JPH04321027A - Direct positive color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a cyan image satisfactory in maximum image density and minimum image density and good in developed hue and high in color reproduction performance by using a combination of a specified cyan coupler and a specified nucleating agent. CONSTITUTION:The cyan coupler is a compound represented by formula I and the photosensitive layer containing this cyan coupler contains also the nucleating agent represented by formula II. In formulae I and II, R<1> is H, halogen, or alkyl; R<2> is alkyl, aryl, or a heterocyclic group; R<3> is H, halogen, alkyl, carbonamide, or the like; X<11> is H or a group releasable by coupling; Z is a nonmetallic atomic group necessary to form a 5-or 6 membered heterocyclic ring; R<11> is an aliphatic group; R<12> is H or an aliphatic or aromatic group; Y is a counter ion for balancing molecular charge; (n) is 0 or 1, thus permitting the obtained cyan image to be good in developed hue and high in color reproduction performance.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a direct positive color photographic material which makes it possible to directly obtain a positive image using an internal latent image type silver halide emulsion. In particular, the present invention relates to a direct positive color photographic material suitable for creating color proofs used for plate inspection and adjustment in color plate making and printing processes.

0002

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

As a method for producing a positive image using a conventionally known direct positive color silver halide photographic light-sensitive material, there is a method using an internal latent image type silver halide emulsion which has not been fogged in advance. This method is a method in which a photographic light-sensitive material is subjected to surface development after image exposure, after being subjected to fogging treatment, or while being subjected to fogging treatment, to directly obtain a positive color image.

The above-mentioned internal latent image type silver halide photographic emulsion which is not fogged in advance is a type in which photosensitive nuclei are mainly inside the silver halide grains, and a latent image is mainly formed inside the grains upon exposure. A silver halide photographic emulsion.

[0005] Various techniques are known to date in this field. For example, US Patent Nos. 2,592,250, 2,466,957, 2,497,875, and 258
No. 8982, No. 3317322, No. 3761266, No. 3761276, No. 3796577 and British Patent No. 1151363, No. 1150553, No. 10
The main ones are those described in the specifications of No. 11062.

The mechanism for forming a direct positive image is explained as follows. That is, when imagewise exposed, a so-called internal latent image is generated on the silver halide, and then by performing a fogging treatment, a surface desensitization effect due to this internal latent image is activated (i.e., the silver halide in the exposed area is development nuclei (fogging nuclei) are not generated on the surface of the silver halide), but development nuclei are selectively generated only on the surface of the silver halide in the unexposed areas, and then by performing normal surface development processing, the unexposed areas become photographic. An image (positive image) is formed. The above-mentioned fogging treatment methods include a method called "photofogging method" in which the entire photosensitive layer is exposed to light, and a method called "chemical fogging method" using a nucleating agent.

In recent years, direct positive color silver halide photographic light-sensitive materials using internal latent image type silver halide emulsions that are not fogged in advance have been accepted for their simplicity of processing process, and have been used for copying purposes, etc. It has been used for

[0008] The process of producing color printed matter includes the steps of color-separating a color original and converting it into a halftone image to create a transmission halftone image. A printing plate is made from the obtained transmission halftone image, but prior to this, the final printed matter (actual printing)
There is a process of inspecting the condition, characteristics, etc., and performing necessary calibration (color calibration). Conventionally, the color proofing method has been to create a printing plate and make a trial print. However, in recent years, various color proofs have been created in order to speed up the proofreading process and reduce costs.

Known methods for producing color proofs include photopolymers, diazo methods, surprint methods and overlay methods using photo-adhesive polymers (for example, US Pat. No. 3,582,327, Japanese Unexamined Patent Publication No. 56-
501217, 59-97140). However, all of these methods require overlapping and transferring images, and the process is complicated, requiring a lot of time and cost, as it is necessary to overlay and transfer multiple images. .

[0010] JP-A-56-104335 discloses a method for producing a color proof using a color photosensitive material, and this method has great advantages in terms of simple process and low cost. Moreover, it has features such as excellent tone reproducibility.

The method for producing a color proof using the above-mentioned color photographic light-sensitive material uses a silver halide color photographic light-sensitive material of a color development method having continuous gradations, and a magenta (M) color photographic material is used.
The color, cyan (C), yellow (Y), and ink (B) color plates are sequentially exposed in close contact like printing a color negative onto color paper, and then subjected to specified color development processing to obtain a color proof. It's a method. This method has features that the process is simpler and easier to automate than the various methods mentioned above.

There are several possible silver halide color photographic materials that can be used for such color proofs. Among these, the transmission black-and-white dot images used in the production process of color printed matter mentioned above are often positive, especially in Japan and Europe, so they are not suitable for use as silver halide color photographic materials for color proofing. Positive-positive photosensitive materials are often used. Among them, the above-mentioned direct positive type color photographic materials, whose practical technology has been rapidly progressing in recent years, are attracting attention as being most suitable for color proofing applications because of their ease of processing. In particular, the above-mentioned method of obtaining a positive image using a nucleating agent (
The chemical fogging method has the advantage that images with stable performance can be obtained and the processing system (particularly the development processing apparatus) can be designed relatively easily compared to the case of using the optical fogging method.

Conventionally, nucleating agents include hydrazine compounds or heterocyclic quaternary ammonium salts (US Pat. Nos. 3,615,615, 3,719,494, and 37,347).
No. 38, No. 3759901, No. 3854956 No. 4
No. 094683, No. 4306016, British Patent No. 12
83835, Japanese Patent Application Laid-open Nos. 52-3426 and 52-69613) are well known.

[0014]

[Problems to be Solved by the Invention] As mentioned above, with the diversification of uses for direct positive color photographic materials, the requirements for the images (image quality) obtained are becoming increasingly strict.
It is desired that the image has a high maximum image density and a low minimum image density, that is, a large ratio between the maximum image density and the minimum image density. Particularly in color proof applications, it is important to achieve high whiteness by reducing the minimum image density in order to obtain good color reproducibility.

In order to obtain such high maximum image density and low minimum image density, for example, US Pat.
The quaternary salt-based nucleating agent having a thioamide-based silver halide adsorption group described in Specification No. 4, the quaternary salt-based nucleating agent described in JP-A-63-34535, or JP-A-2-000844. There is a method of using a nucleating agent such as a nucleating agent. Also,
JP-A-63-15248 or JP-A-1-3190
No. 32 also discloses a useful nucleating agent that provides the same effect as above.

A positive color image is formed by the production of a coloring dye through a coupling reaction between an oxidized developing agent and a coupler in the presence of a nucleating agent as described above. It is desired that the coupling rate is fast and the coloring property is good enough to provide high coloring density in a short period of time. It is desired that the coloring dyes produced are yellow, magenta, and cyan dyes with little side absorption and provide color images with good color reproducibility.

Among the above couplers, magenta couplers and cyan couplers are difficult to obtain color images with relatively high color reproducibility, so various improvements have been made. As for cyan couplers, 2,5-diacylaminophenol cyan couplers have traditionally been preferably used, as described in the above-mentioned publications. However, according to the inventor's study, the conventionally used phenolic couplers have little absorption in the unnecessary blue light region, but among them, those with good coloring properties have absorption wavelengths closer to the short wavelength side. It was found that these materials had unnecessary absorption in the green light region, while those with absorption wavelengths in the appropriate region had a problem of low color development.

[0018] As a method for solving the problems of cyan couplers, there is a method of using two types of couplers (Japanese Unexamined Patent Publication No. 60-221752). However, even when this method is used, the coloring properties obtained are poor, the hue of the coloring dye is poor, and it has not yet been possible to obtain a color image with sufficiently satisfactory color reproducibility.

Therefore, an object of the present invention is to provide a direct positive color photograph that provides a high maximum image density and a low minimum image density, has good color hue, has high color reproducibility, and can produce color images including cyan-colored images. The purpose of the present invention is to provide photosensitive materials.

[0020]

[Means for Solving the Problems] As described above, the present inventors have made efforts to realize a cyan image that satisfies both the maximum and minimum image density, has good color development hue, and has high color reproducibility. After much consideration. As a result, it has been found that the above-mentioned problems can be solved by selectively using the cyan coupler and nucleating agent. That is, the inventors have discovered that the above object can be achieved by using a specific cyan coupler and a specific nucleating agent in combination, and have completed the present invention.

The present invention provides a direct positive color photographic material comprising at least one photosensitive layer containing an internal latent image type silver halide emulsion and a cyan coupler which has not been fogged in advance on a support, wherein the cyan coupler is The following general formula (Cy) (Cy):

[Formula, R1 represents a hydrogen atom, a halogen atom or an alkyl group, R2 represents an alkyl group, an aryl group or a heterocyclic group, and R3 represents a hydrogen atom, a halogen atom,
It represents an alkyl group, an alkoxy group, an aryloxy group or a carbonamide group, and X11 represents a hydrogen atom or a coupling-off group. is a compound represented by the following general formula (Fa) (
Fa):

[In the formula, Z represents a nonmetallic atom group necessary to form a 5- to 6-membered heterocycle, R11 represents an aliphatic group, and R1
2 represents a hydrogen atom, an aliphatic group, or an aromatic group (Z,
R11 and R12 may be substituted), provided that
R12 may further combine with the heterocycle completed by Z to form a ring, and at least one of the groups represented by Z, R11, and R12 is an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group. containing a group or R
11 and R12 may form a 6-membered ring to form a dihydropyridinium skeleton, Y represents a counter ion for charge balance, and n represents 0 or 1. ] A direct positive color photographic material characterized by containing a nucleating agent shown in the following.

