JPS63226652A - Direct positive color image forming method - Google Patents

Abstract

PURPOSE:To rapidly and stably obtain the high max. coloring density and the low min. image density by incorporating a specified coupler in an inner latent image type silver halide sensitive material which is not previously fogged, and by developing the obtd. material with a low pH, in the presence of a nucleus forming agent and a specified nucleus forming accelerator. CONSTITUTION:The photosensitive material is provided with at least one layer of a photographic emulsion layer contg. an inner latent image type silver halide particle which is not previously fogged, and a color image forming coupler mounted on the supporting body. The titled method applies in imagewisely exposing said photosensitive material and then developing the obtd. material with a surface developer in the presence of the nucleus forming agent and the p-phenylene diamine (p-PDA) type coloring developer. The photosensitive material is developed with a developer in the presence of the nucleus forming agent and the nucleus forming accelerator such as a nitrogen- contg. heterocyclic ring compd. shown by the formula at pH of <=11.5, and said coupler has a nondiffusing property and is composed of a compd. capable of forming or releasing a nondiffusing dye by an oxidative-coupling with the p-PDA type coloring developer. Thus, the direct positive color image having the high max. coloring density and the low min. image density is rapidly and stably obtd. by developing at a low pH.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention produces a direct positive color image by subjecting a direct positive silver halide photographic light-sensitive material to imagewise exposure and then color development R* treatment in the presence of a nucleating agent. The present invention relates to an image forming method for obtaining.

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

Excluding special methods, the methods used to create positive images using conventionally known direct positive silver halide photographic materials are mainly divided into two types in consideration of their practical usefulness. be able to.

One type is to use it on a silver halide emulsion that has been fogged in advance, and to eliminate fogging nuclei (#I) in the exposed area by utilizing the normalization or Barschel effect. By destroying it, a solid image g1 is obtained directly after development.

The other type uses an internal fa@ type halogenated emulsion that is not fogged, and directly obtains a positive image by performing surface development after image exposure and after fogging treatment, or while performing fogging treatment. .

Inside the top! The type 11 silver halide photographic emulsion is a type of silver halide photographic emulsion having photosensitive nuclei mainly inside the silver halide grains, and in which m-images are mainly formed inside the grains upon exposure.

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

Various techniques are known in this technical field. For example, U.S. Pat. jriλ.

2jO No. 2. Hiro 66, Rij7, Rij No. λ.

zrr,? ! λ No. J, j/7, 32- (Same No. 2
．． Hiro? No. 7,171), No. 3,74/.

No. 266, No. J, 76/, No. 276, No. 3゜7? l
s, 177 and British Patent No. 1. /11゜363,
Same 1st. /10,113 issue (same/, Oii, ot2 issue)
The main ones are those described in each specification etc.

By using these known methods, it is possible to produce direct positive type photographic materials with relatively high sensitivity.

'Also, for details of the direct positive image formation mechanism, see, for example, T.)i, James [The Theory of the
Photographic Process J (The Theor
y of the PhotographicP
rocess) 1st edition Chapter 7/Page ♂~/9! and US Pat. No. 3.7t/, 276, etc.

19. Due to the surface desensitization effect caused by the so-called internal m-image generated inside the silver halide by the initial imagewise exposure, fog nuclei are selectively generated only on the surface of the silver halide grains in the unexposed areas. It is believed that a photographic image (direct positive image) is then formed in the unexposed area by subjecting it to a conventional so-called surface development process.

As mentioned above, as a means for selectively generating fog nuclei, a method of applying a second exposure to the entire surface of the photosensitive layer, which is generally called "light fogging method" (for example, British Patent No. 1./11,
No. 363) and a method using a nucleating agent called "chemical fogging method" are known. This latter method is discussed, for example, in [Research D
isclosure) magazine volume izi &/j/62
(Published January 2015), pages 76-7.

To directly form a positive color image, the internal latent image type silver halide photosensitive material is subjected to fogging treatment, or surface color development treatment is performed while fogging treatment is applied, and then bleaching and fixing (or bleach-fixing) are performed. can be achieved. After the bleaching and fixing treatments, washing and/or stabilizing treatments are usually performed.

(Problems to be solved by the invention) Among these methods, the conventional chemical fogging method
A nucleating agent that only becomes effective at a high pH of /j or higher is used, and therefore, under this high pH condition, the developing agent tends to deteriorate due to air oxidation, resulting in a significant decrease in developing activity. be. Furthermore, since the developing speed is slow, processing time is long, and in particular, when a low pH developer is used, processing time is further increased.

On the other hand, the photofogging method does not require high pH conditions and is relatively advantageous in practice. However, there are various technical problems in serving various purposes in the wide field of photography. That is, since the photofogging method is based on the formation of fog nuclei by photodecomposition of silver halide, the appropriate exposure illuminance and exposure depth vary depending on the type and characteristics of the silver halide used. Therefore, it is difficult to obtain a certain level of performance, and furthermore, the developing device is complicated and expensive.

As described above, with the conventional fogging method, it is difficult to obtain a stable and good direct positive image. As a means to solve this problem, JP-A-Sho has developed a compound that exhibits a nucleating effect even at a pH below 2. 2-Δri No. 473, U.S. Patent No. 3. t/j
,t/! No. 3゜r! ;0. t3? However, these nucleating agents act on silver halide during storage of the sensitive material before processing, or the nucleating agents themselves decompose, ultimately reducing the maximum image density after processing. There are drawbacks.

US Pat. No. 3,227,362 describes the use of hydroquinone derivatives to increase the development rate of medium densities. However, even when this is used, the development speed is not sufficient, and in particular, an insufficient development speed can be obtained with a developer having a pH of less than /2.

Further, JP-A-40-701≠3 describes that a mercapto compound having a carboxylic acid group or a sulfonic acid group is added to increase the maximum image density.゛But-
The effect of adding these compounds is small. Moreover, the pH of the developer is /2. O, and the stability of the developer is insufficient.

JP-A-66-3141 Hiror discloses a treatment solution containing a tetrazaindene compound in the presence of a nucleating agent (pH/2.
It is mentioned that processing with O) reduces the minimum image density and prevents the formation of a re-inversion negative image. However, this method does not increase the maximum image density or increase the development speed.

Furthermore, Japanese Patent Publication No. Akihiro J-/270 describes the addition of triazoline-thione and tetrazoline-thione compounds as antifoggants for sensitive material K for directly forming positive images by the photofogging method. However, even with these methods, it was not possible to achieve high maximum image density and fast development speed.

As described above, there has never been a technique to stably obtain a direct positive color image having a high maximum color image density and a low minimum image density in a short processing time using a color developer having a low pH (pH less than 12).

Furthermore, direct positive emulsions with high sensitivity generally have the problem of frequently generating re-inversion negative images upon high-intensity exposure.

Therefore, an object of the present invention is to process an internal latent image type silver halide photosensitive material that has not been fogged in advance with a low pH color developing solution in the presence of a nucleating agent to obtain a high maximum color density and a low minimum image density. It is an object of the present invention to provide a method for quickly and stably forming a direct positive color image having the following properties.

Another object is to provide a method for forming direct positive color images with less occurrence of re-inverted negative images during high-intensity exposure.

Another object of the present invention is to provide a method for directly forming a positive color image in which the maximum image density and minimum image density are less likely to change from the optimum values even if the temperature and pH of the color developer are changed, and the brown color reproducibility is less likely to change. .

Furthermore, it is an object of the present invention to provide a direct positive color image forming method in which the maximum image density and the minimum image density do not easily vary from the optimum values even if the color development time varies with respect to the standard time, and the brown color reproducibility does not easily change.

Another object of the present invention is to provide a method for directly forming a positive color image in which the maximum image density is less likely to decrease and the minimum image density is less likely to increase when a photosensitive material is stored for a long period of time.

Another object of the present invention is to provide a method for directly forming positive color images with stable performance and less deterioration of the developer due to air oxidation.

(Means for Solving the Problems) The present inventors have discovered that the object of the present invention is to support at least one photographic emulsion layer containing internal latent image type silver halide grains and color image-forming couplers that have not been fogged in advance. In the method of directly forming a positive color image by imagewise exposing a photosensitive material held on the body and developing it with a surface developer in the presence of a nucleating agent and a p-phenylenediamine color developer, The treatment is carried out at pH 11.0 in the coexistence of a nucleating agent and a nitrogen-containing heterocyclic compound (nucleating promoter) that promotes this nucleating action. The color coupler itself is substantially non-diffusive, and furthermore, the color coupler is substantially non-diffusive by oxidative coupling with a p-phenylenediamine color developer. It has been found that this can be effectively achieved by a direct positive color image forming method characterized by a compound that produces or releases a color pigment.

In particular, the present invention is 11. j or less (preferably //.

This is based on the unexpected discovery that the function of a nucleation accelerator is significantly exhibited by the use of a color developing solution with a low pH (below 0).

Here, the term "nucleating agent" refers to 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.

In addition, a "nucleation accelerator" refers to a nucleating agent that does not substantially have the function of the nucleating agent described above, but promotes the action of the nucleating agent to increase the maximum density of a direct positive image and/or to maintain a constant direct positive image. A substance that acts to speed up the development time required to obtain density.

Examples of the nucleation accelerator useful in the present invention include compounds represented by the following general formulas CI 2 ), (II 2 ), (m 2 ), or (VI).

In general formula (I), Q is preferably a carbon atom, a nitrogen atom,
Composed of at least one type of oxygen, sulfur, and selenium atoms! Or represents a group of atoms necessary to form a t-membered heterocycle.

The heterocycle may also be fused with a carbon aromatic ring or a heteroaromatic ring.

Examples of the heterocycle include tetrazoles, triazoles, imidazoles, thiadiazoles, oxadiazoles, selenadiazoles, oxazoles-thiazoles-benzoxazoles, benzthiazoles, benzimidazoles, pyrimidines, etc. It will be done.

M is a hydrogen atom, an alkali metal atom (e.g., sodium atom, potassium atom, etc.), an ammonium group (e.g., trimethylammonium group-dimethylbenzylammonium group, etc.), or a group that can become M=H or an alkali metal atom under alkaline conditions. (For example, an acetyl group, a cyanethyl group, a methanesulfonylethyl group, etc.).

In addition, these heterocycles include a nitro group, a chlorine atom (e.g., chlorine atom, bromine atom, etc.), a mercapto group, a cyanide group, a substituted or unsubstituted alkyl group (e.g.,
Methyl group, ethyl group, propyl group-t-butyl group, methoxyethyl group, methylthioethyl group, dimethylaminoethyl group, morpholinoethyl group, dimethylamineethylthioethyl group, diethylaminoethyl group, dimethylaminopropyl group, dibroble aminoethyl group, dimethylaminohexyl group, methylthiomethyl group, methoxyethoxyethoxyethyl group, trimethylammonioethyl group, cyanethyl group, etc.), teryl group (e.g. phenyl group,
Hiro-methanesulfonamidophenyl group, Hiro-methylphenyl group, 3-methoxyphenyl group, Hiro-dimethylaminophenyl group, 3, μm dichlorophenyl group, naphthyl group, l.

