin, thiazolidinethione). , = NCS- partial structure, etc.) and the like. Among the groups represented by X, some of the groups capable of forming silver sulfide at the time of development have an adsorptivity for silver halide grains, and can also serve as an adsorptive group AD. The FR compounds used in the present invention and examples thereof are described in JP-A Nos. 57-150845, 59-50439, 59-157638, 59-170840 and 6
0-37556, 60-147029, 60-
It is described in each specification such as 128446.

An example of AD is shown below. The free bond is −
It binds to (L) _m- X and-(TIME) _n- .

Among these redox compounds, the compound represented by the general formula (IV) is preferable, and the compound represented by the general formula (V) is more preferable.

[0045]

[Chemical 11]

In the formula, R ⁹¹ represents a hydrogen atom or an alkyl group, R ⁹² represents an alkyl group, an aryl group, a heterocyclic group, an amino group or an alkoxy group, and X represents —CO— or —S.
Represents O ₂ — or —COCO—. R ⁹³ and R ⁹⁴ represent a hydrogen atom or a substituent having a Hammett substituent constant σ _p of 0.3 or less. Further, T ₁ and FR have the same contents as those in the general formula (III).

Specific examples of the compounds used in the present invention are shown below.

[0048]

[Chemical 12]

[0049]

[Chemical 13]

[0050]

[Chemical 14]

[0051]

[Chemical 15]

[0052]

[Chemical 16]

[0053]

[Chemical 17]

[0054]

[Chemical 18]

[0055]

[Chemical 19]

[0056]

[Chemical 20]

[0057]

[Chemical 21]

[0058]

[Chemical formula 22]

[0059]

[Chemical formula 23]

[0060]

[Chemical formula 24]

[0061]

[Chemical 25]

[0062]

[Chemical formula 26]

[0063]

[Chemical 27]

[0064]

[Chemical 28]

[0065]

[Chemical 29]

[0066]

[Chemical 30]

[0067]

[Chemical 31]

[0068]

[Chemical 32]

[0069]

[Chemical 33]

[0070]

[Chemical 34]

[0071]

[Chemical 35]

[0072]

[Chemical 36]

[0073]

[Chemical 37]

[0074]

[Chemical 38]

[0075]

[Chemical Formula 39]

The FR compound described above may be contained in any of the layers constituting the light-sensitive material, but is preferably contained in the silver halide emulsion layer. The addition amount of the FR compound used in the present invention is in the range of 10 ^-9 to 10 ^-1 mol, preferably 1 mol per 1 mol of silver halide contained in the FR compound-containing layer or the adjacent layer. 10 ^-6 to 10 ^-1 mol range,

When the FR compound is introduced into the silver halide emulsion layer, a known method (for example, US Pat. No. 232) is used.
The method described in the specification of No. 2027) is used. For example, a method in which the following solvent is dissolved and then dispersed in a hydrophilic colloid is used. The following can be mentioned as a solvent that can be used. Phthalic acid alkyl ester (eg, dibutyl phthalate, dioctyl phthalate), phosphoric acid ester (eg, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid ester (eg, acetyl citric acid) Tributyl), benzoic acid ester (eg, octyl benzoate), alkylamide (eg, diethyllaurylamide), fatty acid ester (eg, dibutoxyethyl succinate, diethyl azelate), trimesic acid ester (eg, trimesic acid) Tributyl) or an organic solvent having a boiling point of about 30 ° C to 150 ° C, for example, lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutane. Ketone, beta-ethoxyethyl acetate, methyl cellosolve acetate.

The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used. In addition, Japanese Patent Publication Sho 51-3985
The dispersion method using a polymer described in JP-A-51-59943 and JP-A-51-59943 can also be used. When the FR compound has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

The silver halide emulsion used in the color photographic light-sensitive material of the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the surface of silver halide grains, or a latent image is mainly silver halide grains. Any of the so-called internal latent image type emulsions formed inside may be used. However, as described above, a type (a direct positive color photographic light-sensitive material) of a type having an emulsion layer containing an internal latent image type silver halide grain which is not fogged in advance can be preferably used as the silver halide emulsion layer. The internal latent image type silver halide grains not previously fogged will be described later.

The grains contained in the silver halide emulsion used in the present invention are preferably silver bromide, silver chlorobromide or silver chloride containing substantially no silver iodide. The term "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. Further, regarding the halogen composition distribution of silver halide grains, a so-called uniform structure grain having the same composition in any portion of the silver halide grain, a core inside the silver halide grain and a shell (shell) surrounding it. ) (A single layer or a plurality of layers) has a so-called laminated structure having different halogen compositions, or a structure having a non-layered portion having a different halogen composition inside or on the surface (in the case of being on the surface of the particle, edges, corners or There are particles having a structure in which parts of different compositions are bonded on the surface), and these can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the above structure, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. Alternatively, it may be one that positively has a continuous structural change. Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide /
A silver chloride ratio can be used. This ratio is
Wide range depending on the purpose, but the silver chloride ratio is 2%
The above is preferable.

A so-called high silver chloride emulsion having a high silver chloride content is preferably used for a light-sensitive material suitable for rapid processing. The silver chloride content of the high silver chloride emulsion is preferably 90 mol% or more,
95% or more is more preferable. In such a high silver chloride emulsion, a structure having a silver bromide localized layer in the inside and / or on the surface of the silver halide grain as described above is preferable. The halogen composition of the localized layer preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. Or it may be on the surface. As one preferable example, there may be mentioned one epitaxially grown at the corner portion of the grain. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, an almost pure silver chloride emulsion having a silver chloride content of 98 mol% to 100 mol% can also be preferably used.

The average grain size of silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. The thickness is preferably 1 μm to 2 μm (more preferably 0.2 μm to 1.2 μm). Further, the particle size distribution thereof is preferably a so-called monodisperse coefficient of variation of 20% or less (standard deviation of particle size distribution divided by average particle size), preferably 15% or less. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodispersed silver halide emulsions having different grain sizes or a plurality of emulsions having the same size but different sensitivities are used in the emulsion layers having substantially the same color sensitivity. The particles can be mixed in the same layer or multi-layered in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The silver halide grains contained in a photographic emulsion have a regular crystal form such as a cube, octahedron, dodecahedron or tetradecahedron, a spherical shape,
It is possible to use a material having an irregular crystal shape such as a plate shape, or a material having a composite shape of these. It may also be a mixture of those having various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form are contained in an amount of 50% or more, preferably 70% or more, more preferably 90% or more. In addition to these, an emulsion having tabular grains having an average aspect ratio (circular equivalent diameter / thickness) of 5 or more, preferably 8 or more as a projected area exceeding 50% of all grains can be preferably used.

The silver chlorobromide emulsion used in the present invention is described in P. Glaf
Chides "Chimie et Photograph-ique" (Paul Mon
tel, 1967), GF Duffin, "(Photog
raph-ic Emulsion Chemistry "(Focal Press, 1
966), V. L. Zelikman et al, "Making a
nd Coating Photographic Emulsion "(Focal Press, Inc., 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. You may use. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is,
A so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced in the process of emulsion grain formation or physical ripening. Examples of compounds used include cadmium, zinc, lead, copper, thallium, salts such as bismuth, or Group VIII elements iron, ruthenium, rhodium, palladium, osmium,
Examples thereof include salts of iridium and platinum, or complex salts. Of these metals, lead, iridium, bismuth and rhodium are preferred. The addition amount of these compounds may vary depending on the purpose, but is 10 ^-9 to 10 ^-2 mol (more preferably 10 ^-7 mol) with respect to the silver halide.
10 to ³ mol) is preferred. For the method of incorporating these metals, see US Pat. Nos. 3,761,276 and 43,954.
No. 78 and JP-A-59-216136.