Preferred embodiments of the photographic material of the present invention are as follows. (1) In the general formula (Fa), the heterocycle completed by Z is quinolinium. (2) In general formula (Fa), R12 combines with the heterocycle completed by Z to form a ring. (3) In the general formula (Fa), Z is a substituent, and the following formula: and m is 0 or 1). (4) In (3) above, the divalent linking group represented by L11 is -arylene-SO2NH-, -arylene-NHCONH-, or -arylene-CONH-
It is. (5) In the general formula (Fa), Y is a perchlorate ion or a trifluoromethanesulfonate ion. (6) In the general formula (Cy), X11 is a halogen atom (especially chlorine).

[0023]

Effects of the Invention By using the direct positive color photographic material of the present invention containing the compound (nucleating agent) represented by the general formula (Fa) and the cyan coupler represented by the general formula (Cy), the maximum density is high; Furthermore, it is possible to obtain a cyan image with a low minimum density, a good developed hue, and good color reproducibility. Therefore, the direct positive color photographic material of the present invention is suitable for producing color proofs.

The direct positive color photographic material of the present invention will be explained below. The direct positive color photographic light-sensitive material of the present invention comprises a support and at least one light-sensitive layer containing an internal latent image type silver halide emulsion and a cyan coupler which have not been fogged in advance. The photosensitive layer may have a single-layer structure, but it usually consists of a red-sensitive layer (red-sensitive emulsion layer) containing an internal latent image type silver halide emulsion that has not been fogged in advance and a cyan coupler, and an internal latent image that has not been fogged in advance. The support has at least one green-sensitive layer containing a type silver halide emulsion and a magenta coupler, and a blue-sensitive layer containing an internal latent image type silver halide emulsion and a yellow coupler which have not been fogged in advance. be.

The cyan coupler represented by the general formula (Cy) according to the present invention is a phenolic cyan coupler,
As mentioned above, it is usually included in the red sensitive layer.

The phenolic cyan coupler represented by the general formula (Cy) will be explained in detail below.

In the general formula (Cy), R1 is a hydrogen atom, a halogen atom (F, Cl, Br, I), or a linear, branched or cyclic group having 1 to 18 carbon atoms, which may be substituted. represents an alkyl group. Here, examples of substituents on the alkyl group include a halogen atom, an aryl group, an alkoxy group, and an alluroxy group.

In the general formula (Cy), R2 is an optionally substituted linear, branched or cyclic alkyl group having 1 to 36 carbon atoms (preferably 4 to 30 carbon atoms), or an optionally substituted alkyl group having 6 to 36 carbon atoms. represents an optionally substituted aryl group (preferably 12 to 30) or a heterocyclic group having 2 to 36 carbon atoms (preferably 12 to 30). Here, the term "heterocyclic group" refers to at least one N, O, S, P, Se and T in the ring.
represents a heterocyclic group optionally forming a 5- to 7-membered condensed ring having a hetero atom selected from e. Examples of these are 2-furyl, 2-thienyl, 2-pyridyl, 4-
Examples include pyridyl, 4-pyrimidyl, 2-imidazolyl, and 4-quinolyl.

R2 may have a substituent. Examples of substituents include halogen atoms, cyano groups, nitro groups, carboxyl groups, sulfo groups, alkyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkylsulfonyl groups, and aryl groups. Examples include sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, carbonamido group, sulfonamido group, carbamoyl group, sulfamoyl group, imido group, ureido group, alkoxycarbonylamino group or sulfamoylamino group. (hereinafter referred to as substituent group A). Examples of preferable substituents among these are aryl group, heterocyclic group, aryloxy group,
It is an alkylsulfonyl group, an arylsulfonyl group or an imido group.

In the general formula (Cy), R3 is a hydrogen atom, a halogen atom, or a carbon atom having 1 to 16 carbon atoms (preferably 1 to 8 carbon atoms).
), an alkyl group having 1 to 16 carbon atoms (preferably 1 to 8)
an alkoxy group having 6 to 24 carbon atoms (preferably 6 to 18 carbon atoms)
) represents an aryloxy group or a carbonamide group having 1 to 24 carbon atoms (preferably 1 to 18 carbon atoms). The above group may be substituted with a substituent selected from the above substituent group A.

In the general formula (Cy), X11 represents a hydrogen atom or a coupling-off group that can be separated by a coupling reaction with an oxidized product of an aromatic primary amine developer. Examples of the coupling-off group include a halogen atom, a sulfo group, an alkoxy group having 1 to 36 carbon atoms (preferably 1 to 24 carbon atoms), and an alkoxy group having 6 to 36 carbon atoms (preferably 6 to 24 carbon atoms).
aryloxy group, having 2 to 36 carbon atoms (preferably 2 to 36 carbon atoms)
24), an acyloxy group having 1 to 36 carbon atoms (preferably 1 to 24), an alkylsulfonyl group having 6 to 36 carbon atoms (
an arylsulfonyl group having preferably 6 to 24 carbon atoms, an alkylthio group having 1 to 36 carbon atoms (preferably 2 to 24 carbon atoms), an arylthio group having 6 to 36 carbon atoms (preferably 6 to 24 carbon atoms), and an arylthio group having 4 to 36 carbon atoms (preferably 6 to 24); is an imide group of 4 to 24),
Carbamoyloxy group having 1 to 36 carbon atoms (preferably 1 to 24 carbon atoms) or carbamoyloxy group having 1 to 36 carbon atoms (preferably 2 to 24 carbon atoms)
Examples include heterocyclic groups (eg, pyrazolyl, imidazolyl, 1,2,4-triazol-1-yl, and tetrazolyl) that are bonded to the coupling active position through the nitrogen atom. Here, the above group may be substituted with a substituent selected from the substituent group A.

[0032] Below, R1, R2, of general formula (Cy),
Examples of preferred groups for R3 and X11 are shown below.

The above R1 is preferably F, Cl or an alkyl group substituted with at least one halogen atom, particularly preferably represented by -C(CF2)mF or -C(CF2)nH It is the basis. Here, m and n each represent an integer of 1 to 16 (preferably 1 to 8).

The above R2 is preferably an alkyl group, particularly preferably an alkyl group substituted at the 1-position with an aryloxy group, an alkylsulfonyl group, an allursulfonyl group, an imido group, or a heterocyclic group.

The above R3 is preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methoxy group or an acetamido group, and particularly preferably a hydrogen atom.

The above X11 is preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, or a heterocyclic thio group, more preferably a hydrogen atom or a chlorine atom, and especially a chlorine atom. be.

[0037] R1 and R in the general formula (Cy) are as follows:
Specific examples of 2, R3 and X11 are shown below.

Example of R1; F, Cl, -CF3, -(
CF2 )2 F, -(CF2)4 F, -(CF2
)6 F, -(CF2)8 F, -CF2 H, -
(CF2)3H, -(CF2)5H, -(CF
2)7H, -(CF2)9H, -CF2Cl
, -(CF2)3Cl

Example of R2;

[C5]

[C6]

[C7]

[0040]

[Chemical formula 8]

[Chemical formula 9]

[Chemical formula 10]

[0041]

[Chemical formula 11]

[Chemical formula 12]

[Chemical formula 13]

[0042]

[Chemical formula 14]

[Chemical formula 15]

[Chemical formula 16]

[0043]

[Chemical formula 17]

[Chemical formula 18]

[Chemical formula 19]

[0044]

[C20]

[C21]

[C22]

[0045]

[C23]

[C24]

[C25]

[0046]

[C26]

[C27]

Examples of R3; H, F, Cl, -CH3
, -CH(CH3)2, -OCH3, -OCF3
, -OCH2 CH2 OCH3 , -NHCOCH
3, -NHCOCF3, -NHCOC4H9-
t (t represents tertiary),

[0048]

[C28]

[C29]

Example of X11; H, F, Cl, SO3 H
, -CH2 COOCH3 , -OCH2 CH2 C
H2 COOH, -OCH2 CONHCH2 CH2
OOCH3, -OPO(OC2H5)2, -O
COCH3, -OSO2CH3, -OCONHC
2H5, -SCH2COOH, -SCH2CH
2 COOH,

[0050]

[C30]

[Chemical formula 31]

[C32]

[0051]

[Chemical formula 33]

[C34]

[C35]

[0052]

[C36]

[C37]

[C38]

[0053]

[C39]

[C40]

Specific examples of the cyan coupler represented by the general formula (Cy) are shown below.

(Cy-1)

[C41]

(Cy-2)

[C42]

(Cy-3)

[C43]

(Cy-4)

[C44]

(Cy-5)

[C45]

(Cy-6)

[C46]

(Cy-7)

[C47]

(Cy-8)

[C48]

(Cy-9)

[C49]

(Cy-10)

[C50]

(Cy-11)

[C51]

(Cy-12)

[C52]

(Cy-13)

[C53]

(Cy-14)

[C54]

(Cy-15)

[C55]

(Cy-16)

[C56]

(Cy-17)

[C57]

(Cy-18)

[C58]

(Cy-19)

[C59]

(Cy-20)

[C60]

The cyan coupler represented by the above general formula (Cy) can be synthesized by the method described in US Pat. .

