JPH0727185B2 - Direct positive color photosensitive material and direct positive color image forming method - Google Patents

Description

The present invention relates to a direct positive color photographic material using an internal latent image type silver halide emulsion.

(Prior Art) Photographic methods for obtaining direct positive images without the need for reversal processing steps or negative films are well known.

As a method for directly forming a positive image using an internal latent image type silver halide emulsion, various techniques have been known so far, for example, U.S. Pat.Nos. 2,592,250 and 2,466,957.
No. 2,497,875, No. 2,588,982, No. 3,317,322
No. 3, No. 3,761,266, No. 3,761,276, No. 3,796,57
No. 7, British Patent Nos. 1,151,363 and 1,150,553 (No. 1,011,062), and the like, are mainly described.

Further, in the core / shell type internal latent image direct positive emulsion,
For example, U.S. Pat.No. 3,761,276 discloses that lead, bismuth, iridium as a doping agent inside a silver halide grain may be added by adding various polyvalent metals or chemically sensitizing with gold or sulfur. The maximum density of the obtained image is increased by incorporating gold etc. and further chemically sensitizing the surface of the silver halide grains with gold, sulfur, etc.
Techniques for reducing maximum concentration and US Pat. No. 4,395,47
No. 8 specification sensitizes the core particles with gold and adds a polyvalent metal (lead, magnesium, copper, zinc, cadmium, bismuth, palladium, etc.) to the shell part to produce a re-inversion negative image generated in the image. The suppression technique is further described in JP-A-59-216136, in which core / shell type particles comprising a metal-doped and chemically sensitized particle size of two or more kinds have a larger particle size / core. Techniques for obtaining a wide exposure latitude with good stability over time by doping a large number of polyvalent metal ions into the inner core of the shell type particle are described.

On the other hand, as a coupler for forming a color image, various yellow color-forming couplers are known, and particularly a coupler having a high coupling speed called a high-speed coupler is useful. For example, JP-A-49-106329, copper 47-26133. And U.S. Pat. Nos. 3,408,194 and 3,582,322.

(Problems to be Solved by the Invention) Since the high-speed yellow color coupler has a high coupling speed, the development speed can be increased and it is particularly suitable for rapid processing. Further, there is an advantage that the treatment dependence due to the change of the treatment composition, the change of the treatment temperature, the pH, etc. is relatively small, but it is still not practically sufficient and further improvement is desired. Above all, the breakage of the foot of the characteristic curve tends to become worse with the development time, and in particular, improvement of this point is necessary.

The sensitivity of the foot portion of the characteristic curve corresponds to the highlight portion on the practical screen, and is important for improving the image quality.

Accordingly, it is an object of the present invention to provide a direct positive color light-sensitive material and a direct positive color image forming method in which, in the case of containing a high speed yellow color forming coupler, breakage of the foot of the characteristic curve is less dependent on the development time. .

(Means for Solving the Problems) The above object of the present invention is to provide at least one unfogged internal latent image type silver halide emulsion layer on a support and at least a compound represented by the following general formula ( In a direct positive color light-sensitive material containing a high speed yellow color coupler represented by I), the internal latent image type silver halide emulsion layer contains a core / shell type silver halide emulsion, and the core / shell type silver halide is cadmium. , A silver halide grain (core) chemically aged in the presence of an ion or compound of lead or Group VIII metal and a gold ion or compound, and a silver halide shell coating the core. It has been effectively achieved by a direct positive color light-sensitive material characterized by certain things.

General formula (I) (In the formula, Q represents an N-arylcarbamoyl group, and Y
Represents a coupling-off group having an oxygen atom or a nitrogen atom as a leaving atom. ) In the present invention, a high-speed yellow color-forming coupler is prepared by combining an ion or compound of cadmium, lead or a metal of Group VIII of the Periodic Table with a gold ion or compound among various metal dopants and chemical sensitizers. It was discovered that the core / shell type internal latent image direct positive color light-sensitive material contained has an unexpected effect that the dependence of the breakage of the characteristic curve on the development time can be reduced.

Further, the above-mentioned light-sensitive material still exhibits the above-mentioned effects of the present invention even when it is developed with a low pH color developing solution having a pH of 10.0 to 11.0, and a high maximum density can be obtained.