The silver halide emulsion used in the present invention is
Usually, it is preferable that chemical sensitization and spectral sensitization are performed. Regarding the chemical sensitization method, treatment such as sulfur sensitization typified by unstable sulfur compound addition, noble metal sensitization typified by gold sensitization, reduction sensitization, or selenium sensitization is performed alone or in combination. be able to. As the compound used for the chemical sensitization, those described in JP-A No. 62-215272, page 18, lower right column to page 22, upper right column of the specification are preferably used. In the above chemical sensitization treatment, as described in JP-A-1-197742, in the presence of a mercapto compound, JP-A-1-254946, JP-A-2-69738, and JP-A-2-273735.
Thiosulfinic acid, sulfinic acid, and sulfite may be added as described in the publication. The chemical sensitization method for core particles is described in JP-A-2-199450 and 2-19.
The method described in Japanese Patent No. 9449 can be used. A detailed specific example is given in Research Disclosure No. 17643-III (issued in December 1978)
There is also a patent described on page 23. Spectral sensitization is performed for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity, that is, a so-called spectral sensitizing dye. Examples of the spectral sensitizing dye include FM Harm
er `` Heterocyclic compounds-Cyanine dyes and rela
ted compounds "(John Wiley & Sons (NewYork, Londo
n) Published by the company, 1964). Specific examples of the compound and the spectral sensitization method are described in JP-A-62-215272, No. 2
Those described on page 2, upper right column to page 38 are preferably used. A detailed specific example is given in Research Disclosure No. There are also patents described on pages 23 to 24 of 17643-IV (issued in December 1978).

The non-pre-fogged internal latent image type silver halide emulsion preferably used in the present invention will be described. An internal latent image type silver halide emulsion which has not been fogged in advance is an emulsion in which the surface of silver halide grains is not fogged and which contains a silver halide which mainly forms a latent image inside the grain. Specifically, the silver halide emulsion is fixed on the transparent support in a fixed amount (0.5 to 3 g / m 2).
² ) Apply and expose to light for a fixed time of 0.01 to 10 seconds, and in the following developer (internal type developer),
When developed at 0 ° C. for 5 minutes, the maximum density measured by a usual photographic density measuring method was the same amount of the above coated silver halide emulsion, which was similarly exposed in the following developing solution (surface type developing solution): Those having a density at least 5 times higher than the maximum density obtained when developed at 18 ° C. for 6 minutes are preferable, and those having a density at least 10 times higher are more preferable. Internal type developer Metol 2.0 g Sodium sulfite (anhydrous) 90.0 g Hydroquinone 8.0 g Sodium carbonate (monohydrate) 52.8 g KBr 5.0 g KI 0.5 g Water-added 1000 ml Surface type developer Metol 2 .5G L-ascorbic acid _{10.0g NaBO 2 · 4H 2 O 35.0g} KBr 1.0g water to make 1000ml

Specific examples of the internal latent image type silver halide emulsion include, for example, conversion type silver halide emulsions described in US Pat. No. 2,592,250; or US Pat. Nos. 3,761,276, 3,850,637 and 3,923,513. , 4035185 and 43954.
78, 4504570, JP-A-52-
No. 156614, No. 55-127549, No. 53-6
0222, 56-22681, 59-2085
No. 40, No. 60-107641, No. 61-1337.
No. 62-215272, German Patent No. 2332802c2, Research Disclosure No. 23510 (issued in November 1983), page 236; specification of U.S. Pat. No. 4,789,627, further having a silver chloride shell; JP-A-63-10160 relating to silver chlorobromide core-shell emulsions;
No. 63-47766, and Japanese Patent Application No. 1-24
No. 67; Japanese Patent Application Laid-Open No. 63-191145 and Japanese Patent Application Laid-Open No. 1-5214 relating to emulsions doped with metal ions.
Examples thereof include core / shell type silver halide emulsions described in JP-A No. The internal latent image type silver halide grains which have not been fogged in the present invention are preferably core / shell type. The internal latent image type core / shell silver halide emulsion has a core / shell silver halide molar ratio of 20/1 or less and 1/10.
0 or more is particularly preferable.

The photographic emulsion used in the present invention contains an antifoggant or stabilizer for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. You can For specific examples, see Research Disclosure No.
17643-VI (issued in December 1978) and E.I.
J. Birr, "Stabilization of Photographic Silv
er Halide Emulsion "(Focal Press), 1974.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 17643, VII-CG, and No. 30710 mentioned above.
5, VII-C to G.
Yellow couplers include, for example, U.S. Pat.
No. 1, No. 4,022,620, No. 4,326,024, No. 4,4
01,752, 4,248,961, Japanese Patent Publication 58-10739, British Patents 1,425,020, 1,476,760, U.S. Patents
3,973,968, 4,314,023, 4,511,649,
Those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,63 are preferred.
6, U.S. Pat.Nos. 3,061,432 and 3,725,067,
Research Disclosure No. 24220 (June 1984
Month), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A 61-7.
No. 2238, No. 60-35730, No. 55-118034, No. 60-185951
U.S. Pat.Nos. 4,500,630, 4,540,654, and
Those described in 4,556,630 and International Publication WO88 / 04795 are particularly preferable. Examples of cyan couplers include phenol-based and naphthol-based couplers, and US Pat.
52,212, 4,146,396, 4,228,233, and
4,296,200, 2,369,929, 2,801,171,
No. 2,772,162, No. 2,895,826, No. 3,772,002
No. 3, No. 3,758,308, No. 4,334,011, No. 4,32
7,173, West German Patent Publication 3,329,729, European Patent 12
1,365A, 249,453A, U.S. Pat.No. 3,446,622
No. 4, No. 4,333,999, No. 4,775,616, No. 4,45
1,559, 4,427,767, 4,690,889, and
Those described in 4,254,212, 4,296,199 and JP-A-61-42658 are preferable. Furthermore, JP-A-64-553,
Pyrazoloazole couplers described in JP-A Nos. 64-554, 64-555 and 64-556 and imidazole couplers described in US Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in US Pat.
3,451,820, 4,080,211 and 4,367,282,
No. 4,409,320, No. 4,576,910, British patent 2,1
No. 02,137 and European Patent No. 341,188A.