The amount of cyan coupler represented by the above general formula (Cy) used in the photosensitive material is in the range of 1 x 10 -5 mol to 1 x 10 -2 mol per m 2 of the photosensitive material, preferably: In the range of 1 x 10-4 mol to 5 x 10-2 mol, more preferably 2 x 10-4 mol to 1 x 10
-3 moles.

Next, the nucleating agent represented by the following general formula [Fa] will be explained in detail. The nucleating agent is a substance that acts to directly form a positive image during surface development of an internal latent image type silver halide emulsion that has not been fogged in advance.

General formula [Fa]:

[C61]

In the general formula [Fa], the heterocycle completed by Z is, for example, quinolinium, benzothiazolium,
Benzimidazolium, pyridinium, thiazolinium, thiazolium, naphthothiazolium, selenazolium, benzoselenazolium, imidazolium, tetrazolium, indolenium, pyrrolinium, acridinium, phenanthridinium, isoquinolinium, oxazolium, naphthooxazolium and benzoxa Examples include zolium nuclei.

Substituents for Z include alkyl groups, alkenyl groups, aralkyl groups, aryl groups, alkynyl groups, hydroxy groups, alkoxy groups, aryloxy groups, halogen atoms, amino groups, alkylthio groups, arylthio groups,
Acyloxy group, acylamino group, sulfonyl group, sulfonyloxy group, sulfonylamino group, carboxyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, ureido group, urethane group, carbonate group, hydrazine group, hydrazone group , or an imino group. As the substituent for Z, for example, at least one substituent is selected from the above substituents, but in the case of two or more substituents, they may be the same or different. Moreover, the above-mentioned substituents may be further substituted with these substituents. Further, as a substituent for Z, a heterocyclic quaternary ammonium group completed with Z via a suitable linking group L may be included. In this case, it takes a so-called dimer structure.

Preferred examples of the heterocycle completed by Z include quinolinium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, and isoquinolinium nuclei. More preferred are quinolinium and benzothiazolium, most preferred is quinolinium.

[0082] The aliphatic group of R11 and R12 has 1 carbon number.
~18 unsubstituted alkyl groups and substituted alkyl groups in which the alkyl moiety has 1 to 18 carbon atoms. Examples of the substituent include those described as the substituent for Z.

The aromatic group represented by R12 has 6 to 6 carbon atoms.
Examples of the 20 groups include phenyl group and naphthyl group. Examples of the substituent include those described as the substituent for Z. R12 is preferably an aliphatic group, most preferably a methyl group, a substituted methyl group, or a case in which it is bonded to a heterocycle further completed by Z to form a ring.

At least one of the groups represented by R11, R12 and Z has an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or R11
and R12 form a 6-membered ring to form a dihydropyridinium skeleton, which may be substituted with the group described above as a substituent for the group represented by Z.

At least one of the groups or substituents on the ring represented by R11, R12 and Z may be an alkynyl group or an acyl group, or R11 and R12 may be linked to form a dihydropyridinium skeleton. Preferably, it further preferably contains at least one alkynyl group, most preferably a propargyl group.

[0086] At least one of the substituents R11, R12 and Z preferably has a group represented by the following formula. Formula: X12-(L11)m - Here, X12 represents an adsorption promoting group to silver halide, L11 represents a divalent linking group, and m represents 0 or 1. In the present invention, it is preferable that Z has a group represented by the above formula as a substituent.

Preferred examples of the adsorption-promoting group to silver halide represented by X12 include a thioamide group, a mercapto group, and a 5- or 6-membered nitrogen-containing heterocyclic group. These may be substituted with the substituents listed as substituents for Z. The thioamide group is preferably an acyclic thioamide group (eg, thiourethane group, thiourido group, etc.).

The mercapto group of X12 is a heterocyclic mercapto group (for example, 5-mercaptotetrazole, 3
-mercapto-1,2,4-triazole, 2-mercapto-1,3,4-thiadiazole, 2-mercapto-
1,3,4-oxadiazole, etc.) are preferred.

The 5- or 6-membered nitrogen-containing heterocycle represented by can give.

The divalent linking group represented by L11 is an atom or atomic group containing at least one of C, N, S, and O. Specifically, for example, alkylene group, alkenylene group, alkynylene group, arylene group, -O-,
-S-, -NH-, -CO-, -SO2- (these groups may have a substituent), etc. alone or in combination.

Examples of combinations include -COO-, -CO
NH-, -SO2NH-, -OCONH-, -NHCO
NH-, -NHSO2 NH-, -alkylene-CON
H-, -arylene-SO2 NH-, -arylene-
NHCONH-, -arylene-CONH-, etc. are preferred.

In the present invention, the divalent linking group represented by L11 includes -arylene-SO2 NH-,
-arylene-NHCONH-, and -arylene-
CONH- is more preferred.

Counter ions Y for charge balance include, for example, bromide ion, chloride ion, iodide ion, p-toluenesulfonate ion, ethylsulfonate ion, perchlorate ion, trifluoromethanesulfonate ion,
Examples include thiocyanine ion, boron tetrafluoride ion, and phosphorus hexafluoride ion.

Among these, preferred are bromide ion, iodide ion, perchlorate ion, or trifluoromethanesulfonate ion, and more preferred are iodide ion, perchlorate ion, or trifluoromethanesulfonate ion.

In the present invention, R12 is preferably bonded to the heterocycle completed by Z to form a ring.

[0096] These compounds and their synthesis methods are described in, for example, Research Disclosure (Research D).
isclosure) magazine, No. 22,534 (19
Published in January 1983, pp. 50-54), and No. 23,
Patent cited in 213 (Published August 1983, pp. 267-270), Japanese Patent Publication No. 49-38164, No. 5
No. 2-19452, No. 52-47326, Japanese Unexamined Patent Publication No. 1973
-69163 Publication, Publication No. 52-3426, Publication No. 55-1
No. 38742, No. 60-11837, U.S. Patent No. 43
It is described in the 06016 specification and the 4471044 specification.

Specific examples of the nucleating agent represented by the general formula [Fa] are listed below, but the invention is not limited thereto.

[Fa-1]

[C62]

[Fa-2]

[C63]

[Fa-3]

[C64]

[Fa-4]

[C65]

[Fa-5]

[C66]

[Fa-6]

[C67]

[Fa-7]

[C68]

[Fa-8]

[C69]

[Fa-9]

[C70]

[Fa-10]

[C71]

[Fa-11]

[C72]

[Fa-12]

[C73]

[Fa-13]

[C74]

[Fa-14]

[C75]

[Fa-15]

[C76]

[Fa-16]

[C77]

[Fa-17]

[C78]

[Fa-18]

[C79]

[Fa-19]

[C80]

[Fa-20]

[Chemical formula 81]

When the compound represented by the above general formula [Fa] is incorporated into a photographic light-sensitive material, water such as alcohols (for example, methanol, ethanol), esters (for example, ethyl acetate), ketones (for example, acetone), etc. It may be added to the hydrophilic colloid solution as a solution in an organic solvent that is miscible with the colloid, or as an aqueous solution if it is water-soluble. When added to a photographic emulsion, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added after chemical ripening is completed. In the present invention, the general formula [F
The nucleating agent represented by a] may be contained in a hydrophilic colloid layer (for example, an intermediate layer) or an undercoat layer adjacent to the silver halide emulsion layer, but if it is contained in the silver halide emulsion, preferable.

The amount of the nucleating agent added varies depending on the characteristics of the silver halide emulsion actually used, the chemical structure of the nucleating agent, and the development conditions, so it can vary over a wide range. Practically preferred is a range of 10-6% to 10% by weight, and more preferred is a range of 10-5% to 1% by weight based on the amount of silver.

The unfogged internal latent image type silver halide emulsion used in the present invention contains silver halide grains whose surfaces are not fogged and which forms latent images mainly inside the grains. More specifically, a silver halide emulsion is deposited on a transparent support in a certain amount (
0.5 to 3 g/m2), exposed to light for a fixed time of 0.01 to 10 seconds, and developed in the following developer (internal type developer) at 20°C for 5 minutes. The maximum density measured by the photographic density measurement method is obtained when a silver halide emulsion coated in the same amount as above and exposed in the same manner is developed in the following developer (surface type developer) at 18°C for 6 minutes. preferably at least 5 times greater, more preferably at least 1
It has a concentration 0 times greater.

0121 Internal type developer Metol

2.0g Sodium sulfite (anhydrous)
90.0g
hydroquinone
8.0g
Sodium carbonate (monohydrate)
52.8g KB
r
5.0g
KI

Add 0.5g water

1000cc surface type developer Metol

2.5g L-ascorbic acid
10.
0g NaBO2 ・4H2 O
35.0
g KBr

Add 1.0g water

1000cc

Specific examples of internal latent image type emulsions include conversion type silver halide emulsions described in US Pat. No. 2,592,250, US Pat. Nos. 3,761,276 and 3,850,637,
No. 3923513, No. 4035185, No. 4395
Specifications of No. 478 and No. 4504570, Japanese Unexamined Patent Publication No. 1983
-156614, 55-127549, 53-
No. 50222, No. 56-22681, No. 59-208
No. 540, No. 60-107641, No. 61-3137
No. 62-215272, Research Disclosure Magazine No. No. 23510 (issued in November 1983) on page 236, as well as U.S. Pat.
-47766, Japanese Patent Application No. 1-2467, JP-A-63-191145 concerning emulsion doped with metal ions,
Examples include core/shell type silver halide emulsions described in JP-A-1-52146. The molar ratio of silver halide between the core and the shell of the internal latent image type core-shell silver halide emulsion is particularly preferably 20/1 or less and 1/100 or more.

