JPS63191145A - Direct positive color photosensitive material - Google Patents

Abstract

PURPOSE:To prevent degradation of the cut at the foot part of a characteristic curve according to development time by using a chemically matured silver halide particle (core) and silver halide shell coating the core to constitute the core/shell type silver halide incorporated into an internal latent image type silver halide emulsion layer of a photosensitive material contg. a specific high- speed yellow color image forming coupler. CONSTITUTION:The internal latent image type silver halide emulsion layer of the direct positive color photosensitive material contg. one layer of the internal latent image type silver halide emulsion layer which is not previously fogged and at least the high-speed yellow color image forming coupler expressed by the formula as the color image forming coupler on a base contains the core/shell type silver halide emulsion. Said core/shell type silver halide is composed of the silver halide particle (core) chemically matured in the presence of cadmium, lead or ion or compd. of group VIII metals of periodic table or gold ion or compd. and the silver halide shell coating the core. In the formula, Q denotes an N-aryl carbomoyl group, Y denotes a coupling elimination group consisting of an oxygen atom or nitrogen atom as an elimination atom.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a direct positive color light-sensitive material using an internal latent image type silver halide emulsion.

BACKGROUND OF THE INVENTION Photographic methods that provide direct positive images without the need for reversal processing steps or negative film are well known.

Various techniques are known to date for directly forming positive images using internal latent image type silver halide emulsions; for example, U.S. Pat. No. 2,592,250;
No. 466.957, No. 2゜497.875, No. 2
．． No. 588,982, No. 3,317,322, No. 3. 761. No. 266, No. 3,761,276, No. 3,796.577 and British Patent No. 1. 1
51. No. 363, No. 1,150,553 (No. 1,
No. 011.062) The main ones are those described in each specification etc.

In addition, in core/shell type internal latent image direct positive emulsions,
For example, U.S. Patent No. 3,761,
In the specification of No. 276, lead, bismuth, iridium, gold, etc. are incorporated as a doping agent inside silver halide grains,
Furthermore, a technique is disclosed in which the maximum density of the obtained image is increased and the minimum density is decreased by chemically sensitizing the surface of the silver halide grains with gold, sulfur, etc., and US Pat.
, 395,478, the core particles are sensitized with gold and a polyvalent metal (lead, magnesium, copper, zinc, cadmium, bismuth, palladium, etc.) is added to the shell, thereby causing re-inversion in the image. A technique for suppressing negative images is further disclosed in Japanese Patent Application Laid-Open No. 59-216136,
In metal-doped and chemically sensitized core/shell particles with two or more particle sizes, by doping the inner core of the larger core/shell particle with more polyvalent metal ions, Techniques for obtaining good stability over time and a wide exposure lactude have been described.

On the other hand, various yellow color-forming couplers are known as couplers for color image formation, and couplers with a high coupling speed called high-speed couplers are particularly useful.
No. 33, U.S. Patent No. 3,408,194, U.S. Patent No. 3,58
It is described in various specifications such as No. 2,322.

(Problems to be Solved by the Invention) Since the fast yellow color forming coupler has a fast coupling speed, the development speed can be increased, and it is particularly suitable for rapid processing. Furthermore, although it has the advantage of being relatively less dependent on treatment due to changes in treatment composition, treatment temperature, pH, etc., it is still insufficient for practical use, and further improvements are desired. Among these, there is a tendency for the sharpness of the toe part of the characteristic curve to worsen with development time, and improvement in this respect is especially necessary.

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

Accordingly, an object of the present invention is to provide a direct positive color light-sensitive material in which the toe of the characteristic curve is less dependent on development time when it contains a fast yellow color forming coupler.

(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 a color image forming coupler having at least the following general formula:
In the direct positive color light-sensitive material containing the fast yellow color forming 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 emulsion is Comprising silver halide grains (core) chemically aged in the presence of cadmium, lead, or ions or compounds of metals from group Ⅰ of the periodic table and gold ions or compounds, and a silver halide shell covering the cores. This was effectively achieved using a direct positive color photosensitive material characterized by the following.