The high speed yellow coupler represented by formula (I) will be described in detail below.

In the formula, the N-arylcarbamoyl group represented by Q is
It is preferable that the phenyl group of the N-phenylcarbamoyl group be substituted with a plurality of substituents, and examples of the substituent include an alkyl group, an aryl group, a heterocyclic group, and an alkoxy group (eg, methoxy group, 2-methoxyethoxy group). Group), an aryloxy group (for example, 2,4-di-tert-aminophenoxy group, 2-chlorophenoxy group, 4-cyanophenoxy group, etc.), an alkenyloxy group (for example,
2-propenyloxy group etc.), acyl group (eg acetyl group, benzoyl group etc.), ester group (eg
Butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyl group, etc.), sulfonamide group (for example, methanesulfonamide group, arylsulfonamide group, butanesulfonamide group, etc.), amide group ( For example, acetylamino group), carbamoyl group (eg, ethylcarbamoyl group, dimethylcarbamoyl group, butylcarbamoyl group, etc.), sulfamoyl group (eg, N-methyl-N-octadecylsulfamoyl group, propylsulfamoyl group, butylsulfamoyl group). Famoyl group), sulfamoylamino group (eg, dipropylsulfamoylamino group), imide group (eg, saxinimide group, hydantoinyl group, etc.), ureido group (eg, phenylureido group). Dimethylureido group, etc.), aliphatic or aromatic sulfonyl group (eg, methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio group (eg, ethylthio group, phenylthio group, etc.), hydroxy group, cyano group, Examples thereof include a carboxy group, a nitro group, a sulfo group, and a halogen atom (chlorine, bromine, fluorine, etc.). The above groups may be further substituted with groups as described above.

Preferred Q is represented by the following general formula (II).

General formula (II) (In the formula, Q ₁ represents a halogen atom or an alkoxy group,
Q ₂ represents a hydrogen atom, a halogen atom or an alkoxy group which may have a substituent. ) R ¹ represents an alkyl group which may have a substituent. This alkyl group may be straight-chain or branched, but is preferably branched.

The substituent which Q ₂ and R ¹ may have is, for example, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a dialkylamino group or a heterocyclic group (for example, N-
Morpholino groups, N-piperidino groups, 2-furyl groups, etc.), halogen atoms, nitro groups, hydroxy groups, carboxyl groups, sulfo groups, alkoxycarbonyl groups and the like are typical examples. Of these, an aryloxy group is preferable as the substituent for the alkyl group of R ¹ .

Preferred leaving group Y includes groups represented by the following general formulas (III) to (IX).

R ² represents an optionally substituted aryl group or heterocyclic group.

R ³ and R ⁴ are each a hydrogen atom, halogen atom, carboxylic acid ester group, amino group, alkyl group, alkylthio group, alkoxy group, alkylsulfonyl group, alkylsulfinyl group, carboxylic acid group, sulfonic acid group, unsubstituted Alternatively, it represents a substituted, phenyl group or heterocycle, which groups may be the same or different.

W ₁ in the formula Represents a non-metal atom required to form a 4-membered ring, 5-membered ring or 6-membered ring.

Among the general formula (VI), preferred are (VII) to (XVI)
It is represented by.

In the formula, R ⁵ and R ⁶ each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydroxy group, and R ⁷ , R ⁸ and R ⁹ each represent a hydrogen atom, an alkyl group, an aryl group, It represents an aralkyl group or an acyl group, and W ₂ represents an oxygen atom or a sulfur atom. The above groups may be further substituted.

The substituent of Y [preferably R ² to R ⁹ in formula (III) to formula (IX)] or the substituent of Q [preferably formula (I)
R ¹ ] in I) may be a divalent group to form a bicyclic body, or may be a group connecting the polymer main chain and the mother nucleus of the coupler.

Among the above Y, those represented by the general formulas (VI) to (IX) are particularly useful in the present invention.

It is preferred that the couplers of general formula (I) have at least one so-called ballast group.

Specific examples thereof include those described in the following patent specifications.