The internal latent image type silver halide grains which are not fogged in advance include Mn, Cu, Zn, Cd, Pd, and Bi.
Alternatively, at least one metal selected from the group consisting of metals belonging to Group VIII of the periodic table may be incorporated.

Mn, Cu, Zn, Cd, Pd, which are contained in the internal latent image type silver halide grains that are not fogged in advance,
The amount of Bi or metal belonging to Group VIII of the periodic table is preferably 10-9 to 10-2 mol, more preferably 10-7 to 10-3 mol, per mol of silver halide.

Among the metals mentioned above, particular preference is given to using lead, iridium and bismuth and rhodium.

When these metals are mixed with a silver ion solution and an aqueous halogen solution to form silver halide grains, the metal ions can be made to coexist in the form of an aqueous solution or an organic solvent solution and incorporated into the grains. Alternatively, after forming the grains, metal ions may be added in the form of an aqueous or organic solvent solution and then further coated with silver halide.

Methods for incorporating these metals are described in US Pat. No. 3,761,276, US Pat.

The shapes of the silver halide grains used in the present invention are cubic, octahedral, dodecahedral, and dodecahedral (Japanese Patent Laid-Open No. 2-22
3948), irregular crystal forms such as spherical, and the length/thickness ratio value described in JP-A-1-131547 and JP-A-1-158429 is 5 or more. In particular, an emulsion may be used in which 8 or more tabular grains account for 50% or more of the total projected area of the grains. Further, emulsions having composite forms of these various crystal systems or mixtures thereof may be used.

The composition of silver halide includes silver chloride, silver bromide, and mixed silver halide, and the silver halide preferably used in the present invention does not contain silver iodide or contains silver iodide. At most, 3 mol% or less of salt (iodine) silver bromide, (
silver chloride or silver bromide.

The average grain size of silver halide grains (in the case of spherical or nearly spherical grains, the grain diameter is taken as the grain size, and in the case of cubic grains, the vertical length is taken as the grain size, respectively, and expressed as an average based on the projected surface). , 1.5 μm or less, 0.1 μm
It is preferably at least m, but particularly preferably at most 1.2 μm and at least 0.2 μm. The particle size distribution may be narrow or wide, but in order to improve granularity and sharpness, the particle number or weight should be within ±40% of the average particle size, preferably within 30%, most preferably ± It is preferable to use in the present invention a so-called "monodisperse" silver halide emulsion having a narrow grain size distribution in which 90% or more, especially 95% or more of all grains fall within 20%.

In addition, in order for the light-sensitive material to satisfy the target gradation, two or more types of monodispersed silver halide emulsions with different grain sizes or two or more types of monodisperse silver halide emulsions with different grain sizes are used in the emulsion layer having substantially the same color sensitivity, or two or more types of monodisperse silver halide emulsions with the same size and sensitivity are used. A plurality of particles having different properties can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions may be mixed or layered for use.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the grains by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. As a chemical sensitization method for core particles, methods described in JP-A-2-199450 and JP-A-2-199449 can be used. Japanese Patent Application Publication No. 197742
In the presence of a mercapto compound as described in Publication No. 1-254946, No. 2-69738, No. 2
Thiosulfinic acid, sulfinic acid, and sulfite may be added as described in JP-A-273735. For detailed examples, see Research Disclosure Magazine No. 1
No. 7643-III (published in December 1978), page 23, etc.

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 cyanine dyes, merocyanine dyes and complex merocyanine dyes, which may be used alone or in combination. Further, the above dyes and supersensitizers may be used in combination. For detailed specific examples, please refer to research
Disclosure magazine No. 17643-IV (197
It is in the patent described on pages 23-24 (published in December 1998).

The photographic emulsion used in the present invention may contain an antifoggant or a stabilizer for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Can be done. For detailed specific examples, see Research Disclosure Magazine No.
17643-VI (issued December 1978) and E
．． J. “Stabilization o” by Birr
f Photographic Silver Hai
'lde Emulsion' (Focal Pres.
s), published in 1974.

In the present invention, various color couplers other than the above-mentioned cyan coupler can be used in combination. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or virazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. These cyan which can be used together in the present invention,
Specific examples of magenta and yellow couplers can be found in "Research Disclosure" magazine no. 17643 (1978
(Published December 2016), page 25, Section VII-D, No. 187
17 (published in November 1979) and JP-A-62-21
No. 5272 and the patents cited therein.

Among them, 5 preferably used in the present invention
The -prazolone type magenta coupler is a 5-pyrazolone type coupler in which the 3-position is substituted with an arylamino group or an acylamino group (particularly a sulfur atom separation type two-equivalent coupler).

More preferred are pyrazoloazole couplers, and among them are pyrazolo[5,1-c][1,2,4]triazoles described in US Pat. No. 3,725,067. U.S. Patent No. 45006 in terms of low yellow side absorption of the dye and light fastness.
Even more preferred are the imidazo[1,2-b]pyrazoles described in US Pat. No. 30, and particularly preferred are the pyrazolo[1,5-b][1,2,4]triazoles described in US Pat.

Examples of yellow couplers include US Pat. No. 3,933,501, US Pat. No. 4,022,620, US Pat.
No. 1,476,760 and the like are preferred.

[0139] Colored couplers for correcting unnecessary absorption in the short wavelength range of the generated dyes, couplers in which coloring dyes have appropriate diffusivity, colorless couplers, and releasing development inhibitors along with coupling reactions. DIR couplers and polymerized couplers can also be used.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are described in Research Disclosure no. 17643, patents described in sections VII to F, JP-A-57-151944, JP-A-57-
154234, 60-184248, US Pat. No. 4,248,962, and JP-A-63-146035 are preferred.

[0141] As a coupler that releases a nucleating agent or a development accelerator in an image form during development, British Patent No. 2097
No. 140, Specifications of No. 2131188, JP-A-59
Preferred are those described in WO 88/01402 and WO 88/01402.

[0142] The standard usage amount of the above color coupler is:
The amount ranges from 0.001 to 1 mol per mol of photosensitive silver halide, preferably 0.0 for yellow couplers.
1 to 0.5 mol, and for magenta couplers, 0.03 mol to 0.5 mol.

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.

[0144] In the light-sensitive material of the present invention, a color fog preventive agent or a color mixture preventive agent can be used. Representative examples of these are described in JP-A-62-215272, pages 185-193.

Compounds that release photographically useful groups include:
JP 63-153540, JP 63-259555, JP 2-61636, JP 2-2440
41 and No. 2-308240.

A color enhancer can be used in the present invention for the purpose of improving the color development of the coupler. Representative examples of compounds are JP-A-62-215272, 121-125.
Examples include those listed on page.

The photosensitive material of the present invention contains dyes that prevent irradiation and halation (for example, JP-A-2-85
Compounds described in Publications No. 850 and No. 2-89047 may also be used. Further, as a dye dispersion method, a solid microcrystal dispersion method may be used. ), ultraviolet absorbers, plasticizers, optical brighteners, matting agents, air antifogging agents, coating aids, hardeners, antistatic agents, slipperiness improvers, etc. can be added. Representative examples of these additives are listed in Research Disclosure magazine no. 17643 VII-XIII (19
Published in December 1978) pages 25-27, and 18716
(published November 1979), pages 647-651.

[0148] As mentioned above, the photographic material of the present invention has the following characteristics:
Generally, a support has a red-sensitive layer (red-sensitive emulsion layer), a green-sensitive layer (green-sensitive emulsion layer), and a blue-sensitive layer (blue-sensitive emulsion layer). The order of these layers can be arbitrarily selected as necessary. The preferred layer arrangement order is from the support side to red sensitivity,
Green sensitivity, blue sensitivity, or green sensitivity, red sensitivity, and blue sensitivity from the support side. In particular, in the present invention, it is preferable to configure in the former order. Further, each of the above-mentioned emulsion layers may be made up of two or more emulsion layers having different sensitivities, or a non-light-sensitive layer may be present between two or more emulsion layers having the same color sensitivity. As mentioned above, the red-sensitive emulsion layer usually contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but in some cases, the green-sensitive layer contains a yellow-forming coupler. Different combinations can also be used, such as using a mixture of couplers and magenta couplers.

In the photographic light-sensitive material of the present invention, the emulsion layer and other layers are as described in Research Disclosure Magazine No. 176
43VVII (issued December 1978), page 28, European Patent No. 0102253, and Japanese Patent Application Laid-Open No. 61-97655. Also, Research Disclosure Magazine No. 17643X
The coating method described in Section V, pages 28-29 can be used.

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

In the present invention, when the above-mentioned nucleating agent is used, it is preferable to use a nucleating agent to promote the action of the nucleating agent. A nucleation accelerator is a substance that does not substantially function as a nucleating agent, but promotes the action of the nucleating agent to increase the maximum density of a direct positive image and/or to obtain a certain maximum density of a direct positive image. A substance that acts to speed up the development time required for

[0152] Such nucleation accelerators include tetrazaindenes, triazaindenes and pentazaindenes having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group. and JP-A No. 63-106656, Nos. 5-1
Examples include the compounds described on page 6. Also, JP-A No. 63-226652, No. 63-106656, No. 6
Examples include the compounds described in No. 3-8740.