General formula (I) Hx (wherein, Q represents an N-arylcarbamoyl group, Y
represents a coupling-off group having an oxygen atom or a nitrogen atom as the leaving atom. ) In the present invention, among various metal dopants and chemical sensitizers, cadmium, lead, or an ion or compound of a metal from group Ⅰ of the periodic table is used in combination with a gold ion or compound to produce a fast yellow coloring coupler. In the core/shell type internal latent image direct positive color photosensitive material containing the present invention, an unexpected effect has been found in that the dependence of the end of the characteristic curve on the development time can be reduced.

-a The high speed yellow coupler represented by formula (I) will be explained 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 is substituted with a plurality of substituents, such as an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (e.g., a methoxy group, a 2-methoxy ethoxy group, etc.), oryloxy group (e.g., 2,4-dite
rt-aminophenoxy group, 2-chlorophenoxy group,
4-cyanophenoxy group), alkenyloxy group (
For example, 2-propenyloxy group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), ester group (
For example, butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, pendyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), sulfonamide group (for example, methanesulfonamide group, arylsulfonamide group, butanesulfonamide group, etc.), amide groups (e.g., acetylamino group, etc.), carbamoyl groups (e.g., ethylcarbamoyl group, dimethylcarbamoyl group, butylcarbamoyl group, etc.), sulfamoyl groups (e.g., N-methyl-N=niophtadecylsulfamoyl, propylsulfamoyl group) , butylsulfamoyl group, etc.), sulfamoylamino group (e.g., dipropylsulfamoylamino group, etc.), imide group (e.g., succinimide group, hydantoinyl group, etc.), ureido group (e.g., phenylureido group, dimethylureido group, etc.) ), aliphatic or aromatic sulfonyl! (for example,
methanesulfonyl group, phenylsulfonyl group), aliphatic or aromatic thio group (e.g. ethylthio group, phenylthio group, etc.), hydroxyl group, cyano group, carboxy group, nitro group, sulfo group, halogen atom (chlorine, bromine, fluorine etc.). The above groups may be further substituted with groups as mentioned above.

A preferable Q is represented by the following general formula (n).

General formula (II) I (In the formula, Q represents a halogen atom or an alkoxy group, and Q2 represents a hydrogen atom, a halogen atom, or an alkoxy group which may have a substituent.) R1 has a substituent. Represents an optionally alkyl group. This alkyl group may be linear or branched, but branched is preferred.

Examples of substituents that Q2 and R1 may have include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, dialkylamino groups, and heterocyclic groups (e.g., N-morpholino groups, N-piperidino groups, 2- Typical examples include furyl group, etc.), halogen atom, nitro group, hydroxy group, carboxyl group, sulfo group, and alkoxycarbonyl group. Among these, as a substituent for the alkyl group of R1, an aryloxy group is preferable.

Preferred leaving groups Y are represented by the following general formula (I[[) to (IX
) including groups represented by the general formula.

0R2(III) Rz represents an optionally substituted aryl group or heterocyclic group.

(IV) (V)R',
R' is each a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl represents a group or a heterocycle, and these groups may be the same or different.

"" W + "" ■ Represents a nonmetallic atom required to form a 5-membered ring or a 6-membered ring.

-i Formulas (Vl) are preferably (■) to (XV
I).

■ Ra Shaku' In the formula, R' and R' each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryoloxy group, or a hydroxy group, and R? , R8 and R9 are each a hydrogen atom,
It represents an alkyl group, an aryl group, an aralkyl group, or an acyl group, and W2 represents an oxygen or sulfur atom. The aforementioned groups may be further substituted.

A substituent of Y [preferably, a substituent of formula (I [[) to 2 (IX)
R2 to R9) or the substituent of Q (preferably R' in II (II)) may be a divalent group to form a bicyclic group, or a group connecting the polymer main chain and the coupler core. It may be.

Among the above Y, those represented by -i formulas (Vl) 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.