Alkenyl groups (e.g. allyl groups, etc.), aralkyl groups (
For example, <methyl group, ≠-methylbenzyl group-phenethyl group, Hiro-methoxybenzyl group, etc.), alkoxy group (
For example, methoxy group to ethoxy group, methoxyethoxy group,
methylthioethoxy group, dimethylaminoethoxy group, etc.), aryloxy group (e.g. phenoxy group, ≠-methoxyphenoxy group, etc.), alkylthio group (e.g. methylthio group, ethylthio group, propylthio group-methylthioethyl group, dimethylamine ethylthio group) Groups - methoxyethylthio group, morpholinoethylthio group, dimethylaminopropylthio group, piperidinoethylthio group, pyrrolidinoethylthio group, morpholinoethylthioethylthio group - imidazolylethylthio group, copyridylmethylthio group, diethylamineethyl thio group (e.g., phenylthio group, ≠-dimethylaminophenylthio group, etc.), heterocyclic oxy group (e.g., copyridyloxy group, 2-imidazolyloxy group, etc.), heterocyclic thio group (e.g., phenylthio group, ≠-dimethylaminophenylthio group, etc.), groups (e.g. 2-benzthiazolylthio group, Hiro-virazolylthio group, etc.), sulfonyl groups (e.g. evamethanesulfonyl group, ethanesulfonyl group, p-)luenesulfonyl group, methoxyethylsulfonyl group, dimethylaminoethylsulfonyl group, etc.), carbamoyl groups (e.g. unsubstituted carbamoyl group, methylcarbamoyl group, dimethylaminoethylcarbamoyl group, methoxyethylcarbamoyl group, morpholinoethylcarbamoyl group, methylthioethylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (e.g. unsubstituted sulfamoyl group, methylsulfamoyl group, imidazolylethylsulfamoyl group, phenylsulfamoyl group, etc.), carbonamide group (e.g. acetamide group, benzamide group, methoxypropionamide group, dimethylaminepropionamide group, etc.), Sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, etc.), acyloxy group (e.g. acetyloxy group-benzoyloxy group, etc.), sulfonyloxy group (e.g. methanesulfonyloxy group, etc.), ureido groups (e.g., unsubstituted ureido groups, methylureido groups,
ethylureido group, methoxyethylureido group, dimethylaminopropylureido group, methylthioethylureido group, morpholinoethylureido group, phenylureido group, etc.), thioureido group (e.g., unsubstituted thioureido group, methylthioureido group, methoxyethylthioureido group) group, etc.), acyl group (e.g. acetyl group-benzoyl group, methoxybenzoyl group, etc.), heterocyclic group (e.g. / -morpholino group, l-pi is lysino group, 2
-Pyridyl group-≠-pyridyl group, 2-chenyl group, nopyrazolyl group, l-imidazolyl group, ochchitrahydrofuryl group, tetrahydrochenyl group, etc.), oxycarbonyl group (e.g. methoxycarbonyl group, phenoxydicarbonyl group) , methoxyethoxycarbonyl group, methylthioethoxycarbonyl group, methoxyethoxyethoxyethoxycarbonyl group, dimethylaminoethoxycarbonyl group 1 morpholinoethoxycarbonyl group, etc.), oxycarbonylamino group (e.g. methoxycarbonylamino group, phenoxycarbonylamino group, coethyl group) xyloxycarbonylamino group, etc.), amino group (e.g. unsubstituted amine group, dimethylamino group, methoxyethylamino group, anilino group, etc.), carboxylic acid or its salt, sulfonic acid or its salt - substituted with hydroxyl group, etc. However, from the viewpoint of nucleation promoting effect, it is preferable that carboxylic acid or its salt - sulfonic acid or its salt, and not substituted with hydroxyl group.

In the formula, M has the same meaning as in general formula (I).

X represents an oxygen atom, a sulfur atom or a selenium atom.

R'' R6, R7 and R8 each represent a hydrogen atom, a substituted or unsubstituted alkyl group (e.g. -methyl group, ethyl group, propyl group - cordimethylaminoethyl group, etc.), a substituted or unsubstituted aryl group (e.g., phenyl group, 2-
methylphenyl group, etc.), substituted or unsubstituted alkenyl group (e.g., pro-vinyl group, l-methylvinyl group,
etc.) - or a substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group, etc.).

R is a straight-chain or branched alkylene group (e.g. - methylene group, ethylene group, propylene group, butylene group, hexylene group, l-methylethylene, !-, etc.) - a straight-chain or branched alkenylene group (e.g., vinylene group) , l-methylvinylene group, etc.) - linear or branched aralkylene group (
For example, it represents a penzylidene group, etc.), an arylene group (for example, phenylene, naphthylene, etc.). The above group represented by R may be further substituted.

Z is a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, etc.), a nitro group, a cyano group, a substituted or unsubstituted amino group (including salt form, e.g., an amine group, a hydrochloride of an amino group) , methylamino group, dimethylamine group, hydrochloride of dimethylamino group, dibutylamino group, dipropylamino group, N-dimethylamine ethyl-N-methylamino group, etc.), quaternary ammonio group (e.g. trimethylammonio group, dimethylbenzylammonio group,
), alkoxy groups (e.g., methoxy, ethoxy, 2-methoxyethoxy, etc.), aryloxy groups (
For example, phenoxy group, etc.), alkylthio group (e.g. -methylthio group, butylthio group, 3-dimethylaminopropylthio group, etc.), arylthio group (e.g. phenylthio group, etc.), heterocyclic oxy group (e.g. λ- pyridyloxy group, niimidazolyloxy group, etc.), heterocyclic thio group (e.g. cobenzthiazolylthio group -≠
-pyrazolylthio group, etc.), sulfonyl group (e.g. Id,
methanesulfonyl group, ethanesulfonyl group, p-1 luenesulfonyl group, etc.), carbamoyl group (e.g., unsubstituted carbamoyl group, methylcarbamoyl group, etc.), sulfamoyl group (e.g., unsubstituted sulfamoyl group, methylsulfamoyl group) -, etc.), carbonamide groups (e.g., acetamide groups, benzamide groups, etc.), sulfonamide groups (e.g., methanesulfonamide groups, benzenesulfonamide groups, etc.), acyloxy groups (e.g., acetyloxy groups, benzoyloxy groups), , etc.), ureido groups (e.g., unsubstituted ureido groups, methylureido groups, ethylureido groups, etc.), acyl groups (e.g., acetyl groups, benzoyl groups, etc.), thioureido groups (e.g., unsubstituted thioureido groups, methylthioureido group, etc.), sulfonyloxy group (e.g., methanesulfonyloxy group,
p-) luenesulfonyloxy group, V, >, heterocyclic group (e.g. /-morpholino group, /-pyro 1Jdino group,
λ-pyridyl group, ≠-pyridyl group, 2-chenyl group, /
-pyrazolyl group, /-imidazolyl group, λ-tetrahydrofuryl group, cochthrahydrochenyl group, etc.), oxycarbonyl group (e.g., methoxycarbonyl group, methylthiomethoxycarbonyl group - phenoxycarbonyl group, etc.), oxysulfonyl group (For example, methoxysulfonyl group, phenoxysulfonyl group, ethoxysulfonyl group.

), oxycarbonylamino group (e.g., ethoxycarbonylamino group, phenoxycarbonylamino group, ≠
-dimethylaminophenoxycarbonylamino group, etc.)
Or represents a mercapto group.

n represents O or /.

"R" In the formula, R' represents a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a nitro group, a mercapto group, an unsubstituted amino group, or a +Y→-R-Z group. R" represents a hydrogen atom, an unsubstituted amine group, or l. M, R, Z,
Y, n, R', R", R3, R", R', R
', R7, t7'cHR''ail and it is the general formula (
They have the same meaning as each of II).

In terms of the nucleation promoting effect, in the compound of general formula (I[), preferably X is a sulfur atom and Y is -S-. Further, R is preferably a linear or branched alkylene group.

Among the compounds of general formula (m), R' is preferably a hydrogen atom or +Y→-R-Z, and Y is -S-. Further, R'' is +Y'±1R-Z, and m=0.R is preferably a linear or branched alkylene group or arylene group.

General formula (IV) 7.

Q′ direction-M In the formula, M has the same meaning as in general formula (1).

Q′ can form iminosilver! or represents an atomic group necessary to form a 6-membered heterocycle, preferably consisting of at least one of carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, and selenium atoms! or 6 represents an atomic group necessary to form a negative heterocycle. Moreover, the above-mentioned heterocycle may be fused with a carbon aromatic ring or a heteroaromatic ring. Examples of the heterocycle formed by Q' include indazoles, benzimidazoles, benzytriazoles, benzoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles, triazoles, tetrazoles, and tetrazain. Examples include denes, doriazaindenes, diazaindenes, pyrazoles, and indoles, but those other than tetraazaindenes and benzotriazoles are preferred from the viewpoint of nucleation promoting effect.

These heterocycles may be substituted with a substituent applicable to the heterocycle of general formula (1) above, or may be substituted with a hydroxyl group, but a carboxylic group, a xyl group, or a salt thereof It is preferable that the compound is not substituted with a sulfo/acid group or its weir from the viewpoint of nucleation promoting effect.

General formula (V) ■ R″′ In the above general formula (V), R″′ is a hydrogen atom or -
Represents an R-Z group. M, R and Z each have the same meaning as in the above general formula (I[).

General formula ([) In the above general formula (VI, 1), H/II represents a hydrogen atom and nine represents a -R-Z group, R and RIO represent a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, etc.) , a substituted or unsubstituted amino group (e.g., an unsubstituted amino group,
dimethylamino group, methylamine group, butylamino group,
methoxyethylamino group, etc.), nitro group, substituted or unsubstituted alkyl group (e.g. methyl group, ethyl group,
Propyl group, t-butyl group, methoxyethyl group, methylthioethyl group, dimethylaminoethyl group, morpholinoethyl group, dimethylamineethylthioethyl group, diethylaminoethyl group, dimethylaminopropyl group, methylthiomethyl group, methoxyethoxyethoxyethyl group ,etc)
, alkenyl groups (e.g. allyl group, l-methylvinyl group, etc.), aralkyl groups (e.g. benzyl group, ≠-methylbenzyl group).

phenyl group, ≠-methoxybenzyl group, etc.) or aryl group (e.g., phenyl group, ≠-methanesulfo/amidophenyl group, ≠-methylphenyl group, 3-methoxyphenyl group% μm dimethylaminophenyl group, 3p4A
-dichlorophenyl group, naphthyl group, etc.) represented by gold. M
, R and 2 each have the same meaning as in the general formula (■) above.

The nucleation accelerator used in the present invention is produced by Berichte der Deutschen Hemitschen Gesellschaft
Chete der Deutschen Chemi
schen Ge5ellschaft boundary r, '7'
7 (lrFt), Japanese Patent Application Publication No. 10-37 Ko 3, same j/-
jλ31, US Patent 3,2F! , No. 27.

US patent! , No. 376.310, Berichte der Deutsche/Hemitsien Gesellschaft (Beric
Hte der Deutschen Chemi
schenGese order 5chaft) 22. r6J
r(/IIri), Ll, ko4tlj(lrFt), Journal of Chemical Society (J, Che
m, Soc, )/932. /106, Journal of the American Chemical Society (J, Am
.

Chem, Soc, )7/, 4Looo(iyty),
U.S. Patent No. J11,311, λ,! ≠/.

P2≠ issue, Advances in Heterocyclic Chemistry (Advanceo 1nHeter)
cyclic chemistry)? , 1ts(
/ri+f)-Organic Synthesis [Organi
c 5ynthesis) ■-yo6ri (/ri1?), Journal of the American Chemiriki/L/ ・Society (J, Am, Chem, Soc,) Hiroj, =
3riO (/ri23), Hemisie Berichte (Chemi
sche Berichte) Ta, Hirozzj (lt
ry&), Tokuko Akihiro 0-2Ir≠ri6, Tokuko Akihiro 0-2Ir≠ri6, Tokuko Akihiro
No. O-190Jlt, US Patent J, 10t,! No. 67,
Same 3. ≠No. 20,470, same, core/.

No. 22, same j, /37. j7J' issue, same 3. /41r
, ott issue, same 3. j11. At No.3, At3゜oto,
o2r issue, same J, 27/, /! II No. j, 211.
tri No. 7, same 3. J9♂, J Tata, 3,1111.
Ot6, special public show 4L3-II/j! No. 3, U.S. Pat.
Otsu/! , 1/Otsu No. 3, 4! Koo, tta, same 3.
07/, 4Ltj issue, same co.

≠4t≠, No. 403, same 2. Hirogu Hiro, No. 606, same co.
Hiroshi ≠ IAl No. 307, same co, ri 3! It can be easily synthesized by the method described in .

[2H5, rIA is
♂t 17ri0
9/ Rig Tata ioo 1ot106,
107//I
//? N)is(J2L;l
(3 /22 /ko3/ko4!
/21SI
J2NHUti2Uti and 4tig (II) l roller
1271+21
/2? i3o
/J//! 4L/J
j/31 /jril≠Ol≠
l /g2 /4c3
The nucleation accelerator can be contained in the light-sensitive material or in the processing solution, but especially in the internal latent image type silver halide emulsion and other hydrophilic colloid layers (intermediate layer, protective layer, etc.). It is preferable to contain it. Particularly preferred is a layer in or adjacent to a silver halide emulsion.

The amount of nucleation accelerator added is 10-6 per mole of silver halide.
~10 mol is preferred, more preferably 10 ~
/Q moles.

In addition, when the nucleation accelerator is added to the processing solution, that is, the developer or its pre-bath VC, 10-8 to 10
molar is preferred, more preferably 10 −70
It is a mole.

Two or more types of nucleation accelerators may be used in combination.

The general formula (1) used in the present invention, (II8(II
], (F/), (V), and (Vl) are represented by general formulas (II), (1■), and (V).
is preferable, and nucleation accelerators represented by general formula (II) and uI[) are more preferable.

The unfogged internal latent image type silver halide emulsion used in the present invention is an emulsion containing silver halide in which the surface of the silver halide grains is not fogged in advance and forms a latent image mainly inside the grains. However, more specifically,
A certain amount of silver halide emulsion is coated on a transparent support, and 0. The maximum density measured by the usual photographic density measurement method when exposed for a fixed time of 0/ to 10 seconds and developed for 5 minutes at /8 °C in the following developer MA (internal type developer) is A silver halide emulsion coated in the same amount as and exposed in the same manner is shown in Example 1 below. ! Sumpling wetness (surface type developer)
of the maximum density obtained when developed for 6 minutes at 20 °C in a at least! Preferably, those with a concentration that is twice as large, more preferably those that have a concentration that is at least an io times greater.

Surface developer B Metol λ, 51j-Ascorbic acid 10y NaBO2.4' H20j j NoKRr
/y add water
/ l Internal developer A Metol 2 Sodium sulfite (
Anhydrous) Ta0 Hydroquinone
t Soda carbonate (-water salt) j2. Yono KBr! yKI
o, add yonomizu
Conversion type silver halide emulsions and core/shell type silver halide emulsions can be mentioned.
-j2. l'/j, same≠7-jjr/V, same j, 2
-/3 Hiroshi 72/ issue, same Yoko/! At/≠ issue, same j-
No. 1,0222, same! J-tt2/r, same as j-1t
No. 727, same! -/27!4'ri number, same J-7-/3
tt'AI No., j1-70227, 69-2C#
j, Hiro O issue, same! 9-21A/3 No. Otsu, same AO-/'0
7 Otohiro No. 1, same tO-2≠7237, same A/-2/4
# No., ° same & / -'j / No. 37, Special Public ShojA-
/1939 issue, same jr-/≠72 issue, same rr-/4Li
Yo issue, same jr-693! No. 5r-7orssr,
Patent application Sho J/-31112≠, U.S. Patent No. 320AJ/3
No. 33/73 No. 416041370, European Patent No. 00/7/The composition of silver halide includes silver chloride and silver bromide, as well as mixed silver halides, such as silver chlorobromide and chloroiobromide. Representative examples include silver and silver iodobromide. The silver halide preferably used in the present invention is silver iodobromide, silver iodochloride, or silver iodobromide, which does not contain silver iodide or contains less than 3% by mole of silver iodide.

The average grain size of silver halide grains (in the case of spherical or near-spherical grains, the grain diameter is taken as the grain size, and in the case of cubic grains, the ridge length is taken as the grain size, and based on the projected area (average grain size) is 2μ The following is preferably 0.78 or more,
Particularly preferred is 7 μ or less o and ir μ or more. 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 10≠0 inches (more preferably within ±30%, most preferably within ±30%) of the average particle size. It is preferable to use a so-called "monodisperse" silver halide emulsion in the present invention, which has a narrow grain size distribution in which 0% or more, especially qr% or more of the total grains fall within ±2o% (preferably within ±2o%). In addition, in order to satisfy the six gradations targeted by a light-sensitive material, two or more types of monodispersed silver halide emulsions with different grain sizes are used in an emulsion layer having substantially the same color sensitivity, or two or more types of monodisperse silver halide emulsions with the same size but different sensitivities are used. Multiple particles can be mixed in the same layer or coated in separate layers.
Ru. Furthermore, two or more types of polydisperse silver halogenide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
), may have an irregular crystal shape such as a spherical shape, or may have a composite shape of these crystal shapes. Further, tabular grains may be used, and in particular, an emulsion may be used in which tabular grains having a length/thickness ratio of 5 or more, particularly r or more, occupy a factor of 50 or more of the total projected area of the grains. An emulsion consisting of a mixture of these various crystal forms may also be used.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination.

The photographic emulsions used in the present invention are spectrally sensitized with photographic sensitizing dyes in a conventional manner. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. For more detailed examples and how to use them, please refer to Research Disclosure (RD).
Magazine /76≠3 (December /97r)■ etc.

The photographic emulsion used in the present invention contains benzenethiosulfonic acids, benzenesulfinic acids, thiocarbonyl compounds, etc. for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to stabilize photographic performance. can be contained.

For more detailed examples of antifoggants or stabilizers and their uses, see, for example, U.S. Pat. rij44
．． No. 4'74L, No. 3, No. 912, No. 917-7, Special Publication No. 32-21tAO, Research Disclosure (RD) Magazine/7otsu≠3 (/7g, 72/72) VIA
~VIM and E. J. Birr, “Stabilization of Silver Halide Photographic Emulsions” (5tabilization of Photo
graphicSi Iver Hal 1cle
Emulsio, ns) Focal Press (Foc
al I'ress), 1q7ti annual publication, etc.

The nucleating agent used in the present invention can be contained in the sensitive material or in the processing solution for the sensitive material, preferably in the sensitive material.

When contained in a sensitive material, it is preferably added to the round silver halide emulsion layer, but as long as the nucleating agent is adsorbed to the silver halide by diffusion during coating or processing, it may be added to other layers such as , an intermediate layer, an undercoat layer or a back layer. When adding a nucleating agent to the processing solution, add it to the developer solution or a low p
It may be contained in the H pre-bath.

When a nucleating agent is contained in the sensitive material, the amount used is preferably p70 to 10 mol per 7 mol of silver halide;
More preferably, the amount is 10 7 to 10 −3 mol.

In addition, when adding a nucleating agent to the processing solution, the amount used is:
It is preferably from pio' to 10 moles per liter, more preferably from lo-4 to l0-2 moles.

As the nucleating agent that can be used in the present invention, all compounds conventionally developed for the purpose of nucleating latent silver halide can be used. Two or more types of nucleating agents may be used in combination. To explain in more detail, the nucleating agent includes, for example, “
Research Disclosure J
Disclosure ) magazine i22,! 311 (
/ Published January 913 30~j4! These compounds are broadly classified into three types: hydrazine compounds, quaternary heterocyclic compounds, and other compounds.

First of all, as a hydrazine compound, for example, the above-mentioned Research Disclosure magazine A / J R / Otsu 2 (1
971, Published//Month, pp. 76-77) and the same magazine JFa
-2j + j/0 (/9 r J year/month issue 3tA pages 6-362). More specifically, those described in the following patent specifications can be mentioned. First, examples of hydrazine-based nucleating agents having silver halide adsorption groups include, for example, U.S. Pat.

No. 010.207, No. 41,037,127, No. 3,7/♂, Hiroshi 70, Hiroshi No. 2, 2 Otsu 9. No. 29, No. ≠, No. 27A, No. 36, No. ≠, Cocoa, 7 Hiro, r
No. 4t, 31! , IC# issue, same issue ≠, Hiro! Di, 3
≠7, British Patent No. 2,0//.

39/B issue, Tokukai Sho! ≠−7≠, No. 729, same! −／
Otsu 3. ! No. 33, same ta! -7≠, No. 536, and the same AO
Examples include those described in No. -/79.73≠.

Other hydrazine-based nucleating agents include, for example, % Kaishoj.
7-♂2. r29, U.S. Patent No. G,! A0.63, same number ≠, ≠7r, and even same λ, j otsu j, 7g! No. and 2. J'r♂, wa? Examples include the compound described in No. 2.

Next, examples of quaternary heterocyclic compounds include the aforementioned Research Disclosure magazine A2λ, Yo3≠ and Tokuko Akihiro9.
-31. /A4L, same f2-/? .

Hiro! No. 2, same! r2-Hiroshi 7.32A, Tokukai Sho! 2-6
9. Otsu No. 73, same! 2-3. ≠No. 26, same j-/3♂
, 7≠2, same Otsu 0-11. ♂No.37, US Patent No.≠,
3ot, oit issue, and "Research Disclosure" magazine &23, 2/3 (Published in January, 9g3, pp. 267-270).

The nucleating agent useful in the present invention is preferably a compound represented by the following general formula (:N-I) or [N-II).

General formula CN-I] (In the formula, Z represents a group of nonmetallic atoms necessary to form a !- to t-membered heterocycle, and Z may be substituted with a substituent. R1 is an aliphatic group. and R2 is a hydrogen atom, an aliphatic group, or an aromatic group. R1 and R2 may be substituted with a substituent. However, at least one of the groups represented by R1, R2, and Z is It contains an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or R1 and R2 form a 6-membered ring to form a dihydropyridinium skeleton. Furthermore, at least one of the substituents of R1, R2, and Z , X1+L1-)m. Here, Xl is an adsorption promoting group to silver halide, and L
l is a divalent linking group. Y is a counterion for charge balance, n is 0 or l, m is O or /
It is. ) To explain in more detail, the heterocycle completed by 2 is, for example, quinolinium, benzothiazolium, benzimidazolium, pyridinium, thiazolinium, thiazolium, naphthothiazolium, selenazolium, benzoselenazolium, imidazolium, tetrazolium, Mention may be made of indolenium, pyrrolinium, acridinium, phenanthridinium, inquinolinium, oxacillium, naphthoxacillium and benzoxacillium nuclei. Substituents for Z include alkyl groups, alkenyl groups,
Aralkyl group, aryl group, alkynyl group, hydroxy group, alkoxy group, aryloxy group, halogen atom,
Amine group, alkylthio group, arylthio group, acyloxy group, acylamino group, sulfonyl group, sulfonyloxy group, sulfonylamino group, carbamoyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyan group, ureido group, urethane group, Examples include a carbonate ester group, a drazine group, a hydrazone group, and an imino group. As the substituent for Z, for example, at least seven substituents are selected from the above substituents, but if two or more substituents are used, 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 may be included. In this case, it takes a so-called dimer structure.

The heterocycle completed by Z preferably includes quinolinium, benzothiazolium, (zuimidazolium, pyridinium, acridinium, phenanthridinium, and inquinolinium nucleus. More preferably quinolinium, benzothiazolium , benzimidazolium, preferably quinolinium and benzothiazolium.

The aliphatic groups of R1 and R2 are an unsubstituted alkyl group having /~1♂ carbon atoms and a substituted alkyl group having /-/r carbon atoms in the alkyl moiety. Examples of the substituent include those described as the substituent for Z.

The aromatic group represented by R2 has 6 to 20 carbon atoms, such as phenyl group and naphthyl group. Examples of the substituent include those described as the substituent for Z.

At least one of the groups represented by R1, R2 and Z has an alkyl group, an acyl group, a hydrazine group, or a hydrazine group, or R1 and R2 form a Z-membered ring, and a dihydropyridinium core is formed. However, these may be substituted with the groups described above as substituents for the group represented by Z.

The hydrazine group preferably has a substituent, especially an acyl group or a sulfonyl group.

The hydrazone group preferably has an aliphatic group or an aromatic group as a substituent.

As the acyl group, for example, a formyl group and an aliphatic or aromatic ketone are preferred.

Some of the alkynyl substituents possessed by either R1, R2 or Z have already been described, but to explain in more detail, they preferably have 2 to/g carbon atoms, such as an ethynyl group. , pro/2lugyl group, 2-
Examples thereof include butynyl group, /-methylpropargyl group, /,/-dimethylpropargyl group, 3-butenyl group, and ethynyl group.

Furthermore, these may be substituted with the groups mentioned as substituents for Z. Examples thereof include, for example, a 3-phenylpropargyl group, a 3-methoxycarbonylpropargyl group, a Hiro-methoxyr--y'thinyl group, and the like.

At least seven of the substituents to the groups or rings represented by R1, R2 and Z are preferably alkynyl groups or acyl groups, or R1 and R2 are preferably linked to form a dihydropyridinium core, Furthermore, R1, R2
It is most preferable that at least one alkynyl group is included as a substituent to the group or ring represented by and Z.

Preferred examples of the adsorption promoting group to silver halide represented by Xl include a thioamide group, a mercapto group, or! to 6-membered nitrogen-containing heterocyclic groups.

The thioamide adsorption promoting group represented by Xl is a divalent group represented by -C-amino, and may be a part of a ring structure, or may be an acyclic thioamide group. Useful thioamide adsorption promoting groups are described, for example, in U.S. Pat.
030. 2nd issue, 2nd issue, 03/, /27th issue, 2nd issue, 2nd issue, 2nd issue, 2nd issue, 03/, /27th issue,
No. 010.207, same≠, 2≠J, No. 037, same≠,
2jj, jl1 issue, same≠, 2otsu A, 0/3 issue, and same≠, 27t, 3A≠ issue, and Research Disclosure.
re ) Magazine Vol. 1j/Volume A/Evening/1, 2 (/ri 7th Year//
month), and the same No. 17A Makiya/7 Otsu 2 Otsu (/ri 7r 72
You can choose from those disclosed in May).

Specific examples of acyclic thioamide groups include thiourido groups, thiourethane groups, dithiocarbamate groups, etc., and specific examples of cyclic thioamide groups include ≠-thiazoline-corthion, ≠-imidacilline-2-thione, etc. , lowthiohydantoin, rhodanine, thiobarbic acid, tetrazoline-terthion, /, 2.
≠-triazoline-3-thione, l, 3. ≠-thiadiazoline-2-thione, /, 3. Examples include ≠-oxadiazoline-2-thione, benzimidacillin-2-thione, benzoxazoline-2-thione, and benzothiazoline-corchion, which may be further substituted.

In the mercapto group of Xl, -SH group is directly bonded to the group represented by R1, R2 or Z, and 13H group is bonded to the substituent to the group represented by R1, R2 or Z. , after all, the mercapto group is an aliphatic mercapto group, an aromatic mercapto group, or a heterocyclic mercapto group (-8
If the carbon atom to which the H group is bonded is adjacent to a nitrogen atom, the number is the same as the number of cyclic thioamide groups that have a tautomeric relationship with this, and the specific examples of this group are the same as those listed above.) can be mentioned.

Represented by Xl! The 6-membered nitrogen-containing heterocyclic group consists of a combination of nitrogen, oxygen, sulfur, and carbon! Examples include negative to 6-membered nitrogen-containing heterocycles. Among these, preferred are benzotriazole, triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, triazine, and the like.・
These may be further substituted with a suitable substituent.

Examples of the substituent include those described as the substituent for Z. More preferred nitrogen-containing heterocycles are benzotriazole, triazole, tetrazole, and indazole, and most preferred is benzotriazole.

The divalent linking group represented by Ll includes C1N, S,
It is an atom or atomic group containing at least seven types of O.

Specifically, for example, alkylene group, alkenylene group, alkynylene group, arylene group, -0-1-S-1-NH
-1-N=, -CO-1so2 (these groups may have a substituent), etc. alone or in combination.

The counterion Y for charge balance may be any anion capable of canceling the positive charge generated by the quaternary ammonium salt in the heterocycle, such as bromide ion, chloride ion,
These include iodide ion, p-toluenesulfonate ion, ethylsulfonate ion, perchlorate ion, trifluoromethanesulfonate ion, and thiocyanate ion. In this case, n is /. When the heterocyclic quaternary ammonium salt contains an anionic substituent such as a sulfoalkyl substituent,
The salt can be in the form of a betaine, in which case no counterion is required and n is O. When the heterocyclic quaternary ammonium salt has two anionic substituents, e.g. two sulfonalkyl groups, Y is a cationic counterion, e.g. an alkali metal ion (sodium ion, potassium ion, etc.). ) and ammonium salts (triethylammonium, etc.).

Specific examples of the compound represented by the general formula [:N-1] are listed below, but the invention is not limited thereto.

(,'H2Cai, (,H ((31C2H5 CH2C; CH (lta C2I(5 α9S CII) S
Connecting λ, patents cited in 63≠ (IP published July 13, !O~! daytime page) and US Patent No.≠.

It can be synthesized by the method described in No. 177/, θHiromu, etc., or similar methods thereof.

Note that the general formula [N-1] used in the present invention
It is particularly preferable that the nucleating agent represented by (1) to (7) below takes the form shown below, with the case (7) being the most preferable.

When (1) is used as a substituent and has an adsorption promoting fund to silver halide represented by X.

(2) In (11) above, the adsorption promoting group to silver halide represented by Xi is composed of a thioamide group, a heterocyclic mercapto group, or a nitrogen-containing heterocycle that forms iminosilver.

(3) In the case where the above-mentioned 121 K k is a heterocyclic ring completed by Z, it is quinolinium, inquiturium, naphtopyridinium, or benzothiazolium.

(4) In the above +211c, the heterocycle completed by 2 is quinolinium.

(5) When the above +21E%-ite, R, R or ZCI has an alkynyl group as a substituent.

(6) In the above (5), when R is a propargyl group.

(7) In (2) above, the thioamide group in %X is a thiourethane group, and the heterocyclic mercapto group in -aX is a mercaptotetrazole.

(8) In the above (6), when R1 is combined with n heterocycle completed by Z to form a complete ring.

General formula [N-II] R'' , represents an ail group, an alkoxy group, an aryloxy group, or a haamine group;
G represents a carbonyl group, a sulfonyl group, a sulfokyl group, a phosphoryl group, or an iminomedelene group (HN=c-); R and R24 are both hydrogen atoms, or one is a hydrogen atom and the other is a furkylsulfonyl group, an aryl Represents either a sulfonyl group or an acyl group. Ratio G
, R23, R''b and hydrazine nitrogen may form a hydrazone structure (,=N-N==C; )'r.The groups mentioned above may be substituted with a substituent if possible. ) In the general formula [N-n)IC, the aliphatic group represented by R21 is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by R21 is a monocyclic or cocyclic aryl group, such as a phenyl group or a naphthyl group.

The heterocycle for R21 is a 3 to 1 O membered saturated or unsaturated heterocycle containing at least one of N, 0, or S atoms, and these may be monocyclic,
Furthermore, the entire ring fused with another aromatic ring or heterocycle may be released. Preferably as a heterocycle! to 6-membered aromatic heterocyclic group, such as a pyridyl group, a quinolinyl group, an imidazolyl group, a benzimidazolyl group, and the like.

R21 may be substituted with a substituent. Examples of the substituent include the following. These groups may be further substituted.

For example, an alkyl group, an aralkyl group, an alkoxy group, an alkyl or aryl group, or an amino group.

Acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group,
These include halogen atoms, cyano groups, sulfo groups, and carboxyl groups.

These groups may be linked to each other to form a ring when possible.

R21 is preferably an aromatic group, an aromatic heterocycle or an aryl-substituted methyl group, and more preferably an aryl group.

Among the groups represented by R22, when G is a carbonyl group, preferred are a hydrogen atom, an alkyl group' (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamide zorobyl group). base, etc.)
, aralkyl group (e.g. 〇-hydroxybenzyl group, etc.), aryl group (e.g. phenyl ts, s+z-dichlorophenyl group, 0-methanesulfonamidophenyl group)
≠-methanesulfonylphenyl group, etc.), and a hydrogen atom is particularly preferred.

When 2G is a sulfonyl group, R22 is an alkyl group (for example, a methyl group, an aralkyl group (for example, 0-hydroxyphenylmethyl group), an aryl group (for example, a phenyl group), or a substituted amino group (for example, dimethylamino group). etc.) are preferred.

As the substituent for R22, in addition to the substituents listed for R, for example, an acyl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group, a nitro group, etc. can be applied.

These substituents may be further substituted with these substituents. Further, if possible, these groups may be linked to each other to form a ring.

Among R or R1, R21 preferably contains a diffusion-resistant group such as a coupler, a so-called ballast group. How many carbon atoms does this palust group have? In the above, alkyl group, phenyl group,
It consists of a combination of one or more of an ether group, an amide group, a ureido group, a urethane group, a sulfonamide group, a thioether group, etc.

R21 or 122 may have all of the groups X+L+M2 that promote adsorption of the compound represented by the general formula [N-It, 1 to the surface of the silver halide grains.

Here, X2 has the same meaning as X1 in the above general formula [N-1], and is preferably a thioamide group (excluding thiosemicarbazide and its substituted products)% mercapto group. to 6-membered nitrogen-containing heterocyclic group. L2 represents a bivalent consolidated fund and has the same meaning as L in the general formula [N-1] above. m2 is O or l.

More preferably, X is a cyclic thioamide group (i.e., a mercapto-substituted nitrogen-containing heterocycle, such as λ-mercaptothiadiazole group, 3-mercapto-l, 2.≠-triazole group, !-mercaptotetrazole group, comercapto-1. J, a Hiro-oxadiazole group, a comelcaptobenzoxazole group, etc., or a nitrogen-containing heterocyclic group (for example, a benzotriazole group, a benzimidazole group, an indazole group, etc.).

123 and 124 are most preferably hydrogen atoms.

G in the general formula [N-It) is most preferably a carbonyl group.

As the general formula [N-U], those having an adsorption fund to silver halogenide are more preferable. Particularly preferred adsorption groups on silver halide are the mercapto group, cyclic thioamide group, and ureido group mentioned in the above general formula [N-I].

Specific examples of the compound represented by the general formula [N-II] are shown below. However, the present invention is not limited to the following compounds.

n SI ( - (II) Cr2H25NHNHCH O The method for synthesizing the compound represented by the general formula [N-II) used in the present invention is described, for example, in Research Disclosure magazine/! , / Otsu 2 (II, 1976, pages 76-77), Koko, 63 Hiromu (July, 1976, pages 76-77), and Otsu 23,! 10 (19&'3/I month 3≠
6-332) and U.S. Patent No. ≠,
No. 810.207, same No. ≠.

26 de, ri 2 hiro issue, same number ≠, 2 pro, 3 otsu ≠ issue.

Same @ ≠, 271.7μ issue, same issue ≠, Jlr! , 10
r issue, Hiromu Dodai, It! 9. j≠7, μ, ≠71,
? λ No., same No. Hiroshi,! No. 60.631, British Patent No. 2.
oii, 1riB issue, and JP-A-60-/7F, 73
You can refer to Hirogo etc.

It is particularly preferable that the nucleating agent represented by the general formula [N-II] take the forms shown in (1) to (7) below, and the form shown in +71 is most preferable.

When (1) is substituted with a group that promotes adsorption to silver halide represented by X2.

(2) In the case where the adsorption promoting group to silver halide represented by X2 in (1) above is a heterocyclic mercapto group or a nitrogen-containing heterocycle forming imino silver.

(3) In the above (2), when the group represented by G R22 is a formyl group.

(4) In the above (3), when R23 and R24 are hydrogen atoms.

+s+ In (3), when R21 is an aromatic group.

(6) In the above (3), when R carries a ureido group as a substituent.

(7) In (2) above, the heterocyclic mercapto group represented by n is! -Merkabutoteruzole or! -Mercapto7. If λ, ≠-triazole.

The nucleating agents represented by the general formulas (II) to (Vt) according to the present invention are the nucleating agents represented by the general formula [N-1] and the nucleating agents represented by the general formula [N-n) t'L % and is preferably used in combination with a nucleating agent having a mercapto group, a cyclic thioamide group, or a nitrogen-containing heterocyclic group as an adsorption group on silver halide.

To further enhance the effects of the nucleation accelerator according to the present invention, all of the following compounds can be used in combination with the nucleation accelerators represented by the above general formulas (1) to (VI).

Hydroquinones (e.g. U.S. Patent J, J27.5
1λ, Hiroshi, 27? , Compounds described in Rit No. 7); Chromans (7t, for example, described in U.S. Patent≠, Coro 1r, No. 6.?/No. 6, JP-A No. 10303/1997, Research Disclosure No. 1126j (/P7 9) ); Quinones (for example, the compounds described in Research Disclosure No. 2/207. (1911)); Amines (for example, the compounds described in U.S. Pat. ):
Oxidizing agents (for example, JP-A No. 2Q-2400J, Research Disclosure/No. 6931 (IQ7R))
described compounds); catechols (for example, JP-A-66
210/J issue or J'j-4j? ≠μ, compounds described): Compounds that release nucleating agents during development (e.g. compounds described in JP-A-107029); ureas described in 2 (e.g. compounds described in JP-A-60-95333); Bisindanes (for example, the compounds described in JP-A-Sho!!;-1.69 Hiromu).

A variety of color couplers can be used to form direct positive color images. Useful color couplers are
A compound that generates or releases a substantially non-diffusible dye through a coupling reaction with an oxidized form of a p-phenylenediamine color developer. Typical examples of useful color couplers include:
These include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds and open-chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers used in the present invention can be found in Research Disclosure Magazine &l7A4
LJ (/971/February issue) ■-ri section and same &/1
It is described in the patent cited in No. 717 (issued in February 2007).

Among them, typical yellow couplers that can be used in the present invention include oxygen atom elimination type and nitrogen atom elimination type yellow m=equivalent couplers. Especially α−
Piparoylacetanilide couplers are preferable because they have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Further, as a pyrazolone magenta coupler that can be preferably used in the present invention, the 3-position is substituted with an arylamino group or an acylamino group! - Pyrazolone couplers (especially sulfur atom-eliminating two-equivalent couplers).

More preferred are pyrazoloazole couplers: Pyrazolo C!, especially as described in U.S. Pat. No. 3,723,01,7. +/c) C/r'+Hiro] triazoles, etc. are preferred, but from the viewpoint of low yellow side absorption of the coloring dye and light fastness, U.S. Patent No. 1I,
Imidazo [/.

[lambda]-b] Pyrazole C is even more preferable, and pyrazole C as described in U.S. Pat.
/, t-b) I:/ν2?・≠]Triazole is particularly preferred. “Cyan couplers that can be preferably used in the present invention include:
A phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group at the meta position of the phenol nucleus described in US Patent J, 77u, 002, and others 2. ! -Diacylamino intercalated phenolic couplers are also preferred from the viewpoint of color image fastness.

Also, U.S. Patent No. 2,474,293, U.S. Pat.
．． The use of toll-based and phenol-based couplers described in No. 212 and the like are also preferred in terms of hue, coupling activity, and color image fastness.

Colored couplers to correct unnecessary absorption in the short wavelength range of the dyes produced, couplers in which coloring dyes have appropriate diffusivity, non-coloring couplers, and DIR couplers that release development inhibitors along with coupling reactions. Alternatively, couplers that release development accelerators or polymerized couplers can also be used.

The standard usage amount of color couplers is in the range of 1 mole of photosensitive silver halide to 1 mole, preferably o, oi to 0 for yellow couplers.
11 mole, 0.003 to O for magenta coupler,
J mole, and cyan coupler: C is 0.002 to 0
, J%#T6ru.

The light-sensitive materials produced using the present invention may contain hydroquinone derivatives, amine phenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamide phenols as color antifogging agents or color mixing inhibitors. It may also contain derivatives and the like.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
Hindered phenols, mainly 6-hydroxychromans, t-hydroxycoumarans, Spirochroman M, p-alkoxyphenols, and bisphenols,
Typical examples include gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the heptaenolic hydroxyl group of each of these compounds. In addition, (bissalicylaldoximad) nickel complexes and (bis-N,N-dialkyldithiocarbamad) nickel complexes are representative of the yellow dye image due to heat, humidity, and light. To prevent deterioration,
Compounds having fractional structures of hindered amine and hindered phenol in the same molecule, such as those described in US Pat. No. 44,261,393, give good results. In order to completely prevent the deterioration of magenta dye images, especially the deterioration caused by light, spiroindanes described in JP-A-JA-/J96≠Hiroshi and JP-A-KOKAI Sho! ! The hydroquinone diether or monoether-substituted chromans described in No. -r-t3j give preferable results. These compounds are usually for their corresponding color couplers! The purpose can be achieved by emulsifying the S decoupler and adding it to the photosensitive layer. In order to prevent cyan dye images from being degraded by heat and especially light,
It is effective to introduce all the ultraviolet absorbers into the layers on both sides adjacent to the cyan coloring layer. Further, an ultraviolet absorber can also be added to a hydrophilic colloid layer such as a protective layer.

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

The photosensitive material of the present invention includes dyes that prevent irradiation and halation, ultraviolet absorbers, plasticizers, fluorescent brighteners, matting agents, air fog preventive agents, coating aids, hardeners, and antistatic agents. It is possible to add a slip property improver, etc. Representative examples of these additives are listed in Research Disclosure Magazine &
/ 71-Ko 3 (published February 1997r) and the same /
It is described in lr7/l (published in January 2017).

The present invention provides at least two different spectral sensitivities t on a support.
- It can also be applied to multi-layer, multi-color photographic materials.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one 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 the red sensitivity, °
Sensitive to green, sensitive to blue, or sensitive to blue, red, and green from the support side. Further, each of the emulsions 1 may be made up of two or more emulsion layers having different sensitivities, or a non-photosensitive layer may be present between two or more emulsions 1- having the same sensitivity. The red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains an i10-forming coupler.
- Although it is usual to include each type of coupler, different combinations can be used depending on the case.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to provide an auxiliary layer such as a pack layer or a white reflective layer as appropriate.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic materials. be done. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (eg, polyethylene, polypropylene, ethylene/butene copolymers), etc., coated or laminated paper, etc.

The support may be colored with a dye or pigment all around it.

It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion to photographic emulsion layers and the like. The support surface is coated before or after priming.
Glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. may also be applied.

Various known coating methods such as dip coating, roller coating, curtain coating, and extrusion coating can be used to coat the silver halide photographic emulsion layer and other hydrophilic colloid layers.

The present invention can be applied to various color photosensitive materials.

For example, representative examples include color reversal films for slides or TVs, and color reversal hoverers. It can also be applied to full-color copying machines and color code copies for saving all images on CRTs. The present invention can also be applied to black-and-white light-sensitive materials using a mixture of three color couplers, as described in Research Disclosure, published July 23, 2007.

The color developing solution used in the development of the light-sensitive material of the present invention is a so-called surface developer that does not substantially contain a silver halide solvent, and contains p-phenylenediamine color developing agent as its main component. (It is an alkaline aqueous solution of 11.
It is meant that some amount of silver halide solvent may be included as long as it does not impede the purpose of the invention. A typical example of the p-phinidine diamine compound is 3-methyl-Hiro-amino-N.

N-diethylaniline, 3-methyl-Hiro-amino-N-
Ethyl-N-β-hydroxylethylaniline, 3-methyl-≠-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-≠-amino-N
-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates or fl p -)
Luenesulfonate, Tetraphenylborate, p-(
Examples include t-octyl)benzenesulfonate. These diamines are generally more stable in their salt form than in their free state.

Color developing agents are generally used in amounts of about 0.0.0% per color developer/l.
/? - a concentration of about 309, more preferably a color developer/
It is used at a concentration of about iy - about /j per liter.

Further, the amount of replenishment of the color developer can be completely reduced by using a replenisher in which the concentration of rogens, color developing agents, etc. is adjusted.

The color development processing time of the present invention is usually j minutes or less, but in order to speed up the processing, it is preferable to carry out the color development processing in a processing time of 2 minutes 30 seconds or less. Further, the time is preferably 70 seconds to λ minutes, and the shorter the time, the better, as long as sufficient color density can be obtained.

In order to prevent pollution, facilitate preparation of the developer, and improve storage stability, it is preferable that the color developer does not substantially contain benzyl alcohol. The term "substantially free" means an indyl alcohol concentration of 2 at/l or less, preferably 0.1 ml/l or less, and most preferably no benzyl alcohol at all.

The silver halide color light-sensitive material of the present invention may contain a color developing agent or a precursor thereof for the purpose of simplifying and speeding up processing. Precursors are preferable for inclusion in the light-sensitive material because they increase the stability of the photosensitive material. Specific examples of the developer breaker include indoaniline compounds, thick base compounds, aldol compounds, and urethane compounds.

The silver halide color light-sensitive material of the present invention may contain various l-phenyl-3-pyrazolidones in order to promote color development.

The color developing solution of the present invention includes patent application No. 4/-231A1.2.
The pH buffer described on pages 14L to 22 of the specification,
Preservatives and metal chelate compounds can be included. It can also contain halide ions such as bromide ions and iodide ions, and competitive couplers such as citrazic acid.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process using a single bath bleaching constant N (Brix), or may be carried out separately. Furthermore, in order to speed up the processing, a method may be employed in which bleaching is followed by bleach-fixing, or a method in which bleaching and fixing is carried out after fixing. As the bleaching agent used in bleaching or bleach-fixing, iron (III) organic complex salts and persulfates are preferred from the viewpoint of rapid processing and environmental pollution.

Among the organic complex salts of iron(IIl), ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, /,2-diaminopro/ξ-tetraacetic acid, methyliminodiacetic acid, l,3-diaminopropanetetraacetic acid,
Iron complex salt of glycol ether diamine tetraacetic acid is preferred because it has a high bleaching edge.

Preferred persulfates include alkali metal persulfates such as potassium persulfate and sodium persulfate, and ammonium persulfate.

The amount of bleach per liter of bleach solution is 0. /-2 mol is appropriate, the preferred pH range of the bleaching solution is O6 to ♂ in the case of ferric ion complex salt, and the OS% is aminopolcarboxylic acid, aminopolyphosphonic acid, phosphonolytic acid, organic phosphonic acid. In the case of a ferric ion complex salt of an acid, θ is 7.0. In the case of persulfates, a concentration of 0.1-u mol/l and a pH in the range of / to j are preferred.

The fixing agents used for fixing or bleach-fixing are known fixing agents, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid, 3 These are water-soluble silver halide dissolving agents such as thioether compounds such as 2-dithia-/ and I-octanediol and thioureas, and these can be used in combination or in combination.

When fixing or bleach-fixing, the fixing agent concentration is 0.2~
Hiromole/l is desirable. In the Mayu bleach-fixing process,
Ferric ion complex salt f-10,1 per 1 liter of bleach-fix solution
-2 mol, and the fixing agent preferably ranges from 0.2 to .mu.mol.

In addition, the pH of the fixing and bleach-fix solutions is usually G, Q to O, O.
are preferred, and particularly preferred are t, o-, r, and o.

The fixer or bleach-fixer contains preservatives such as sulfites (e.g. sodium sulfite, potassium sulfite, ammonium sulfite), bisulfites, hydroacylamine, hydrazine, in addition to the aforementioned additives that may be added to the bleach solution. , bisulfite adducts of aldehyde compounds (for example, acetaldehyde sodium bisulfite), etc. can be included. Furthermore, various fluorescent brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, methanol, and other solvents can be used as goldstone.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of bleaching accelerators for bleaching include mercapto group or f
Examples of c include compounds having a disulfide group tV, thiazolidine derivatives, thiourea derivatives, iodides, polyethylene oxides, polyamines, etc., and in addition, JP-A No. 2003-120001, JP-A No. ≠ issue, same j3
- Tahiro Taco No. 7, same≠-j t717, same J-j-
24yo06 and the same! The compounds described in ♂-/63 Rihiro O and iodine and bromine ions can also be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred in US Pat. No. 3, Ir. ? ! r, West German Patent No. 1. Kota O1! Compounds described in No. r/2 and JP-A-53-23630 are preferred. Furthermore, U.S. Patent No. ≠,! ! Compounds described in No. 2゜r3≠ are also preferred. These bleach accelerators may be added to the photosensitive material.

After the fixing step fc, ti bleach-fixing step, treatment steps such as washing with water and stabilization are generally performed.

In the washing process and the stabilization process, various known compounds may be added for the purpose of preventing precipitation and stabilizing the washing water. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid, bactericidal agents and anti-inflammatory agents that completely prevent the growth of various bacteria, algae, and molds (for example, "Journal of Antibacterial and・Anti 7 Jungar Ageen (J, Ant 1bact,
Ant i fung.

Agents) Jvol, / /, &! , p 20
7-2 J An ammonium salt, a surfactant for preventing drying load and unevenness, etc. can be added as necessary. Or West's ``Photographic Science and Engineering Link Magazine (Photograph).

Sci, Eng-) J + Volume 3, 3ata ~ 3r
It is also possible to add the compounds described in ``Target'' (/91.!) etc. It is particularly effective to add chelating agents, bactericidal agents and anti-piping agents.

In the washing process, it is common to use multi-stage countercurrent washing (for example, a coke tank) of λ class or more to save washing water. In the further VC, a multistage countercurrent stabilization treatment process as described in JP-A-57-♂j≠3 may be performed instead of the water washing process. In addition to the above-mentioned elephant additives, various compounds are added to this stabilizing bath for the purpose of total image stabilization. For example, various buffering agents (e.g. borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia) to adjust the membrane pHk (e.g. pH 3~). Typical examples include monocarboxylic acids, dicarboxylic acids, polycarboxylic acids (all used in combination) and aldehydes such as formalin. Other chelating agents (inorganic phosphoric acid,
(aminopolycarboxylic acid, selvage phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericides, anti-piping agents (thiazole series, inthiazole series, halogenated phenols, sulfanilamide, benzotriazole, etc.), surfactants Various additives may be used, such as a brightening agent, a fluorescent whitening agent, and a metal salt hardener, and two or more compounds having the same or different purposes may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate, etc. as a membrane pHi % adjuster after treatment in order to improve the image storage property.

The washing and stabilization processing time of the present invention varies depending on the type of photosensitive material and processing conditions, but is usually 20 seconds to 10 minutes, preferably 10 seconds to 10 seconds! It's a minute.

It is used in various processing solutions talo'c-to°C in the present invention. A temperature of 33°C or 3r0c is standard, but higher temperatures can be used to accelerate processing and shorten the overall processing time, or conversely, lower temperatures can improve image quality and stability of the processing solution. Can be done.

In order to speed up the process, each processing time can be made shorter than the standard time if necessary and within a reasonable range.

Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition.

Each treatment bath may be provided with heaters, temperature sensors, liquid level sensors, circulation pumps, filters, various floaters, various squeegees, etc., as necessary.

EXAMPLE Emulsions A, B, C and D were prepared in accordance with the present invention.

Emulsion A Aqueous solution of potassium bromide and silver nitrate 10 μm per 1 mole of Af3. Hiro-dimethyl-/3-thiazolidine-corchion was added simultaneously to an aqueous gelatin solution with vigorous stirring at 750C over about 20 minutes to obtain a monodispersed octahedral odor with an average particle size of 0.4 Lμm. Obtained silver emulsion gold. To this emulsion were added 6rn9 sodium thiosulfate and ibiauric acid salt (≠ hydrate) per mole of silver.
Chemical sensitization treatment was performed by heating at c for to minutes.

Using the thus obtained silver bromide particles as cores, further growth was achieved by further treatment for ≠0 minutes in the same precipitation environment as the first time, and finally octahedral monodisperse core/shell bromide with an average particle diameter of 0.7 μm. A silver emulsion was obtained. After washing with water and desalting, sodium thiosulfate and chloroauric acid (Horozysate) were added to this emulsion in amounts of p/j4 per mole of silver, and heated at 6q0C for 60 minutes to perform chemical sensitization treatment, and to remove the internal latent image. Type/-Silver halide emulsion A was obtained.

Emulsion B /l'' kpKBr o, smol, NaC60,2 mol and KIO,00/j mol A mixed solution/l with a concentration of 20 ff of gelatin was added and dissolved, and then 700 ccf of a solution of silver nitrate 1 mol/l was added at 600C. It was added to the mixed solution over 20 minutes, and physical ripening was further performed for 2.0 minutes.

Next, wash with water to remove all water-soluble halides, add 20ff of gelatin, and further add water to 1λoocr.
, vc was prepared. A silver halide emulsion with an average grain size of O, a μm was obtained.

This emulsion was prepared using an aqueous solution of silver nitrate of 5ooa:, 1/1 at 600C, and λ mol/l of chloride)
An aqueous solution of IJ-00ccf was added at the same time to completely precipitate the silver chloride shell, followed by washing with water. Average particle size 0.7
A silver halide emulsion Bt of .mu.m was obtained.

Emulsion C: An aqueous solution of potassium bromide and an aqueous solution of silver nitrate are simultaneously deeply stirred into an aqueous gelatin solution at 0C for 7s, taking approximately 0 minutes, to form a regular octahedral silver bromide emulsion with an average grain size of approximately 00gμ. (core particle). However, in this emulsion... before precipitation of the silver halide grains, 30% of gelatin solution was added to the gelatin aqueous solution.
≠-Dimethyl-7゜3-thiazoline-2-thione was added, the pH was maintained at approximately O during the precipitation process, and the pAg was approximately ♂,
I kept it at 7. The silver bromide grains were mixed with 3.0% sodium thiosulfate per mole of silver. ≠m9 and potassium chloroaurate3. Hirom9
All the chemical sensitization treatments were carried out by adding. The chemically sensitized grains were further allowed to elongate in the same precipitation environment as the core grains were formed, and finally formed into 2μ regular octahedral core/shell silver bromide grains. Further, to this were added iodocarita, t×io' mol/silver mol, and N-vinyl vinyl OIJ ton polymer (weight average molecular weight 31,000) φ, 2×IOf/kf mol to obtain emulsion C.

Emulsion: An aqueous solution of potassium bromide and an aqueous solution of silver nitrate are stirred vigorously into an aqueous gelatin solution containing potassium bromide at 7!0C.
It took about 60 minutes to prepare a silver bromide emulsion by mixing at the same time. Before complete precipitation (before simultaneous mixing) vc,
In an aqueous gelatin solution, as a silver halide solvent, there is a deficiency of 1 mole of silver, 150 m9 of 3, ≠ = dimethyl-! , 3-thiazoline-2-thione and benzimidazole/sfk added. When the precipitation was completed, octahedral silver bromide crystals with a uniform grain size and an average grain size of about 0.2 microns were produced. Next, 1 mole of silver, p-thiosulfate, and 1 mole of silver, potassium chloroaurate, and Hiromi were added to the silver bromide particles and heated at 7!0C for a minute. Chemical sensitization treatment was performed. The inner core silver bromide emulsion chemically sensitized in this way was then simultaneously mixed with each aqueous solution of potassium bromide and silver nitrate for t≠j minutes in the same manner as the first time to form an internal latent image. The core/shell silver bromide emulsion was precipitated, and 1 mol Ag of hydrogen peroxide was added as a precipitation agent, heated at 7!0C for r minutes, and washed with water to form an emulsion with an average grain size of 1.0 microns. Tokutsugu.

Next, to this internal latent image type core/shell silver bromide emulsion were added 6 fc of silver per mole, 0.7 m of Q sodium thiosulfate, and 20 m9 of poly[N-vinylpyrrolidone] per mole of silver.
The particles were heated at °C for up to minutes, and the grain surfaces were chemically sensitized (ripened) to obtain emulsion Di.

Example 1 A coating solution prepared as below was coated with polyethylene onto a double-sided laminated paper support and a color photographic paper shop/
~3/ was created.

[Preparation of coating solution] Add ethyl acetate and solvent <c> to a container containing magenta coupler (a) and color image stability (b)' and dissolve. This solution f10% contains all dobuflubenzenesulfonium. It was emulsified and dispersed in an aqueous solution of 10 tizelatin.

This emulsified dispersion and the core/shell type internal latent image silver halide emulsion A (containing a green-sensitive dye and an irradiation dye) were mixed and dissolved, and gelatin was added to give a density as shown in Table 1. In addition, a nucleating agent (the above-mentioned exemplified compounds to
') @ 9 per mole of silver ≠.

A coating solution was prepared by adding 7×10 −5 mol and the nucleation accelerator listed in Table 1 in an amount of ≠, 7×/, 0′ mol per mol of silver.

This coating liquid was applied onto polyethylene laminate paper. At the same time, an ultraviolet absorbing layer having the composition shown below was coated on this layer, and a protective layer having the composition shown below was further applied thereon.

Ultraviolet absorption layer gelatin 1.60J/ is colloidal silver
0.10 p/m2 Protective layer gelatin 1.33 fj/m" 0.17 f/m" acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) Table 1 Bottom emulsion A of green-sensitive layer Silver amount 0.3 97m2 gelatin magenta coupler (e) ≠, 6 x l0-4m0l/m2
Color image stabilizer (f) 0, /Hiroshi 7/
rrL2 solvent (g) 0 ,≠
λ77m2 nucleating agent (exemplary compound tO) Nucleating accelerator (Table 2) Green-sensitive dye (CH2) 2SO3Na Anti-irradiation dye for green-sensitive emulsion layer /:/,
! Mixture (weight ratio) (g) of l:, z:, z mixture (weight ratio) A green filter was applied to the color photographic paper thus prepared.
(5P-2 manufactured by Fuji Photo Film ■) After applying wedge exposure (1710 seconds, loCMS) throughout, the following processing steps A (color developer 1) H/0, 2), B (
pH of the color developer: 11.2) and C (pH of the color developer:
/2. O) was applied to each sample, and the magenta color image density was measured.

The results obtained are shown in Table 2.

From the results in Table 2, it can be seen that in the system using all the nucleation accelerators according to the present invention, p It can be seen that the maximum magenta color density (Dmax) is unexpectedly increased compared to the system in which the processing step c=2 using a developing solution was performed.On the other hand, in the system that does not use the nucleation accelerator according to the present invention, the processing Compared to the case where Process C is applied, Dmax is significantly lowered when processing step A or Bi is applied, and conversely, the minimum color density (Dmin), which represents the fogging density of a direct positive image, increases markedly. Recognize.

Furthermore, processing step AeM according to the present invention produced fewer re-inversion negative images during high-intensity exposure than processing step B on a page-by-page basis.

Processing step A Color development 3 minutes 30 seconds 336C bleach fixing
≠O seconds 33°C stable ■ 20 seconds 336C ■ 20 seconds 33°C stable ■ 20 seconds 33°C The replenishment method for the stable bath is to replenish the stable bath ■ and guide the overflow liquid from the stable bath ■ to the stable bath ■. A so-called countercurrent replenishment method was adopted in which the overflow liquid from stabilizing bath (1) was introduced into stabilizing bath (2).

[Color developer]

Mother liquor diethylenetriaminepentaacetic acid 2.02 Benzyl alcohol /2. I S'diethylene glycol 3. ≠ 7 Sodium sulfite
2.0? sodium bromide
0.267 hydroxylamine sulfate 2.
tO? Sodium chloride 3.2093
-Methyl-Hiro-Amino-N-Hiro, 2? Ethyl N-(
β-methanesulfonamidoethyl)-aniline potassium carbonate 30.0? Add all the water ioooomep )(/
0,20 pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution]

Mother liquor ammonium thiosulfate Ilo? Sodium bisulfite io y di℃thylenetriaminepentaacetic acid j6 Iron (I[l) ammonium heptaate /hydrate ethylenediaminetetraacetic acid 2! ? Add sodium/dihydrate brine to 1000mlpHg
The pH was adjusted with aqueous ammonia or hydrochloric acid.

[Stabilizing liquid]

Mother liquor l-hydroxyethylidene /, Am1-/,
/' -Diphosphonic acid (60%) Mother liquor Bismuth chloride 0-33? Polyvinylpyrrolidone 0.23? ammonia water
x, zmlml nitriloic acid acetate Na
/, 0? ! -Chloroctyl-Hiroichi isothiazolin-3-one yoQ m9 co-octyl-Hiro-inthiazolin-3-one to m9 Fluorescent brightener (Hiroshi, Hiro'-diaminostilbene series) /, o? Add water ioooomip) (7,!
; Adjust pH with potassium hydroxide or hydrochloric acid.

Processing step Bi was the same as processing step A except that the color development time was adjusted to i/min 30 seconds and the processing solution was adjusted to p) (i11., 2).

Further, processing step C is the same as processing step B except for adjusting the color developer's p size and color Ovc.

Example 2 A full multilayer color photographic paper having the layer structure shown in Table 3 was prepared using a core/shell type internal latent image emulsion BQ on a paper support laminated on both sides with polyethylene.

The coating solution was prepared as follows.

7th layer coating liquid preparation nitrogen coupler (a) / 0?
and color image stabilizer (b)2. 1 ornl of ethyl acetate to Jf
Add and dissolve solvent (C) Hiromlf and dissolve this solution f10% sodium dodecylbenzenesulfonate! TILlt included b
10 mL of an aqueous solution of Tigelatin was emulsified and dispersed. On the other hand, the above-mentioned silver halide emulsion B (containing Ag70f/Kg)
Add the red-sensitive dye shown below to 2.0% per mole of silver halide.
Added 0x10' moles and made it into a red-sensitive emulsion Off
Tsukutsu nine. The emulsified dispersion and emulsion were completely mixed and dissolved, and the concentration was adjusted with gelatin so that the composition shown in Table 3 was obtained, and the nucleating agent (exemplary compound 55) was added to EXlo per mole of Ag.
A coating solution for the first layer was prepared by adding 7 x 10 moles of the nucleation accelerator tAg1 per mole of Ag as shown in the table above.

The coating solutions for the second to seventh layers are also prepared in the same manner as the first layer coating solution. l-oxy-3 as gelatin hardening agent in each layer
, j-dichloro-s-) riazine sodium salt was used.

The following spectral sensitizers were used in each emulsion.

In the third layer, the magenta coupler (e), the color image stabilizer (f), the solvent (g), the green-sensitive sensitizing dye, and the anti-irradiation dye described in Example 1 were used. is the same as Other additives are as follows: p0 back-sensitive emulsion layer; anti-irradiation dyes for red-sensitive emulsion layer: the following dyes:

Red-sensitive emulsion layer: The structural formulas of the compounds used in this example, such as couplers, are as follows.

(1) Color image stabilizer (II) Ultraviolet absorber (1) Color mixing inhibitor 0) Solvent (T-T) Solvent (is o CgHl g O+VP=0(a)
Cyan coupler (b) Color image stabilizer (c) Solvent (d) Color mixture inhibitor After adjusting the coating liquids of the 1st to 7th layers to balance the surface tension and viscosity, apply them simultaneously to form a full multilayer color photographic paper. I made a mistake.

Color photographic paper shop obtained in this way /~/! All samples were exposed and developed under the same conditions as in Example 1.

The results obtained for magenta colored images are shown in Table ≠.

As is clear from the results in Table 1, the same effect as that obtained in Example 1 was obtained in the full multilayer color photographic paper system coated on the red-sensitive emulsion layer, green-sensitive emulsion layer, and blue-sensitive emulsion layer. I know what I'm getting.

Example 3 Sample Ya/~/3 was prepared with the same formulation and layer structure as the full multilayer color photographic paper of Example 2, except for the following changes.

Changes (1) Internal latent image emulsion: Emulsion C (2)
) Nucleating agent: Exemplary compound 3'X,
10 mol/Ag mol (3) Nucleation accelerator...Table 5 (4) 3rd
Layer (green-sensing layer)...Main composition as shown below
Usage amount Emulsion C silver 0. /7g/m2 Gelatin / , ! A g/m
2 magenta coupler (C) 3.31rxlO-4
mol/m2 color image stabilizer (f) O
, tyg/m2 Nucleating agent and nucleating accelerator solvent (g) o, more than 27 m2 (5) Yellow coupler (k)...
... The following compound (6) cyan coupler (a
) ・・・・・・(e) Magenta coupler (f) Color image stabilizer (g) Solvent λ:/mixture (weight ratio) (k) Yellow coupler α l:l mixture (molar ratio) Like this The color photographic paper A/=/3 obtained in Example 1 was subjected to wedge exposure through a red filter, followed by the same processing steps A and C as in Example 1 (however, color development was performed for 3♂'C for 2 minutes and 3 times, respectively). 001 minutes), and the cyan color image density was measured. All the results obtained are shown in Table 5.

Table 5 As is clear from the results in Table 5, the cyan color image density was also pH 7o compared to the case of processing step C using a pH/2.0 color developer.

It can be seen that the effect of the nucleation accelerator is significantly greater in the case of processing step A using the color developing solution.

Example 4 Changes (1) Internal latent image type emulsion... The above emulsion D (2) Nucleation accelerator... Added 93 x 10-6 per liter to the color developing solution (3 ) Nucleating agent... Said exemplary compound 6! After applying wedge exposure to the color photographic paper thus obtained through a green filter, the same processing step B(!:C) as in Example 1 was carried out (however, each development was carried out at 35oC for 2 minutes and 30 minutes).
) to measure the magenta color image density.

The results obtained are shown in Table 6.

As is clear from the results in Table 1, processing step B according to the present invention (pH of the color developer is /1.! or less) is more effective than comparative processing step C (pH of the color developer is /1.! or less). 2)km
It can be seen that the maximum color density (Dmax) is higher than that in the case where the nucleation accelerator has a large effect. In addition, it is better to add the nucleation accelerator to the color developing solution than to add it directly to the photosensitive material.
In) was observed to be large.

Example 5 Nucleation accelerator f: A full multilayer color photographic paper was prepared in the same manner as in Example 2, except for the changes shown in Table 7.

The resulting oak photographic paper A/-/≠ was exposed to light under the same conditions as in Example 1, and developed in step At/C.

Table 7 shows the results obtained for magenta colored images.

Table 7 As is clear from the results in Table 7, it can be seen that the same effect as n obtained in Example λ can be obtained.

Example 6 Preparation of Emulsion E An aqueous solution of potassium bromide and an aqueous solution of silver nitrate 0.3 t per mole of 3. ≠-Dimethyl-7゜3-thiazoline-corchion was added to the gelatin aqueous solution with vigorous stirring at 750C for about 20 minutes, and the mixture was added to form monodispersed octahedral particles with an average particle size of 0.4 μm. A silver bromide emulsion was obtained. To this emulsion were added sodium thiosulfate and chlorauric acid (≠ water [) t-t- each per mole of silver, and to
Chemical sensitization treatment was performed by heating for minutes. In this way, the special silver bromide grains are used as cores and further grown by further treatment for ≠0 minutes in the same precipitation environment as the first time, and finally the octahedral monodisperse core/shell silver bromide grains have an average grain size of 0.7 μm. An emulsion was obtained.

After washing with water and desalting, this emulsion was mixed with 1 liter per mole of silver.

zmy amounts of sodium thianoate and chloroauric acid (≠
A chemical sensitization treatment was carried out by heating for 60 minutes (water weir) for 60 minutes to obtain an internal latent image type silver halide emulsion Et-. The particle size distribution factor was 10%.

[Preparation of coating solution]

A full multilayer color photographic paper having the structure shown in Table 1 was prepared by laminating both sides with polyethylene using a core/shell type internal M(VI emulsion) on a T paper support.

Prepare the coating solution as follows.

Preparation of first layer coating solution: nitrogen coupler (p)/Or and color image stabilizer (b)2. Add 10 ethyl acetate and solvent (c) Hirogo to jt and dissolve it, and this solution contains 10 sodium tidetecylbenzenesulfonate (jrrtlf) / 0
It was emulsified and dispersed in Oml of an aqueous solution of chigelatin. On the other hand, the following red-sensitive dye was added to the silver halide emulsion (containing 70 t/Kg of Ag) per t mole of silver halide, o''x
, io mol was added to make a red-sensitive emulsion and 90ff of the red-sensitive emulsion was prepared. Mix and dissolve the emulsified dispersion, emulsion, and development accelerator (q), adjust the concentration with gelatin so that it has the composition shown in Table 1, add nucleating agent + 20 kl, jX/0
mol/Ag mol, as shown in Table 3, with various changes in the nucleation accelerator.

oy, io mol/Ag mol was added to prepare a first layer bag cloth liquid.

The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution so as to have the compositions shown in Table 1.

As a gelatin hardener in each layer /-oxo-3,! -Dichloros-triazine sodium 111E'r was used.

The spectral sensitizer and ylang ion preventing dye used in each emulsion were those used in Examples 1 and 2 above.

Additives different from the additives used in the above examples/and
p), (q), (r), rs), (t), (u),
The entire structural formula of and (v) is shown below.

(p) l:l mixture (molar ratio) of 7 uncouplers (q) Development accelerator (r) Magenta coupler C3H17 (t) (s) Color image stabilizer (1) Solvent (u) Yellow coupler l In this way The color photographic paper prepared was subjected to wedge exposure (//I 0 seconds, 10 cMs), and after t, the following processing steps A, B, and C were performed, and the magenta color image density was measured.

The results obtained are shown in Table 2.

Processing step A Time Temperature color development 1 minute 10 seconds 37°C bleach fixing
≠θ seconds 37°C stable ■ 2θ seconds
Stable at 37°C ■ 20 seconds The replenishment method for the 37°C stable bath is to replenish the stable bath ■, lead the overflow liquid from the stable bath ■ to the stable bath ■, and lead all 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 λ, 01 benzyl alcohol /2. IP diethylene glycol 7.44? sodium sulfite
Ko, 0? sodium bromide
Q.λ6? Hydroxylamine sulfate 2.
lrO? Sodium chloride 3.20f
f3-methyl-μm amino-N-Hiroshi, co! ? Ethyl-N
-(β-methanesulfonamidoethyl)-aniline potassium carbonate! 0.0? Add water 1000100OH1o
, λ0 p)1 was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution]

Mother liquor ammonium thiosulfate Ilo? Sodium bisulfite /θ 1 diethylenetriaminepentaacetic acid j6 f iron acid ulI) ammonium l hydrate ethylenediaminetetraacetic acid co j1 sodium l
Water salt l-mercapto-/, j, 0. ! r r
≠-Add triazole water 1ooo door lpu
t<, tpH was adjusted with aqueous ammonia or hydrochloric acid.

[Stabilizing liquid]

Mother liquor/-hydroxyethylidene/, 6m1-/,/
' -diphosphonic acid (toti) bismuth monochloride 0. j! ? Polyvinylpyrrolidone θ,! ! ? ammonia water
λ, jml nitrilotriacetic acid/JNa
/, 0? j-Chloroctyl-Hiroichi Inchianoline-3-one jOrn9 Co-octyl-Hiro-Isothiazoline-3-one! Q ■ Fluorescent whitening agent (≠, ≠' - Shea water / 70 + 1ooo p)
i7. JPO was prepared using potassium hydroxide or salt.

Processing step C: Same as A except that the total pH of the color developer was adjusted to 11.0.

Processing step C: pE of color developer (same as A except that it was set to total/2.0.

Samples A/-/J containing the nucleation accelerator gold of the present invention are:
Compared to additive-free A/4L, in processing steps A and H, the maximum image density (Dmax) was significantly higher and the minimum image density (Dmin) was lower, showing favorable photographic characteristics. A/-/3 showed the surprising effect that Dmax was higher in A%B with lower p)l than in treatment step C at pH/2.0. On the other hand, in Alg of the comparative example, VcDmax decreased as the pH decreased.

Furthermore, cyan and yellow! When similar measurements were made for I change, similar trends were shown.

Example 7 Constituent sound of the third layer @IO As shown in the table, nucleating agent (exemplified compound j4/L) Kanehiro, 0x10 mol 1 mol A
g, Nucleation accelerator gold No. 11, with various changes as shown in 3.
．． Color photographic paper A/~r'5 (rxio) was prepared in the same manner as in Example 6 except that 1 mol of Ag was added and the yellow coupler was changed to Qc).

It was exposed and processed in the same manner as in Example 6, and a positive color image was obtained and the magenta density was totally measured, and the results are shown in Table ii.

It can be seen that the same results as in Example 6 were obtained.

Also when measuring cyan and yellow degrees.

Similar results were obtained.

Example? The cyan coupler was changed to the following, the nucleating agent (exemplary compound II) was μ, /×10 mol/Ag mol, and the nucleation accelerator was 1.!×10 mol/A g mol as shown in the table. Color photographic paper was prepared in the same manner as in Examples ≦ with the exception of various additions and additions.Exposure and processing were carried out in the same manner as in Example 6 to obtain positive color images.

The cyan concentration was measured and all the results are shown in Table 1.

Similar results to Examples 6 and 7 were obtained. Similar results were obtained when measuring magenta and yellow degrees.

Example? Nucleating agent (exemplified compound 26) k! ,! x10-6 mol/A
Color photographic paper A/~6 ft was prepared in the same manner as in Example 6 except that g mol was added and the nucleation accelerator was omitted. Exposure was carried out in the same manner as in Example 6, except that the nucleation accelerator f3×10 mol/l was added to the color developing solution as shown in Table 7. The yellow intensity was measured and the results are shown in Table 73.

As is clear from the results in Table 13 above, it can be seen that when the nucleation accelerator is added to the developer, the same effect as when added to the photosensitive material can be obtained.

(Effects of the Invention) 1. According to the present invention, a direct positive color image having a high maximum color density and a low minimum image density can be formed quickly and stably by processing with a low pH color developer. Direct positive color images can be obtained with less generation of re-inverted negative images during high-intensity exposure.

Furthermore, even if the temperature and pH of the color developer vary, the maximum image temperature and minimum image density do not vary from the optimum values, and a direct positive color image can be produced in which the color development property is not easily changed.

Furthermore, even if the color development time 11 changes from the standard time,
It is possible to obtain a direct positive color image in which the maximum image density and minimum image density do not easily vary from the r&normal value, and the brown color reproducibility does not change easily.

Further, the photosensitive material containing all the nucleation accelerators of the present invention has the advantage that the maximum image density is less likely to decrease and the minimum image density is less likely to increase even when stored for a long period of time.

Since the PT of the bulk color developing solution is low, it also has the advantage of being less likely to deteriorate due to air oxidation.

Claims (1)

Scope of Claims: (1) After imagewise exposure of a light-sensitive material having at least one photographic emulsion layer containing internal latent image type silver halide grains and a color image-forming coupler on a support, which have not been previously fogged, In a method of directly forming a positive color image by developing with a surface developer in the presence of a nucleating agent and a p-phenylenediamine color developer, the developing treatment is performed using a nucleating agent and the nucleating action is promoted. A developer having a pH of 11.5 or less is used in the coexistence of a nitrogen-containing heterocyclic compound (nucleation accelerator), and the color coupler itself is substantially non-diffusible and p-phenylene 1. A direct positive color image forming method characterized by a compound that generates or releases a substantially non-diffusible dye upon oxidative coupling with a diamine color developer. (2) The direct positive color image forming method according to claim 1, wherein the pH of the developer is 11.0 or less. (3) Claims (1) or (2), wherein the nucleation accelerator is a compound represented by the following general formula (I):
The direct positive color image forming method described in . General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, Q represents the atomic group necessary to form a 5- or 6-membered heterocycle. The heterocycle may also be fused with a carbon aromatic ring or a heteroaromatic ring. M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group that cleaves under alkaline conditions. (4) Claims (1) or (2), wherein the nucleation accelerator is a compound represented by the following general formula (II).
The direct positive color image forming method described in . General formula (II) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, M has the same meaning as that in general formula (I). X represents an oxygen atom, a sulfur atom or a selenium atom. Y is -S-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R^1
, R^2, R^3, R^4, R^5, R^6, R^7 and R^8 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkenyl group or aralkyl group. represent R is a linear or branched alkylene group, a linear or branched alkenylene group, a linear or branched aralkylene group,
Or represents an arylene group. Z is a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted amino group, a quaternary ammonium group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a heterocyclic oxy group, a heterocyclic thio group , sulfonyl group, carbamoyl group, sulfamoyl group, carbonamido group, sulfonamido group, acyloxy group, sulfonyloxy group, ureido group, thioureido group, acyl group, heterocyclic group, oxycarbonyl group, oxysulfonyl group, oxycarbonylamino group Or represents a mercapto group. n represents 0 or 1. (5) Claim (1) or (5) wherein the nucleation promoter is a compound represented by the following general formula (III);
Direct positive color image forming method described in section 2). General formula (III) ▲ Numerical formulas, chemical formulas, tables, etc.
Represents Z. R'' represents a hydrogen atom, an unsubstituted amino group, or a -(Y')_m-R-Z group.Y' has ▲a mathematical formula, a chemical formula, a table, etc.▼, ▲a mathematical formula, a chemical formula, a table, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and m represents 0 or 1. M, R, Z, Y, n, R^1, R^2, R^3, R^4
, R^5, R^6, R^7 and R^8 each have the same meaning as in the general formula (II) above. (6) The direct positive color image forming method according to claim (1) or (2), wherein the nucleation accelerator is a compound represented by the following general formula (IV). General formula (IV) ▲ Numerical formulas, chemical formulas, tables, etc. It has the same meaning as that of general formula (I). (7) The direct positive color image forming method according to claim (1) or (2), wherein the nucleation accelerator is a compound represented by the following general formula (V). General formula (V) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R'' represents a hydrogen atom or a -R-Z group. (8) Claims (1) or (2), wherein the nucleation accelerator is a compound represented by the following general formula (VI).
The direct positive color image forming method described in . General formula (VI) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R'' represents a hydrogen atom or -R-Z group,
R^9 and R^1^0 represent a hydrogen atom, a halogen atom, a substituted or unsubstituted amino group, a nitro group, a substituted or unsubstituted alkyl group, an alkenyl group, an aralkyl group, or an aryl group, respectively. However, M, R and Z
each has the same meaning as each of the above general formula (II). (9) The direct method according to claim (1) or (2), wherein the nucleation accelerator is contained in an internal latent image type silver halide emulsion layer or other hydrophilic colloid layer. Positive color image forming method. (10) Direct positive color image formation according to claim (1) or (2), wherein the nucleating agent is a compound represented by the following general formula [N-I] and/or [N-II]. Method. General formula [N-I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula [N-I], Z represents a group of nonmetallic atoms necessary to form a 5- to 6-membered heterocycle; It may be substituted with a substituent. R^1 is an aliphatic group, and R^2 is a hydrogen atom, an aliphatic group, or an aromatic group. R^1 and R^2 may be substituted with a substituent. However, R^1,
At least one of the groups represented by R^2 and Z contains an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or R^1 and R^2 form a 6-membered ring, and dihydro Forms a pyridinium skeleton. Y is a counter ion for charge balance, and n is 0 or 1. General formula [N-II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In formula [N-II], R^2^1 is an aliphatic group, an aromatic group,
or represents a heterocyclic group: R^2^2 represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group; G represents a carbonyl group, a sulfonyl group, a sulfoxy group, or a phosphoryl group; group or iminomethylene group (▲There are mathematical formulas, chemical formulas, tables, etc.▼): R^2^3 and R^2^4 are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group, Represents either an arylsulfonyl group or an acyl group. However, a hydrazone structure (▲numerical formula, chemical formula, table, etc. available▼) may be formed by including G, R^2^3, R^2^4, and hydrazine nitrogen. ]