Specific examples of the nucleation accelerator are listed below. S-1

[C82] S-2

[Chemical formula 83] S-3

[Chemical formula 84]

[0154]S-4

[Chemical formula 85] S-5

[C86] S-6

[Chemical formula 87]

0155]S-7

[Chemical formula 88] S-8

[Chemical formula 89] S-9

[C90]

The nucleation accelerator can be contained in the photosensitive material or in the processing solution, but it can also be included in the internal latent image type silver halide emulsion and other hydrophilic colloid layers (
It is preferable to include it in an intermediate layer, a protective layer, etc.). Particularly preferred is a layer in or adjacent to a silver halide emulsion.

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

[0158] When adding a nucleation accelerator to the processing solution, that is, the developer or its pre-bath, 1 liter of nucleation accelerator should be added.
Preferably 0-8 to 10-3 mol, more preferably 1
It is 0-7 to 10-4 mol.

[0159] Two or more types of nucleation accelerators can also be used in combination.

[0160] Known photographic additives that can be used in the present invention include those listed in the aforementioned Research Disclosure No. 17643
(December 1978) and the same No. 18716 (19
(November 1979), and the relevant sections are summarized in the table below.

[0161] Additive type RD
17643 RD18716 ─
──────────────────────────
─── 1 Chemical sensitizer
Page 23 Page 648 Right column
2 Sensitivity enhancer
Same as above
3 Spectral sensitizer, 23-2
Page 4 Page 648 Right column ~
supersensitizer
Page 649 right column 4 increase
Whitening agent page 24
5 Antifoggant
Pages 24-25 Page 649 Right column ~
stabilizer
Page 650 right column
6 Light absorbers, page 25, right column, page 649, right column ~
filter dye,
Page 650 left column Ultraviolet absorber 7 Stain inhibitor Page 25 right column 8 Dye image stabilizer 2
Page 5 9 Hardener
Page 26 Page 651 Left column
10 Binder 2
Page 6 Same as above
────────────────────────
──────

[0162] In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are formed of a flexible support such as a plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal, which is commonly used in photographic light-sensitive materials. applied to the body. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc. The support may be colored using dyes or pigments.

Various known methods can be used to coat the silver halide photographic emulsion layer and other hydrophilic colloid layers, such as dip coating, roller coating, curtain coating, and extrusion coating. . In the present invention, as described above, it is preferable that the emulsion layer etc. be formed using the simultaneous multilayer coating method, and in this case, U.S. Pat. , No. 3508947, etc. may be used.

Next, the color development processing method will be explained. The internal latent image type silver halide emulsion-containing light-sensitive material of the present invention can be developed directly into a positive image by using a surface developer. A surface developer is one in which the development process is substantially induced by latent images or fog nuclei on the surface of silver halide grains.

[0165] The color developer used in the present invention contains:
Contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto. (1) N,N-diethyl-p-phenylenediamine, (
2) 2-amino-5-diethylaminotoluene, (3)
2-amino-5-(N-ethyl-N-laurylamino)
Toluene, (4) 4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline, (5) 2-methyl-4
-[N-ethyl-N-(β-hydroxyethyl)amino]aniline, (6) 4-amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-aniline, Among these, compounds represented by (2), (4), (5) and (6) are preferred.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. Such examples include (7) N-ethyl-N-β-(methanesulfonamidoethyl)-3-ethyl-4 aminoaniline sulfate, (8
) N-ethyl-hydroxyethyl-4-aminoaniline sulfate, and the like.

In the present invention, in particular, (7) or (
Compounds represented by 8) are preferred. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g, more preferably about 0.1 g to about 20 g, per liter of developer.
5g to about 10g.

[0168] Color developers also require sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl compound sulfite adducts as preservatives. It can be added accordingly. The preferred amount added is 0.5g to 10g per liter of color developer.
More preferably, it is 1 g to 5 g.

[0169] As compounds that directly preserve the developing agent, various hydroxylamines, JP-A-63-4
Hydroxamic acids described in Publication No. 3138, No. 63-17
Hydrazines described in Publication No. 0642 and JP-A-2-64
Hydrazine derivatives and hydroxylamine derivatives described in JP-A No. 632, phenols described in JP-A-63-44657 and JP-A-63-58443, JP-A No. 63-58443;
α-Hydroxyketones and α described in Publication No.-44656
-aminoketones and/or 63-3624
It is preferable to add various saccharides described in Publication No. 4. In addition, in combination with the above compounds, JP-A-63-4235, JP-A-63-24254, JP-A-63-21647, JP-A-63-
No. 146040, No. 63-27841, and No. 63
Monoamines described in various publications such as No.-25654, JP-A-63-30845, JP-A-63-146040, and JP-A-6
Diamines described in various publications such as No. 3-43439, polyamines described in JP-A-63-21647 and JP-A-63-26655, polyamines described in JP-A-63-44655, Nitroxy radicals described in JP-A-63-53551, JP-A-63-43
140 and 63-53549, oximes described in JP-A-63-56654, and tertiary amines described in JP-A-63-239447. is preferable.

[0170] Other preservatives include JP-A-57-441
48 and 57-53749, salicylic acids described in JP-A-59-180588, alkanolamines as described in JP-A-54-3532, JP-A-56-94349. Polyethyleneimines described in the above publication, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544, and the like may be contained as necessary.

The content of these compounds in the color developer is preferably as follows per liter of color developer:
o. 5g to 50g, more preferably 1.0 to 30g,
Particularly preferably, it is 1.5 g to 20 g.

[0172] These compounds may be present in the photosensitive material. In addition, color developing agents present in each solution (for example, due to being brought in from the color developer), not only in color developers, but also in bleach and bleach-fix solutions, water washes, or water wash substitute stabilizers, Acting on the oxidant,
It can give good performance.

[0173] The color developer used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0, and the color developer may contain compounds of other known developer components. be able to.

[0174] In order to maintain the above pH, it is preferable to use various buffers. Carbonates, phosphates, tetraborates, and hydroxybenzoates are especially soluble as buffering agents.
Excellent buffering ability in the high pH range of pH 9.0 or higher.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate,
Trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), o-
Examples include potassium hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

[0176] The amount of the buffer added to the color developer is 0.
．． It is preferably 1 mol/liter or more, especially 0
．． It is preferably 1 mol/liter to 0.4 mol/liter.

[0177] In addition, various chelating agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer.

The chelating agent is preferably an organic acid compound, and examples thereof include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Specific examples are shown below, but the invention is not limited to these. 1,2-dihydroxybenzene-3,5-disulfonic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'- Tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orhydrohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4- tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid and two or more of these chelating agents may be used in combination as necessary.

[0179] These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example, it is about 0.1 g to 10 g per liter.

[0180] Any development accelerator can be added to the color developer if necessary. However, the color developer used in the present invention preferably does not substantially contain benzyl alcohol from the viewpoints of formulation properties and prevention of color staining. Here, "substantially" means that the content is 2 ml or less per liter of developer, preferably not at all.

Other development accelerators include:
No. 16088, No. 37-5987, No. 38-7826
No. 44-12380, No. 45-9019, and U.S. Pat. No. 3,813,247, etc.;
p-phenylenediamine compounds represented by No. 0-15554, JP-A-50-137726, and JP-B No. 44-
30074, JP-A-56-156826 and JP-A-56-156826
Quaternary ammonium salts represented by No. 2-43429, etc., U.S. Patent Nos. 2,494,903 and 3,128,18
No. 2, No. 4,230,796, No. 3,253,919
No. 41-11431, U.S. Patent No. 2,482
, No. 546, No. 2,596,926 and No. 3,58
Amine compounds described in No. 2,346, etc., Japanese Patent Publication No. 37-Sho.
No. 16088, No. 42-25201, U.S. Patent No. 3,
No. 128,183, Special Publication No. 41-11431, No. 42
Polyalkylene oxides shown in -23883 and U.S. Patent No. 3,532,501, etc., and others 1-
Phenyl-3-pyrazolidones, imidazoles, etc. can be added as necessary.

[0182] In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-
Nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole,
Representative examples include nitrogen-containing heterocyclic compounds such as hydroxyazaindolizine and adenine.

[0183] The color developer used in the present invention may contain a fluorescent brightener. As the fluorescent whitening agent, 4,4'-diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 0 to 5 g/liter, preferably 0.1 g to 4 g/liter.

[0184] Also, if necessary, alkyl sulfonic acid,
Various surfactants such as aryphosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added.

[0185] The processing temperature of the color developer of the present invention is 20~
The temperature is 50°C, preferably 30-40°C. Processing time is 2
The time is 0 seconds to 5 minutes, preferably 30 seconds to 2 minutes. The smaller the amount of replenishment, the better, but 100 per m2 of photosensitive material.
~1500 ml, preferably 100-800 ml. More preferably, it is 100 ml to 400 ml.

Next, the desilvering process will be explained. The desilvering process is generally performed using any process such as a bleaching process-fixing process, a fixing process-bleach-fixing process, a bleaching process-bleach-fixing process, or a bleach-fixing process. Good too. The process period of the desilvering process is 1 minute 30 seconds or less, more preferably 15 seconds to 60 seconds.