JP 42-23902, JP 44-3660, JP 50-19435, JP 59-46384, JP 59-45442, JP 59-174836, JP 59-177553 No., Japanese Patent Publication No. 59-1775
No. 54, JP-A-59-177.555, JP-A-59-
177556, JP 59-177557, JP 60-41042, JP 60-55340, JP 60-185951, U.S. Pat. 688°54
No. 4, No. 2,698, 79.5, No. 2.772.16
No. 1, No. 2,908,573, No. 2゜895.826
No. 2,920,961, No. 3,519,429, JP-A-47-37636, U.S. Pat. No. 4,124,3
No. 96, No. 4.443.536, Special Publication No. 43-229
No. 00, No. 43-29417, No. 44-6992,
No. 45-41474, No. 46-19025, No. 46
-19026, 46-19032, 48-25
No. 932, No. 49-16056, JP-A No. 49-296
No. 39, No. 49-53437, No. 50-134644
No. 53-76834, No. 53-82411, No. 53-141622, No. 55-7702, No. 55-
No. 93153, No. 56-30126, No. 59-124
No. 341, U.S. Pat. No. 2,186.719, U.S. Patent No. 3,48
8゜193, JP-A-47-4,481, JP-A-49-Sho.
No. -8228, No. 49-110344, No. 50-20
No. 723, German Published Patent No. 2707.488, U.S. Patent No. 4,458,011, French Painting Patent No. 1.202,940, U.S. Patent No. 3. 133. No. 815, U.S. Pat. No. 3,1
No. 61,512, U.S. Patent No. 3,183,095, Japanese Patent Publication No. 16190/1972, U.S. Patent No. 3,547,944, No. 3,285.747, British Patent No. 1,128,03
No. 7, Special Publication No. 47-9314, Japanese Patent Application Publication No. 71-6 of 1972
No. 40, No. 50-48922, No. 51-1'26°8
No. 31, No. 52-47728, No. 52-119.32
No. 3, No. 55-38, 599, etc.

The yellow coupler represented by the general formula (I) is
It can be synthesized by the methods described in Japanese Patent Publication No. 4-48541, Japanese Patent Publication No. 58-10739, US Pat. No. 4,326,024, Research Disclosure No. 18053, and the like.

Specifically, the yellow coupler represented by the general formula (I) is disclosed in, for example, Japanese Patent Publications Nos. 45-19955, 45-19956, 48-95873, 50-130442, and 50-139738. , No. 51-21827, No. 52
-23933, 52-115219, 54-4
No. 8541, No. 55-38576, No. 56-8704
No. 1, No. 59-45442, No. 59-222837, No. 60-24547, No. 60-69653, U.S. Pat. No. 2,298,443, No. 2. 407. 210
No. 2,710,802, No. 3,384゜657, British Patent No. 980,507, U.S. Patent No. 3,265,5
No. 06, Buddhist temple patent 1. 558. 452, U.S. Pat. No. 3,841,880, U.S. Pat. No. 3.894.875, U.S. Pat.
, No. 874,948, No. 4.157,919, No. 3,
No. 664,841, Special Publication No. 49-17372, No. 49
-17373, U.S. Patent No. 3,770,446, JP-A-54-99433, JP-A-55-7702, JP-A-56-
No. 30127, No. 56-74250, British Patent 1.4
No. 34,472, JP-A-53-82332, JP-A No. 55-
No. 2300, No. 55-36900, No. 47-2613
No. 3, JP-A-55-598, JP-A-48-73147
No. 51-102636, No. 52-20023,
No. 52-58922, No. 52-90932, No. 52
-115219, 55-161239, 59-
174839, U.S. Patent 3,277.155, British Patent 1,040,710, U.S. Patent 3,277.55
No. 4, No. 3,408,194, No. 3゜415.652
No. 3,447,928, British Patent No. 1,204,6
No. 80, Special Publication No. 47-8750, No. 48-25933
No. 49-13゜576, No. 50-10728,
No. 51-10783, No. 57-37859, No. 55
-7579, JP-A No. 51-53825, JP-A No. 52-1
Examples include yellow couplers described in specifications such as No. 27330 and US Pat. No. 4,182.630.

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

(Y-1) (Y-2) (Y-3) CH.

(Y-4) CH.

=0 (Y-7) Hz day of the week (Y-8) Hx CH, -C-COCHC -C (Y-9) Hs SO□( (Y-10) CH3 H (Y-11) (Y-12) COOCHi (Y-13) (Y-14) (Y-15) CH3 deceased (Y-16) CH.

OOH ■ Hl (Y-21) CH.

I -C-C CzHs (Y-22) CH.

-CH2CHC,H9 C,H.

(Y-25) CH3 I CH, -C-NH CH, CH, 0 (Y-26) CH3 I CH3-C-NH CH.

UUth UsH+ r (t) (Y-2
7) CH3Hx (Y-28) CH.

(I3(,1 to H・ 30□CH.

(Y-29) CH.

(Y-30) CH3 CH, -N- (Y-33) II OCCH3 heat CH3 -CH ■ (Y-35) (Y-36) (Y-37) CH1 CHl (Y-38) CH.

H C diamond l N HS OzC1bH3s (Y-39) CH3 (Y-40) CH3 CH3CC0CHC0 The following ratios of x, y, and z all represent weight ratios.

(Y-41) +CH2CHX CH2
CH)yl
+(Y-42) CH.

x/y/z =50/4515(Y-43) CH3 +CH,C)xC
H2CH-)-=-I Ct'i, I (Y-44) CH3x/y/z=55/4015(Y-45)-(-CH2CH, CHICH-h- Inside of the silver halide grain of the present invention The amount of lead, cadmium, and group II metals that should be added to the core is determined by the core halogenation i.
Preferably 10-9 to 10-2 mol, 1
More preferably 0-6 to 10-4 mol.

In addition, the amount of gold added is 10 per mole of core silver halide.
-'' to 10-1 mol is preferable, and 10-5 to 10-'' mol is more preferable.

Among lead, cadmium, and group II metals, use of lead is most preferred.

There are no particular restrictions on the manner in which these metals are used, but
It may be in the form of a single salt or a complex salt as long as it is soluble in an aqueous solvent.

Among these, it is preferable to use it in the form of nitrate, acetate, sulfate, or hydrochloride.

Further, the manner in which gold is used is the same as described above, but it is preferably used in the form of chloroauric acid, potassium chloroaurate, and sodium chloroaurate.

Ions or compounds of lead, cadmium, or Group II metals and gold ions or gold compounds need only coexist when the core silver halide emulsion is chemically ripened; for example, a lead compound may be added during the formation process of silver halide grains. However, it is not necessary to add both metal compounds at the same time, such as adding a gold compound during chemical ripening.

The degree of chemical ripening is such that the maximum density obtained by processing the core/shell type silver halide emulsion with internal latent imager A is equal to the maximum density obtained by processing it with surface developer B under the conditions detailed later. It is preferable to increase the amount by at least 5 times or more, more preferably by 10 times or more.

It is also possible to chemically sensitize the shell surface of core/shell type silver halide grains. In this case, it is best to carry out chemical sensitization so that the above conditions are met. Sensitizers can be used, and among them, it is preferable to use a sulfur sensitizer and a gold sensitizer together.

Regarding the internal latent image type emulsion that is not pre-fogged and can be used in the present invention, patent application No. 6, filed on October 27, 1986,
1-253716 (Applicant: Fuji Photo Film Co., Ltd.), page 28, line 14 to page 31, line 2, regarding silver halide grains that can be used in the present invention, are described in page 31, line 2 of the same specification. It is described on page 32, line 11, and silver chlorobromide and silver chloride are particularly preferred.

Magenta and cyan color couplers that can be used in addition to the high-speed yellow coloring coupler of the present invention, and yellow couplers that can be used in combination with the high-speed yellow coupler of the present invention are described on page 33, line 18 to page 40, end line, respectively, of the same specification. . Nucleating agents that can be used in the present invention are described in the same specification from page 49, line 6 to page 67, line 2, and the use of compounds represented by general formulas [N-1] and (N-2) is particularly recommended. preferable. Specific examples of these include the 56th to
(N-I-1) and (N-T-10) described on page 58 and (N-■-1] to (N-I) described on pages 63 to 66 of the same specification.
The use of I-12) is preferred.

Regarding the nucleation accelerator that can be used in the present invention, see the same specification No. 6.
It is described on page 8, line 11 to page 71, line 3, and specific examples include (A-1) to page 69 to page 70 of the same.
(A-13) is preferably used.

The color developer used in the development of the light-sensitive material of the present invention is described in the same specification from page 71, line 4 to page 72, line 9, and in particular aromatic primary amine color developer. As a specific example, p-phenylenediamine type compounds are preferable, and representative examples thereof include 3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline, 3-methyl-4-amino -N-ethyl-N
-(β-hydroxyethyl)aniline, 3-methyl-4
Examples include -amino-N-ethyl-N-methoxyethylaniline and salts thereof such as sulfates and hydrochlorides. Further, the development treatment of the present invention is carried out at a pH of 11.5 or lower, preferably at a pH of 11.0 to 10.0. Furthermore, it is preferable that the color developing solution of the present invention does not substantially contain Hensyl alcohol.

(Examples) The present invention will be illustrated below with reference to Examples, but the present invention is not limited by these in any way.

Example 1 1) Preparation of emulsion Emulsion A-1 (for comparison) An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were mixed with 0.56 g of 3,4-dimethyl-1°3-thiazoline-2,000 ions per mole of Ag. Added simultaneously to the added gelatin aqueous solution while stirring vigorously at 75°C for about 20 minutes,
A monodisperse octahedral silver bromide emulsion (coefficient of variation: 9%) with an average grain size of 0.21 μm was obtained. A chemical sensitization treatment was carried out by adding 55 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) per mole of silver to this emulsion and heating at 75°C for 80 minutes. Using the thus obtained silver bromide grains as cores, they were further grown by further treatment for 40 minutes in the same precipitation environment as the first time, and finally the average grain size was 0.
．． A core/shell silver bromide emulsion of 45 μm octahedral monodisperse (9% variation law) was obtained.

After washing with water and desalting, this emulsion contained 3.1 mol of silver per mole of silver.
1 L of sodium thiosulfate and chloroauric acid (tetrahydrate) were added and heated at 60°C for 60 minutes for chemical aggravation treatment to obtain internal latent image type silver halide emulsion A-1.

Emulsions A-2 to A-13 (invention) Emulsions A-2 to A-13 (invention) except that the metal compounds shown in Table 1 were added to each emulsion in the amount shown in Table 1 per mole of Ag during the first chemical aggravation treatment. -1 Emulsion A-2
~A-13 was produced.

Table 1 Emulsions A-14 to A-16 (for comparison) Emulsions A-4 and A-6 except that the metal compound was added immediately before shell formation rather than during the first chemical sensitization treatment.
and A-8 in exactly the same manner as emulsions A-14 and A-8, respectively.
15 and A-16 were manufactured.

Emulsion B-1 (for comparison) An aqueous solution of sodium chloride and an aqueous solution of silver nitrate were added to an aqueous gelatin solution containing 34 mg of 1,3-dimethyl-1°3-imidacylin-2-ion per mol of Ag at 50°C with vigorous stirring. It took about 28 minutes to add them at the same time.
A monodisperse silver chloride emulsion with an average grain size of about 0.45 μm was obtained. Chemical aggravation treatment was carried out by adding 20 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) per mole of silver to this emulsion and heating it at 57° C. for 60 minutes.

Using the thus obtained silver chloride grains as cores, they were further grown by further treatment for 20 minutes in the same precipitation environment as the first time, and finally a three-dimensional monodisperse core/shell chloride emulsion with an average grain size of 0°65 μm was obtained. I got it. The coefficient of variation in particle size was approximately 14%.

After washing with water and desalting, this emulsion contains 1.0% per mole of silver. 2 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) were added, and chemical sensitization was performed by heating at 60° C. for 15 minutes to obtain internal latent image type silver halide emulsion B-1.

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

Table 2 Emulsion Addition amount of lead acetate B-28X10-'mol B-38'X10-'mol B-48X10-'mol Emulsion C-1 (for comparison) Mixed aqueous solution of potassium bromide and potassium chloride and aqueous solution of silver nitrate 0.7 g of 1゜3-dimethyl- per mole of Ag
1,3-Imidacylin-2-ion was added simultaneously to an aqueous gelatin solution to which 1,3-imidacillin-2-ion had been added, with vigorous stirring, at 65°C for about 7 minutes. %) of a monodisperse silver chlorobromide emulsion was obtained. Chemical aggravation treatment was carried out by adding 110 mg of sodium thiosulfate and 77 mg of chloroauric acid (tetrahydrate) per mole of silver to this emulsion and heating at 65° C. for 60 minutes.

Using the thus obtained silver chlorobromide particles as a core, the particles were further grown by further treatment for 50 minutes in the same precipitation environment as the first time, and finally a monodisperse core/shell silver chlorobromide with an average particle diameter of 0°6 μm was obtained. An emulsion was obtained.

The coefficient of variation in particle size was approximately 12%.

After washing with water and desalting, this emulsion contains 1.2 mg of thiosulfate per mole of silver and 1.2 mg of chlorauric acid (4
Aqueous salt) was added thereto, and chemical aggravation treatment was performed by heating at 60° C. for 60 minutes to obtain an internal latent image type silver halide emulsion C-1.

Emulsions C-2 to C-4 (invention) Emulsions C-2 to C-4 were prepared in exactly the same manner as Emulsion C-1, except that lead nitrate was added in the amount shown in the table below per mole of Ag before core grain formation. C-4 was manufactured.

Table 3 Emulsion Addition amount of lead nitrate C-23X10-6 mole C-33X10-' mole C-43XIO-" mole Emulsion D-1 (for comparison) Mixed aqueous solution of potassium bromide and sodium chloride and nitric acid i
Add 0.5 g of 3゜4-dimethyl-1,3-thiazoline-2-ion per mole of Ag to an aqueous gelatin solution with vigorous stirring at 55°C for about 5 minutes. A monodisperse silver chlorobromide emulsion having an average grain size of about 0.2 μm (silver bromide content 40 mol %) was obtained.

A chemical sensitization treatment was carried out by adding 35 mg of sodium thiosulfate and 20 mg of chloroauric acid (tetrahydrate) per mole of silver to this emulsion and heating it at 55° C. for 60 minutes.

Using the thus obtained silver chlorobromide particles as a core, the particles were further grown by further treatment for 40 minutes in the same precipitation environment as the first time, and finally a monodisperse core/shell silver chlorobromide with an average particle diameter of 0°4 μm was obtained. An emulsion was obtained.

The coefficient of variation in particle size was approximately 15%.

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

Emulsions D-2 to D-4 (invention) Lead acetate (3
Emulsions D-2 to D-4 were prepared in exactly the same manner as Emulsion D-1, except that Emulsion D-1 was added.

Table 4 Emulsion Addition amount of lead acetate D-21.5X10-6 mol D-3X10-' mol D-4X10-'' mol A multilayer color photosensitive material having the layer structure shown below on a paper support laminated on both sides with polyethylene. A layer was created.

The coating solution was prepared as follows.

Preparation of Ell Coating Solution 13.4 g of cyan coupler (ExCC-1), 5.7 g of color image stabilizer (ExSA-1) and poly? -(E
Add and dissolve 40 cc of ethyl acetate and 7.7 cc of solvent (ExS-1) to 10.7 g of xP-1), and dissolve this solution in 10.7 g.
The mixture was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing 3 cc of 0% sodium dodecylbenzenesulfonate.

A unidirectional latent image emulsion containing 63 g/kg of Ag was added with the following red-sensitivity-enhancing dyes at a rate of 2.5 x 10-' per mole.
A molar addition was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below. 82nd layer to E9th layer and 81st layer
The coating solution for the 82nd layer was also prepared in the same manner as the coating solution for the 81st layer. The gelatin hardening agent for each layer is 1-oxy-
3,5-dichloro-3-triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Red-sensitive emulsion layer; (Halogen (2.5X10-' mol per mol of IJI); Green-sensitive emulsion layer (per mol of silver halide; Blue-sensitive emulsion layer O3; 5OsH-N (CzHs)i per mol of silver halide; 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 structure) The composition of each layer is shown below. The numbers represent the amount of application. Silver halide emulsion and colloidal silver represent coating amounts in terms of silver.

Support Polyethylene laminated paper [The polyethylene on the first layer side contains a white pigment (Tio2) and a bluish dye (ulmarine blue)] No. Elli Silver halide emulsion 0.39g gelatin 1. 35g cyan coupler (ExCC-1) 0.40g color image stabilizer (Ex
SA-1) 0.17g poly? -(ExP-1)
0.32g solvent (ExS-1) 0.23g development regulator (ExGC-1) 32mg stabilizer (ExA-1) 5. 8mg nucleation accelerator (ExZS-1) 0.37mg nucleation agent (
ExZK-1) 9.9ug E2 layer gelatin 1.6g ultraviolet absorber (ExUV-1) 0.62g color mixture prevention agent (
ExKB-1) 0.06g solvent (ExS-2
) o, 24g E3rd layer silver halide emulsion 0.27g gelatin 1.79g magenta coupler (ExMC-1) 0. 32 g color image stabilizer (E
xSA-2) 0.20g solvent (ExS-3)
0.65 g Development control agent (ExGC-1)
22mg stabilizer (ExA-1) 4
mg Nucleation accelerator (ExZS-1) 0.26mg
Nucleating agent (ExZK-1) 3.4 μg No. E4
Layered gelatin 0.53g Ultraviolet absorber (ExUV-1) 0.21g Color mixing prevention agent
(ExKB-2) 0.02g solvent (ExS-
2) 0.08g E5N colloidal silver 0.10g gelatin 0.53g ultraviolet absorber (Ex
UV-1) 0.21g color mixture prevention agent (ExKB
-2) 0.02g solvent (ExS-2) 0
．． 08g E6 layer E4J! 87th layer silver halide emulsion same as l 0.26g gelatin 1.83g yellow coupler (ExYC-1) 0.83g color image stabilizer (ExSA-
3) 0.19g solvent (ExS-4) 0.
35g developer (ExGC-1) 32mg stabilizer (ExA-1) 2. 9mg nucleation accelerator (ExZS-1) 0.2mg nucleation agent (
ExZK-1) 2.5 μg No. E81i! Gelatin 0.53g Ultraviolet absorber (UV-1) 0.21g Solvent (Sol
v-3) 0.08g No. E91! Gelatin 1. 33g polyvinyl alcohol acrylic 0.17g modified copolymer (degree of modification 17%) Liquid paraffin 0.03g polymethyl methacrylate latex particles (average particle size 2.8 μm) 0.05 No. B1
11 Gelatin 8.7g No. B2 [ Same as No. E91 (ExCC-1) '2:9:8 mixture of cyan coupler (ExMC-1) magenta coupler (ExS-4) solvent (ExUV-1) ultraviolet absorber (by weight Ratio) (ExKB-1) Color mixing inhibitor (ExKB-2) Color mixing inhibitor (ExGC-1) Development regulator (ExA-1) Stabilizer 4-hydroxy-6-methyl-1,3,3a.

7-Chitrazaindene (ExZS-1) (ExZK-1) 6-nitoxythiocarbonylamino-2-methyl-1-
Propargyl quinolinium trifluoromethanesulfonate The color photosensitive material thus prepared was subjected to wedge exposure (I/10 seconds, 10 CMS) and then subjected to the following processing step A to develop color at a color development time of 125 seconds and 145 seconds. Image density was measured.

Color development time 125 seconds and 1 at yellow density 0.5
Table 5 shows the change in foot sensitivity (Δ(S+4s-3exs)) after 45 seconds.

Processing step A Time Temperature color development 125 seconds, 145 seconds 37℃ bleach fixing 40 seconds 37℃ stability ■
Stable at 37℃ for 30 seconds ■ 3
0 seconds The replenishment method for the 37°C stable bath is to replenish the stable bath ■ and guide the overflow liquid from the stable bath ■ to the stable bath ■.
The so-called countercurrent replenishment method was adopted.

[Color developer]

Mother liquor Diethylenetriaminepentaacetic acid 2.0g Benzyl alcohol 12.8g Diethylene glycol 3.4g Sodium sulfite
2.0g sodium bromide
0.26g 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 30.0g Water was added to 1000ml pH 10.20 The pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution]

Mother liquor Ammonium thiosulfate 110g Sodium bisulfite Log Iron ethylenediaminepentaacetate 56g Iron (I 1000mβpH6,
5 pH was adjusted with aqueous ammonia or hydrochloric acid.

Rinse water for stabilizing bath> Tap water was filled with an H-type strongly acidic cation exchange resin (Diaion 5K-IB, manufactured by Mitsubishi Kasei Corporation) and an OH-type strong basic anion exchange resin (Diaion 5A-1OA, manufactured by Mitsubishi Kasei Corporation). After passing water through a hotbed column to obtain the following water quality, 20 mg/l of sodium isocyanurate dichloride was added as a disinfectant.

Calcium ion t, 1mg/l Magnesium ion 0.5mg/l pH6,9 Table 5 It was done.

As can be seen from Table 5, the metal-added emulsions of the present invention all showed smaller changes in sensitivity due to development time than the samples of emulsions A-D-1 that were only gold sensitized. Among metals, lead ions have a particularly large effect.

However, lead ions have the disadvantage that the maximum image density (Dmax) decreases if the amount added is too large, so it is preferable to use them in an amount suitable for the emulsion.

Further, metals other than the metal of the present invention, such as aluminum,
Even if iron, zinc, tin, etc. were added according to the present invention, no improvement in the change in foot sensitivity due to development time was observed.

Furthermore, when sensitization other than gold sensitization, such as sulfur sensitization, is combined, the minimum image density becomes high and the reversal performance is poor, which is not preferred.

Example 2 A multilayer color light-sensitive material was prepared in exactly the same manner as in Example 1, except that the yellow coupler in the blue emulsion layer, the amount of coated silver, and the amount of nucleating agent added were changed as shown in Table 6. Created.

Table 6 *1) Yellow couplers were added in equimolar amounts per m2 of each ExYC-1.

*2) (ExYC-2) *3) (ExYC-3) *4) Indicated by the number of the yellow coupler mentioned above.

It was treated in the same manner as in Example 1, and foot sensitivity was measured in the same manner. The results are shown in Table 7.

Table 7 Dmax was sufficiently high in all cases.

These results show that the effects of the present invention are exhibited only when combined with the high speed yellow coloring coupler of the present invention.

Example 3 Emulsions C-1 to C-4 were coated on a paper support in the same manner as in Example 1, but without adding the enzyme nucleation accelerator (ExZS-1) and the nucleating agent (ExZK-1). Coated. The color photosensitive 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 starting 15 seconds after the start of development.

Changes in foot sensitivity and maximum density (D
max) was measured. The results are shown in Table 8.

Table 8 Similar results were obtained when fogging was performed using the optical fogging method.

Example 4 Emulsions A-1 to A-4 and D-1 to D-4 in the same manner as in Example 1 except that the nucleating agent (ExZK-1) was replaced with the following (Ex
ZK-2) and the amount added was also changed as shown below.

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/pogreen
0.10 mg/blue // 0.07 mg/bo The thus prepared color photosensitive material was developed in the same manner as in Example 1, except that the pH of the color developer was adjusted to 10°8, and color development was carried out for 90 seconds and 11°C.
The change in foot anger level (Δ(S++.-8,.) from 0 seconds was measured. The results are shown in Table 9.

Table 9 Similar results were obtained.

(Effects 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 toe portion of the characteristic curve on the development time can be reduced.

Claims (1)

[Scope of Claims] Containing at least one unfogged internal latent image type silver halide emulsion layer on a support and at least a fast yellow color forming coupler represented by the following general formula (I) as a color image forming coupler. In the direct positive color light-sensitive material, the internal latent image type silver halide emulsion layer includes a core/shell type silver halide emulsion, and the core/shell type silver halide contains cadmium, lead, or group V of the periodic table.
A direct method comprising a silver halide grain (core) chemically aged in the presence of Group III metal ions or compounds and gold ions or compounds, and a silver halide shell covering the core. Positive color photosensitive material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (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 the leaving atom. )