Examples of couplers in which the color forming dye has a suitable diffusibility include US Pat. No. 4,366,237 and British Patent 2,12.
5,570, European Patent 96,570, West German Patent (Publication)
Those described in 3,234,533 are preferable. Colored couplers for correcting unnecessary absorption of color forming dyes are described in Research Disclosure No. 17643, Item VII-G, No. 307.
105 VII-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57
-39413, U.S. Pat.Nos. 4,004,929, 4,138,258
And those described in British Patent No. 1,146,368 are preferred.
Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181, and a dye capable of reacting with a developing agent described in U.S. Pat.No. 4,777,120 to form a dye. It is also preferable to use a coupler having a precursor group as a leaving group.
Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are described in RD 17643, VII-F above.
And Patent Nos. 307105 and VII-F, JP-A-57-151944, 57-154234, 60-184248,
63-37346, 63-37350, U.S. Patent 4,248,962,
Those described in JP-A-4,782,012 are preferable. RD No.1
The bleaching accelerator releasing couplers described in 1449, 24241 and JP-A-61-201247 are effective for shortening the processing time having a bleaching ability, and in particular, the above-mentioned tabular silver halide grains. The effect is great when it is added to the photosensitive material using.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,3.
38,393, 4,310,618 and the like, multi-equivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds described in JP-A-60-185950 and JP-A-62-24252. Alternatively, DIR redox-releasing redox compounds, couplers that release dyes that undergo color restoration after separation described in European Patents 173,302A and 313,308A, ligand-releasing couplers described in U.S. Pat. -75747 couplers releasing leuco dyes, U.S. Pat.
Examples thereof include couplers that release the fluorescent dye described in No. 181.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di
-2-Ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecaneamide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctylazese) Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate, etc., aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
Organic solvents above 160 ° C can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Gelatin is advantageously used as the binder or protective colloid which can be used in the intermediate layer which is the emulsion layer or the non-photosensitive layer of the light-sensitive material of the present invention, but other hydrophilic colloids are also used. Can be used. In the light-sensitive material of the present invention, an antifoggant or a color mixing inhibitor can also be used. Typical examples of these are JP-A-62-21527.
The compounds described in Japanese Patent Publication No. 2, pages 185 to 193 can be mentioned. Examples of the compound releasing a photographically useful group include JP-A Nos. 63-153540 and 63-259.
No. 555, JP-A Nos. 2-61636 and 2-24.
The compounds described in each publication of No. 4041 and No. 2-308240 are mentioned. In the present invention, a color forming enhancer can be used for the purpose of improving the color forming property of the coupler. Typical examples of the compounds are JP-A-62-215272, 121-
The thing described in page 125 is mentioned. Dyes that prevent irradiation or halation may be used in the light-sensitive material of the present invention (for example, the compounds described in JP-A Nos. 2-85850 and 2-89047) may be used. Solid fine crystal dispersion method may be used.), UV absorber, plasticizer, fluorescent whitening agent, matting agent, air antifoggant, coating aid, film hardening agent, antistatic agent, slipperiness improver, etc. Can be added. Typical examples of these additives are listed in Research Disclosure No. 17643
Items VII to XIII (issued in December 1978) 25 to 2
7 pages, and 18716 (issued in November 1979) 6
47-651.

The color photographic light-sensitive material of the present invention preferably has at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on the support. And it is preferable that the non-photosensitive layer is provided adjacent to these layers. The order of each layer of the red-sensitive emulsion layer, the green-sensitive emulsion layer and the blue-sensitive emulsion layer can be arbitrarily selected as required. The preferred order of layer arrangement is red-sensitive, green-sensitive, blue-sensitive from the support side or green-sensitive, red-sensitive and blue-sensitive from the support side. Further, each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. . It is usual that the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but in some cases, the green-sensitive layer contains a yellow coupler and a magenta coupler. It is also possible to use different combinations such as mixed use.
As described above, the light-sensitive material of the present invention is provided with a non-light-sensitive layer in addition to the silver halide emulsion layer. Examples of such a layer include a protective layer, an intermediate layer, a filter layer, an antihalation layer, There are auxiliary layers such as a back layer and a white reflective layer.

The color photographic light-sensitive material of the present invention preferably contains a nucleating agent. The nucleating agent functions as a development accelerator when the color photographic light-sensitive material is a normal color photographic light-sensitive material (for example, a color negative film). Further, in the direct positive color photographic light-sensitive material which is a preferred embodiment of the present invention, the nucleating agent acts during the surface development processing of the internal latent image type silver halide emulsion which has not been fogged in advance to form a direct positive image. Work. It is a substance used when carrying out the so-called "chemical fogging method". The nucleating agent is a silver halide emulsion layer,
Alternatively, it may be contained in any of the adjacent non-photosensitive layers (for example, an intermediate layer, an undercoat layer or a back layer), but it may be halogenated together with the cyan coupler represented by the formula (CaI) or the formula (CbI). It is preferably contained in the silver emulsion layer. Examples of the nucleating agent that can be used in the present invention include, for example, Research Disclosure Magazine,
No. 22534 (January 1983), pp. 50-54, ibid., No. 15162 (November 1976) 76-77
Page, No. 23510 (November 1983) 346
To 352, quaternary heterocyclic compounds, hydrazine compounds and the like. Two or more kinds of these nucleating agents may be used in combination. The nucleating agent used in the present invention is represented by the formula (N- which is described in JP-A-2-90154 or JP-A-3-155543.
I)) quaternary heterocyclic compounds, or JP-A-2-
A hydrazine compound represented by the formula (N-II) described in JP-A-90154 or JP-A-3-95546 is preferable.

Typical nucleating agents represented by the above formulas (NI) and (N-II) are as follows. (N-I-1) 7- (3-Cyclohexylmethoxythiocarbonylaminobenzamide) -10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate (N-I-2) 6- ( 3-Ethoxythiocarbonylaminobenzamido) -1-propargyl-2,3-trimethylenequinolinium trifluoromethanesulfonate (N-I-3) 6-ethoxythiocarbonylamino-2
-Methyl-1-propargylquinolinium trifluoromethanesulfonate (N-I-4) 7- [3- (5-mercaptotetrazol-1-yl) benzamide] -10-propargyl-
1,2,3,4-Tetrahydroacridinium perchlorate (N-II-1) 1-formyl-2- {4- [3- {3-
[3- (5-Mercaptotetrazol-1-yl) phenyl] ureido} benzsulfonamide] phenyl} hydrazine (N-II-2) 1-formyl-2- {4- [3- (5-
Mercaptotetrazol-1-yl) benzenesulfonamide] phenyl} hydrazine

In the present invention, it is preferable to use the quaternary heterocyclic compound and the hydrazine compound in combination. In the present invention, the amount of the nucleating agent added varies depending on the characteristics of the silver halide emulsion actually used, the chemical structure of the nucleating agent and the developing conditions, and therefore can be varied over a wide range. About 1 x 1 per mole of silver
A range of 0 ^-8 moles to about 1 × 10 ^-2 moles is practically useful, with about 1 × 10 ^-5 moles to about 1 × 10 ⁵ moles per silver mole being preferred.
^-3 mol range. The nucleating agent may be added to the treatment liquid. In particular, it is effective when directly performing the fogging process on the positive color photographic light-sensitive material. In this case, it is preferable to add it to a low pH pre-bath as described in JP-A-58-178350. When the nucleating agent is added to the treatment liquid, the amount used is preferably 10 ^-8 to 10 ^-1 mol per liter of the treatment liquid, and 10 ^-7 to 10 ^-3.
Molar is more preferred.

In the present invention, the fogging treatment of the direct positive color photographic light-sensitive material is carried out in combination with the "chemical fogging method" using the above nucleating agent or separately in the "light fogging method".
You may carry out using. The overall exposure in the "light fog method", that is, fog exposure is performed after imagewise exposure, before color development processing or during color development processing. That is, the imagewise exposed light-sensitive material is exposed in a color developing solution or in a pre-bath of the color developing solution, or is taken out from these solutions and dried before being exposed. Is most preferred. As a light source for fogging exposure,
For example, JP-A-56-137350 and JP-A-58-702.
A light source having a high color rendering property (as close to white as possible) as described in JP-A No. 23 is preferable. The illuminance of light is 0.01-
2000 lux, preferably 0.05 to 30 lux, more preferably 0.05 to 5 lux is suitable. The light-sensitive material using a higher-sensitivity emulsion is preferred to have low illuminance. The illuminance may be adjusted by changing the luminous intensity of the light source, or by changing the light exposure by various filters, the distance between the light-sensitive material and the light source, or the angle between the light-sensitive material and the light source. Further, the illuminance of the fogging light can be increased from low illuminance to high illuminance continuously or stepwise. It is preferable to immerse the light-sensitive material in a color developing solution or a solution of its pre-bath so that the solution sufficiently penetrates into the emulsion layer of the light-sensitive material before irradiation with light. The time from the permeation of the liquid to the light exposure is generally 2 seconds to 2 minutes, preferably 5 seconds to 1
Minutes, more preferably 10 seconds to 30 seconds. The exposure time for fogging is generally 0.01 second to 2 minutes, preferably 0.1 second to 1 minute, more preferably 1 second to 40 seconds.

In the embodiment of the color photographic light-sensitive material of the present invention, particularly the direct positive color photographic light-sensitive material, when the above nucleating agent is used, a nucleating accelerator for promoting the action of the nucleating agent is used. Is preferred. A nucleating accelerator does not substantially function as a nucleating agent, but accelerates the action of the nucleating agent to increase the maximum density of the direct positive image and / or obtain a certain maximum density of the direct positive image. Means a substance that has the function of accelerating the development time required. In the present invention, the nucleation accelerator described in JP-A-2-89048 can be preferably used. The nucleation accelerator is a silver halide emulsion layer or an adjacent non-photosensitive layer (intermediate layer, protective layer, etc.)
However, it is preferably contained in the silver halide emulsion together with the cyan coupler represented by the formula (CaI) or the formula (CbI) and the nucleating agent. The amount of nucleation accelerator added is 1 per mol of silver halide.
0 ^-6 to 10 ^-2 mol is preferable, and more preferably 10 ^-5.
It is about 10 ^-2 mol. The nucleation accelerator may be contained in the processing solution (that is, the developing solution or its pre-bath). In that case, 10 ^-8 to 10 ^-3 mol per liter of the processing solution is preferable, and more preferable. It is 10 ⁻⁷ to 10 ⁻⁴ mol.

Known photographic additives that can be used in the present invention are described in Research Disclosure No. 1764
3 (Dec. 1978) and No. 3 of the same. 18716 (1
(November 979), and the relevant parts are summarized in the table below. Additive type RD17643 RD18716 1 Chemical sensitizer, page 23, page 648, right column 2 Sensitivity enhancer, same as above 3 Spectral sensitizer, pages 23 to 24, page 648, right column ~ Supersensitizer, page 649, right column 4, whitening agent 24 Page 5 antifoggant page 24-25 page 649 right column-stabilizer page 650 right column 6 light absorber, page 25 right column page 649 right column-filter dye, page 650 left column ultraviolet absorber 7 anti-stain agent 25 Page right column 8 Dye image stabilizer page 25 9 Hardener 26 page 651 Left column 10 Binder 26 page Same as above

In the color photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are a flexible support usually used for photographic light-sensitive materials, such as a flexible support such as plastic film, paper and cloth, or rigidity such as glass, pottery and metal. Is coated on a support. Useful as the flexible support are films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate, a baryter layer or an α-olefin polymer. Examples include paper coated or laminated with (eg, polyethylene, polypropylene, ethylene / butene copolymer).
The support may be colored with a dye or pigment. For coating the silver halide photographic emulsion layer and other hydrophilic colloid layers, various known methods such as dip coating method, roller coating method, curtain coating method and extrusion coating method can be used. Also, if necessary, US Patent No. 2
No. 681294, No. 2761791, No. 3526
Multiple layers may be simultaneously coated by the method described in each specification such as No. 528 and No. 3508947.

Next, a color image forming method using the color photographic light-sensitive material of the present invention will be described. The color image forming method of the present invention forms a color image by subjecting the above color photographic light-sensitive material to image exposure, and then performing development processing with a developer containing a specific color developing agent represented by the formula (D). It is characterized by The development processing method may be a conventionally known method. Various exposure means can be used for exposing the light-sensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination light source or the writing light source.
Natural light (sunlight), incandescent lamp, halogen atom sealed lamp, mercury lamp, fluorescent lamp and flash light source such as strobe or metal burning flash bulb or semiconductor laser,
Light emitting diodes and plasma light sources can also be used as recording light sources. In addition, a phosphor screen (CRT or the like) emitted from a phosphor excited by an electron beam or the like, a liquid crystal (LC
D) or lanthanum-doped lead titan zirconate (PLZT) or the like may be used as an exposure means in which a linear or planar light source is combined with a microshutter array. The spectral distribution used for exposure can be adjusted with a color filter as needed. In particular, a high-density beam light such as various lasers such as a gas laser (He-Ne laser, Ar laser, He-Cd laser) and a semiconductor laser is used as a light source, and this is moved relative to the photosensitive material. An exposing means of a so-called scanning exposure method (scanner method) for exposing an image by means of is preferable for exposing the light-sensitive material of the present invention. As a scanning exposure apparatus, for example, a color copying machine AP-5 manufactured by Fuji Photo Film Co., Ltd.
000 can be used.

In the case of exposure by the scanning exposure system, the time for exposing the silver halide is the time required for exposing a certain minute area. As this minute area, the minimum unit for controlling the light quantity from digital data is generally used, and is called a pixel. Therefore, the exposure time per pixel varies depending on the size of the pixel. The size of this pixel depends on the pixel density.
It is 2000 dpi. In the color photographic light-sensitive material of the present invention, the pixel size is set to 1 pixel when the pixel density is 400 dpi, and the exposure time per pixel is 10 ^-3 seconds or less (preferably 10 ^-6 to 10 ^-4 seconds). ) Is used for scanning exposure.

The color developing agent used in the color image forming method of the present invention is represented by the following formula (D).

[0107]

[Chemical 40]

Examples of the alkyl group represented by R ^D1 include an alkyl group having 1 to 8 carbon atoms.
As such examples, methyl, ethyl, butyl or methoxyethyl are preferred. Examples of the alkylene group represented by R ^D2 include an alkylene group having 2 to 6 carbon atoms. As such an example, ethylene or trimethylene is preferable. Specific examples of the developing agent represented by formula (D) are shown below.

[0109]

[Chemical 41]

In the present invention, the compound represented by the above (D-2) or (D-3) is preferable. The above formula (D)
The amount of the color developing agent represented by is preferably about 0.1 g to about 20 g, and more preferably about 0.5 to about 10 g per liter of the developing solution. An aromatic primary amine type color developing agent other than the above may be used in combination, but if the developing agent represented by the formula (D) is 50
It is preferable that the content is at least mol%. The developing solution used in the color image forming method of the present invention is the same as the conventional color developing solution except that the developing agent is the above specific compound. The development processing method is also the same as the development processing method known per se, except that the above-described developing solution is used. The photographic light-sensitive material after the above color development processing is usually bleached,
A desilvering process consisting of a fixing process is applied, and after the desilvering process,
Generally, washing and / or stabilization treatment is performed. Regarding the above-mentioned series of processing steps, JP-A-3-12
The method described on pages 380 to 381 of Japanese Patent No. 0537 can be preferably used.

The color photographic light-sensitive material of the present invention has various uses, but is suitable for making color prints, color copies and color proofs. The color proof making method of the present invention can use a conventional color proof making method other than using the color photographic light-sensitive material of the present invention as described above. That is, the color proof making method of the present invention is
The color photographic light-sensitive material of the present invention is subjected to color separation and halftone image conversion, using a cyan plate halftone dot image film, an magenta halftone dot image film, a yellow plate halftone dot image film and a black halftone dot image film, This is a method of forming a color image by sequentially exposing with red light, green light and blue light and then performing color development processing as described above. As an apparatus for carrying out such a method, for example, a fine checker 850H manufactured by Fuji Photo Film Co., Ltd. (exposure time: 0.
02-0.3 seconds).

[0112]

【Example】

Example 1 Preparation of Sample 101 A paper support (thickness 10) laminated on both sides with polyethylene.
(0 micron), the following first to eleventh layers were applied to the front side, and the twelfth to thirteenth layers were applied to the back side to form a color photographic light-sensitive material. The polyethylene coated on the first layer contains titanium oxide (4 g / m ² ) as a white pigment and a trace amount (0.003 g / m ² ) of ultramarine as a bluing dye (the chromaticity of the surface of the support is L 88 in the ^* , a ^* , and b ^* systems.
It was 0, -0.20, -0.75. ).

(Photosensitive layer composition) The components and coating amount (g /
m ² unit). However, the addition amount of the sensitizing dye is shown in mol per mol of silver. For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer is Emulsion E described below.
It was made by changing the particle size by changing the temperature according to the manufacturing method of M-1. However, as the emulsion for the 11th layer, a Lippmann emulsion which was not surface-sensitized was used.

First Layer (Antihalation Layer) Black Colloidal Silver …… 0.10 Color Mixing Inhibitor (Cpd-7) …… 0.05 Color Mixing Inhibitor Solvent (Solv-4, 5 Equivalents) …… 0.12 Gelatin …… 0.40

Second layer (intermediate layer) Gelatin: 0.40 Dye (Cpd-32): 0.005

Third Layer (Red Sensitive Layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, and 3 equivalents 5.4 × 10 ^{−4 in} total) (average grain size of 0. 40μ, particle size distribution 10%, octahedron) ...... 0.25 gelatin ...... 0.40 cyan coupler (ExC-1, 2, 3 1: 0.6: 0.2) ...... 0.25 anti-fading agent (Cpd-1, 2, 3) 4,30 each equivalent) 0.18 Anti-staining agent (Cpd-5,15 each equivalent) 0.003 Coupler dispersion medium (Cpd-6) 0.30 Coupler solvent (Solv-1, 3, 5 etc.) Amount) …… 0.12

4th layer (intermediate layer) Gelatin: 0.70 Color mixing inhibitor (Cpd-7): 0.08 Color mixing inhibitor solvent (Solv-4, 5 equivalents): 0.16 Polymer latex (Cpd-8): … 0.10

Fifth Layer (Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4 2.6 × 10 ⁻⁴ ) (average grain size 0.40 μ, grain size distribution 10%). , Octahedron) ・ ・ ・ 0.20 Gelatin ・ ・ ・ 0.70 Magenta coupler (ExM-1, 2 each equivalent) ・ ・ ・ 0.11 Yellow coupler (ExY-1) ・ ・ ・ 0.02 Anti-fading agent (Cpd-9, 26, 30, 31) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 in 10: 7: 7: 1 ratio) ...... 0.025 Coupler dispersion medium (Cpd-6) ...... 0.05 Coupler solvent (Solv- Equal amount of 4, 6) 0.15

6th layer (intermediate layer) Same as 4th layer

Seventh Layer (Blue Sensitive Layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6 each equivalent weight 3.5 × 10 ⁻⁴ ) (average grain size 0.60 μm, Particle size distribution 11%, octahedron) 0.32 Gelatin 0.80 Yellow coupler (Equivalent to ExY-2, 3, 4) 0.30 Antifading agent (Cpd-14) 0.10 Antifading agent (Cpd-) 30) ...... 0.05 Anti-staining agent (Cpd-5, 15 in 1: 5 ratio) ...... 0.007 Coupler dispersion medium (Cpd-6) ...... 0.05 Coupler solvent (Solv-2) ...... 0.10

Eighth layer (ultraviolet absorber-containing layer) Gelatin: 0.60 Ultraviolet absorber (equal amounts of Cpd-2, 4, and 16) 0.40 Color-mixing inhibitor (equal amounts of Cpd-7 and 17): 0.03 Dispersion medium (Cpd-6) ...... 0.02 UV absorber solvent (Solv-2, 7 each equivalent) ...... 0.08 Anti-irradiation dye (Cpd-18, 19, 20, 21, 27 10:10: 13:15:20 ratio) …… 0.05

Ninth layer (protective layer) Fine grain silver iodobromide (99 mol% silver bromide, average size 0.05 μ) …… 0.03 Acrylic modified copolymer of polyvinyl alcohol (molecular weight 50,000) …… 0.01 Polymethylmethacrylate particles (Average particle size 2.4μ) and silicon oxide (average particle size 5μ) Equivalent ...... 0.05 Gelatin ...... 0.05 Gelatin hardening agent (Equivalent for H-1 and H-2) ...... 0.18

10th Layer (Back Layer) Gelatin ... 2.50 Ultraviolet Absorber (Equivalent of Cpd-2, 4, 16) 0.50 Dye (Equivalent of Cpd-18, 19, 20, 21, 27) ... … 0.06

Eleventh Layer (Back Layer Protective Layer) Polymethylmethacrylate particles (average particle size 2.4 μ) and silicon oxide (average particle size 5 μ) Equivalent ... 0.05 Gelatin ... 2.00 Gelatin hardener (H-1 , H-2 equal amount) …… 0.14

Preparation of Emulsion EM-1 An aqueous solution of potassium bromide and an aqueous solution of silver nitrate containing 3 × 10 ⁻⁸ mol of rhodium bromide and 3 × 10 ⁻⁶ mol of iridium chloride ammonium salt per 1 mol of silver were vigorously stirred in an aqueous gelatin solution. However, the addition was carried out simultaneously at 65 ° C. over 15 minutes to obtain octahedral silver bromide grains having an average grain size of 0.23 μ. At this time, 0.3 g of 3,4-dimethyl-1,3 per mol of silver was used.
-Thiazolin-2-thione was added. 1 silver in this emulsion
Chemical sensitization was carried out by sequentially adding 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mol and heating at 75 ° C. for 80 minutes. Using the particles thus obtained as a core, the particles are further grown in the same precipitation environment as the first time,
Finally, an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.4 μ was obtained. Coefficient of variation of particle size is about 10%
Met. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver.
The mixture was heated at 0 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion.

ExZK-1 was used as a nucleating agent in each photosensitive layer.
Was used in an amount of 10 ^-3 % by weight with respect to the silver halide, and Cpd-22, 28 and 29 were used in amounts of 10 ^-2 % by weight as nucleation accelerators.
Furthermore, alkanol XC (Du
Pont) and sodium alkylbenzene sulfonate as coating aids and succinate and Magefac F-
120 (manufactured by Dainippon Ink and Chemicals, Inc.) was used. For the layer containing silver halide and colloidal silver, a stabilizer (Cpd-23,
24 and 25 equivalent amounts) were used. The film thickness of the photosensitive layer side of this sample was 9.0 μm. This sample was designated as sample number 101. The compounds used in the examples are shown below.

[0127]

[Chemical 42]

[0128]

[Chemical 43]

[0129]

[Chemical 44]

[0130]

[Chemical formula 45]

[0131]

[Chemical formula 46]

[0132]

[Chemical 47]

[0133]

[Chemical 48]

[0134]

[Chemical 49]

[0135]

[Chemical 50]

[0136]

[Chemical 51]

[0137]

[Chemical 52]

Solv-1 di (2-ethylhexyl) sebacate Solv-2 trinonyl phosphate Solv-3 di (3-methylhexyl) phthalate Solv-4 tricresyl phosphate Solv-5 dibutyl phthalate Solv-6 trioctyl phosphate Solv- 7 Di (2-ethylhexyl) phthalate

H-1 1,2-bis (vinylsulfonylacetamido) ethane H-2 4,6-dichloro-2-hydroxy-
1,3,5-triazine Na salt

ExZK-17- (3-ethoxythiocarbonylaminobenzamide) -9-methyl-10-
Propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate

(Preparation of Sample 102) Sample 101 was prepared in the same manner as in Sample 101 except that FR hydroquinone shown in Table 1 was added to the third, fifth and seventh layers in an amount of 3 × 10 ⁻⁸ mol / m ^2. did. (Preparation of Samples 103 to 105) In the sample 102, the FR coupler shown in Table 1 was added to the layer shown in Table 1 in an amount of 2 × 10.
It was prepared in the same manner as the sample 102 except that ^-7 mol / m ^{2 was} added. (Preparation of Sample 106) In Sample 101, the third,
FR hydroquinone shown in Table 1 was added to layers 5 and 7 at 3 × 10 ^-8
The sample was prepared in the same manner as the sample 101 except that mol / m ^{2 was} added. (Preparation of Samples 107 to 109) In the sample 106, the FR coupler shown in Table 1 was added to the layer shown in Table 1 in an amount of 2 × 10.
The sample 106 was prepared in the same manner as the sample 106 except that ^-7 mol / m ^{2 was} added.

(Preparation of Sample 110) Sample 110 was prepared in the same manner as in Sample 101 except that FR hydroquinone shown in Table 1 was added to the third, fifth and seventh layers in an amount of 3 × 10 ⁻⁸ mol / m ^2. did. (Preparation of Samples 111 to 113) In the above Sample 110, the FR coupler shown in Table 1 was added to the layer shown in Table 1 in an amount of 2 × 10.
It was prepared in the same manner as the sample 110 except that ^-7 mol / m ^{2 was} added. (Evaluation as color photographic light-sensitive material) The sample thus prepared was divided into two, and one of them was stored (incubated) for 3 days in an environment of 50 ° C. and 55% RH. Each of the samples prepared as described above is exposed to white through a wedge, and after color development processing in processing step 1 shown below,
The maximum and minimum image densities of the yellow component were measured. The results are shown in Table 1. From Table 1, it can be seen that the compound of the present invention has a high maximum image density, a low minimum image density, and excellent storage stability. Similar results were obtained for the magenta component and the cyan component.

[Processing Step 1] The above exposed sample was continuously processed in the following processing steps until the cumulative replenishment amount of the liquid became 3 times its tank volume. Process time between temperature tank volume replenishment rate color developing 135 seconds 38 ° C. 28 liters 240 ml / m ² bleach-fixing 40 seconds 35 ° C. 11 liters 320 ml / m ² water washing (1) 40 sec 35 ° C. 7 liters - washing (2) 40 seconds 35 ° C 7 liter 320 ml / m ² dry 30 seconds 80 ° C Replenishment rate indicates the replenishment rate per 1 m ^{2 of} sample. The replenishing system for the washing water was a countercurrent replenishing system for guiding the overflow solution of the washing bath (2) to the washing bath (1). At this time, the carry-out amount of each processing solution by the light-sensitive material was 35 ml / m ² .

Color developer D-sorbit 0.15 g sodium naphthalenesulfonate / 0.15 g formalin condensate nitrilotris (methylenephosphonic acid) 1.8 g pentasodium salt diethylenetriaminepentaacetic acid 0.5 g 1-hydroxyethylidene-1,1-0.15 g diphosphone Acid Diethylene glycol 12.0 ml Benzyl alcohol 13.5 ml Potassium bromide 0.70 g Benzotriazole 0.003 g Sodium sulfite 2.8 g Hydroxylamine / 1/2 sulfate 4.5 g Triethanolamine 6.5 g 4- [N-ethyl-N- (β-hydroxy 4.2 g Ethyl) amino] aniline sulfate / 1/2 hydrate Potassium carbonate 30.0 g Optical brightener (diaminostilbene type) 1.3 g Water is added to 1000 ml pH (25 ° C) (pH adjusted with KOH or sulfuric acid) 10.35

Bleach-fixing solution Ethylenediaminetetraacetic acid ・ sodium ・ dihydrate 4.0 g Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ammoni 55.0 g Ume ・ dihydrate Ammonium thiosulfate (750 g / l) 168 ml p-toluenesulfinate 30.0 g Ammonium sulfite 35.0 g 5-Mercapto-1,3,4-triazole 0.5 g Ammonium sulfate 10.0 g Water was added to 1000 ml pH (25 ° C) (pH adjustment with ammonia water or acetic acid) 6.50

Washing water Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.50

[0147]

[Table 1]

Example 2 Preparation of Sample 201 A paper support (thickness 10) laminated on both sides with polyethylene.
(0 micron), the following 1st to 14th layers were multilayer-coated and the 15th to 16th layers were coated on the back side to prepare a color photographic light-sensitive material. The polyethylene coated on the first layer contains titanium oxide (4 g / m ² ) as a white pigment and a trace amount (0.003 g / m ² ) of ultramarine as a bluing dye (the chromaticity of the surface of the support is L 88 in the ^* , a ^* , and b ^* systems.
It was 0, -0.20, -0.75. ).

(Photosensitive layer composition) The components and coating amount (g /
m ² unit). For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer was produced according to the production method of Emulsion EM1. However, as the emulsion of the 14th layer, a Lippmann emulsion which was not surface-sensitized was used.

First Layer (Antihalation Layer) Black Colloidal Silver 0.10 Color Mixing Inhibitor (Cpd-7) 0.05 Gelatin 0.70

Second layer (intermediate layer) gelatin 0.70

Third Layer (Low Sensitivity Red Sensitive Layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) (average grain size 0.22 μ, grain size distribution [variation coefficient ] 7%, octahedron) 0.06 Silver chlorobromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) (5 mol% silver chloride, average grain size 0.42μ, grain size distribution 9) %, Octahedron) 0.08 gelatin 1.02 cyan coupler (ExC) 0.20 anti-fading agent (Cpd-1, 2, 3, 4, 30 equivalents) 0.18 anti-staining agent (Cpd-5) 0.001 coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Solv-1, 2, 3 equivalents) 0.18

Fourth Layer (High Sensitivity Red Sensitive Layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) (average grain size 0.58 μ, grain size distribution 14%, Octahedral) 0.16 Gelatin 1.05 Cyan coupler (ExC) 0.25 Anti-fading agent (Cpd-1, 2, 3, 4, 30 equivalents) 0.14 Coupler dispersion medium (Cpd-6) 0.02 Coupler solvent (Solv-1, 2, 3) Equivalent) 0.18

Fifth Layer (Intermediate Layer) Gelatin 1.00 Color mixing inhibitor (Cpd-7) 0.08 Color mixing inhibitor solvent (Solv-4, 5 equivalents) 0.16 Polymer latex (Cpd-8) 0.10

Sixth Layer (Low Sensitivity Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4) (average grain size 0.25 μ, grain size distribution 8%, octahedron) 0.04 Silver chlorobromide spectrally sensitized with a green sensitizing dye (ExS-4) (5 mol% silver chloride, average grain size 0.40μ, grain size distribution 10%, octahedron) 0.06 Gelatin 0.80 Magenta coupler (ExM -1, 2, 3 equivalents) 0.10 Anti-fading agent (equal amounts of Cpd-9, 26, 30) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 in 10: 7: 7: 1 ratio) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-4, 6 equivalents) 0.15

Seventh Layer (High-Sensitivity Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4) (average grain size 0.65 μ, grain size distribution 16%, octahedron) 0.10 Gelatin 0.80 Magenta coupler (ExM-1, 2, 3 equivalents) 0.10 Anti-fading agent (equal amounts of Cpd-9, 26, 30) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 at 10: 7: 7: 1 ratio) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-4, 6 equivalents) 0.15

8th layer (intermediate layer) Same as 5th layer

Ninth layer (yellow filter layer) Yellow colloidal silver (particle size 100Å) 0.12 Gelatin 0.70 Color mixing inhibitor (Cpd-7) 0.03 Color mixing inhibitor solvent (Solv-4, 5 equivalents) 0.10 Polymer latex (Cpd-) 8) 0.07

10th layer (intermediate layer) Same as 5th layer

Eleventh Layer (Low Sensitivity Blue Sensitive Layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (average grain size 0.40 μ, grain size distribution 8%, octahedron). 0.07 Silver chlorobromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (silver chloride 8 mol%, average grain size 0.60 μ, grain size distribution 11%, octahedron) 0.14 gelatin 0.80 yellow coupler (ExY-1, 2, 3 equivalents) 0.30 Anti-fading agent (Cpd-14) 0.10 Anti-fading agent (Cpd-30) 0.05 Anti-staining agent (Cpd-5, 15 in 1: 5 ratio) 0.007 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10

Twelfth Layer (High Sensitivity Blue Sensitive Layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (average grain size 0.85 μ, grain size distribution 18%, octahedron). 0.15 Gelatin 0.60 Yellow coupler (ExY-1, 2, 3 equivalents) 0.28 Anti-fading agent (Cpd-14) 0.10 Anti-fading agent (Cpd-30) 0.05 Anti-staining agent (Cpd-5, 15 in 1: 5 ratio) ) 0.007 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10

13th layer (UV absorbing layer) Gelatin 1.00 UV absorber (Cpd-2, 4, 16 equivalents) 0.50 Color mixing inhibitor (Cpd-7, 17 equivalents) 0.03 Dispersion medium (Cpd-6) 0.02 UV Absorbent solvent (Solv-2, 7 equivalents) 0.08 Anti-irradiation dye (Cpd-18, 19, 20, 21, 27 in 10: 10: 13: 15: 20 ratio) 0.05

Fourteenth Layer (Protective Layer) Fine silver chlorobromide (97 mol% silver chloride, average size 0.1 μ) 0.03 Polyvinyl alcohol acryl-modified copolymer (molecular weight 50,000) 0.01 Polymethylmethacrylate particles (average particle Size 2.4 μ) and silicon oxide (average particle size 5 μ) Equivalent 0.05 gelatin 1.80 Gelatin hardening agent (H-1, H-2 equivalent) 0.18

Fifteenth layer (back layer) Gelatin 2.50 Ultraviolet absorber (Cpd-2, 4, 16 equivalents) 0.50 Dye (Cpd-18, 19, 20, 21, 27 equivalents) 0.06

Sixteenth Layer (Back Layer Protective Layer) Polymethylmethacrylate particles (average particle size 2.4 μ) and silicon oxide (average particle size 5 μ) Equivalent 0.05 gelatin 2.00 Gelatin hardener (H-1, H- 2 equivalents) 0.14

Preparation of Emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution at 75 ° C. over 15 minutes with vigorous stirring,
Octahedral silver bromide grains having an average grain size of 0.35μ were obtained. At this time, 0.3 g of 3,4-dimethyl-1,3 per mol of silver was used.
-Thiazolin-2-thione was added. 1 silver in this emulsion
Chemical sensitization was carried out by sequentially adding 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mol and heating at 75 ° C. for 80 minutes. Using the particles thus obtained as a core, the particles are further grown in the same precipitation environment as the first time,
Finally, an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.7 µ was obtained. Coefficient of variation of particle size is about 10%
Met. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver.
The mixture was heated at 0 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion.

ExZK-1 is used as a nucleating agent in each photosensitive layer.
Is 10 ^-3 % by weight with respect to the silver halide, and Cpd-22, 28 and 29 are 10 ^-2 % by weight each as a nucleation accelerator.
Using. Further, in each layer, alkanol XC (Dupont) and sodium alkylbenzene sulfonate as an emulsification / dispersion aid, and succinate and Magefa as coating aids are used.
cF-120 (manufactured by Dainippon Ink and Chemicals, Inc.) was used. As a stabilizer for the layer containing silver halide and colloidal silver (Cpd-
23, 24, 25) was used. This sample is Sample No. 20
It was set to 1. The compounds used in the examples are shown below.

[0168]

[Chemical 53]

[0169]

[Chemical 54]

[0170]

[Chemical 55]

[0171]

[Chemical 56]

[0172]

[Chemical 57]

[0173]

[Chemical 58]

[0174]

[Chemical 59]

[0175]

[Chemical 60]

[0176]

[Chemical formula 61]

[0177]

[Chemical formula 62]

[0178]

[Chemical formula 63]

[0179]

[Chemical 64]

[0180]

[Chemical 65]

(Preparation of Sample 202)
And the F shown in Table 2 in the third, fourth, sixth, seventh, eleventh and twelfth layers.
1 x 10 R hydroquinone^-7Mol / m²Except added
It was prepared in the same manner as the sample 201. (Preparation of Samples 203 to 205) Smell in Sample 202
The FR coupler shown in Table 2 was added to the layer shown in Table 2 in an amount of 1 × 10.
^-6Mol / m²Same as Sample 202 above except added
Created. (Preparation of Sample 206) In Sample 201, the third,
FR Hydro shown in Table 2 in 4, 6, 7, 11 and 12 layers
1 x 10 non^-7Mol / m²Sample 20 above except that it was added
It was created in the same manner as 1. (Preparation of Samples 207 to 209) Smell in Sample 206
The FR coupler shown in Table 2 was added to the layer shown in Table 2 in an amount of 1 × 10.
^-6Mol / m²Same as Sample 206 above except added
Created.

(Preparation of Sample 210) In Sample 201, the F shown in Table 2 was formed on the third, fourth, sixth, seventh, eleventh and twelfth layers.
It was prepared in the same manner as in Sample 201 except that 1 × 10 ⁻⁷ mol / m ^{2 of} R hydroquinone was added. (Preparation of Samples 211 to 213) In the sample 210, 1 × 10 of the FR coupler shown in Table 2 was added to the layer shown in Table 2.
It was prepared in the same manner as the sample 210 except that ^-6 mol / m ^{2 was} added. (Evaluation as color photographic light-sensitive material) The sample thus prepared was divided into two, and one of them was stored (incubated) for 3 days in an environment of 50 ° C. and 55% RH. Each of the samples prepared as described above is exposed to white through a wedge, and after color development processing is performed in processing step 2 shown below,
The maximum image density and the minimum image density of the cyan component were measured.
The results are shown in Table 2. From Table 2, it can be seen that the compounds of the present invention have a high maximum image density, a low minimum image density, and excellent storage stability. Similar results were obtained for the yellow component and the magenta component.

[Processing Step 2] Using an automatic processor, continuous processing was carried out by the method described below until the cumulative replenishment amount of the replenisher for the color developing solution became three times the tank volume. Processing process time Temperature Tank capacity Replenishment amount Color development 135 seconds 38 ° C 11 liters 350 ml / m ² Bleach fixing 40 seconds 34 ° C 3 liters 300 ml / m ² Washing with water (1) 40 seconds 32 ° C 3 liters-washing with water (2) 40 Second 32 ℃ 3 liter 350 ml / m ² Dry 30 s 80 ℃ Replenishment method of washing water is to replenish the washing bath (2) with the washing bath (2).
The so-called countercurrent replenishment system was used in which the overflow liquid of (1) was introduced into the washing bath (1). At this time, the carry-out amount of each processing solution by the light-sensitive material was 35 ml / m ² .

The composition of each processing liquid is as follows. [Color developer] [Tank solution] [Replenisher] D-Sorbit 0.15g 0.20g Sodium naphthalenesulfonate / formalin condensate 0.15g 0.20g Nitrilotris (methylenephosphonic acid) pentasodium salt 1.8g 1.8g Diethylenetriaminepentaacetic acid 0.5 g 0.5 g 1-hydroxyethylidene-1,1-diphosphonic acid 0.15 g 0.15 g diethylene glycol 12.0 ml 16.0 ml benzyl alcohol 13.5 ml 18.0 ml potassium bromide 0.70 g-benzotriazole 0.003 g 0.004 g sodium sulfite 2.4 g 3.2 g disodium -N, N-bis (sulfonate ethyl) hydroxylamine 8.0g 10.6g triethanolamine 6.0g 8.0g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid 1 water salt 6.0g 8.0g Potassium carbonate 30.0g 25.0g Optical brightener (diaminostilbene type) 1.3g 1.7g Add water 1000ml 1000ml pH (25 ° C) (pH adjusted with KOH or sulfuric acid) 10.30 10.79

[Bleach-fixing solution] [Tank solution] [Replenishing solution] Ethylenediaminetetraacetic acid / 2 sodium / dihydrate 4.0 g Same as tank solution Ethylenediaminetetraacetic acid / Fe (III) / Ammonium / dihydrate 55.0 g Thio Ammonium sulfate (750 g / liter 168 ml sodium p-toluenesulfinate 30.0 g Ammonium sulfite 35.0 g 5-mercapto-1,3,4-triazole 0.5 g Ammonium nitrate 10.0 g Water was added to 1000 ml pH (25 ° C) (ammonia water) Or adjust the pH with acetic acid) 6.5

[Washing Water] [Both tank solution and replenisher] Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

[0187]

[Table 2]

Example 4 Among the samples used in Example 1 above, Sample 101, Sample 110 and Sample 111 were used, and a plate making film having a halftone image was used using Fine Checker FC850H manufactured by Fuji Photo Film Co., Ltd. After making them adhere to each other, red exposure (SC-60 filter manufactured by Fuji Photo Film Co., Ltd.) and green exposure (BPB- manufactured by Fuji Photo Film Co., Ltd.)
53 filter), and then blue light exposure (BPN45 and SC-42 filter manufactured by Fuji Photo Film Co., Ltd.), respectively. At that time, a plate-making film for an unimage and a black image was overlapped with each other during red exposure, a plate-making film for a magenta image and a black image was overlapped during green exposure, and a plate-making film for a yellow image and a black image was further overlapped during blue exposure. In this way, the cuff roof was created.
The image formation in this case was performed according to the color development processing according to the above-described Example 1.

The minimum halftone dot area of the color-proof yellow image obtained as described above was observed with a 100-fold magnifying glass. As a result, the color photographic light-sensitive material (Sample 111) containing the compound of the present invention was able to reproduce up to 2% halftone dot image.
The comparative sample 101 was able to reproduce only 4% and the comparative sample 110 was 3%.

Example 5 As a light source, a helium-neon gas laser (wavelength 63
3 nm and 543 nm) and argon laser (wavelength 4
58 nm), a light flux having a diameter of 80 μm at a pitch of 100 μm is moved perpendicularly to the scanning direction by a scanning exposure of 1.6 m / s, and a sequential scanning exposure (substantial exposure time of about 5 × 10 ⁻⁵ I assembled a device that can. Using this apparatus, the comparative samples 101, 110 and the sample 111 were exposed and then processed using the processing liquid B, and the reproducibility of the halftone image of the obtained image was evaluated. As a result, the color photographic light-sensitive material of the present invention (Invention Sample 111) was able to reproduce well up to 2% halftone dot image, but the color photographic light-sensitive material of Comparative Example was 5% in Comparative Sample 101, Only halftone images up to 3% could be reproduced.

[0191]

The coupler of the formula (I) or (II) which releases the fogging agent or the development accelerator and the coupler of the formula (III) which releases the fogging agent or the development accelerator. By combining with a redox compound, a direct positive color photographic light-sensitive material which gives a high maximum image density and a low minimum image density, is capable of rapid processing, and is excellent in storability can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location G03C 7/407 G03F 3/10 B

Claims (4)

[Claims] 1. A blue-sensitive layer, a green-sensitive layer and a red-sensitive layer containing a non-pre-fogged internal latent image type silver halide grain and a color image-forming coupler, and a non-photosensitive layer adjacent thereto. In a direct positive color photographic light-sensitive material in which at least one layer is provided, at least one of the blue-sensitive layer, the green-sensitive layer, the red-sensitive layer and the non-photosensitive layer has the following general formula (I) or (II) Containing at least one coupler which releases a fogging agent or a development accelerator, and at least one redox compound which releases a fogging agent or a development accelerator represented by the following general formula (III): A direct positive color photographic light-sensitive material characterized in that (I) Cp- (TIME) _n -FA (II) BALL-Cp- (TIME) _n -FA (III) RED- (TIME) _n -FA In the above formula, Cp is an aromatic primary amine development. Represents a coupler residue capable of undergoing a coupling reaction with an oxidized form of a drug. B
ALL represents a diffusion-resistant group which can be separated from Cp by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. RED represents a compound residue capable of undergoing a redox reaction with an oxidized product of an aromatic primary amine developing agent. TIME
Represents a timing group that further releases FA after leaving Cp or RED by a coupling reaction. n represents 0 or 1, and FA is, when n is 0,
It is a group capable of leaving from Cp or RED by a coupling reaction, and a group capable of being released from TIME when n is 1 (in the case of the compound represented by (II) in the above formula,
FA does not have to leave Cp or TIME after the coupling reaction). Here, FA represents a so-called fogging agent or development accelerator which acts on silver halide grains during development to generate fog nuclei capable of initiating development. Examples of FA include a group that acts reductively on silver halide grains during development to produce fog nuclei or a group that acts on silver halide grains to produce silver sulfide nuclei which are fog nuclei that can initiate development. be able to. 2. The color photographic light-sensitive material according to claim 1 is imagewise exposed and then represented by the following formula (D): [In the formula, R ^D1 represents an alkyl group and R ^D2 represents an alkylene group, provided that R ^D1 and R ^D2 may be linked to each other to form a ring. ] The color image forming method characterized by performing color development processing using the developing agent represented by these. 3. The cyan photographic halftone dot image film, the magenta halftone dot image film, the yellow halftone dot image film and the black halftone dot obtained by color separation and halftone image conversion of the color photographic light-sensitive material according to claim 1. A method for producing a color proof, characterized in that a point image film is used to sequentially perform exposure with red light, green light, and blue light, and then color development processing is performed. 4. A color image forming method, which comprises subjecting the color photographic light-sensitive material according to claim 1 to scanning exposure for an exposure time of 10 ⁻³ seconds or less per pixel, and then performing color development processing.