(Desilvering step) The bleaching solution, bleach-fixing solution and fixing solution used in the desilvering step will be explained. As the bleaching agent used in the bleaching solution or bleach-fixing solution, any bleaching agent can be used, but in particular organic complex salts of iron(III) (e.g., aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid) Complex salts of phosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as ecunic acid, tartaric acid and malic acid; sulfates; hydrogen peroxide and the like are particularly preferred from the viewpoint of bleaching power and prevention of environmental pollution.

Aminopolycarboxylic acids, aminopolyphosphonic acids, useful for forming organic complexes of iron(III);
Or, to list organic phosphonic acids or their salts, ethylenediaminetetraacetic acid, diethyleneditriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, imino Examples include diacetic acid, glycol ether diamine tetraacetic acid, and the like.

These compounds include sodium, potassium,
Either lithium or ammonium salt may be used. Among these compounds, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,
, 3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because of their high bleaching power.

Among these, organic complex salts of iron (III) can be prepared using ferric phosphate or the like and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid, from the viewpoint of rapid processing. A ferric ion complex salt may be formed in solution. Further, the chelating agent may be used in excess of the amount required to form the ferric ion complex. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/liter, preferably 0.05 to 0.50 mol/liter.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. For example, US Pat. No. 3,893,858,
German Patent No. 1290812, JP-A-53-9
Publication No. 5630, Research Disclosure No. 171
No. 29 (July 1978 issue), compounds having a mercapto group or disulfide bond, and
No. 506, JP-A-52-20832, JP-A No. 53-327
Thiourea compounds described in No. 35, US Pat. No. 3,706,561, and halides such as iodine and bromide ions are preferred because they have excellent bleaching power.

In addition, the bleach or bleach-fix solution used in the present invention may contain bromides (for example, potassium bromide, sodium bromide, ammonium bromide) or chlorides (for example,
Rehalogenating agents such as potassium chloride, sodium chloride, ammonium chloride) or iodides (eg, ammonium iodide) can be included. Boric acid, borax, if necessary
One or more inorganic acids and organic acids having pH buffering capacity such as sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, and these Alkali metal or ammonium salts or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, namely, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate; or a thiocyanic acid such as sodium thiocyanate or ammonium thiocyanate. Salt; ethylene bisthioglycolic acid, 3,6-
These are water-soluble silver halide dissolving agents such as thioether compounds such as dithia-1,8-octanediol and thioureas, and these can be used alone or in combination of two or more. Also, JP-A-55-155354
A special bleach-fixing solution consisting of a combination of the fixing agent described in the above publication and a large amount of a halide such as potassium iodide may also be used.

In the present invention, thiosulfates, particularly ammonium thiosulfates, are preferably used. The amount of fixing agent per liter is preferably from 0.3 to 2 mol, more preferably from 0.5 to 1.0 mol. The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 10, more preferably 5 to 10.
-9 is particularly preferred.

The bleach-fix solution may also contain various other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fix solution and fixing solution in the present invention contain sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (
For example, ammonium bisulfite, sodium bisulfite,
It is preferred to contain a sulfite ion releasing compound such as potassium bisulfite, etc.), metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). The content of these compounds is preferably about 0.02 to 0.0.50 mol/liter in terms of sulfite ion, and more preferably 0.0 mol/liter.
It is 4 to 0.40 mol/liter.

As a preservative, sulfite is generally added, but ascorbic acid, carbonyl bisulfite adducts, carbonyl compounds, etc. may also be added.

Furthermore, buffering agents, optical brighteners, chelating agents,
Antifoaming agents, antifungal agents, etc. may be added as necessary.

Aqueous Solution and/or Stabilization In the processing of the present invention, aqueous solution and/or stabilization treatment is generally carried out after desilvering treatment such as fixing or bleach-fixing.

The amount of washing water in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the purpose, the washing water temperature, the number of washing tanks (stages), the replenishment method such as countercurrent, forwardflow, etc.
It can be set in a wide range depending on various other conditions. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers.
of Motion Picture and Tel
(evision Engineers) Volume 64, P2
48-253 (May 1955 issue), the number of stages in the normal multi-stage countercurrent system is 2.
-6 is preferable, and 2-4 is especially preferable.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, from 0.1 liter to 0.5 liter per m 2 of photosensitive material. The increased residence time of water in the tank causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material. In the processing of the color light-sensitive material of the present invention, the method for reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively as a solution to such problems. In addition, isothiazolone compounds and thiabendazoles described in JP-A No. 57-8542,
Chlorine-based disinfectants such as chlorinated sodium isocyanurate described in JP-A No. 61-120145, JP-A-61-267
Benzotriazole, copper ion, etc. described in No. 761, "Chemistry of antibacterial and antifungal agents" by Hiroshi Horiguchi, "Microbial sterilization, sterilization, and antifungal technology", edited by Sanitation Technology Society, "Edited by Japan Antibacterial and Antifungal Society" It is also possible to use disinfectants listed in the Antibacterial and Antifungal Dictionary.

Furthermore, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used in the washing water.

[0203] The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing solution, such as an aldehyde compound typified by formalin, a buffer for adjusting the membrane pH suitable for dye stabilization, and an ammonium compound. In addition, in order to prevent bacterial growth in the liquid and to provide anti-mold properties to photosensitive materials after processing,
The various fungicides and antifungal agents mentioned above can be used.

[0204] Furthermore, surfactants, optical brighteners, and hardening agents can also be added. In the processing of the photosensitive material of the present invention, when stabilization is carried out directly without passing through a water washing process,
All known methods described in Japanese Patent No.-220345 and the like can be used.

Others: 1-hydroxyethylidene-1,
It is also a preferred embodiment to use a chelating agent such as 1-diphosphonic acid or ethylene diamino tetramethylene phosphonic acid, or a magnesium or bismuth compound.

[0206] In the present invention, a so-called rinsing solution can also be used as a washing solution or a stabilizing solution used after the desilvering treatment.

[0207] The pH of the water washing step or stabilization step is 4 to 1.
0, preferably 5-8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but generally it is between 15 and 45
℃, preferably 20 to 40℃. The time can be set arbitrarily, but a shorter time is preferable. Preferably it is 30 seconds to 3 minutes, more preferably 30 seconds to 2 minutes. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, etc., and the effects of the present invention are also greater.

A specific preferred replenishment amount is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the prebath per unit area of the photosensitive material. Or it is 1 liter or less, preferably 500 ml or less per m2 of photosensitive material. Further, replenishment may be performed continuously or intermittently.

[0209] The liquid used in the water washing and/or stabilization step is as follows:
Furthermore, it can also be used in a pre-process. An example of this is to flow the overfloat of washing water reduced by a multi-stage countercurrent system into a bleach-fixing bath, which is a pre-bath, and replenishing the bleach-stabilizing bath with concentrated liquid to reduce the amount of waste liquid.

[0210] The direct positive color photographic material of the present invention is
Although it has various uses, it is particularly suitable for creating color proofs.

Various exposure means can be used to expose the photosensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination or writing light source. Natural light (sunlight)
, incandescent lamps, halogen-filled lamps, mercury vapor lamps, fluorescent lamps, and flash light sources such as strobes or metal-fired flashbulbs are common. Gaseous, dye solution or semiconductor lasers, light emitting diodes and plasma light sources emitting light in the wavelength range from ultraviolet to infrared can also be used as recording light sources. In addition, fluorescent screens (such as CRT) and liquid crystals (such as CRTs) emitted from fluorescent substances excited by electron beams, etc.
An exposure means that combines a linear or planar light source with a micro-shutter array using lanthanum-doped lead titanium zirconate (PLZT) or the like can also be used. If necessary, the spectral distribution used for exposure can be adjusted using color filters. In addition, Fuji Photo Film (
The scanning exposure method used in the color copier AP-5000 manufactured by Co., Ltd. can be used.

[0212]

[Examples] The present invention will be explained in more detail below with reference to Examples. However, the present invention is not limited to these examples.

[Example 1] (Preparation of sample 101) The following 1st to 11th layers were placed on the front side of a paper support (thickness 100 μm) laminated on both sides with polyethylene, and the 12th to 13th layers were placed on the back side. A color photographic light-sensitive material (comparative sample) was prepared by applying the layers in a multilayer manner. 1st
Titanium oxide (4g/m2
) as a white pigment, and a trace amount (0.003g/m2
) as a blue-tinged dye (the chromaticity of the surface of the support is 88.0, -0.20, - for L*, a*, b* systems).
0.75).

(Photosensitive layer composition) The components and coating amount (g/
m2). However, the amount of sensitizing dye added is expressed in moles per mole of silver. Regarding silver halide, the coating amount is shown in terms of silver. The emulsions used in each layer were prepared by changing the grain size by changing the grain formation temperature according to the method for manufacturing emulsion EM-1 described below. However, as the emulsion for the 11th layer, a Lippmann emulsion whose surface was not chemically sensitized was used.

