JPH0820699B2 - Direct positive color photographic light-sensitive material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a direct positive color photographic light-sensitive material having good color reproducibility and improved image whiteness.

[Prior Art] There is known a photographic method for directly obtaining a positive image without requiring a reversal processing step or a negative film.

The method used to form a positive image using a conventionally known direct positive silver halide photographic light-sensitive material is
Except for special ones, in consideration of practical usefulness, they can be mainly divided into two types.

One type uses a fog-fogged silver halide emulsion in advance, and directly develops a positive image after development by destroying fog nuclei (latent image) in the exposed area by utilizing solarization or the Herschel effect. I will get it.

The other type is one in which an internal latent image type silver halide emulsion which is not fogged is used and surface development is carried out either after image exposure and after fog treatment or while fog treatment is carried out to directly obtain a positive image.

Further, the above-mentioned internal latent image type silver halide photographic emulsion is a type of silver halide photographic in which a silver halide grain has a photosensitive nucleus mainly inside and a latent image is mainly formed inside the grain upon exposure. An emulsion.

This latter type of method is generally higher in sensitivity than the former type and is suitable for applications requiring high sensitivity, and the present invention relates to this latter type.

Various techniques have been known so far in this technical field. For example, U.S. Patent Nos. 2,592,250 and 2,466,9
No. 57, No. 2,497,875, No. 2,588,982, No. 3,317,322
Nos. 3,761,266, 3,761,276, 3,796,577 and British Patent Nos. 1,151,363, 1,150,553, 1,011,
The main thing is described in each specification of No. 062.

By using these known methods, a photographic photosensitive material having a relatively high sensitivity as a direct positive type can be produced.

For details of the mechanism of forming a direct positive image, see, for example, "The Theory of the Photographic Process" by TH Geems.
Graphical Process), 4th Edition, Chapter 7, pp. 182-193 and U.S. Pat. No. 3,761,276.

That is, the fog nuclei are selectively generated only on the surface of the unexposed silver halide grains due to the surface desensitizing effect caused by the so-called internal latent image generated inside the silver halide by the first imagewise exposure. Then, a normal, so-called surface development treatment is applied to the photographic image (direct positive image) on the unexposed area.
Is believed to be formed.

As described above, as a means for selectively generating a fog nucleus, a method of giving a second exposure to the entire surface of a photosensitive layer, which is generally called a "light fogging method" (for example, British Patent No. 1,151,363)
Nucleating agent called “chemical fogging method”
ng agent) is known. This latter method is described, for example, in “Research Disclosure”, Vol. 151, No. 15162.
(Issued November 1976), pp. 76-78.

To directly form a positive color image, the internal latent image type silver halide light-sensitive material is subjected to fog treatment, or surface color development processing is performed while performing fog treatment, followed by bleaching and fixing (or bleach-fixing) treatment. Can be achieved. bleaching·
After the fixing process, a washing and / or stabilizing process is usually performed.

[Problems to be solved by the invention]

In the direct positive image formation using the light fog method or the chemical fog method, the developing speed is slower and the processing time is longer than in the case of a normal negative type, so that the pH and / or the solution of the developing solution are conventionally used. A method of increasing the temperature to shorten the processing time has been used. However, there is a problem that the minimum image density of the obtained direct positive image generally increases when the pH is high. Also, under high pH conditions, the developing agent is liable to deteriorate due to air oxidation, and also absorbs carbon dioxide in the air.
pH tends to drop. As a result, there is a problem that the developing activity is significantly reduced.

On the other hand, cyan dyes that have been conventionally used in color photographic light-sensitive materials usually have unnecessary absorption of magenta and yellow components, and magenta dyes usually have unnecessary absorption of yellow and cyan components. This causes a decrease in saturation in color reproduction. As a solution to this problem, a pyrazoloazole type magenta coupler has been developed.

However, when the above-mentioned pyrazoloazole type coupler is directly used in a positive color photographic light-sensitive material, development is remarkably suppressed, and a new problem arises that the low density portion of the image is softened.

As a means for increasing the developing speed for direct positive image formation, a method using a hydroquinone derivative (US Pat.
227,552), those using a mercapto compound having a carboxylic acid group or a sulfonic acid group (JP-A-60-170843), and the like. However, even if these compounds are used, the effect is small, and no technique has been found that effectively improves the maximum density of the positive image and achieves the minimum image density contrast enhancement.

Therefore, the first object of the present invention is to provide a photographic light-sensitive material which gives a direct positive image excellent in color reproducibility.

It is a second object of the present invention to provide a photographic light-sensitive material which gives an image in which the minimum density portion has a high contrast and whiteness is improved by developing for a short time.

[Means for solving problems]

The above object of the present invention is to use at least one pre-fogged internal latent image type halogen on a support for use in an image forming method in which color development processing is performed with a color developing solution having a pH of less than 11 in the presence of a nucleating agent. In a direct positive color light-sensitive material having a silver halide emulsion layer and a color image forming coupler, at least one of magenta couplers represented by the following general formulas (Ia) and / or (Ib) and the following general formula (II) and / or ( This is achieved by a direct positive color photographic material characterized by containing at least one nucleation accelerator represented by III).

(In the formula, R ¹¹ and R ¹² represent a hydrogen atom or a substituent, which may be the same or different from each other, and X is a hydrogen atom or a coupling reaction with an aromatic primary amine developer oxidant. Represents a group capable of splitting off by R ¹¹ and R ¹² ,
Alternatively, X may be a divalent group to form a bis form.

General formula (II) In the formula, Q represents an atomic group necessary for forming a 5- or 6-membered heterocycle, and this heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring, Y is a hydrogen atom, Represents a divalent linking group consisting of an atom or an atom group selected from a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, and R represents at least one of a thioether group, an amino group, an ammonium group, an ether group or a heterocyclic group. Represents an organic group containing, n represents 0 or 1, m represents 0, 1 or 2, and M represents a hydrogen atom, an alkali metal atom, an ammonium group or a group capable of cleaving under alkaline conditions.

General formula (III) In the formula, Q'represents an atomic group necessary for forming a 5- or 6-membered heterocycle capable of forming iminosilver, and Y, R, n, M
Has the same meaning as in the general formula (II), and m ′ represents 1 or 2.

The present inventors have shown that in a direct positive photographic light-sensitive material, at least one of the magenta couplers represented by the general formula (Ia) and / or (Ib) and the general formula (II) and / or (III) By including at least one of the nucleation accelerators, it is surprising that a direct positive image having a sufficient maximum density and a hardened minimum density in the presence of the nucleating agent is excellent in color reproducibility. The present invention has been completed and found that it can be obtained by developing in a short time even if a processing solution having a pH is used.

The magenta coupler represented by formula (Ia) or (Ib) used in the present invention is described in detail below.

Among the pyrazoloazole type magenta couplers represented by the general formula (I), preferred are those represented by the following general formulas (Ia) and (Ib).

In formulas (Ia) and (Ib), R ¹¹ and R ¹² may be the same or different from each other, and each is a hydrogen atom,
Halogen atom, alkyl group, aryl group, heterocyclic group,
Cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group,
Anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group , A sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and particularly preferred are an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an acylamino group, and an anilino group. Is. X represents a hydrogen atom, a halogen atom, a carboxy group, or a group which is coupled to carbon at the coupling position via an oxygen atom, a nitrogen atom or a sulfur atom and which is capable of coupling off. R
¹¹ , R ¹² or X may be a divalent group to form a bis form.

Further, it may be in the form of a polymer coupler in which the coupler residue represented by the general formula (Ia) or (Ib) is present in the main chain or side chain of the polymer, and particularly has a portion represented by the general formula (Ia) or (Ib). Polymers derived from vinyl monomers are preferred, where R ¹¹ , R ¹² or X represents a vinyl group or a linking group.

The linking group represented by R ¹¹ , R ¹² , or X in the case where the vinyl monomer contains the compounds represented by the general formulas (Ia) and (Ib) is an alkylene group (a substituted or unsubstituted alkylene group, For example, methylene group, ethylene group, 1,
10 _{decylene, -CH 2 CH 2 OCH 2 CH} 2 -, etc.), with phenylene group (a substituted or unsubstituted phenylene group, for example, 1,
4-phenylene group, 1,3-phenylene group, -NHCO-, -CONH-, -O-, -OCO- and aralkylene groups (for example, And a group formed by combining those selected from.

 The following are preferred linking groups.

_{-NHCO, -, - CH 2 CH} 2 - _{-CONH-CH 2 CH 2 NHCO-,} -CH 2 CH 2 O-CH 2 CH 2 -NHCO-, The vinyl group may have a substituent other than those represented by the general formulas (Ia) and (Ib), and a preferable substituent is a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms (for example, Represents a methyl group or an ethyl group).

Monomers including those represented by the general formulas (Ia) and (Ib) may form a copolymer with a non-color forming ethylene-like monomer that does not couple with the oxidation product of an aromatic primary amine developing agent.

As is well known in the art of polymer color couplers, non-color forming ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomer couplers are the physical and / or chemical properties of the copolymer formed such as Solubility, compatibility with photographic colloid composition binders such as gelatin, its flexibility,
It can be selected such that thermal stability and the like are positively affected.

The polymer coupler used in the present invention may be either water-soluble or water-insoluble, and among them, polymer coupler latex is particularly preferable.

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

These couplers are generally used in an amount of 1 × 10 ^-3 to 5 × 10 ^-1 mol, preferably 5 × 10 ^-3 mol per mol of silver in the emulsion layer.
^-2 mol to 5 × 10 ^-1 mol is added.

Two or more types of the above-mentioned couplers and the like can be used in combination in the same layer in order to satisfy the characteristics required for the light-sensitive material. It can also be used in combination with other magenta couplers.

To introduce the coupler into the silver halide emulsion layer, a known method such as the method described in US Pat. No. 2322027 is used. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphonate, triphenyl phosphonate, tricresyl phosphonate, dioctyl butyl phosphonate), citric acid ester (eg acetyl) Tributyl citrate), benzoic acid esters (eg octyl benzoate), alkylamides (eg diethyllaurylamide), fatty acid esters (eg dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (eg tributyl trimesate)
Or an organic solvent having a boiling point of about 30 ° C. to 150 ° C., for example, ethyl acetate, lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate,
After being dissolved in methyl cellosolve acetate or the like, it is dispersed in a hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

Next, the nucleation accelerators represented by the general formulas (II) and (III) will be described in detail.

The term "nucleating accelerator" as used herein means a nucleating agent (the term "nucleating agent" acts on the surface development treatment of an internal latent image type silver halide emulsion which has not been fogged in advance to directly form a positive image. Functioning as a substance that acts as a)
A substance that promotes the action of a nucleating agent, increases the maximum density of a direct positive image, and / or shortens the development time required to obtain a constant direct positive image density. Two or more nucleation accelerators can be used in combination.

The nucleation accelerator used in the present invention is represented by the general formula (II) and / or (III).

In the general formula (II), Q is preferably an atom group necessary for forming a 5- or 6-membered heterocyclic ring composed of at least one atom of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom. Represents The heterocycle may be fused with a carbon aromatic ring or a heteroaromatic ring.

Examples of heterocycles include tetrazole, triazole, imidazole, thiadiazole, oxadiazole, selenadiazole, oxazole, thiazole, benzoxazole, benzothiazole,
Examples include benzimidazoles and pyrimidines.

M represents a hydrogen atom, an alkali metal atom (eg, a sodium atom, a potassium atom, etc.), an ammonium group (eg,
A trimethylammonium group, a dimethylbenzylammonium group, etc.) and a group which can be M = H or an alkali metal atom under alkaline conditions (eg, an acetyl group, a dianoethyl group, a methanesulfonylethyl group, etc.).

In addition, these heterocycles may be nitro group, halogen atom (eg, chlorine atom, bromine atom, etc.), mercapto group, cyano group, and substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, propyl group, t-group). Butyl group,
A cyanoethyl group, an aryl group (e.g., phenyl, 4-methanesulfonamidophenyl, 4-methylphenyl, 3,4-dichlorophenyl, naphthyl,
Alkenyl group (eg, allyl group, etc.), aralkyl group (eg, benzyl group, 4-methylbenzyl group, phenethyl group, etc.), sulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group, Carbamoyl group (for example, unsubstituted carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group,
), A sulfamoyl group (eg, an unsubstituted sulfamoyl group, a methylsulfamoyl group, a phenylsulfamoyl group, etc.), a carbonamide group (eg, an acetamido group,
Benzamide group, etc.), sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide group, p-
Toluenesulfonamide group, etc.), acyloxy group (eg acetyloxy group, benzoyloxy group, etc.), sulfonyloxy group (eg methanesulfonyloxy group,
Etc.), a ureido group (for example, an unsubstituted ureido group, a methylureido group, an ethylureido group, a phenylureido group,
Etc.), thioureido group (eg unsubstituted thioureido group, methylthioureido group, etc.), acyl group (eg acetyl group, benzoyl group, etc.), oxycarbonyl group (eg methoxycarbonyl group, phenoxycarbonyl group, etc.) , An oxycarbonylamino group (eg, a methoxycarbonylamino group, a phenoxycarbonylamino group,
2-ethylhexyloxycarbonylamino group, etc.),
It may be substituted with a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a hydroxyl group or the like, but a carboxylic acid or a salt thereof, a carphonic acid or a salt thereof, or a one not substituted with a hydroxyl group is effective in promoting the nucleation. preferable.

Preferred examples of the heterocyclic ring represented by Q include tetrazole, triazole, imidazole, thiadiazole and oxadiazole.

Y represents a divalent linking group consisting of an atom or an atom group selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. Examples of the divalent linking group include -S- and-
O-, These linking groups are linear or branched alkylene groups (for example, methylene group, ethylene group, and
It may be bonded via a propylene group, a butylene group, a hexylene group, a 1-methylethylene group, etc.) or a substituted or unsubstituted arylene group (a phenylene group, a naphthylene group, etc.).

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are each a hydrogen atom, a substituted or unsubstituted alkyl group (for example, a methyl group, an ethyl group, Propyl group, n
-Butyl group, etc.), a substituted or unsubstituted aryl group (e.g., phenyl group, 2-methylphenyl group, etc.),
It represents a substituted or unsubstituted alkenyl group (eg, propenyl group, 1-methylvinyl group, etc.) or a substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group, etc.).

R represents an organic group containing at least one thioether group, amino group (including salt form), ammonium group, ether group or heterocyclic group (including salt form). Examples of such an organic group include those in which a group selected from a substituted or unsubstituted alkyl group, alkenyl group, aralkyl group, or aryl group is combined with the above-mentioned groups. Is also good. For example, dimethylaminoethyl group, aminoethyl group, diethylaminoethyl group, dibutylaminoethyl group, hydrochloride of dimethylaminopropyl group, dimethylaminoethylthioethyl group,
4-dimethylaminophenyl group, 4-dimethylaminobenzyl group, methylthioethyl group, ethylthiopropyl group, 4-methylthio-3-cyanophenyl group, methylthiomethyl group, trimethylammonioethyl group, methoxyethyl group, methoxyethoxyethoxy Ethyl group, methoxyethylthioethyl group, 3,4-dimethoxyphenyl group,
3-chloro-4-methoxyphenyl group, morpholinoethyl group, 1-imidazolylethyl group, morpholinoethylthioethyl group, pyrrolidinoethyl group, piperidinopropyl group, 2-pyridylmethyl group, 2- (1-imidazolyl )
Ethylthioethyl, pyrazolylethyl, triazolylethyl, methoxyethoxyethoxyethoxycarbonylaminoethyl and the like. n represents 0 or 1, m represents 0, 1 or 2, and preferably 1 or 2.

In the general formula (III), in the formula, Y, R, n, M
Are the same as those in formula (II), and m is 1 or 2
And Q'represents an atomic group necessary for forming a 5- or 6-membered heterocycle capable of forming with iminosilver. 5 or 6 preferably selected from carbon, nitrogen, oxygen, sulfur and selenium
Represents a group of atoms necessary for forming a heterocyclic ring of a member. Also,
This heterocyclic ring may be fused as a carbon aromatic ring or a heteroaromatic ring. Examples of the heterocycle formed by Q ′ include indazoles, benzimidazoles, benzotriazoles, benzoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles, triazoles, tetrazoles and tetraazas. Indenes, triazaindenes, diazaindenes,
Pyrazoles, indoles and the like.

The nucleation accelerator represented by the general formula (II) is preferably one represented by the following general formulas (IV) to (VII).

General formula (IV) In the formula, M, R, Y and n have the same meanings as in formula (II). X represents an oxygen atom, a sulfur atom or a selenium atom, preferably a sulfur atom.

General formula (V) In the formula, R ′ is a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom, etc.), a nitro group, a mercapto group, an unsubstituted amino group, and a substituted or unsubstituted alkyl group (eg, a methyl group, an ethyl group, Alkenyl group (eg, propenyl group, 1-methylvinyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, etc.),
An aryl group (e.g. phenyl group, 2-methylphenyl group, etc.), or represent Y _n R.

R ″ represents a hydrogen atom, an unsubstituted amino group or Y _n R, and when R ′ and R ″ represent Y _n R, they may be the same or different.

However R ', one at least of R "represents Y _n R.

M, R, Y and n have the same meanings as those in formula (II).

General formula (VI) In the formula, R represents Y _n R. Where M, R, Y,
Each of n has the same meaning as in formula (II).

General formula (VII) The general formula (II) of the present invention, specifically (IV) to
Although the compound represented by (VII) is shown, the compound of the present invention is not limited thereto.

The nucleation accelerator used in the present invention is Berichte der.
Germany Chien Hemitsien Gezershyaft (Berich
te der Deutschen Chemischen Gesellschaft) 28 , 77
(1895), JP-A-50-37436, JP-A-51-3231, US patent
3,295,976, U.S. Patent 3,376,310, Berichte Der.
Germany Chien Hemitsien Gezershyaft (Berich
te der Deutschen Chemischen Gesellschaft) 22 , 568
(1889), 29, 2483 (1896), Journal of the Chemical Society (J.Chem.Soc.) 1932 , 1806, Journal of the American Chemical Society (J.Am.Chem.Soc.) .) 71 , 4000 (1949), US Patent 2,
No. 585,388, No. 2,541,924, Advances in Heterocyclism Chemistry (Advances in Hetero
Cyclic Chemistry) 9 , 165 (1968), Organic Synthesis IV, 569 (1963), Journal of the American Chemical Society (J.Am.Chem.Soc.) 45, 2390 (1923) ), Chemische Berichte 9,465 (1876), Japanese Patent Publication No. 40-28496, Japanese Patent Application Laid-Open No. 50-89034, and US Pat. No. 3,106,467.
Nos. 3,420,670, 2,271,229, 3,137,578,
3,148,066, 3,511,663, 3,060,028, 3,2
No. 71,154, No. 3,251,691, No. 3,598,599, No. 3,148,06
No. 6, JP-B-43-4135, U.S. Pat.No. 3,615,616, 3,42
0,664, 3,071,465, 2,444,605, 2,444,606
No. 2,444,607, No. 2,935,404 and the like.

The amount of nucleation accelerator added is 10 ^-6 per mol of silver halide.
To ^10-2 mol are preferred, more preferably 10 ^-5 to 10 ^-2 mol.

The non-pre-fogged internal latent image type silver halide emulsion used in the present invention is an emulsion containing silver halide in which the surface of silver halide grains is not pre-fogged and a latent image is mainly formed inside the grains. More specifically, a specific amount (0.5 to 3) of a silver halide emulsion is coated on a transparent support.
g / m ² ) and exposed to it for a fixed period of time of 0.01 to 10 seconds.
When developed for 5 minutes, the maximum density measured by the usual photographic density measuring method was applied in the same manner as above, and the silver halide emulsion exposed in the same manner was developed in the following developing solution B (surface type developing solution). Those having a density at least 5 times higher than the maximum density obtained when developed at 20 ° C. for 6 minutes are preferable, and those having a density at least 10 times higher are more preferable.

Internal developer A Metol 2 g Sodium sulfite (anhydrous) 90 g Hydroquinone 8 g Sodium carbonate (monohydrate) 52.5 g KBr 5 g KI 0.5 g Water is added 1 Surface developer B Metol 2.5 g L-ascorbic acid 10 g NaBO ₂ .4H ₂ O 35 g KBr 1 g Water 1 is added 1 Specific examples of the internal latent type emulsion are described in US Pat.
Convergence type silver halide emulsions described in US Pat. Nos. 3,761,276 and 3,850,637.
No. 3, No. 3,923,513, No. 4,035,185, No. 4,395,478,
4,504,570, JP-A-52-156614, 55-127549,
53-60222, 56-22681, 59-208540, 60-10
7641, 61-3137, Japanese Patent Application No. 61-32462, Research Disclosure Magazine No. 23510 (issued in November 1983) P236, core / shell type silver halide emulsions described in the patent Can be mentioned.

The shape of the silver halide grains used in the present invention may be a regular crystal such as cubic, octahedral, dodecahedral or tetradecahedral, an irregular crystal shape such as spherical, etc. Plate-shaped particles having a thickness ratio of 5 or more may be used. Further, it may be an emulsion having a composite form of these various crystal forms, or an emulsion composed of a mixture thereof.

The composition of silver halide includes silver chloride, silver bromide, and mixed silver halide. The silver halide preferably used in the present invention contains no silver iodide or contains 3% mol or less of salt (iodine). ) Silver bromide, (iodo) silver chloride or (iodo) silver bromide.

The average grain size of silver halide grains is 2 μm or less.
0.1 μm or more is preferable, but 1 μm or less and 0.15 μm or more is particularly preferable. The particle size distribution may be narrow or wide, but within ± 40% of the average particle size in terms of number of particles or weight to improve graininess and sharpness,
It is preferable to use a so-called "monodisperse" silver halide emulsion having a narrow grain size distribution such that 90% or more of all grains fall within ± 20%. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes or a plurality of emulsions having the same size but different sensitivities in emulsion layers having substantially the same color sensitivity. Can be mixed in the same layer or multi-layer coated in another layer. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the surface of the grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization or the like alone or in combination. Detailed specific examples are found in the patents described in, for example, P23 of Liesachi Dice Clothier No.17643-III (issued in December 1978).

The photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye in a conventional manner. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above dye and supersensitizer may be used in combination. Specific examples are described in, for example, the patents described in Liesachi Dice Clothier magazine No. 17643-IV (issued in December 1978) P23 to 24.

The photographic emulsion used in the present invention may contain an antifoggant or stabilizer for the purpose of preventing fog during the production process of a light-sensitive material, storage or photographic processing, or stabilizing photographic performance. For more detailed examples, see, for example, Liesachi Day Closer Magazine No.17643-VI (197
Published in December 8) and “Stabilization of” by EJBirr
Photographic Silver Halide Emulsions "(Focal Pres
s, published in 1974).

In order to directly form a positive color image, various cyan and yellow color couplers can be used in the present light-sensitive material together with the pyrazoloazole type magenta coupler of the formula (Ia) or (Ib). Further, a magenta coupler other than the pyrazoloazole-based magenta coupler used in the present invention can be used in combination.

Useful color couplers are compounds which undergo a coupling reaction with the oxidant of a p-phenylenediamine color developing agent to produce or release a substantially non-diffusible dye, which itself is substantially non-diffusible. It is a compound. Typical examples of useful color couplers are naphthol or phenol compounds and closed or heterocyclic ketomethylene compounds.

Specific examples of these cyan, magenta and yellow couplers which can be used in the present invention are described in "Research Disclosure", No. 17643 (December 1978), Item VII-D and No. 18717 (November 1979). Issued)).

Among them, as the yellow coupler which can be used in the present invention, oxygen atom-releasing type and nitrogen atom-releasing type yellow two-equivalent couplers can be exemplified. Especially α
The -pivaloyl acetanilide type couplers are preferable because the fastness, especially the light fastness, of the color forming dye is excellent, while the α-benzoyl acetanilide type couplers can obtain a high color density.

Cyan couplers preferably used in the present invention are phenol type cyan couplers having an alkyl group of ethyl group or more at the meta position of the phenol nucleus described in U.S. Pat.No. 3,772,002, and other 2.5 diacylamino-substituted phenol type couplers are also colored. It is preferable in terms of image fastness.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the photosensitive silver halide,
Preferably 0.01 to 0.5 moles for yellow couplers,
It is 0.003 to 0.5 mol for the magenta coupler and 0.002 to 0.5 mol for the cyan coupler.

The light-sensitive material produced by using the present invention includes a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamide phenol, as a color antifoggant or a mixing inhibitor. You may contain a derivative etc.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Examples of the organic discoloration inhibitor include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxy Benzenes,
Typical examples include aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Compounds having both hindered amine and hindered phenol partial structures in the same molecule as described in U.S. Pat. No. 4,268,593 give good results in preventing the yellow dye image from deteriorating due to heat, humidity and light. Further, in order to prevent the deterioration of the magenta dye image, particularly the deterioration due to light, substitution of spiroindanes described in JP-A-56-159644 and hydroquinone diether or monoether described in JP-A-55-89835. The chromans given give favorable results. These compounds can achieve their purpose by adding 5 to 100% by weight, based on the corresponding color coupler, to the photosensitive layer, usually by co-emulsifying the coupler with the coupler. In order to prevent deterioration of the cyan dye image due to heat and especially light, it is effective to introduce an ultraviolet absorber into both layers adjacent to the cyan color developing layer. Further, an ultraviolet absorber can be added to a hydrophilic colloid layer such as a protective layer.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

To the light-sensitive material of the present invention, it is possible to add a dyeing agent for preventing irradiation or halation, an antistatic agent, a smoothness improving agent and the like.

Representative examples of these additives are described in "Research Disclosur No. 17643 (December 1978) and 18716 (November 1979).

The present invention is also applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a support.
The order of these layers can be arbitrarily selected as required. The preferred order of layer arrangement is red-sensitive, green-sensitive, and blue-sensitive from the support side or blue-sensitive, red-sensitive, and green-sensitive from the support side.
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 sensitivity. Usually, a cyan-forming coupler is contained in the red-sensitive emulsion layer, a magenta-forming coupler is contained in the green-sensitive emulsion layer, and a yellow-forming coupler is contained in the blue-sensitive emulsion layer, but different combinations can be used depending on circumstances.

In addition to the silver halide emulsion layer, the light-sensitive material according to the present invention is preferably provided with an auxiliary layer such as a protective layer, an intermediate layer, a filter layer, an anti-halation layer, a back layer and a white reflective layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are a flexible support such as plastic film, paper, cloth or the like usually used for photographic light-sensitive materials or glass, ceramics,
It is applied to a rigid support such as metal. Useful as flexible supports are cellulose nitrate, cellulose acetate,
Cellulose acetate butyrate, polystyrene, polyvinyl chloride,
The film may be a film made of a semi-synthetic or synthetic polymer such as polyethylene terephthalate or polycarbonate, a baryta layer, or a paper coated or laminated with a α-olefin polymer (eg, polyethylene, polypropylene, ethylene / butene copolymer). The support may be colored with a dye or pigment. It may be black for the purpose of shading. The surface of these supports is generally subbed to improve adhesion with photographic emulsion layers and the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment or the like before or after the undercoating treatment.

The silver halide photographic emulsion layer and other hydrophilic colloid layers can be coated by, for example, a dip coating method, a roller coating method,
Various known coating methods such as a curtain coating method and an extrusion coating method can be used.

The present invention can be applied to various color light-sensitive materials. Typical examples are color reversal films for slides or televisions, reversal papers, and the like. It can also be applied to full-color copiers and color hard copies for storing CRT images. The present invention can also be applied to a black-and-white light-sensitive material using a three-color coupler mixture described in "Research Disclosure No. 17123 (issued in July 1978).

The light-sensitive material of the present invention is developed, bleached and fixed by a surface developing solution containing an aromatic primary amine color developing agent after or while being subjected to imagewise exposure and after being subjected to a fogging treatment with a nucleating agent. Thus, a positive color image can be directly formed.

As the fogging treatment in the present invention, a method of developing treatment in the presence of a nucleating agent, which is so-called "chemical fogging method", is used as described above. You may develop in the presence of a nucleating agent and fog light. Further, a light-sensitive material containing a nucleating agent may be fog-exposed.

Regarding the nucleating agent used in the present invention, Japanese Patent Application No. 61-22629
No. 50, page 1, line 1 to page 53, and it is particularly preferable to use the compounds represented by the general formulas [NI] and [N-II].

Specific examples of the compound represented by the general formula [NI] are shown below.

(N-I-1) 5-Ethoxy-2-methyl-1-propargylquinolinium bromide (N-I-2) 2,4-Dimethyl-1-propargylquinolinium bromide (N-I-3) 2 -Methyl-1- {3- [2- (4-
Methylphenyl) hydrazono] butyl} quinolinium
Iodide (N-I-4) 3,4-dimethyl-dihydropyrido [2,1
-B] benzothiazolium bromide (NI-5) 6-ethoxythiocarbonylamino-
2-Methyl-1-propargylquinolinium trifluoromethanesulfonate (N-I-6) 2-methyl-6- (3-phenylthioureido) -1-propargylquinolinylium bromide (N-I-7) 6- (5-benzotriazolecarboxamide) -2-methyl-1-propargylquinolinium trifluoromethanesulfonate (NI-8) 6- [3- (2-mercaptoethyl)
Ureido] -2-methyl-1-propargylquinolinium trifluoromethanesulfonate (N-I-9) 6- {3- [3- (5-mercapto-
1,3,4-thiadiazol-2-ylthio) propyl] ureido} -2-methyl-1-propargylquinolinium trifluoromethanesulfonate (NI-10) 6- (5-mercaptotetrazole-
1-yl) -2-methyl-1-propargylquinolinium iodide (N-11) 1-propargyl-2- (1-propenyl) quinolinium tonofluoromethanesulfonate (N-12) 6-ethoxy Thiocarbonylamino-
2- (2-methyl-1-propenyl) -1-propargylquinolinium trifluoromethanesulfonate (NI-13) 10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate ( NI-14) 7-ethoxythiocarbonylamino-
10-Propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate (NI-15) 6-ethoxythiocarbonylamino-
1-Propargyl-2,3-pentamethylenequinolinium trifluoromethanesulfonate (N-16) 7- [3- (5-mercaptotetrazol-1-yl) benzamide] -10-propargyl-
1,2,3,4-Tetrahydroacridinium perchlorate (NI-17) 6- [3- (5-mercaptotetrazol-1-yl) benzamido] -1-propargyl-
2,3-Pentamethylenequinolinium bromide (N-18) 7- (5-mercaptotetrazole-
1-yl) -9-methyl-10-propargyl-1,2,3,4
-Tetrahydroacridinium bromide (NI-19) 7- [3- {N- [2- (5-mercapto-1,3,4-thiadiazol-2-yl) thioethyl] carbamoyl} propanamide] -10 -Propargyl-1,2,3,4-tetrahydroacridinium tetrafluoroborate (NI-20) 6- (5-mercaptotetrazole-
1-yl) -4-methyl-1-propargyl-2,3-pentamethylenequinolinium bromide (NI-21) 7-ethoxythiocarbonylami-10
-Propargyl-1,2-dihydroacridinium trifluoromethanesulfonate (NI-22) 7- (5-mercaptotetrazole-
1-yl) -9-methyl-10-propargyl-1,2-dihydroacridinium hexafluorophosphate (NI-23) 7- [3- (5-mercaptotetrazol-1-yl) benzamide] -10-Propargyl-
1,2-dihydroacridinium bromide Specific examples of the compound represented by the formula (N-II) are shown below.

(N-II-1) 1-formyl-2- {4- [3- (2
-Methoxyphenyl) ureido] phenyl} hydrazine (N-II-2) 1-formyl-2- {4- [3- {3
-[3- (2,4-di-tert-bentylphenoxy) propyl] ureido {phenylsulfonylamino] phenyl} hydrazine (N-II-3) 1-formyl-2- {4- [3- ( 5
-Mercaptotetrazol-1-yl) benzamide]
Phenyl hydrazine (N-II-4) 1-formyl-2- [4- {3- [3
-(5-Mercaptotetrazol-1-yl) phenyl] ureido {phenyl] hydrazine (N-II-5) 1-formyl-2- [4- {3- [N
-(5-Mercapto-4-methyl-1,2,4-triazol-3-yl) carbamoyl) propanamide {phenyl] hydrazine (N-II-6) 1-formyl-2- {4- [3-} N
-[4- (3-Mercapto-1,2,4-triazole-4
-Yl) phenyl] carbamoyl} propanamide] phenyl} hydrazine (N-II-7) 1-formyl-2- [4- {3- [N
-(5-Mercapto-1,3,4-thiadiazol-2-yl) carbamoyl] propanamide} phenyl] -hydrazine (N-II-8) 2- [4-benzotriazole-5-
Carboxamido) phenyl] -1-formylhydrazine (N-II-9) 2- [4- {3- (N- (benzotriazole-5-carboxamido) carbamoyl] propanamide} phenyl] -1-formylhydrazine (N- II-10) 1-formyl-2- {4- [1- [N
-Phenylcarbamoyl) thiosemicarbamide] phenyl] hydrazine (N-II-11) 1-formyl-2- {4- [3- [3
-Phenylthioureido) benzamide] phenyl｝-
Hydrazine (N-II-12) 1-formyl-2- [4- (3-hexylureido) phenyl] hydrazine (N-II-13) 1-formyl-2- {4- [3- (5
-Mercaptotetrazol-1-yl) benzenesulfonamide] phenyl} hydrazine (N-II-14) 1-formyl-2- {4- [3- {3
-[3- (5-Mercaptotetrazol-1-yl) phenyl] ureido} benzenesulfonamide] phenyl} hydrazine The color developing solution used in the development processing of the light-sensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent, but p-
A phenylenediamine compound is preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N.
-Β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates.
Two or more of these compounds can be used in combination depending on the purpose.

Color developing solutions include alkali metal carbonates, pH buffers such as borates or phosphates, bromide salts, iodide salts,
It is common to include a development inhibitor such as benzimidazoles, benzothiazoles or mercapto compounds, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonate, triethylenediamine (1,4-diazabicyclo [2,2,2] octane)
Various preservatives such as ethylene glycol, organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammoniums, development accelerators such as amines, dye-forming couplers, competitive couplers, sodium boron hydride, etc. Various fogging agents, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, various chelating agents typified by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1
-Diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-di (0-hydroxyphenylacetic acid) and salts thereof It can be raised as a representative example.

The pH of these color developers is 9 or more and less than 11. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed, but it is generally 1 or less per 1 square meter of the light-sensitive material, and is reduced to 300 ml or less by reducing the bromide ion concentration in the replenishing acid. You can also When the replenishment amount is reduced, it is preferable to prevent the evaporation of liquid and air oxidation by reducing the contact area of the treatment tank with air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.
Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include ferricyanide; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, toclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. it can. Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleaching accelerators are described in the following specifications; US Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-9.
5,630, Research Disclosure No. 17,129 (July 1978) and the like compounds having a mercapto group or a disulfide bond; azolidine derivatives described in JP-A-50-140,129; US Pat. No. 3,706,561 Thiourea derivatives described above; iodide salts described in JP-A-58-16,235; polyoxyethylene compounds described in West German Patent No. 2,748,430; polyamine compounds described in JP-B-45-8836; bromide ions and the like are used. it can. Of these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and particularly preferred are the compounds described in U.S. Patent No. 3,893,858, West German Patent No. 1,290,812, and JP-A-53-95,630. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective in bleach-fixing color photographic materials for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are generally used, and ammonium thiosulfate is most widely used. Can be used. As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

In the present invention, a washing bath is a processing liquid component adhered to or stored in a color light-sensitive material, and photographic performance after processing,
It is a bath whose main purpose is to wash out the constituent components of the color light-sensitive material that should be removed in order to ensure image stability.

Further, the stabilizing bath refers to a bath having an image stabilizing function which cannot be obtained by the washing bath, in addition to the function as the above washing bath. For example, a bath containing formalin corresponds to this. . What is the amount brought in from the front bath?
It means the volume of the pre-bath admixed with and absorbed by the light-sensitive material, and the color light-sensitive material sampled immediately before entering the water-washing bath is immersed in water to extract the pre-bath components. It can be calculated by measuring the amount of bath components.

In the present invention, the replenishing amount to the washing bath or the alternative thereof is 350 ml or less, preferably 90 to 350 ml, and more preferably 120 ml per 1 m ^{2 of the} color light-sensitive material to be processed.
~ 290 ml.

The pH of the washing or stabilizing bath is 4-10, preferably 5-9, more preferably 6.5-8.5.

It is preferable to use softened water as the washing water or the stabilizing solution. Examples of the water softening treatment method include using an ion exchange resin or a reverse osmosis device.

As the ion exchange resin, a sodium type strong acid cation exchange resin in which the counter ion of the exchange group is sodium is preferable, and an H type strong acid cation exchange resin and an ammonium type strong acid cation exchange resin can also be used. Furthermore, it is also preferable to use an H-type strongly acidic cation exchange resin and an OH-type strongly basic anion exchange resin in combination. As the resin substrate, a copolymer of styrene and divinylbenzene is preferable, and the amount of divinylbenzene charged during production is 4 to 4% of the total amount of monomers charged.
16% (w / w) is preferable.

As an example of such an ion exchange resin, Mitsubishi Kasei Co., Ltd. brand name Diaion SK-1B or PK-216 can be mentioned.

Although various types of reverse osmosis devices can be used, those using a cellulose acetate or polyether sulfone membrane are suitable. When the pressure is 20 kg / cm ² or less, noise is small and it is easy to use.

Water reduced in calcium and magnesium by such an ion exchange resin or reverse osmosis treatment apparatus causes less growth of bacteria and mold, and brings good results by combining with the present invention. .

Various known compounds may be added to the washing process and the stabilizing process for the purpose of preventing precipitation and stabilizing the washing water. For example, chelating agents such as inorganic phosphoric acid, aminoporcarboxylic acid, and organic phosphonic acid, bactericides and antifungal agents that prevent the development of various bacteria, algae, and molds (for example, “Jearn of Antibacterial・ Anti-Fungal Agents (J.Antidact.Antifung.Agent
s) ”vol.11, No.5, compounds described in p207-223 (1983) and compounds described in Hiroshi Horiguchi's" Chemistry of antibacterial and antifungal "), magnesium salts, aluminum salts, bismuth salts, etc. If necessary, a metal salt, an alkali metal and an ammonium salt to be used, or a surfactant for preventing drying load and unevenness can be added. Alternatively, compounds described in West, "Photographic Science and Engineering Magazine (Phot.Sci.Eng.)", Volume 6, pp. 344-359 (1965), etc. may be added. It is particularly effective to add a chelating agent, a bactericidal agent or a fungicide.

The water washing step is performed by multi-stage countercurrent water washing of two or more tanks (for example, 2 to 9).
It is common to save water for washing. Further, instead of the washing step, a multistage countercurrent stabilization treatment step as described in JP-A-57-8543 may be carried out. Various compounds other than the above-mentioned additives are added to the stabilizing bath for the purpose of stabilizing an image. For example, adjust the membrane pH (eg pH
3 to 9) various buffers (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, porcarboxylic acid) And the like) and aldehydes such as formalin. Other chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid,
Phosphonocarboxylic acid, etc.), bactericide, antifungal agent (thiazole type, isothiazole type, halogenated phenol, orthophenylphenol, sulfanilamide, benzotriazole, etc.), surfactant, fluorescent brightening agent, Various additives such as a hardener metal salt may be used, and two or more kinds of the same or different target compounds may be used in combination.

Also, ammonium chloride as a membrane pH adjuster after treatment,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve the image storability.

The time for washing and stabilizing treatment in the present invention is usually 20 seconds to 10 minutes, preferably 20 seconds to 3 minutes, although it varies depending on the kind of the photosensitive material and the processing conditions. More preferably 30 seconds to 2 minutes 30
Seconds.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. A temperature of 28 ° C to 38 ° C is standard, but it is possible to raise the temperature to accelerate the treatment to shorten the treatment time, and conversely to lower the temperature to improve the image quality and improve the stability of the treatment liquid. it can.

Further, each processing time can be set shorter than the standard time within a trouble-free range, if necessary, for speeding up.

In addition, in the case of continuous processing, a constant finish can be obtained by using a replenisher of each processing solution to prevent the composition of the solution from varying.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, various floating pigs, various squeegees, etc. may be provided in each processing bath.

〔Example〕

The present invention will be described below with reference to examples, but the present invention is not limited to the examples.

Example 1 A paper support laminated on both sides with polyethylene (thickness 10
A color photographic light-sensitive material was prepared by coating the following first to fourteenth layers on the front side (0 micron) and the fifteenth to sixteenth layers on the back side. The side coated with the first layer of polyethylene contains titanium white as a white pigment and traces of ultramarine as a bluish dye.

(Composition of photosensitive layer) The components and the coating amount in g / m ² are shown below. 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 for the 14th layer, a Lippmann emulsion which did not undergo surface chemical sensitization was used.

First layer (anti-halation layer) Black colloidal silver ・ ・ ・ 0.10 Gelatin ・ ・ ・ 1.30 Second layer (intermediate layer) Gelatin ・ ・ ・ 0.70 Third layer (low sensitivity red sensitive layer) Red sensitizing dye (ExS- 1,2,3) spectrally sensitized silver bromide (average grain size 0.3μ, size distribution [variation coefficient] 8%, octahedron) ... 0.06 red sensitizing dye (ExS-1, 2, 3) ) Spectrally sensitized with silver chlorobromide (silver chloride 5 mol%, average grain size 0.45μ, size distribution 10%, octahedron) ・ ・ ・ 0.10 gelatin ・ ・ ・ 1.00 cyan coupler (ExC-1) ・ ・・ 0.11 Cyan coupler (ExC-2) ・ ・ ・ 0.10 Anti-fading agent (Cpd-2, 3, 4, 13 equivalents) ・ ・ ・ 0.12 Coupler dispersion medium (Cpd-5) ・ ・ ・ 0.03 Coupler solvent (Solv- 0.06 4th layer (high-sensitivity red-sensitive layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) (average) Child size 0.60μ, size distribution 15%, octahedron) ・ ・ ・ 0.14 Gelatin ・ ・ ・ 1.00 Cyan coupler (ExC-1) ・ ・ 0.15 Cyan coupler (ExC-2) ・ ・ 0.15 Anti-fading agent (Cpd-2, (3,4,13 equivalents) ・ ・ ・ 0.15 Coupler dispersion medium (Cpd-5) ・ ・ ・ 0.03 Coupler solvent (Solv-7,2,3 equivalents) ・ ・ ・ 0.15 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 6th layer (low sensitivity) Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-3) (average grain size 0.25 μ, grain size distribution 8%, octahedron) ・ ・ ・ 0.04 Green sensitizing dye (ExS-3) 4) Spectral-sensitized silver bromide (average grain size 0.45μ, grain size distribution 11%, octahedron) ・ ・ ・ 0.06 Gelatin ・ ・ ・ 0.80 Magenta coupler (ExM-1)・ ・ ・ 0.11 Anti-fading agent (Cpd-9) Anti-staining agent (Cpd-10, ・ ・ ・ 0.10 22 equivalents) ・ ・ ・ 0.014 Anti-staining agent (Cpd-23) ・ ・ ・ 0.001 Anti-staining agent (Cpd- 12) ・ ・ ・ 0.01 Color dispersion medium (Cpd-5) ・ ・ ・ 0.05 Coupler solvent (Solv-4,6 equivalent) ・ ・ ・ 0.15 7th layer (high sensitivity green sensitive layer) Green sensitizing dye (ExS- 3,4) spectrally sensitized silver bromide (average grain size 0.8μ, grain size distribution 16%, octahedron) ・ ・ ・ 0.10 gelatin ・ ・ ・ 0.80 magenta coupler (ExM-1) ・ ・ ・ 0.11 fading Inhibitor (Cpd-9) ・ ・ ・ 0.10 Anti-stain (Cpd-10,22 equivalent) ・ ・ ・ 0.013 Anti-stain (Cpd-23) ・ ・ ・ 0.001 Anti-stain (Cpd-12) ・ ・ ・0.01 Color dispersion medium (Cpd-5) ・ ・ ・ 0.05 Coupler solvent (Solv-4,6 equivalent) ・ ・ ・ 0.15 8th layer (intermediate layer) Same as 5th layer 9th layer (yellow filter layer) Yellow colloid Silver ・ ・ ・ 0.20 Gelatin ・ ・ ・ 1.00 Color mixing inhibitor (Cpd-7) ・ ・ ・ 0.06 Color mixing inhibitor solvent (Solv-4,5 equivalent) ・ ・ ・ 0.15 Polymer latex (Cpd-8) ・ ・ ・0.10 10th layer (intermediate layer) Same as 5th layer 11th layer (low sensitivity blue sensitive layer) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5,6) (average grain size 8%, Octahedron) ・ ・ ・ 0.07 Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5,6) (average grain size 0.60μ, grain size distribution 14%, octahedron) ・ ・ ・ 0.10 gelatin ・ ・・ 0.50 Yellow coupler (ExY-1) ・ ・ ・ 0.22 Anti-staining agent (Cpd-11) ・ ・ ・ 0.001 Anti-fading agent (Cpd-6) ・ ・ ・ 0.10 Coupler dispersion medium (Cpd-5) ・ ・ ・ 0.05 Coupler Solvent (Solv-2) ・ ・ ・ 0.05 12th layer (high-sensitivity blue-sensitive layer) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average grain size 1.2μ, grain size distribution) 21%, eight・ ・ ・ 0.25 gelatin ・ ・ ・ 1.00 yellow coupler (ExY-1) ・ ・ ・ 0.41 stain inhibitor (Cpd-11) ・ ・ ・ 0.002 anti-fading agent (Cpd-6) ・ ・ ・ 0.10 coupler dispersion medium ( Cpd-5) ・ ・ ・ 0.05 Coupler solvent (Solv-2) ・ ・ ・ 0.10 13th layer (UV absorbing layer) Gelatin ・ ・ ・ 1.50 UV absorber (Cpd-1, 3, 13 equivalents) ・ ・ ・ 1.00 Color mixing inhibitor (Cpd-6,14 equivalents) ・ ・ ・ 0.06 Dispersion medium (Cpd-5) ・ ・ ・ 0.05 UV absorbing solvent (Solv-1, 2 equivalents) ・ ・ ・ 0.15 Anti-radiation dye (Cpd- (15, 16 equivalents) ...
0.02 Anti-irradiation dye (Cpd-17,18 equivalent) ・ ・ ・
0.02 14th layer (protective layer) Fine grain silver chlorobromide (97 mol% silver chloride, average size 0.2)
μ) ・ ・ ・ 0.05 Acrylic modified copolymer of polyvinyl alcohol (Modification degree 17%) ・ ・ ・ 0.02 Polymethylmethacrylate particles (Average particle size 2.4
Micron), silicon oxide (average particle size 5 micron) Equivalent ・ ・ ・ 0.05 Gelatin ・ ・ ・ 1.50 Gelatin hardening agent (H-1) ・ ・ ・ 0.17 15th layer (back layer) Gelatin ・ ・ ・ 2.50 16th layer (Back protective layer) Polymethylmethacrylate particles (Average particle size 2.4
Micron), silicon oxide (average particle size 5 micron), equivalence ・ ・ ・ 0.05 gelatin ・ ・ ・ 2.00 gelatin hardening agent (H-1) ・ ・ ・ 0.11 how to make emulsion EM1 aqueous solution of potassium bromide and silver nitrate in gelatin aqueous solution With vigorous stirring, they were simultaneously added at 75 ° C. over 15 minutes to obtain octahedral silver bromide grains having an average grain size of 0.40 micron. 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione per mol of silver, 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) were sequentially added to this emulsion at 75 ° C. for 80 minutes. The chemical sensitization treatment was performed by heating. 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 micron was obtained. The coefficient of variation of the particle size is approximately
It was 10%. To this emulsion, 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) were added per mol of silver.
The mixture was heated at 60 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion.

For each photosensitive layer, ExZK-1 was used as a nucleating agent in an amount of 10 ⁻³ % by weight based on the coated amount of silver halide. Further, for each layer, alkanol XC (Dupont) and sodium alkylbenzenesulfonate were used as emulsification / dispersion aids, and succinate and Magefac F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. For the layers containing silver halide and colloidal silver, (Cpd-19, 20, 21) was used as a stabilizer. The compounds used in the examples are shown below.

Cpd-8 polyethyl acrylate EXM-1 Compounds listed in Table 1 Solv-1 Di (2-ethylhexyl) phthalate Solv-2 Trinonylphosphate Solv-3 Di (3-methylhexyl) phthalate Solv-4 Tricresylphosphate Solv-5 Dibutylphthalate Solv-6 Trioctylphosphate Solv- 7 Di (2-ethylhexyl) sebacate H-1 1,2-bis (vinylsulfonylacetamido) ethane ExZK-1 7- [3- (5-mercaptotetrazole-
1-yl) benzamide] -10-propargyl-1,2,3,
4-Tetrahydroacridinium perchlorate Treatment step A Time Temperature Color development 1 min 30 sec 38 ° C Bleach fixing 40 sec 35 ° C water wash 40 sec 30-36 ° C water wash 40 sec 30-36 ° C water wash 15 sec Drying 30 seconds 75 to 80 ° C. The replenishing method of washing water was a so-called countercurrent replenishing method in which the washing bath was replenished, and the overflow solution of the washing bath was introduced into the washing bath and the overflow solution of the washing bath was introduced into the washing bath. At this time, the carry-in ratio of the photosensitive material from the prebath was 35 ml / m ² , and the replenishment ratio was 9.1.

[Color developer] Mother liquor Ethylenediaminetetrakismethylenephosphonic acid 0.5 g Diethylene glycol 8.0 g Benzyl alcohol 12.0 g Sodium bromide 0.6 g Sodium chloride 0.5 g Sodium sulfite 2.0 g N, N-diethylhydroxylamine 3.5 g Triethylenediamine (1,4- Diazabicyclo 〔2,2,
2) Octane) 3.5 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 5.5 g Potassium carbonate 30.0 g Fluorescent brightener (stilbene type) 1.0 g Pure water 1000 ml pH 10.50 pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleaching fixer] Mother liquor = Replenisher Ammonium thiosulfate 100 g Sodium bisulfite 21.0 g Ethylenediaminetetraacetic acid iron (III) ammonium ・ 2
Dihydrate 50.0g Ethylenediaminetetraacetic acid 2 sodium-dihydrate 5.0 g 1000 ml pH 6.3 pH by the addition of pure water was adjusted with aqueous ammonia or hydrochloric acid.

[Wash water]

Pure water was used (mother liquor) Here, pure water was obtained by removing all cations other than hydrogen ions and all anions other than hydroxide ions in tap water to 1 ppm or less by ion exchange treatment.

The color photographic paper prepared as described above was stored at 45 ° C. and 80% RH for 3 days (ink-incubated), subjected to wet exposure (0.1 second, halogen lamp, 3200K, 10 CMS), and then subjected to processing step A. The resulting magenta color image densities were measured and are shown in Table 1.

The addition amount of the nucleation accelerator is 1.25 × 10 ⁻⁴ mol / Ag mol.

Samples Nos. 1 to 3 and Nos. 5 to 7 using the magenta coupler and the nucleation accelerator of the present invention have higher Dmax and lower Dmin than those of Comparative Examples Nos. 4, 8, and 9, and are preferable. It was

Further, when the Macbeth color chart was photographed, sample Nos. 1 to 8 using the magenta coupler of the present invention showed that
Compared with sample No. 9 using the magenta coupler of the comparative example, the saturation of reddish color was high and it was preferable.

Example-2 Instead of the magenta coupler I-4, I-2, I-6,
Example 1 was repeated except that I-16, I-22, I-31, I-32, and I-33 were used, respectively, and similar results were obtained.

Example-3 Example-1 was repeated except that the treatment step B was used, and similar results were obtained.

Processing step B time Temperature color development 70 seconds 38 ° C. Bleach fixing 30 seconds 38 ° C. water washing 30 seconds 38 ° C. water washing 30 seconds 38 ° C. At this time, the replenishment ratio of the washing solution was 8.6 times.

[Color development] Mother liquor Diethylenetriaminepentaacetic acid 0.5 g 1-Hydroxyethylidene-1,1-diphosphonic acid 0.5 g Diethylene glycol 8.0 g Benzyl alcohol 9.0 g Sodium bromide 0.7 g Sodium chloride 0.5 g Sodium sulfite 2.0 g Hydroxylamine sulfate 2.8 g 3 -Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate 2.0 g 3-Methyl-4-amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.0 g Potassium carbonate 30.0 g Fluorescent brightener (stilbene type) 1.0 g Pure water was added to 1000 ml pH 10.50 pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleaching fixer] Mother liquor Ammonium thiosulfate 77 g Sodium hydrogen sulfite 14.0 g Ethylenediaminetetraacetate ammonium iron (III) -2
Hydrochloride 40.0 g Ethylenediaminetetraacetic acid disodium dihydrate 4.0 g 2-Mercapto-1,3,4-triazole 0.5 g Pure water was added to 1000 ml pH 7.0 pH was adjusted with aqueous ammonia or hydrochloric acid.

[Wash water]

(Mother liquor) using pure water Example-4 Preparation of emulsion EM-2 A mixed aqueous solution of potassium bromide and sodium chloride and an aqueous solution of silver nitrate were added to 0.07 g of 3,4-dimethyl-1,3-
Mono-dispersed salty odor with an average particle size of about 0.23 μm (silver bromide content 80 mol%), which was added simultaneously to an aqueous gelatin solution containing thiazoline-2-thione with vigorous stirring at 65 ° C for about 14 minutes. A silver halide emulsion was obtained. 61 mg per mole of silver in this emulsion
Chemical sensitization treatment was carried out by adding sodium thiosulfate (4) and 42 mg of chloroauric acid (tetrahydrate) and heating at 65 ° C. for 60 minutes. The silver chlorobromide grains thus obtained were used as cores for further growth in the same precipitation environment as the first time, and finally a monodisperse core / shell having an average grain size of about 0.65 μm (silver bromide content 70 mol%). A silver chlorobromide emulsion was obtained. Coefficient of variation of particle size is about 12
It was in%. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver, and the mixture was mixed at 60 ° C for 6 hours.
A chemical sensitization treatment was performed by heating for 0 minutes to obtain an internal latent image type silver halide emulsion EM-2.

A color photographic paper was prepared in the same manner as in Example 1 except that the nucleating agent (ExZK-1) was removed from each photosensitive layer by using Emulsion EM-2 and an emulsion corresponding thereto for the sixth and seventh layers.

After this was exposed to the same light as in Example-1, the following processing step C was performed. The same result as in Example-1 was obtained.

Processing process C Time Temperature color development ^{* 1)} 135 seconds 36 ℃ Bleaching fixing 40 seconds 36 ℃ Stable 40 seconds 36 ℃ Stable 40 seconds 36 ℃ Dry 40 seconds 70 ℃ * 1) 1lux after immersion in color developing solution for 15 seconds 15 in white light
Color development processing was performed while light fogging was performed for a second.

[Color developer] Mother liquor Hydroxyethyliminodioic acid 0.5g β-Cyclodextrin 1.5g Monoethylene glycol 9.0g Benzyl alcohol 9.0g Monoethanolamine 2.5g Sodium bromide 2.3g Sodium chloride 5.5g N, N-diethylhydroxyl Amine 5.9 g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate 2.7 g 3-Methyl-4-amino-N-ethyl-N- (β-hydroxyethyl ) Aniline sulfate 4.5 g Potassium carbonate 30.0 g Fluorescent brightener (stilbene type) 1.0 g Pure water was added and 1000 ml pH 10.30 pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleaching fixer] Mother liquor Ammonium thiosulfate 110 g Sodium hydrogen sulfite 12 g Diethylenetriamine Iron (III) pentaacetate 8
0 g diethylenetriamine was added to pentaacetate 5 g 2-mercapto-5-amino-1,3,4-thiadiazole Lumpur 0.3g deionized water 1000 ml pH 6.80 pH was adjusted with aqueous ammonia or hydrochloric acid.

[Stabilizer] Mother liquor 1-Hydroxyethylidene-1,1-diphosphonic acid 2.7g o-phenylphenol 0.2g Potassium chloride 2.5g Bismuth chloride 1.0g Zinc chloride 0.25g Sodium sulfite 0.3g Ammonium sulfate 4.5g Fluorescent brightener (Stilbene system) 0.5 g pure water was added and 1000 ml pH 7.2 pH was adjusted with potassium hydroxide or hydrochloric acid.

〔The invention's effect〕

The direct positive photographic light-sensitive material of the present invention is excellent in color reproducibility and brings about an image suitable for practical use in which high maximum density and improvement in whiteness by increasing the contrast of the minimum density part are achieved.

Note that the above effects are remarkably exhibited even when stored under high temperature and high humidity.

Claims (1)

[Claims] 1. At least one unfogged internal latent image type silver halide on a support for use in an image forming method in which a color developing treatment is performed with a color developing solution having a pH of less than 11 in the presence of a nucleating agent. In a direct positive color light-sensitive material having an emulsion layer and a color image-forming coupler, the following general formula (I
at least one of magenta couplers represented by a) and / or (Ib) and the following general formula (II) and / or (III)
A direct positive color light-sensitive material containing at least one nucleation accelerator represented by (In the formula, R ¹¹ and R ¹² represent a hydrogen atom or a substituent, which may be the same or different from each other, and X is a hydrogen atom or a coupling reaction with an aromatic primary amine developer oxidant. Represents a group capable of splitting off, and R ¹¹ , R ¹² or X may be a divalent group to form a bis form. In the formula, Q represents an atomic group necessary for forming a 5- or 6-membered heterocycle, and this heterocycle may be condensed with a carbon aromatic ring or a heteroaromatic ring, Y is a hydrogen atom, Represents a divalent linking group consisting of an atom or an atom group selected from a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, and R represents at least one of a thioether group, an amino group, an ammonium group, an ether group or a heterocyclic group. Represents an organic group containing
n represents 0 or 1, m represents 0, 1 or 2, and M represents a hydrogen atom, an alkali metal atom, an ammonium group or a group capable of cleaving under alkaline conditions. General formula (III) In the formula, Q ′ represents an atomic group necessary for forming a 5- or 6-membered heterocycle capable of forming imino silver, and Y, R, n and M have the same meanings as those in the above general formula (II), And m'is 1
Or represents 2.