Japanese Examined Patent Publication Nos. 42-23902 and 44-3660, JP-A-50-19435
No. 59-46384, JP-A-59-45442, JP-A-59
-174836, JP-A-59-177553, JP-A-59-177554
JP-A-59-177,555, JP-A-59-177556, JP-A-59-177557, JP-A-60-41042, and JP-A-60-55340.
U.S. Pat. No. 2,688,544, U.S. Pat.
No. 98,795, No. 2,772,161, No. 2,908,573, No. 2,895,82
No. 6, No. 2,920,961, No. 3,519,429, JP-A-47-37636
No. 4, U.S. Pat. Nos. 4,124,396 and 4,443,536, Japanese Patent Publication No. 43-
No. 22900, No. 43-29417, No. 44-6992, No. 45-41474
No. 46-19025, 46-19026, 46-19032,
48-25932, 49-16056, JP-A-49-29639,
49-53437, 50-134644, 53-76834, 53
-83411, 53-141622, 55-7702, 55-931
No. 53, No. 56-30126, No. 59-124341, U.S. Pat.
6,719, 3,488,193, JP-A-47-4,481, JP-A-4
9-8228, 49-110344, 50-20723, German Published Patent 2707,488, U.S. Patent 4,458,011, French Patent 1,20
2,940, U.S. Patent 3,133,815, U.S. Patent 3,161,512
U.S. Patent No. 3,183,095, Japanese Patent Publication No. 43-16190, U.S. Patent Nos. 3,547,944, 3,285,747, and British Patent 1,128,037.
No. 4, Japanese Patent Publication No. 47-9314, JP-A Nos. 48-71,640 and 50-48.
922, 51-126,831, 52-47728, 52-119,3
23, 55-38,599, etc.

The yellow coupler represented by the general formula (I) is described in JP-A-54.
-48541, JP-B-58-10739, U.S. Pat. No. 4,326,024, Research Disclosure 18053 and the like can be used for the synthesis.

The yellow coupler represented by formula (I) is specifically described, for example, in JP-B-45-19955, JP-B-45-19956, and JP-A-48-95873.
JP-A-50-130442, 50-139738, 51-21827
No. 52-23933, No. 52-115219, No. 54-48541,
55-38576, 56-87041, 59-45442, 59
-222837, 60-24547, 60-69653, U.S. patents
2,298,443, 2,407,210, 2,710,802, 3,38
4,657, British Patent 980,507, U.S. Patent 3,265,506,
French Patent 1,558,452, U.S. Patent 3,841,880, 3,894,
875, 3,874,948, 4,157,919, 3,664,841
No. 4, Japanese Patent Publication No. 17372, Japanese Patent No. 49-17373, U.S. Pat.
0,446, JP-A-54-99433, JP-A-55-7702, JP-A-56-30
127, 56-74250, British Patent 1,434,472, JP-A-5
3-82332, 55-2300, 55-36900, 47-261
33, JP-A-55-598, JP-A-48-73147, 51-10
No. 2636, No. 52-20023, No. 52-58922, No. 52-90932
No. 52-115219, No. 55-161239, No. 59-174839
U.S. Patent No. 3,277,155, U.K. Patent No. 1,040,710, U.S. Patent No. 3,277,554, No. 3,408,194, No. 3,415,652, the same.
3,447,928, British Patent 1,204,680, Japanese Patent Publication No.47-8750
No. 48-25933, 49-13,576, 50-10728,
No. 51-10783, No. 57-37859, No. 55-7579.
51-53825, 52-127330, U.S. Pat.No. 4,182,630,
And the yellow couplers described in the specification.

Preferred specific examples of the coupler represented by formula (I) are shown below.

All of the following non-x, y and z represent weight ratios.

The amount of lead, cadmium and Group VIII metal to be added to the inner core of the silver halide grain of the present invention is preferably 10 ^-9 to 10 ^-2 mol, and 10 ^-6 mol per mol of the core silver halide. ~ 10 ^-4
Molar is more preferred. The amount of gold added is preferably 10 ^-8 to 10 ^-1 mol, and 10 ^-5 to 10 ^-1 mol, per 1 mol of the core silver halide.
^-3 mol is more preferred.

Of the lead, cadmium and Group VIII metals, the use of lead is most preferred.

The mode of using these metals is not particularly limited,
It may be in the form of a single salt, a complex salt or a complex salt as long as it can be dissolved in an aqueous solvent.

Among them, it is preferable to use nitrates, acetates, sulfates or hydrochlorides.

The same applies to the case of using gold, but it is preferable to use gold in the form of chloroauric acid or potassium chloroaurate-containing sodium chloroaurate.

Ions or compounds of lead, cadmium or Group VIII metal and gold ions or gold compounds may be present together during the chemical ripening of the core silver halide emulsion, for example, a lead compound is added to the process of forming silver halide grains. Incidentally, the addition of both metal compounds does not have to be simultaneous, such as the addition of a gold compound during the chemical ripening.

The degree of chemical ripening is such that the maximum density obtained by treating the core / shell type silver halide emulsion with the internal latent image solution A under the conditions described later is at least the maximum density obtained by treating the surface developing solution B. It is preferable to carry out 5 times or more, more preferably 10 times or more.

The shell surface of the core / shell type silver halide grain may be chemically sensitized, and in this case, it is preferable that the above conditions are satisfied. For the chemical sensitization of the shell surface, a commonly used chemical sensitizer can be applied, and it is preferable to use a sulfur sensitizer and a gold sensitizer in combination.

Japanese Patent Application No. 61-253716 filed on Oct. 27, 1986 (applicant Fuji Photo Film Co., Ltd.) concerning the internal latent image type emulsion which has not been previously fogged used in the present invention, page 28, 14
Lines to page 31, line 2 and the silver halide grains usable in the present invention are described on page 31, line 3 to page 32, line 11 of the specification, particularly silver chlorobromide and silver chloride. Is preferred.

Magenta and cyan color couplers which can be used in addition to the high speed yellow color coupler of the present invention and yellow couplers which can be used in combination with the high speed yellow coupler of the present invention are described in the same pages, page 33, line 18 to page 40, last line, respectively. . The nucleating agent usable in the present invention is described on page 49, line 6 to page 67, line 2 of the same specification.
1] and [N-2] are preferably used. Specific examples thereof include [NI-1] and [NI-10] described on pages 56 to 58 of the same specification and 63 to 66 of the specification.
Use of [N-II-1] to [N-II-12] described on the page is preferred.

Regarding the nucleation accelerator that can be used in the present invention, see No. 68 of the same specification.
See page 11, line 71 to page 71, line 3, and specific examples thereof include (A-1) to (A-13) on pages 69 to 70.
Is preferably used.

Regarding the color developer used in the development processing of the light-sensitive material of the present invention, it is described on page 71, line 4 to page 72, line 9 of the same specification. In particular, specific examples of aromatic primary amine color developing agents are described. As an example, a p-phenylenediamine compound is preferable, and a typical example thereof is 3-methyl-4-amino-N-.
Ethyl-N- (β-methanesulfonamidoethyl) aniline, 3-methyl-4-amino-N-ethyl-N- (β
-Hydroxyethyl) aniline, 3-methyl-4-amino-N-ethyl-N-methoxyethylaniline and salts thereof such as sulfates and hydrochlorides can be mentioned. The developing process of the present invention is carried out at pH 11.0-10.0. Furthermore, it is preferable that the color developer of the present invention contains substantially no benzyl alcohol.

(Example) The present invention is illustrated by the following examples, but the present invention is not limited thereto.

Example 1 1) Preparation of Emulsion While vigorously stirring an aqueous solution of potassium bromide and an aqueous solution of silver nitrate into an aqueous gelatin solution containing 0.56 g of 3,4-dimethyl-1,3-thiazoline-2-thione added per 1 mol of Ag, 75
Approximately 20 minutes at ℃, added simultaneously, the average particle size is 0.21μ
An octahedral monodispersed silver bromide emulsion having a coefficient of variation of 9% was obtained. To this emulsion, 55 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) were added per mol of silver, and the mixture was heated at 75 ° C. for 80 minutes for chemical sensitization. The silver bromide grains thus obtained are used as cores for further growth by treating for 40 minutes in the same precipitation environment as the first time, and finally they are octadisperse monodisperse with an average grain size of 0.45 μm (variation law 9%).
To obtain a core / shell silver bromide emulsion. After washing with water and desalting, 3.1 mg each of sodium thiosulfate and chloroauric acid (tetrahydrate) were added to 1 mol of silver, and the mixture was heated at 60 ° C for 60 minutes to carry out chemical sensitization treatment, followed by internal latent An image type silver halide emulsion A-1 was obtained.

Emulsions A-2 to A-13 (invention) Emulsion A except that the metal compounds shown in Table 1 were added in the amounts of Table 1 per 1 mol of Ag in each emulsion during the first chemical sensitization treatment. Emulsions A-2 to A just like -1
-13 was produced.

Emulsions A-14 to A-16 (for comparison) Emulsions A-4, A-6 and A-8 exactly the same, except that the metal compound was added immediately before shell formation, not during the first chemical sensitization treatment. To prepare emulsions A-14, A-15 and A-16, respectively.

Emulsion B-1 (for comparison) While vigorously stirring an aqueous solution of sodium chloride and an aqueous solution of silver nitrate into an aqueous gelatin solution containing 34 mg of 1,3-dimethyl-1,3-imidazoline-2-ion added per mol of Ag,
It takes about 28 minutes at 50 ° C and is added at the same time, and the average particle size is about 0.
A 45 μm monodisperse silver chloride emulsion was obtained. 20 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) per mol of silver were added to this emulsion.
Chemical sensitization treatment was performed by adding and heating at 57 ° C. for 60 minutes.

The silver chloride grains thus obtained are used as cores for further growth in the same precipitation environment as in the first treatment for 20 minutes, and finally a standing monodispersed core / shell silver chloride emulsion having an average grain size of 0.65 μm is obtained. Obtained. The coefficient of variation of particle size was about 14%.

After washing with water and desalting, 1.2 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) were added to 1 mol of silver, and the emulsion was added at 60 ° C.
The mixture was heated for 15 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion B-1.

Emulsions B-2 to B-4 (invention) However, Emulsion B- except that the amount of lead acetate (trihydrate) shown below was added per mol of Ag before the first chemical sensitization.
Emulsions B-2 to B-4 were prepared in exactly the same manner as in Example 1.

Table 2 Emulsion Lead acetate addition amount B-2 8 × 10 ^-6 mol B-3 8 × 10 ^-4 mol B-4 8 × 10 ^-2 mol Emulsion C-1 (for comparison) Of potassium bromide and potassium chloride At the same time, the mixed aqueous solution and the aqueous solution of silver nitrate were stirred vigorously in a gelatin aqueous solution to which 0.7 g of 1,3-dimethyl-1,3-imidazoline-2-ion was added per mol of Ag at 65 ° C. for about 7 minutes. Add
A monodisperse silver chlorobromide emulsion having an average grain size of about 0.21 μm (silver bromide content: 70 mol%) was obtained. 110m per mole of silver in this emulsion
Chemical sensitization was performed by adding g of sodium thiosulfate and 77 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 by treatment for 50 minutes in the same precipitation environment as the first time, and finally a monodisperse core / shell silver chlorobromide emulsion having an average grain size of 0.6 μm. Got Coefficient of variation of particle size is about 12
%Met.

After washing with water and desalting, 1.2 mg of sodium thiosulfate and 1.2 mg of chloroauric acid (tetrahydrate) were added to 1 mol of silver and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization. An internal latent image type silver halide emulsion C-1 was obtained.

Emulsions C-2 to C-4 (Invention) Emulsion C- exactly the same as Emulsion C-1 except that lead nitrate was added in an amount shown in the table below per mol Ag before core grain formation.
2 to C-4 were produced.

Table 3 Emulsion Lead nitrate addition amount C-2 3 × 10 ^-6 mol C-3 3 × 10 ^-4 mol C-4 3 × 10 ^-2 mol Emulsion D-1 (for comparison) of potassium bromide and sodium chloride Simultaneously stirring the mixed aqueous solution and the aqueous solution of silver nitrate into a gelatin aqueous solution added with 0.5 g of 3,4-dimethyl-1,3-thiazoline-2-ion per 1 mol of Ag at 55 ° C. for about 5 minutes at the same time. Add
A monodispersed silver chlorobromide emulsion having an average grain size of about 0.2 μm (silver bromide content of 40 mol%) was obtained. 35 mg per mole of silver in this emulsion
Chemical sensitization treatment was carried out by adding 20 mg of sodium thiosulfate and 20 mg of chloroauric acid (tetrahydrate) and heating at 55 ° C. for 60 minutes.

The silver chlorobromide grains thus obtained were used as cores for further growth by treating for 40 minutes in the same precipitation environment as the first time, and finally a monodisperse core / shell silver chlorobromide emulsion having an average grain size of 0.4 μm. Got Coefficient of variation of particle size is about 15
%Met.

After washing with water and desalting, 3 mg of sodium thiosulfate and 3.5 mg of chloroauric acid (tetrahydrate) were added to 1 mol of silver and the mixture was heated at 60 ° C. for 50 minutes for chemical sensitization. An internal latent image type silver halide emulsion D-1 was obtained.

Emulsions D-2 to D-4 (Invention) Emulsion D-1 exactly the same as Emulsion D-1, except that the amount of lead acetate (trihydrate) shown below was added per mole of Ag before core formation. -2-D-4 were manufactured.

Table 4 Emulsion Addition amount of lead acetate D-2 1.5 × 10 ^-6 mol D-3 × 10 ^-4 mol D-4 × 10 ^-2 mol Polyethylene on both sides laminated with the following layer constitution A multilayer color light-sensitive material layer was prepared.

The coating liquid was prepared as follows.

Preparation of coating solution for layer E1 Cyan coupler (ExCC-1) 13.4 g and color image stabilizer (E
xSA-1) 5.7 g and polymer (ExP-1) 10.7 g were dissolved by adding 40 cc of ethyl acetate and 7.7 cc of solvent (ExS-1),
Add this solution to 10% sodium dodecylbenzene sulfonate.
It was emulsified and dispersed in 185 cc of 10% gelatin aqueous solution containing 8 cc.
On the other hand, an internal latent image type emulsion (containing 63 g / kg of Ag) was added with 2.5 × 10 ⁻⁴ mol of the red-sensitizing dye shown below per mol of silver. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer cloth coating liquid having the following composition. The coating solution for the E2 layer to the E9 layer and the B1 and B2 layers is also the E liquid.
It was prepared in the same manner as the one-layer coating solution. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

The following were used as the spectral sensitizing dye for each layer.

The following dyes were used as anti-irradiation dyes.

Anti-irradiation dye for green sensitive emulsion layer Anti-irradiation dye for red-sensitive emulsion layer (Layer constitution) The composition of each layer is shown below. It represents the coating amount per number m ² . The silver halide emulsion and colloidal silver indicate the coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer contains white pigment (TiO ₂ ) and bluing dye (ultra-blue)] E1 layer Silver halide emulsion 0.39g Gelatin 1.35g Cyan coupler (ExCC-1) 0.40g Color image stabilizer (ExSA-1) 0.17g Polymer (ExP-1) 0.32g Solvent (ExS-1) 0.23g Development control agent (ExGC-1) 32mg Stabilizer (ExA-1) 5.8mg Nucleation accelerator ( ExZS-1) 0.37mg Nucleating agent (ExZK-1) 9.9μg E2 layer Gelatin 1.6g UV absorber (ExUV-1) 0.62g Color mixture inhibitor (ExKB-1) 0.06g Solvent (ExS-2) 0.24g Layer E3 Silver halide emulsion 0.27g Gelatin 1.79g Magenta coupler (ExMC-1) 0.32g Color image stabilizer (ExSA-2) 0.20g Solvent (ExS-3) 0.65g Development modifier (ExGC-1) 22mg Stable Agent (ExA-1) 4 mg Nucleation accelerator (ExZS-1) 0.26 mg Nucleating agent (ExZK-1) 3.4 μg E4 layer gelatin 0.53 g Ultraviolet absorber (ExUV-1) ) 0.21g Anti-color mixing agent (ExKB-2) 0.02g Solvent (ExS-2) 0.08g Layer E5 Colloidal silver 0.10g Gelatin 0.53g UV absorber (ExUV-1) 0.21g Color mixing inhibitor (ExKB-2) 0.02 g Solvent (ExS-2) 0.08g Layer E6 Same as layer E4 Layer E7 Silver halide emulsion 0.26g Gelatin 1.83g Yellow coupler (ExYC-1) 0.83g Color image stabilizer (ExSA-3) 0.19g Solvent (ExS-3) 0.35g Development control agent (ExGC-1) 32mg Stabilizer (ExA-1) 2.9mg Nucleation accelerator (ExZS-1) 0.2mg Nucleation agent (ExZK-1) 2.5μg E8 layer Gelatin 0.53g UV absorber (UV-1) 0.21g Solvent (SoIv-3) 0.08g E9 layer Gelatin 1.33g Acrylic modified copolymer of polyvinyl alcohol (Modification degree
17%) 0.17g Liquid paraffin 0.03g Polymethylmethacrylate latex particles (average particle size 2.
8 μm) 0.05 Layer B1 gelatin 8.7g Layer B2 Same as layer E9 (ExA-1) Stabilizer 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (ExZS-1) 2- (3-Dimethylaminopropylthio) -5-mercapto-1,3, 4-thiadiazole hydrochloride (ExZK-1) 6-ethoxythiocarbonylamino-2-methyl-1-
Propargyl quinolinium trifluoromethane sulfonate After exposing the color light-sensitive material thus prepared to wedge exposure (1/10 second, 10 CMS), the following processing step A is applied to develop the color at development times of 125 seconds and 145 seconds. The image density was measured.

Table 5 shows the change in foot sensitivity (Δ (S ₁₄₅ −S ₁₂₅ )) between the color development times of 125 seconds and 145 seconds at a yellow density of 0.5.

Processing Step A Time Temperature Color development 125 seconds, 145 seconds 37 ℃ Bleaching and fixing 40 seconds 37 ℃ Stable 30 seconds 37 ℃ Stable 30 seconds 37 ℃ Stabilization bath replenishment method is to replenish the stability bath and The so-called countercurrent replenishment system was used to lead to the stabilizing bath.

[Color developer] Mother liquor Diethylenetriamine pentaacetic acid 2.0 g Benzyl alcohol 12.8 g Diethylene glycol 3.4 g Sodium sulfite 2.0 g Sodium bromide 0.26 g Hydroxylamine sulfate 2.60 g Sodium chloride 3.20 g 3-Methyl-4-amino-N- 4.25 g Ethyl- N- (β-methanesulfonamidoethyl) -aniline potassium carbonate 30.0 g Fluorescent brightener (stilbene type) 1.0 g Water was added to 1000 ml pH 10.20 pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleaching fixer] Mother liquor Ammonium thiosulfate 110g Sodium bisulfite 10g Ethylenediaminepentaacetic acid 56g Iron (III) ammonium monohydrate Ethylenediaminetetraacetic acid 25g Sodium dihydrate 2-mercapto-1,3,4-0.5g Triazole water 1000 ml pH 6.5 pH was adjusted with aqueous ammonia or hydrochloric acid.

Stabilization bath <Wash water> Tap water was filled with H-type strongly acidic cation exchange resin (Mitsubishi Kasei Co., Ltd. Diaion SK-1B) and OH type strongly basic anion exchange resin (Diaion SA-10A). After water treatment with a mixed bed column to make the following water quality, 20 mg / l of sodium diisocyanurate dichloride was added as a bactericide.

Calcium ion 1.1mg / l Magnesium ion 0.5mg / l pH 6.9 Similar results were obtained for magenta and yellow.

As can be seen from Table 5, in the emulsions containing the metal of the present invention, the toe sensitivity change with the development time is smaller than the samples of the emulsions A to D-1 each subjected to only gold sensitization. Especially among metals, the effect of lead ions is great.

However, lead ions have a drawback that the maximum image density (Dmax) becomes low when the addition amount is too large, and therefore it is preferable to use the addition amount which is preferable for the emulsion.

In addition, metals other than the metal of the present invention, such as aluminum,
The addition of iron, zinc, tin, etc. according to the present invention did not show any improvement in the change in foot sensitivity with the development time.

Further, when a sensitizing method other than the gold sensitizing method, for example, a sulfur sensitizing method is combined, the minimum image density becomes high and the reversal performance is poor, which is not preferable.

Example 2 A multilayer color light-sensitive material exactly the same as in Example 1 except that the yellow coupler in the blue emulsion layer, the silver coating amount and the nucleating agent addition amount in Example 1 were changed as shown in Table 6. It was created.

The treatment was performed in the same manner as in Example 1, and the paw sensitivity was measured in the same manner. The results are shown in Table 7.

All Dmax were sufficiently high.

From the results below, it can be seen that the effects of the present invention are exhibited only in combination with the high speed yellow color coupler of the present invention.

Example 3 Emulsions C-1 to C-4 were coated in the same manner as in Example 1 except that the nucleation accelerator (ExZS-1) and the nucleating agent (ExZK-1) were not applied in coating on a paper support. did. The color light-sensitive material thus prepared was processed in the same manner as in Example 1, except that the entire surface was uniformly exposed to white light of 1 lux for 15 seconds from the start of development for 15 seconds.

In the same manner as in Example 1, changes in foot sensitivity and maximum concentration (Dm
ax) was measured. The results are shown in Table 8.

Fogging was applied using the light fogging method and similar hair results were obtained.

Example 4 Emulsions A-1 to A-4 and D-1 to D-4 were prepared in the same manner as in Example 1 except that the nucleating agent (ExZK-1) was replaced with the following (ExZK-
The coating amount was changed to 2) and the addition amount was changed as follows.

Nucleating agent (ExZK-2) 1-formyl-2- {4- [3- (5-mercaptotetrazol-1-yl) benzamido] phenyl} hydrazine Addition amount: Red-sensitive emulsion layer 0.27 mg / m ² green 0.10 mg / m ² blue 〃 0.07 mg / m ^{2 The} color light-sensitive material thus prepared was processed in the same manner as in Example 1, except that the pH of the color developing solution was set to 10.8 and the change in foot sensitivity between color developing 90 seconds and 110 seconds ( Δ (S ₁₁₀ −S ₉₀ ) was measured.
The results are shown in Table 9.

Similar results were obtained.

(Effect of the Invention) According to the present invention, in a direct positive color light-sensitive material containing a high-speed yellow coupler, the dependence of the characteristic curve on the toe break can be reduced.

Further, the light-sensitive material of the present invention exhibits the above-mentioned effects even when it is developed with a low pH color developing solution having a pH of 10.0 to 11.0, and an image having a high maximum density (D _max ) can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03C 7/36 7/407 (56) References JP-A-59-216136 (JP, A) JP JP-A-59-131938 (JP, A) JP-A-61-52644 (JP, A) JP-A-58-156932 (JP, A)

Claims (2)

[Claims] 1. A direct support comprising on a support at least one layer of previously unfogged internal latent image type silver halide grains and at least a high speed yellow color forming coupler represented by the following general formula [I] as a color image forming coupler. In the positive color light-sensitive material, the internal latent image type silver halide emulsion layer contains a core / shell type silver halide emulsion, and the core / shell type silver halide is cadmium, lead or an ion of Group VIII metal of the periodic table or A direct positive color light-sensitive material comprising a compound, a silver halide grain (core) chemically aged in the presence of a gold ion or a compound, and a silver halide shell coating the core. General formula (I) (In the formula, Q represents an N-arylcarbamoyl group, and Y
Represents a coupling-off group having an oxygen atom or a nitrogen atom as a leaving atom. ) 2. A direct support comprising on a support at least one unfogged internal latent image type silver halide grain and at least a high speed yellow color forming coupler represented by the following general formula [I] as a color image forming coupler. After imagewise exposure of a positive color light-sensitive material, after or while performing fogging treatment with light or a nucleating agent, development with a surface developer,
In the method of directly forming a positive color image by bleaching and fixing, the internal latent image type silver halide emulsion layer contains a core / shell type silver halide emulsion,
Silver halide grains (cores) in which shell type silver halide is chemically ripened in the presence of ions or compounds of cadmium, lead or Group VIII metal of the periodic table and gold ions or compounds
And a silver halide shell covering the core,
A direct positive color image forming method, wherein the surface developer has a pH of 10.0 to 11.0. General formula (I) (In the formula, Q represents an N-arylcarbamoyl group, and Y
Represents a coupling-off group having an oxygen atom or a nitrogen atom as a leaving atom. )