1st layer (antihalation layer) Black colloidal silver

0.10 Color mixing prevention agent (Cpd-7)

0.05 gelatin

0.70

2nd layer (middle layer) Gelatin

0.70

Third layer (red-sensitive layer) Red sensitizing dye (ExS-1, 2, 3, equal amounts of each,
Silver bromide spectrally sensitized with a total of 5.4 x 10-4 (average grain size: 0.4 μm, grain size distribution: 10%, octahedral)

0.25 Gelatin

1.00 Cyan coupler (ExC-1)
0.30 Anti-fading agent (Equivalent amounts of Cpd-1, 2, 3, 4, 30)
0.18 Stain inhibitor (Cpd-5)
0.
003 Coupler dispersion medium (Cpd-6)
0.0
3 Coupler solvent (Equivalent amounts of Solv-1, 2, and 3) 0.12

4th layer (middle layer) Gelatin

1.00 Color mixing prevention agent (Cpd-7)

0.08 Color mixing inhibitor solvent (Solv-
4, 5 each equal amount) 0.16
Polymer latex (Cpd-8)
0.10

021
9] 5th layer (green sensitive layer) Green sensitizing dye (ExS-4, 2.6 x 10-4
) spectrally sensitized silver bromide (average grain size: 0.40 μm, grain size distribution 10%)
, octahedron) 0.25 Gelatin
0.80
Magenta coupler (ExM-1, 2, 3 each equal amount) 0.11 Yellow coupler (ExY-3)
0.03 Antifading agent (Cpd
-9, 26, 30 in equal amounts) 0.
15 Stain inhibitor (Cpd-10, 11, 1
2 and 13 in a 10:7:7:1 ratio)

0.025 Coupler dispersion medium (Cpd-6)

0.05 Coupler solvent (Equivalent amounts of Solv-4 and 6) 0.15

0
220] 6th layer (middle layer) Same as 4th layer

7th layer (yellow filter layer) Yellow colloidal silver (particle size 100 Å)
0.12 Gelatin
0.70
Color mixing inhibitor (Cpd-7)
0.03
Color mixing inhibitor solvent (Equivalent amounts of Solv-4 and 5)
0.10 Polymer latex (Cpd-8)
0.07

[0222] 8th layer (middle layer) Same as 4th layer

9th layer (blue sensitive layer) Blue sensitizing dye (Equivalent amounts of ExS-5 and 6,
Spectrally sensitized with a total of 3.5 x 10-4)
Silver bromide (average particle size: 0.60 μm,
Particle size distribution 11%, octahedral)
0.40 Gelatin
0.8
0 Yellow coupler (Equivalent amounts of ExY-1, 2, and 3) 0.35 Antifading agent (Cpd-14)
0.10 Anti-fading agent (
Cpd-30)
0.05 Stain inhibitor (Cpd-5, 15 in a 1:5 ratio) 0.
007 Coupler dispersion medium (Cpd-6)
0.0
5 Coupler solvent (Solv-2)
0.10

[
0224 Layer 10 (ultraviolet absorbing layer) Gelatin

1.00 Ultraviolet absorber (Cpd-2,
4, 16 each equivalent) 0.50
Color mixing prevention agent (Equivalent amounts of Cpd-7 and 17)
0.03 Dispersion medium (Cpd-6)
0.02 Ultraviolet absorber solvent (Equivalent amounts of Solv-2 and Solv-7)
0.08 Anti-irradiation dyes (Cpd-18, 19, 20, 21,
27 in the ratio of 10:10: 13:15:20)
0.05

11th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%,
average size 0.1μm)
0.03
Acrylic modified copolymer of polyvinyl alcohol
0.01 (molecular weight: 5
0000) Equal amounts of polymethyl methacrylate particles (average particle size: 2.4 μm) and silicon oxide (average particle size: 5 μm)

0.05 gelatin

1.80
Gelatin hardener (equal amounts of H-1 and H-2)
0.18

12th layer (back layer) Gelatin

2.50 Ultraviolet absorber (Cpd-2,
4, 16 each equivalent) 0.50
Dye (equal amounts of Cpd-18, 19, 20, 21, 27) 0.06

13th layer (back layer protective layer) Polymethyl methacrylate particles (
average particle size 2.4μm) and silicon oxide
(average particle size 5 μm) in equal amounts of each
0.05 gelatin

2.00
Gelatin hardener (equal amounts of H-1 and H-2)
0.14

(How to make emulsion EM-1) An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution over 15 minutes at 65° C. with vigorous stirring to form an octahedral odor with an average grain size of 0.23 μm. Silver oxide particles were obtained. At this time, 0.0% per mole of silver.
3g of 3,4-dimethyl-1,3-thiazoline-2-thione was added. A chemical sensitization treatment was performed by sequentially adding 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mole of silver to this emulsion and heating at 75° C. for 80 minutes. The thus obtained grains were used as cores and further grown in the same precipitation environment as in the first precipitation to finally obtain an octahedral monodispersed core/shell silver bromide emulsion with an average grain size of 0.4 μm. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mole of silver,
A chemical sensitization treatment was performed by heating at 60° C. for 60 minutes to obtain an internal latent image type silver halide emulsion.

Each photosensitive layer contains ExZK-1 as a nucleating agent.
and ExZK-2 to silver halide at 10-3, respectively.
wt%, 10-2 wt%, Cpd-2 as nucleation accelerator
2, 28, and 29 were each used in an amount of 10-2% by weight. Furthermore, alkanol XC (Du
Pont) and sodium alkylbenzene sulfonate, succinate ester and Magef as coating aids.
ac F-120 (manufactured by Dainippon Ink and Chemicals Co., Ltd.)
was used. As a stabilizer in the silver halide and colloidal silver containing layer,
Equivalent amounts of Cpd-23, 24, and 25 were used. The compounds used to create the above samples are shown below.

[0230]ExS-1

[Chemical formula 91]

[0231]ExS-2

[C92]

[0232]ExS-3

[C93]

[0233]ExS-4

[C94]

[0234]ExS-5

[C95]

0235 ExS-6

[C96]

[0236] Cpd-1

[C97]

[0237]Cpd-2

[C98]

[0238] Cpd-3

[C99]

Cpd-4

[Chemical formula 100]

[0240]Cpd-5

[Chemical formula 101]

[0241]Cpd-6

[Chemical formula 102]

[0242]Cpd-7

[Chemical formula 103]

[0243]Cpd-8

[Chemical formula 104]

[0244] Cpd-9

[Chemical formula 105]

[0245] Cpd-10

[Chemical formula 106]

[0246]Cpd-11

[Chemical formula 107]

[0247]Cpd-12

[Chemical formula 108]

[0248] Cpd-13

[Chemical formula 109]

[0249] Cpd-14

[Chemical formula 110]

[0250] Cpd-15

[Chemical formula 111]

[0251] Cpd-16

[Chemical formula 112]

[0252] Cpd-17

[Chemical formula 113]

[0253] Cpd-18

[Chemical formula 114]

[0254]Cpd-19

[Chemical formula 115]

[0255] Cpd-20

[Chemical formula 116]

[0256]Cpd-21

[Chemical formula 117]

[0257] Cpd-22

[Chemical formula 118]

[0258] Cpd-23

[Chemical formula 119]

[0259] Cpd-24

[Chemical formula 120]

[0260]Cpd-25

[Chemical formula 121]

[0261]Cpd-26

[Chemical formula 122]

[0262]Cpd-27

[Chemical formula 123]

[0263]Cpd-28

[Chemical formula 124]

[0264]Cpd-29

[Chemical formula 125]

[0265] Cpd-30

[Chemical formula 126]

0266 ExC-1

[Chemical formula 127]

0267 ExM-1

[Chemical formula 128]

0268 ExM-2

[Chemical formula 129]

0269 ExM-3

[Chemical formula 130]

0270 ExY-1

[Chemical formula 131]

0271 ExY-2

[Chemical formula 132]

0272 ExY-3

[Chemical formula 133]

[0273]Solv-1 Di(2-ethylhexyl) sebacate

[0274]Solv-2 trinonyl phosphate

[0275]Solv-3 Di(3-methylhexyl) phthalate

[0276]Solv-4 tricresyl phosphate

[0277]Solv-5 dibutyl phthalate

[0278]Solv-6 trioctyl phosphate

0279 Solv-7 Di(2-ethylhexyl) phthalate

H-1 1,2-bis(vinylsulfonylacetamido)ethane

H-2 4,6-dichloro-2-hydroxy-1,3,5-triazine/Na salt

0282 ExZK-1

[Chemical formula 134]

0283 ExZK-2

[Chemical formula 135]

(Creation of samples 102 to 104) Sample 1 above
01, the cyan coupler (ExC-1) used in the third layer (red sensitive layer) was replaced with the following cyan coupler (ExC-2, ExC-1 and ExC-2 were mixed in 1:
Sample 1 was prepared in the same manner as Sample 101, except that the mixture of Cy-1 and Cy-1 was changed (replaced with equimolar amounts).
02 to 104 were prepared respectively (comparative samples).

Cyan coupler (ExC-2)

[Chem.136
]

Cyan coupler (Cy-1)

[Chemical formula 137]

(Preparation of Sample 105) In preparing the above sample 101, the cyan coupler (ExC-1) used in the third layer (red sensitive layer) was replaced with the above cyan coupler (Cy-1).
1) (replaced with equimolar amount), and the nucleating agent (ExZ
Sample 1 was prepared in the same manner as Sample 101 except that the amounts of K-1 and ExZK-2) were changed to those shown in Table 1 below.
05 (comparative sample).

(Preparation of sample 106) In the preparation of sample 101, nucleating agents (ExZK-1 and ExZK-2) were added.
) as shown below, the nucleating agent (Fa-20
) and the amount added was changed to the amount shown in Table 1 below, but Sample 106 was prepared in the same manner as Sample 101 (comparative sample).

[0289] Nucleating agent (Fa-20)

[Chemical formula 138]

(Preparation of Samples 107 and 108) In the preparation of sample 106, the cyan coupler (ExC-1) used in the third layer (red-sensitive layer) was replaced with the cyan coupler (ExC-2, ExC-1 and ExC-2
(1:1 mixture) (replaced with equimolar amounts)
Samples 107 and 1 were prepared in the same manner as sample 106 except that
08 (comparative samples).

(Preparation of sample 109) In the preparation of sample 106, the cyan coupler (ExC-1) used in the third layer (red-sensitive layer) was replaced with the cyan coupler (Cy-1) used above. (replace with equimolar),
Sample 1 was prepared in the same manner as Sample 101 except that the amount of nucleating agent (Fa-20) added was changed as shown in Table 1 below.
09 (sample of the present invention) was prepared.

(Preparation of samples 110 to 111) Sample 1 above
In creating 09, the cyan coupler (Cy-1) used in the third layer (red-sensitive layer) was changed to the following cyan couplers (Cy-8, 16) (replaced with equimolar amounts). Samples 110 and 111 (samples of the present invention) were prepared in the same manner as sample 109.

Cyan coupler (Cy-8)

[Chemical formula 139]

Cyan coupler (Cy-16)

[C140
]

(Preparation of Sample 112) Sample 109 was prepared in the same manner as Sample 109, except that the nucleating agent (Fa-20) was replaced with the nucleating agent (Fa-18) shown below. Sample 112 (sample of the present invention) was prepared.

[0296] Nucleating agent (Fa-18)

[Chemical formula 141]

(Preparation of sample 113) In the preparation of sample 111, the nucleating agent (Fa-18) used above was used instead of the nucleating agent (Fa-20).
Sample 113 (sample of the present invention) was prepared in the same manner as in Example 1.

(Preparation of Sample 114) Sample 109 was prepared in the same manner as Sample 109 except that the nucleating agent (Fa-20) was replaced with the nucleating agent (Fa-19) shown below. Sample 114 (sample of the present invention) was prepared.

[0299] Nucleating agent (Fa-19)

[Chemical formula 142]

(Preparation of sample 115) In the preparation of sample 111, the nucleating agent (Fa-19) used above was used instead of the nucleating agent (Fa-20).
Sample 115 (sample of the present invention) was prepared in the same manner as in Example 1.

[Evaluation as a direct positive color photographic material] Each silver halide color photographic material (Samples 101 to 115) prepared as described above was subjected to the following processing, and the maximum density of the obtained cyan image was evaluated. (Dmax) and minimum density (Dmin) were measured.

[Exposure treatment] Color temperature 3200°K for each sample
Exposure was carried out through a wedge for 0.1 seconds. After exposure,
The following color development treatment was performed.

[Color development processing] Using the method described below using an automatic developing machine, the cumulative replenishment amount of the solution is 3 of the tank capacity.
Continued processing until doubled.

0304] ────────────────────────
──────────── Treatment process Time Temperature Tank capacity
Replenishment amount ──────────
──────────────────────────
─ Color development 135 seconds 38℃
30 liters 300ml/m2 Bleach fixing 40 seconds 33℃
10 liters 300ml/m2 Water washing (1
) 40 seconds 33℃ 7 liters --- Wash with water (
2) 40 seconds 33℃ 7
Liter 320ml/m2 dry
30 seconds 80℃────────
──────────────────────────
────

[0305] The method of replenishing the washing water is as follows: washing bath (2
), and the overflow liquid from the washing bath (2) is guided to the washing bath (1), using a so-called countercurrent replenishment method. At this time, the amount of bleach-fix solution brought in from the bleach-fix bath to the washing bath (1) by the photosensitive material was 35 ml/m2, and the ratio of the amount of washing water replenishment to the amount of bleach-fix solution brought in was 9.1 times. .

[0306] The composition of each treatment liquid was as follows. ──────────────────────────
──────────── Color developer
Mother liquor
Refill fluid────────────
────────────────────────
D-Sorvit
0.15g 0.20g
Sodium naphthalene sulfonate 0
．． 15g 0.20g Formalin condensate N,N,N-trimethylenephosphonic acid 4.
4g 4.4g Diethylenetriaminepentaacetic acid 0.44g
0.44g 1-hydroxyethylidene-1,1 0.27g 0.
27g -diphosphonic acid diethylene glycol
12.0ml 16.0ml Benzyl alcohol
13.5ml 18.0ml Potassium bromide
0.70g --- Benzotriazole 0
．． 003g 0.004g Sodium sulfite 2
．． 4g 3.2g N,N-bis(2-sulfoethyl) 8.0g
10.6g -N-hydroxyamine・2
Sodium salt D-glucose
2.0g
2.4g triethanolamine
6.0g
8.0g N-ethyl-N-(β-methane
6.4g 8.5g
Sulfonamidoethyl)-3-methyl-4-aminoaniline sulfate Potassium carbonate
30.0g 25.0g Fluorescent brightener (diaminostilbene type) 1.0g
Add 1.2g water
1000ml
1000ml────────────────
──────────────────── pH (
25℃) (adjusted with KOH) 10.30
10.75──────────────
──────────────────────

03
07] ──────────────────────────
──────────── Bleach-fix solution

Mother liquid Replenishment liquid──────
──────────────────────────
────── Ethylenediaminetetraacetic acid・
2.0g Same as mother liquor Disodium dihydrate Ethylenediaminetetraacetic acid Fe(III)
70.0g
Ammonium dihydrate ammonium thiosulfate (700g/liter) 15
0ml Sodium p-toluenesulfinate
35.0g ammonium sulfite
3
5.0g 5-mercapto-1,3,4-triazole 0.5g Ammonium sulfate
1
Add 0.0g water
1000ml───
──────────────────────────
──────── pH (25℃) (adjusted with acetic acid)
6.10────
──────────────────────────
───────

[Washing water] Both the mother liquor and the replenisher were tap water, and H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400, manufactured by Rohm and Haas) were added. Water was passed through the packed mixed bed column to reduce the concentration of calcium and magnesium ions to 3 mg/l or less, and then 20 mg/l of sodium isocyanurate dichloride and 0.15 g/l of sodium sulfate were added. The pH of this solution is 6
．． It was in the range of 5 to 7.5.

[0309] The cyan coloring density of each of the obtained positive images was measured using a densitometer (X-Rite 310, manufactured by X-Rite). In addition, after developing only the cyan image, it was scanned from λ = 400 to 750 nm using a spectrophotometer equipped with an integral class, and the cyan image density was 1 at the maximum peak wavelength.
．． The concentrations at λ=420nm and λ=520nm (D=λ420nm and D=λ520nm) in the case of No. 5 were measured. The results obtained are shown in Table 1 below.

0310]

[Table 1]

[0311] As is clear from the results shown in Table 1, direct positive photographic light-sensitive materials prepared using a cyan coupler and a nucleating agent according to the present invention (invention samples 109 to 109)
No. 115) has good color development and maintains a high maximum image density without increasing the minimum image density. On the other hand, unnecessary absorption in the blue light region and green light region is small (D=λ
420 nm and D=λ520 nm), that is, even when a coupler with good coloring hue is used (Comparative Sample 104), a sufficient maximum concentration cannot be obtained depending on the nucleating agent used. Further, even when the amount of the nucleating agent used was increased (comparative sample 105), a sufficient maximum image density could not be obtained, and attempts to increase the maximum image density conversely resulted in an increase in the minimum image density.

[Evaluation as a direct positive color photographic material] Each of the samples (101 to 115) obtained above was exposed to light in the same manner as above and then subjected to color development, using [N] as a developing agent. -ethyl-N-β-(methanesulfonamidoethyl)-3-ethyl-4-aminoaniline sulfate] was replaced with [N-ethyl-hydroxyethyl-4-aminoaniline sulfate] (in equimolar A cyan image was obtained in the same manner as above except for the following. The cyan image density was then measured in the same manner as above. As a result, the same results as above were obtained.

Claims (1)

[Claims] 1. A direct positive color photographic material comprising, on a support, at least one photosensitive layer containing an internal latent image type silver halide emulsion that has not been fogged in advance and a cyan coupler, wherein the cyan coupler is as follows: General formula (Cy) (Cy): [Formula 1] [In the formula, R1 represents a hydrogen atom, a halogen atom, or an alkyl group, R2 represents an alkyl group, an aryl group, or a heterocyclic group, and R3 represents a hydrogen atom, a halogen atom, or a heterocyclic group. atom,
It represents an alkyl group, an alkoxy group, an aryloxy group or a carbonamide group, and X11 represents a hydrogen atom or a coupling-off group. ], and the photosensitive layer containing a cyan coupler has the following general formula (
Fa) (Fa): [Formula 2, Z represents a nonmetallic atomic group necessary to form a 5- to 6-membered heterocycle, R11 represents an aliphatic group, and R1
2 represents a hydrogen atom, an aliphatic group, or an aromatic group, and (Z
, R11 and R12 may be substituted), provided that R12 may further combine with the heterocycle completed by Z to form a ring, and among the groups represented by Z, R11 and R12, At least one of them may contain an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or R11 and R12 may form a 6-membered ring to form a dihydropyridinium skeleton, and Y is for charge balance. represents a counterion, and n represents 0 or 1. ]
A direct positive color photographic material comprising a nucleating agent represented by: