JPH0218558A - Direct positive image forming method - Google Patents

Abstract

PURPOSE:To provide the high max. image density and low min. density and to enhance the preservable property of a photosensitive material at and under a high temp. and high humidity by executing a fogging processing in the presence of a specific nucleating agent. CONSTITUTION:The direct positive photosensitive material having a layer contg. internal latent image type silver halide particles which are not previously fogged is subjected to a developing processing after or while said material is subjected to the fogging processing in the presence of the nucleating agent expressed by formula I to form a picture image. In formula, A1, A2 both denote H or one is H and the other is sulfonyl, etc.; R1 denotes an aliphat., arom. group, etc.; G1 denotes carbonyl, sulfonyl, etc.; X1 denotes a group which induces the reaction to form a cyclic structure contg. -G1-X1 atoms by splitting -G1-X1 from the molecule. The compd. expressed by formula II, etc., are usable as the nucleating agent expressed by formula. The combination use of a desired nucleation acceleration agent is possible as well.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides a direct positive photographic light-sensitive material having on a support a layer containing at least one unfogged internal latent image type silver halide grains. Regarding the direct positive image forming method in which development is performed after fogging or while fogging, D
The present invention relates to a direct positive image forming method that provides ax.

(Prior art) A preferred method is to use an internal latent image type silver saponide emulsion that has not been fogged in advance, and to perform surface imaging after image exposure and after fogging treatment, or while performing fogging treatment, to directly obtain a positive image. Are known.

The above-mentioned internal latent image type silver halide photographic emulsion is a type of silver halide photographic emulsion that has photosensitive nuclei mainly inside the silver halide grains and a latent image is mainly formed inside the grains upon exposure. when.

Various techniques are known to date in this technical field. For example, U.S. Pat.
, No. 588,982, No. 3,317,322, No. 3,
No. 761,266, No. 3,761.276, No. 3.7
The main ones are those described in British Patent Box No. 96,577 and the specifications of British Patent Box No. 1,151,363, British Patent Box No. 1.150.553, and British Patent Box No. 1,011,062.

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

” - For details on the formation mechanism of direct positive images, for example,
“The Theory of the Photographic Process J” by T.H. James
of the Photo) (ral+l+
ic Process), 4th edition, Chapter 7, ]82
Pages 193 to 193 and U.S. Pat. No. 3,761,276.

In other words, fog nuclei are selectively generated only on the surface of the silver halide grains in unexposed areas due to the surface desensitization effect caused by the so-called internal latent image created inside the silver halide by the initial imagewise exposure. Next, a photographic image is created directly on the unexposed area by not performing the usual so-called surface development treatment (a direct positive image).
is thought to be formed.

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 "photofogging method" (for example, British Patent Box 1,151,
No. 363) and a nucleating agent (U
A method using the following is known: nlcreating agent). This latter method is discussed, for example, in Research Disclosure (Research D).
1closure) Magazine, Volume 151, No.

15162 (published in November 1976), pages 76-78.

A hydrazine compound is well known as a nucleating agent used in the above-mentioned "chemical fogging method".

In addition, heterocyclic quaternary ammonium salts are known as other nucleating agents, such as U.S. Pat.
759°901, 3,854,956, 4.0
No. 94,683, No. 4,306゜016, British Patent 1
, 283,835, JP-A-52-3,426 and JP-A-52-69,613.

(Problem to be solved by the invention) The above hydrazine nucleating agent generally has a maximum concentration (Dmax).
There is a large difference between
(pH>12).

Nucleating agents that act even at low processing pH (pH≦12) include the above-mentioned heterocyclic quaternary ammonium salts, especially the propargyl- or butynyl-substituted nucleating agents described in U.S. Pat. Heterocyclic quaternary ammoniumuno salt compounds are excellent nucleating agents in terms of discrimination in direct positive silver halide emulsions.

However, when a sensitizing dye is added to the silver halide emulsion for the purpose of spectral sensitization, for example, between the sensitizing dye and the heterocyclic quaternary ammonium nucleating agent, the silver halide emulsion Because competitive adsorption occurs, it is necessary to add a large amount of quaternary base nucleating agents with weak adsorption properties.Especially in the case of multilayer color sensitive materials, uneven density and loss of color balance may occur, and sufficient performance cannot be achieved. It could not be said that it shows.

Note that this tendency tends to increase even more when stored under high temperature conditions.

For the purpose of solving the above problem, U.S. Patent Section 4,471°04
No. 4 reports an example of a quaternary base nucleating agent having a Naoamide AgX adsorption promoting group. Here, it is said that the introduction of adsorption groups reduces the amount added to obtain a sufficient Dmax and improves the reduction in Dmax over time at high temperatures, but this effect was not at a fully satisfactory level.

Accordingly, it is a primary object of the present invention to provide a direct positive imaging method that provides high maximum image densities and low minimum image densities.

A second object of the present invention is to form a direct positive image that is stable even when stored under high temperature and high humidity conditions.

(Means for Solving the Problems) The present invention provides a direct positive photographic light-sensitive material having a layer containing at least one unfogged internal latent image type silver halide grains on a support, and after processing. , or a direct positive image forming method in which development is performed while performing a fogging process, wherein the fogging process is carried out in the presence of a compound represented by the following - Shipman (I). Able to achieve purpose.

- Shipman (I) %Formula% In the formula, A and A2 are both hydrogen atoms, or one is a hydrogen atom and the other is a sulfonyl group or an acyl group, and R1
represents an aliphatic group, an aromatic group, or a heterocyclic group, and G1
is carbonyl group, sulfonyl group, sulfoxy group, -p-
group (R2 represents an alkoxy group or aryloxy group), -C-C- group, or iminomethylene group, x
l splits the 10+X part from the remaining molecule, -G, -X
, is a group that causes a cyclization reaction to produce a cyclic structure containing atoms of the moiety. Here, at least one of R1 or Xl represents a group capable of dissociating into an anion having a Ka of 6 or more, or an amine group.

Hereinafter, the novel hydrazine compound represented by the general formula (I) used in the present invention will be explained in detail.

- In Shipman (I), A2 is a hydrogen atom and has 2 carbon atoms.
Alkylsulfonyl groups and arylsulfonyl groups having 0 or less (preferably phenylsulfonyl groups or phenylsulfonyl groups substituted such that the sum of Hammett's substituent constants is -0.5 or more), acyl groups having 20 or less carbon atoms (
Preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more), or a linear, branched, or cyclic unsubstituted and substituted aliphatic acyl group (substituent For example, a halogen atom,
Examples include ether group, sulfonamide group, carbonamide group, hydroxyl group, carboxy group, and sulfonic acid group. ), and A1. Most preferably, both A 2 are hydrogen atoms.

The aliphatic group represented by R1 is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by R1 is a monocyclic or bicyclic aryl group, such as a phenyl group or a naphthyl group.

The heterocycle for R1 is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of N, O, or S atoms, and these may be monocyclic or other may form a condensed ring with an aromatic ring or a hetero ring. Preferably, the heterocycle is an aromatic heterocyclic group with a ring or 6R, such as a pyridine group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, or a benzthiazolyl group. Preferably.

R4 may be substituted with a substituent. Examples of the substituent include the following. These groups may be further substituted.

For example, alkyl groups, aralkyl groups, alkoxy groups, aryl groups, substituted amine groups, acylamino groups, sulfonylamino groups, ureido groups, urethane groups, aryloxy groups,
Examples include sulfamoyl group, carbamoyl group, aryl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, and carboxyl group.

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

Preferred as R1 is an aromatic group, more preferably an aryl group.

-G1 represents a carbonyl group, a sulfonyl group, a sulfooxy group), a -C-C- group, or an iminomethylene group, and G1 is most preferably a carbonyl group.

Xl is a group represented by the general formula (a), -Funenin (a
) -Z In the formula, Zl is a group that can nucleophilically attack G and split the G, -LZ1 moiety from the remaining molecule, and L is a group that can nucleophilically attack G, and L is a group that
It is a divalent organic group that can make a nucleophilic attack on 1 and generate a cyclic structure with G, L, and Zl. More specifically, when the hydrazine compound of general formula (I) generates the next reaction intermediate by oxidation etc., Zl easily nucleophilically attacks 01 to form R-N=N-G-L-ZR. , -N=N is a group that can be split from G, specifically OH, SH, or NHR, (R is a hydrogen atom,
an alkyl group, an aryl group, a heterocyclic group, C0R4 or -S02R, and R1 is a hydrogen atom, an alkyl group,
aryl group, heterocyclic group, etc.) It may be a functional group that directly reacts with G1, such as C00H (here, OH, S H, NHR3C0OH is temporarily protected so that it can be formed with these groups by hydrolysis with an alkali, etc.). Also ON-R.

Alternatively, reacts with a nucleophile such as a hydroxide ion or a sulfite ion, such as CR5, CR5 (Rs and Re represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group). It may also be a functional group that is capable of reacting with Gl.

The divalent organic group represented by L is an atom or atomic group containing at least one of C, N, and 3.0, and specifically includes, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, Heteroarylene group (these groups may have a substituent) to 〇-, -3-+N(
R? represents a hydrogen atom, an alkyl group, an aryl group)
It consists of N2C〇--SO2-, etc., alone or in combination, and preferably the ring formed by G, , Z, and L is 5 or 6 members.

Among those represented by -shipman (a), preferred are those represented by general formula (b) and -shipman (c).

General formula (b) (CRs Rs )m C- I B , m and n are 0 or 1, (m+1) is 0 or 1 when Z is COOH, and when Z is OH3H, N
For HRs, it is 1 or 2 years old. 5 formed by B
Examples of the six-membered ring include a cyclohexene ring, a cycloheptene ring, a benzene ring, a naphthalene ring, a pyridine ring, and a quinoline ring, and Z has the same meaning as -Funenin (a).

- Of the boatmen (b), preferred ones are In-0, n-1
In particular, the ring formed by B is a benzene ring.

General formula (c) In the formula, R6 to R1+ represent a hydrogen atom, an alkyl group (preferably one having 1 to 12 carbon atoms), an alkenyl group (preferably one having 2 to 12 carbon atoms), or an aryl group (preferably one having 2 to 12 carbon atoms). 6 to 12), and may be the same or different. B is an atomic formula necessary to complete a 5-membered ring or 6-membered ring which may have a substituent, and R, 2, R, 3 are hydrogen atoms, alkyl groups, alkenyl groups, aryl groups, or halogen atoms. etc., and may be the same or different.

R14 represents a hydrogen atom, an alkyl group, an alknyl group, or an aryl group.

~14 p represents 0 or 1, and q does not represent 1-4.

R12, R13 and R1 may be bonded to each other to form a ring, as long as Zl has a structure in which G, /\ can undergo intramolecular nucleophilic attack.

R,2,R, is preferably a hydrogen atom, a halogen atom,
or an alkyl group, and R14 is preferably an alkyl group or an aryl group.

q preferably represents 1 to 3; when q is 1, p represents 1; when q is 2, p represents 0 or 1; when q is 3, p represents 0 or 1; Here, when q is 2 or 3, CRl
2 Rl 3 may be the same or different.

Zl has the same meaning as the general formula (,).

As the substituent for Xl, in addition to the substituents listed for R1, 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 form a ring connected to each other.

R+ or Xl, especially R7, preferably contains a diffusion-resistant group such as a coupler, a so-called ballast group. This ballast group has 8 or more carbon atoms and includes an alkyl group, phenyl group, ether group, amide group, ureido group, urethane group,
It consists of a combination of one or more of sulfonamide groups, thioether groups, etc.

R1 or Xl is a group Yl(
It may have L 2 +1. Here, Y is a group promoting adsorption to silver halide, and R2 is a divalent linking group. l is 0 or 1.

Preferred examples of the adsorption-promoting group to silver halide represented by Yl include a thioamide group, a mercapto group, a group having a disulfide bond, or a 6-membered nitrogen-containing heterocyclic group.

The thioamide adsorption promoting group represented by Y 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.
, No. 030,925, No. 4.031127, No. 4.0
No. 80,207, No. 4,245,037, No. 4.25
No. 5511, No. 4,266.013, and No. 4,27
6.364, and “Research Disclosure” (ResearchbI) 1sc1osure)
Magazine Volume 151, No. 15162 (November 1976)
, and Volume 176 N of the same.

17626 (I, December 978).

Specific examples of acyclic thioamide groups include thiourido groups, thiourethane groups, dithiocarbamate groups, etc. Specific examples of cyclic thioamide groups include 4-deazoline-2-thione, 4-imidacyline-
2-thione, 2-thiohydantoin, rhodanine, thiobarbic acid, tetrazoline-5-thione, 1,2.
4-) Riazoline-3-thione, 1.3.4-thiadiazolin-2-thione, 1,3.4-oxadiazoline 2
-thione, benzimidacillin-2-thione, benzoxazoline-2-thione and hendithiazoline-2-thione, which may be further substituted.

The mercapto group of Yl is an aliphatic mercapto group, an aromatic mercapto group, or a heterocyclic mercapto group (if the carbon atom to which the -SH group is bonded is a nitrogen atom, it can be a cyclic thioamide that has a tautomeric relationship with the nitrogen atom). group, and specific examples of this group are the same as those listed above).

Examples of the 5- or 5- or 6-membered nitrogen-containing heterocyclic group represented by Y include 5- or 6-membered nitrogen-containing heterocycles consisting of a combination of nitrogen, oxygen, sulfur, and carbon. Among these, preferred are benzotriazole, triazole, tetrazole, indazole,
Examples include benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, and triazine. These may be further substituted with a suitable substituent.

Examples of the substituent include those described as the substituent for R3.

Among those represented by Y, preferred are cyclic thioamide groups (i.e. mercapto-substituted nitrogen-containing heterocycles, such as 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group). group, 2-mercapto-1,3,4-oxadiazole group, 2-mercaptobenzoxazole group, etc.)
, or a nitrogen-containing heterocyclic group (eg, benzotriazole group, benzimidazole group, indazole group, etc.). Furthermore, two or more Y +-(-L 2-"i groups may be substituted, and may be the same or different.

The divalent linking group represented by R2 includes C, NS, 0
An atom or atomic group containing at least one of the following. Specifically, for example, alkylene group, alkenylene group, alkynylene group, arylene group, -, -3-, -NH-,
-NR (R: monovalent substituent), -Co-, -302-(
These groups may have a substituent or the like alone or in combination.

As a specific example, for example, C0NH-, -NHCONI( 02NH OO H.C.O.O.O. Examples include.

These may be further substituted with a suitable substituent.

Examples of the substituent include those described as the substituent for R1.

Among the substituents that can be dissociated into an anion with a pKa of 6 or more to be substituted on R1 or
A substituent that dissociates into an anion with a Ka of 8 to 13, and hardly dissociates in a neutral or weakly acidic medium, and does not dissociate in an alkaline aqueous solution such as a developer (preferably pH 10.5 to 1).
23) It does not need to be a specific one as long as it is sufficiently dissociated in the medium.

For example, a hydroxyl group, a group represented by R15S02NH- (
Rls is an alkyl group, an aryl group, a heterocyclic group, and -L
, -Y, (L represents the same as L2 above), etc., and these groups may further have a substituent), mercapto group, hydroxyimimethylene group (for example, C
H2COOC2HsN CH2C0CH5 CHCOOC2Hs, etc.).

Further, the amino group may be primary, secondary, or tertiary, and preferably has a conjugate acid having a pKa of 6.0 or more.

Among those represented by general formula <1>, preferred are those represented by general formula (II).

- Boatman (If) In the formula, R3 is a substituent (specifically the same as the substituent for R in general formula (I)), -(L2+IY1 or the previous p
These are listed as substituents that can dissociate into anions with Ka6 or higher, k is 0.1 or 2, and when k is 2, R
37 may be the same or different. R16 is the same as R5 in general formula (I) or represents +2→-Yl, preferably +L2+lYβ. (Here, R2, Y, 1 have the same meanings as those explained in general formula (I)) G1. Xl, Al and A2 have the same meanings as in general formula (I), more preferably R16S0
The 2NH group is a hydrazino group substituted with a value of 0 or p.

-a Specific examples of the compound represented by formula (I) are shown below.

However, the present invention is not limited to the following compounds.

R3 I-18) = 28 In the non-pre-fogged internal latent image type silver halide emulsion used in the present invention, the surfaces of the silver halide grains are not pre-fogged, and furthermore, the halogenated emulsion forms the latent image mainly inside the grains. It is an emulsion containing silver, and more specifically, a silver halide emulsion is deposited on a transparent support in a fixed amount (05 to 3 g/
+n2) was coated, exposed to light for a fixed time of 0.01 to 10 seconds, and developed in the following developer A (internal type developer) at 18°C for 5 minutes. The maximum density measured is the maximum density obtained when a silver halide emulsion coated in the same amount and exposed in the same manner as above is developed in the following developer B (surface type developer) at 20 ° C. for 6 minutes. Those with a concentration at least 5 times greater are preferred, and more preferably those with a concentration at least 10 times greater.

Internal developer A Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone 8g Soda carbonate (-water salt) 52.5゜KBr
517K I
Add 0.5g water
11 Surface type image solution metol 2.5g L-ascorbic acid 10°N a B Oz ・4 H2035gKBr
111 Add water
11 Specific examples of latent emulsions include U.S. Pat.
Conversion type silver halide emulsion described in US Pat. No. 92,250, US Pat. No. 3,761°276,
No. 3,850,637, No. 3,923,513, No. 4,035゜185, No. 4,395,478, No. 4
, No. 504,570, Japanese Unexamined Patent Publication No. 52156614, No. 5
No. 5-127549, No. 53-60222, No. 562
No. 2681, No. 59-208540, No. 60-107
No. 641, No. 613137, Patent Application No. 1981-32462
Issue, Research Disclosure Magazine No. 23510
(Issued in November 1983) P. 236, a core/shell type silver halide emulsion is mentioned.

The shapes of the silver halide grains used in the present invention include regular crystal shapes such as cubes, octahedrons, dodecahedrons, and tetradecahedrons, irregular crystal shapes such as spherical shapes, and length/ Tabular particles having a thickness ratio of 5 or more may be used. Further, emulsions having multiple forms of these various crystal forms or mixtures thereof may be used.

The composition of silver halide includes silver chloride and silver bromide mixed silver halide, and the silver halide preferably used in the present invention does not contain silver iodide, but even if it contains it, it does not contain salts (
(iodine) silver bromide, (iodine) silver chloride or (iodine) silver bromide.

The average grain size of silver halide grains is 2 μm or less.
．． The diameter is preferably 1 μm or more, and particularly preferably 1 μm or less and 0.15 μm or more. The particle size distribution may be narrow or wide, but in order to improve granularity and sharpness, the number or weight of particles should be within ±40% of the average particle size, preferably within ±20% of the total particle size. % or more, so-called "monodisperse" silver halide emulsions having a narrow grain size distribution are preferably used in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes or multiple types of monodisperse silver halide emulsions with the same size but different sensitivities are used in an emulsion layer having substantially the same color sensitivity. The particles can be mixed in the same layer or coated in separate layers.

Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the grains by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. For detailed specific examples, see Research Disclosure Magazine No. 17643 III (December 1978).
It is in the patent described on page 23 (issued in May).

The photographic emulsion used in the present invention is spectrally sensitized using conventional sensitizing dyes. 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. Further, the above-mentioned strong sensitizers may be used in combination. For a detailed example, see Research Disclosure Magazine N.

17643-IV (issued December 1978) P23-2
It is in the patent described in 4 etc.

The photographic emulsion used in the present invention may contain an antifoggant or a stabilizer for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. For detailed examples, see Research Disclosure Magazine No. 17643.
1V (published December 1978) and E, J, Bir.
Author: 5tat+1liaution of Ph
otograpl+1cSilverHailde
Emulsion” (Focal Press), 1
It is described in publications such as 1974.

A variety of color couplers can be used to form direct positive color images in the present invention. A color coupler is a compound that generates or releases a substantially non-diffusible dye through a coupling reaction with an oxidized form of an aromatic primary amine color developer, and is itself a substantially non-diffusible dye. Preferably, it is a compound. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolones or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta, and yellow couplers that can be used in the present invention are given in "Research Disclosure" magazine No. 17643 (published in December 1978), p. 25.
．． ■-D term, same N.

18717 (issued in November 1979) and patent application 1987
-32462 and the patents cited therein.

Card couplers for correcting unnecessary absorption in the short wavelength range of the generated dyes, couplers whose coloring dyes have appropriate diffusivity, colorless couplers, and DIR couplers that release a development inhibitor upon coupling reaction. or polymerized couplers can also be used.

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

A color antifogging agent or a color mixing inhibitor can be used in the light-sensitive material of the present invention.

Representative examples of these are JP-A-62-215272 No. 185~
It is described on page 193.

A color enhancer can be used in the present invention for the purpose of improving the color development of the coupler. A typical example of a compound is JP-A No. 6
Examples include those described in No. 2-215272, pages 121 to 125.

The photosensitive material of the present invention includes dyes that prevent irradiation and halation, ultraviolet absorbers, plasticizers, optical brighteners, matting agents, antifoggants, coating aids, hardeners, and antistatic agents. It is possible to add a slip property improver, etc. Representative examples of these additives are described in Research Disclosure Magazine No. 17643-xm (published in December 1978), pages 25-27, and 18716 (published in November 1979), pages 647-651.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
7 green-sensitive emulsion layers and 7 blue-sensitive emulsion layers each? Have at least one. The order of these layers can be arbitrarily selected as required. The preferred order of layer arrangement is from the support side to red sensitivity,
Green sensitivity, blue sensitivity, or green sensitivity, red sensitivity, and blue sensitivity from the support side. Further, each of the above emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may exist between two or more emulsion layers having the same color sensitivity. . Usually, 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 a yellow-forming coupler, but different combinations may 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 agent,
It is preferable to appropriately provide auxiliary layers such as a back layer and a white reflective layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are described in Research Disclosure Magazine No.

17643V section (Issued in December 1978) p. 28 and the support described in European Patent No. 0,102,253'1 1982-97655. Also, Research Disclosure Magazine No. 17643
The coating method described in section xV, pages 28 to 29 can be used.

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

For example, typical examples include color reversal film for slides or television, color reversal paper, and instant color film. It can also be applied to full-color copying machines and color hard copies for storing images on CRTs. The present invention also relates to [Research Disclosure] Magazine No. 17123.
It can also be applied to black-and-white light-sensitive materials using a mixture of three color couplers, such as those described in J.D. (published in July 1978).

Furthermore, the present invention can also be applied to black and white photosensitive materials.

Examples of black-and-white (B/W) photographic materials to which the present invention can be applied include JP-A-59-208540 and JP-A-60-260.
B/W direct positive photographic materials described in No. 039 (for example, X-ray photosensitive materials, duplex photosensitive materials, micro photosensitive materials,
In addition, in the present invention, it is preferable to use a nucleation accelerator together with the nucleating agent. The nucleation accelerator has no substantial function as a nucleating agent, but is necessary to promote the action of the nucleating agent to increase the maximum density of the direct positive image and/or to obtain a constant direct positive image density. A substance that works to speed up the development time. As a nucleation accelerator, - Shipman (II) or (I
) is preferably used.

- Boatman (I .

L represents a divalent linking group consisting of an atom or atomic group selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, and R48 represents a thioether group, an amino group, an ammonium group, an ether group, or Represents an organic group containing at least one telocyclic group.

n represents 0 or 1, and the sheath represents 0, 1 or 2.

M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group that cleaves under alkaline conditions.

-Funenin (■)7-~ In the formula, Q' represents an atomic group necessary to form a 5- or 6-membered heterocycle capable of forming iminosilver, L, R, , n
, M has the same meaning as that of the above-mentioned shipman (II). 1 candy
or 2.

Also, [(L-)-nR+8]I11 is -Shipin (If
) is synonymous with that of

The above-mentioned shipman (I[) and (Iff) will be further explained.

- In Shipman (II), Q is an atom necessary to form a 5- or 6-membered heterocycle, preferably consisting of at least one of carbon atom, nitrogen atom, oxygen atom, sulfur atom, and selenium atom. represents a group. Further, this heterocycle may be fused with a carbon aromatic ring or a heteroaromatic ring.

Examples of heterocycles include tetrazoles, triazoles, imidazoles, thiadiazoles, oxathiazoles, selenadiazoles, oxazoles, thiazoles, benzoxazoles, hembuthiazoles, henzimitasols, and pyrimidines. etc. can be mentioned.

M is a hydrogen atom, an alkali metal atom (e.g. sodium,
(potassium), an ammonium group (for example, 1-limethylammonium, dimethylbenzylammonium), a group that can become M=H or an alkali metal atom under alkaline conditions (for example, acetyl, cyanoethyl, methanesulfonylethyl).

Furthermore, the above-mentioned heterocycle is a halogen atom (e.g., chlorine, bromine), a mercapto group, a cyan group, a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, propyl, L-butyl, cyanoethyl). , aryl groups (e.g. phenyl, 4methanesulponamidophenyl,
4-methylphenyl, 3,4-dichlorophenyl, naphthyl), alkenyl groups (e.g. allyl), aralkyl groups (e.g. benzyl, 4-methylbenzyl, phenethyl)
, sulfonyl groups (e.g. methanesulfonyl, ethanesulfonyl, p-)luenesulfonyl), carbamoyl groups (
For example, unsubstituted carbamoyl, methylcarbamoyl, phenylcarbamoyl), sulfamoyl groups (for example, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl), carbonamide groups (for example, acetamide, benzamide), sulfonamide groups (for example, methanesulfonamide, benzenesulfone) amide, l)-toluenesulfonamide), acyloxy groups (e.g. acetyloxy, benzoyloxy), sulfonyloxy groups (e.g. methanesulfonyloxy), ureido groups (e.g. unsubstituted ureido, methylureido, ethylureido,
phenylene thiouride), thioureido group (e.g. unsubstituted thiourido, methylthioureido), acyl group (
For example, acetyl, benzoyl), oxycarbonyl group (
For example, methoxycarbonyl, phenoxycarbonyl)
, an oxycarbonylamino group (for example, methoxycarbonylamino, phenoxycarbonylamino, 2-ethylhexyloxycarbonylamino), a carboxylic acid or its salt, a sulfonic acid or its salt, a hydroxyl group, etc. It is preferable to not be substituted with an acid or a salt thereof, a sulfonic acid or a salt thereof, or a hydroxyl group in terms of the effect of promoting nucleation.

Preferred examples of the heterocycle represented by Q include tetrazoles, triazoles, imidazoles, thiadiazoles, and oxadiazoles.

L represents a divalent linking group consisting of an atom or a group of atoms selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. Examples of divalent linking groups include -3-2-0
-, -N 1g ○ O○ II II IIC〇--○C
--C j -C R,20 o2N 11-C-N- R2゜z5 S ○ N-C-N---N-C0 2e, etc. are mentioned.

These linking groups are A or a linear or branched alkylene group (e.g. methylene, ethylene, propylene, butylene, hexylene, 1-methyleneethylene), or substituted or unsubstituted arylene in the ring with the heterocycle described below. It may be bonded via a group (phenylene, naphthicine).

R, 9R2oR2, R22R23, R2, R, R2゜R
7, and R211 are hydrogen atoms, substituted or unsubstituted alkyl groups (e.g., methyl, ethyl, propyl, n-butyl), substituted or unsubstituted aryl groups (e.g., phenyl, 2-methylphenyl), and substituted or unsubstituted aryl groups (e.g., phenyl, 2-methylphenyl). It represents a substituted alkenyl group (eg, propenyl, 1-methylvinyl) or a substituted or unsubstituted aralkyl group (eg, benzyl, phenethyl).

R18 is a thioether group, an amino group (including salt form),
Represents an organic group containing at least one ammonium group, ether group, or heterocyclic group (including salt form). Examples of such organic groups include groups selected from substituted or unsubstituted alkyl groups, alkenyl groups, aralkyl groups, or aryl groups combined with the above groups, but combinations of these groups may also be used. Good too. For example, hydrochloride of dimethylaminoethyl group, aminoethyl group, diethylaminoethyl group, dibutylaminoethyl group, dimethylaminopropyl group, dimethylaminoethylthioethyl group, 4
-dimethylaminophenyl group, 4 dimethylaminobenzyl group, methylthioethyl group, ethylthiopropyl group, 4
~Methylthio-3cyanophenyl group, methylthiomethyl group, trimethylammonioethyl group, methoxyethyl group, methoxyethoxyethoxyethyl group, methoxyethylthioethyl group, 3,4-dimethoxyphenyl group, 3-chloro-4-methoxyphenyl group , morpholinoethyl group,
1-imidazolylethyl group, morpholinoethylthioethyl group, pyrrolidinoethyl group, pyridylmethyl group, 2-pyridylmethyl group, 2-(I-imidazolyl)ethylthioethyl group, pyrazolylethyl group, triazolylethyl group, methoxy Examples include ethoxyethoxyethoxylponylaminoethyl group. n represents O or 1, and the end represents 0.1 or 2.

In general formula (III), L, R, , n, M are general formula (I
I), where m represents 1 or 2 and Q
' represents an atomic group necessary to form a 5- or 6-membered heterocycle that can be formed with iminosilver. It represents an atomic group necessary to form a 5- or 6-membered heterocycle preferably selected from carbon, nitrogen, oxygen, sulfur, and selenium. Further, this heterocycle may be fused as a carbon aromatic ring or a heteroaromatic ring. Examples of the heterocycle formed by Q" include imidazoles, benzimidazoles, benzotriazoles, henzoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles, triazoles, tetrazoles, and tetraazoles. Indenes, triazaindenes, diazaindenes, pyrazoles,
Examples include indoles.

The compound represented by the general formula (II) is represented by the following general formula (
It/), (V), (VI), and (■) are preferably used.

General formula (R') In the formula, M, R, , L, and n have the same meanings as in general formula (II). X represents an oxygen atom, a sulfur atom or a selenium atom, with a sulfur atom being preferred.

- Boatman (V) R1゜In the formula, R29 is 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, a substituted or unsubstituted alkyl group ( For example, methyl group, ethyl group, etc.), alkenyl group (e.g. propenyl group, 1-methylvinyl group, etc.), aralkyl group (e.g. benzyl group, phenethyl group, etc.), aryl group (e.g. phenyl group, 2- methylphenyl group, etc.) or -(L)R+a.

R2O is a hydrogen atom, an unsubstituted amine group, or (L) R
+a, and R2g and R2O are (L> R+s
may be the same or different.

However, at least one of R29 and R3° is -(L)-
Represents R+8.

M, R, s, L, and n are each synonymous with each of the above-mentioned shipman (II).

General formula (Vl) R7 In the formula, R0 represents -(L)-R18. However, M,
R, , L, and n have the same meaning as each of the above-mentioned -Shipin (It).

General Formula (■) In the formula, R32 and R11 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)l has the same meaning as each of the above-mentioned -Sailor (VI).

Specific compounds represented by the general formulas (I[[) to (■)] are shown below, but the compounds that can be used are not limited thereto.

No.

IO ＾-1 CH3 Horn-2゜5 (C112) 3N (CH3) 2・HCI Horn-4
゜horn-5゜horn-6! No 7 No 8゜5 (C112>20CH3 SCH2SCH.

5(CH2>6N(CH3)2-HciS(CH2>5
N(C2Hs)2・HcIS(CH2)23(CI(2
)2N(C)13)2-HCIl- n-10,-S(CH2) 2N(CI, > 3-Ct
! 7/ -11, -5(CH2)2NHCH2・HC1
R102 ■ Cll2CH2N (C2H5)2 CH2CH2N (C11,) 2 ■ CH30CH2 No.

8-27゜horn-28 OCNH(Ctl2)2N(Cl7)20CNII(C
) 12) 2SCH3 N〇8-29゜horn-30゜horn-3Z ``un5 +CH2)2N(C311,-n)2 -CC112)2N(C2H5)2 (CH2)20-CH3 Ro.

N.

l0ff A-22,-(C)12)2S(C112)2N(C)
13) 2n -23, (CH2) 2N(C, lH7-
n) 2rt -24, (Ctl 2) 3N (CH:
+) 2 The nucleation accelerator can be contained in the light-sensitive material or in the processing solution, but it is also used in the internal latent image type silver halide emulsion layer and other hydrophilic colloid layers (intermediate layer and protective layer). It is preferable to incorporate it into a layer (such as a layer). Particularly preferred is the silver halide emulsion layer or its adjacent layer.

The amount of nucleation accelerator added is 10-6 per mole of silver halide.
~10-2 mol is preferred, more preferably 10-5~
It is 10-2 mol.

In addition, when the nucleation accelerator is added to the processing solution, that is, the developer or its pre-bath, 10-8 to 10-3 per 11.
It is preferably mol, more preferably 10-7 to 10-4 mol.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, amine phenol compounds are also useful, but p-phenylenediamine compounds are preferably used, typical examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-diethylaniline, Methyl-4-amino-N-edyl-N
β-hydroxyethylaniline, 3-, methyl 4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-
Examples include β-methoxyedylaniline and their sulfates, hydrochlorides or I)-toluenesulfonates.

Two or more of these compounds can be used in combination depending on the purpose.

The pH of these color developing solutions is 9 to 12, preferably 95 to 11.5.

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

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose.

The silver halide color photographic light-sensitive material used in the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent flow, jet flow, etc., and various other conditions. can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in Journal of Item 1e.
5ociety of MotionPict
ure and Te1evision Eng
ineers Vol. 64 p248-253 (May 1955)
You can obtain it using the method described in the monthly issue).

The silver halide color light-sensitive material used in the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent.

On the other hand, various known developing agents can be used to develop the black-and-white light-sensitive material in the present invention. i.e. polyhydroxybenzenes, such as hydroquinone, 2-chlorohydroquinone, 2-methylhydroquinone, catechol, pyrogallol; aminophenols, such as p-aminophenol, N-methyl-p
-aminophenol, 2,4-diaminophenol, etc.; 3-pyrazolidones, such as 1-phenyl-3-pyrazolidones, 1-phenyl-4,4"-dimethyl 3-pyrazolidone, 1-phenyl-4-methyl 4-hydroxy Methyl-3-pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone, etc.: ascorbic acids, etc.
Can be used alone or in combination. Also, JP-A-58
The developer described in Japanese Patent No. 55928 can also be used.

For detailed specific examples of developers, preservatives, cleaning agents, and developing methods for black-and-white photosensitive materials, and how to use them, see
Research Disclosure 4 Magazine No. 17643 (
(Issued in December 1978) Sections x■ to XXI, etc.

[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples. The present invention is not limited only to these examples.

Example-1 Paper support laminated on both sides with polyethylene, thickness 10
A color photographic material was prepared in which the following 1st to 14th layers were coated on the front side of the film (0 micron), and 15th to 16th layers were coated on the back side. The polyethylene on the first layer coating side contains titanium oxide as a white pigment and a trace amount of ultramarine as a bluish dye (the chromaticity of the surface of the support is L', a''
, b” series was 88.0.0.20-0.75)
.

(Photosensitive layer composition) The components and coating amounts (in gem2 units) are shown below. Regarding silver halide, the coating amount is shown in terms of silver.

The emulsion used in each layer was prepared according to the manufacturing method of emulsion EMI. However, the emulsion for the 14th layer was a Lippmann emulsion that was not surface chemically sensitized.

1st layer (antihalation layer) Black colloidal silver...0.10 Gelatin...0.70 2nd layer (middle layer) Gelatin...0.70 3rd layer (
Low sensitivity red sensitive layer) Silver bromide spectrally sensitized with red sensitizing dyes (ExS-1, 2, 3) (average grain size 0.25μ, size distribution [coefficient of variation 18%, octahedral...004 Silver chlorobromide spectrally sensitized with red sensitizing dyes (ExS-1, 2, 3) (silver chloride 5 mol%, average particle size 0.40μ
Size distribution 10%, octahedral> ...0.08 Gelatin ...1,00 Cyan coupler (ExC-1, 2, 3 equivalents),,, 0.30
Antifading agent (Cpd-1, 2, 3, 4 equivalent)...0
18 Stain inhibitor (C1+d-5)...
0003 force puller dispersion medium (Cpd-6)...
・0.03 coupler solvent (Solv-1, 2, 3 equivalents)
, 0.12 4th layer (high sensitivity red sensitive layer) Silver bromide spectrally sensitized with red sensitizing dyes (ExS-1, 2, 3) (average grain size 060μ, size distribution 15z,
Octahedron)...014 Gelatin...1.00 Cyan coupler (ExC-1, 2, 3 equivalents)...0.30 Anti-fading d double agent (2) d-J, 2, 3.4 etc. Quantity) ・・・01
8 force puller dispersion medium (C1+d-6)...0
．． 03 coupler solvent (Solv-1, 2, 3 equivalents)・
5th M (intermediate layer) Gelatin color mixing inhibitor (Cpd-7) Color mixing inhibitor solvent (Solv ~ 4,5 equivalent) Polymer latex (Cpd-8) 6th layer (low sensitivity green sensitive layer) Green sensitizing dye ( Silver bromide (ExS-4) spectrally sensitized with
Average particle size 0.25μ, size distribution 8L octahedron)・
004 Silver chlorobromide spectrally sensitized with green sensitizing dye (ExS-4) (silver chloride 5 mol%, average particle size 0.40 μ, size distribution 1 oz, octahedral) 006 Gelatin .・0.80 magenta coupler (ExM-1,2 equivalent) ・・011 anti-fading agent (
Cpd-9) ...0.10 stain inhibitor (Cpd-10, 11, 12, 13 at 10 near: 7
:1 ratio)...0025
Power puller dispersion medium (Cpd-6)...0.0
5 coupler solvent (Solv-4, 6 equivalent)...0
．． 151.00 0.10 7th layer (high sensitivity green sensitive layer) Silver bromide (
Average particle size 065μ, size distribution 16z, octahedral)
... 0.10 ... 0.80 1.2 equivalent) ...011 ... 0.10 10.11, 12.13 in 10 near:7:1 ratio...
0025 ... 0.05 ... 015 Gelatin magenta coupler (ExM Anti-fading agent (Cpd-9) Anti-stinting agent (Cpd) Coupler dispersion medium (self + d-6) Coupler solvent (Solv-4, 6 equivalents) ) 8th layer (intermediate layer) Same as 5th layer 9th layer (yellow filter layer) Yellow colloidal silver gelatin Color mixing inhibitor (Cpd-7) Color mixing inhibitor solvent (Solv-4, 5 equivalent) Polymer latex ( Cpd-8) 10th layer (intermediate layer) ... 0.12 ... 007 ... 003 ... 0.10 ... 0.07 11th layer (low sensitivity blue sensitive layer) same as 5th layer Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average grain size 0.40μ, size distribution 8%, octahedral)... 0.07 Blue sensitizing dye (ExS-5) , 6) spectrally sensitized silver chlorobromide (silver chloride 8 mol%, average grain size 0.60μ, size distribution 11z, octahedron)...0.1
4 Gelatin...0.80 Yellow coupler (ExY-1)...0.35
Antifading agent (Cpd-14)...-0,
10 Stain inhibitor (Cpd-515 at 1:5 ratio)
...0.007 Force Blur dispersion medium (Cpd-6) ...0.05 Coupler solvent (Solv-2) ...0.10 12th
Layer (high sensitivity blue sensitive layer) Blue sensitizing dye (silver bromide spectrally sensitized with ExS-5, 6> (average grain size 0.85μ, size distribution 18%, octahedron)...0.15 Gelatin...0.60 Yellow coupler (ExY-])...0.30 Antifading agent (Cpd-14)...0.10
Stain preventive agent (Cpd-5,15 compared to 15)
... 0.007 power puller dispersion medium (Cpd-6) ... 0.05 power puller solv g (Solv-2) ... -0,10 No. 13
Layer (ultraviolet absorbing layer) Gelatin...1.00 Ultraviolet absorber (Cpd-2, 4, 16 equivalent), -o,! 5
゜Color mixing inhibitor (C1] d-7,17 equivalent) -0
,03 dispersion medium (Cpd-6)...
002 Ultraviolet absorber solvent (Solv-2,7 equivalent)...
・008 anti-irradiation dye (Cpd-18,1
9,202] compared to 10.10:13:15)
・ °004 14th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol% 1 average size 02μ
)...003 Acrylic modified copolymer of polyvinyl alcohol...o, oi Polymethyl methacrylate particles (average particle size 24μ
) and silicon oxide (average particle size 5μ) equivalent amount...00
5 Ceratin...1.80 Gelatin hardening agent (H-1, H-2 equivalent)...018 No. 15
N (back layer) Gelatin...250 16th layer (back protective layer) Polymethyl methacrylate particles (average particle size 24μ
) and silicon oxide (average particle size 5μ) equivalent amount
... 005 Gelatin ... 2.00 Gelatin hardening agent ()l-1, t2 equivalent) ...0.14 Emulsion EM
How to make -1: Add an aqueous solution of potassium bromide and silver nitrate to an aqueous gelatin solution containing lead acetate simultaneously over 15 minutes at 75°C with vigorous stirring.
Octahedral silver bromide grains containing 0-'' mole and having an average grain size of 0.40 μm were obtained.The emulsion contained 0.3 g of 3,
4-dimethyl-1,3-thiasoline-2-thione, 6
my sodium thiosulfate and 7m+? A chemical sensitization treatment was performed by sequentially adding chloroauric acid (tetrahydrate) and heating at 75°C for 80 minutes.

The grains thus obtained were used as cores and further grown in the same precipitation environment as the first time, to finally obtain an octahedral monodisperse core/shell silver bromide emulsion with an average grain size of 0.7 μm. The coefficient of variation in particle size was approximately 10%.

To this emulsion, 1.5B of sodium thiosulfate and 1.5B of chloroauric acid (tetrahydrate) per mole of silver were added and heated at 60°C for 60 minutes to perform chemical sensitization treatment. A silver oxide emulsion was obtained.

In each photosensitive layer, the nucleating agents listed in Table 1 were used. Furthermore, each layer contains alkanol XC as an emulsion dispersion aid.
(Dupon) and sodium alkylbenzenesulfonate, succinate ester and Ma as coating aids.
gefac F-120' (manufactured by Dainippon Ink Co., Ltd.) was used. (Cpd-23, 24, 25) was used as a stabilizer in the silver halide and colloidal silver containing layers. This sample was designated as the sample number. The compounds used in the examples are shown below.

ExS~5 SO3H-N(C2H5)3 EMS=6 pd-1 pd-2 ゝCJa(t) pd-9 pd-10 pd-11 pd-4 pd-5 C, d-6 H pd-12 pd- 13 pd-15 Cpd-16 Cpd-17 Cpd-18 Cpd-19 XC-3 XC-1 XC-2 XH-i Cpd-20 Cpd-21 Cpd-23 Cpd-24 XM-2 XY-1 olv-I olv -2 olv-3 olv-4 olv-5 olvJ olv-7 Di(2-ethylhexyl) sebacate trinonyl phosphate di(3-methylhexyl) phthalate tricresyl phosphate dibutyl phthalate trioctyl phosphate di(2-ethylhexyl) phthalate 1.2-Bis(vinylsulfonylacedoamide)ethane H-24,6-dichloro-2-hydroxy 1.3.5-
Triazine Na salt After the color photographic paper thus produced was exposed to wedge light (3200K, 0.5 seconds, 10 CMS), processing step A
A positive image was obtained directly.

The magenta color image density was measured.

Table 1 Comparative Examples - A Samples Nos. 1 to 7 using the nucleating agent of the present invention had higher Dma than Comparative Examples No. 8 and were preferable. Similar results were obtained for cyan and yellow color image densities.

Processing step A Science and engineering color development 135 seconds 38℃ Bleach fixing 40 knots 33 horns washing (I)
40 horns 33 horns washing (2) 40 horns 33 horns 30 horns + 80 horns The replenishment method for washing water is to refill the washing bath (2),
A so-called countercurrent replenishment system was used in which the overflow liquid of 2) was introduced into the washing bath (I). At this time, the amount of bleach-fix solution brought into the washing bath (I) from the bleach-fix bath for photosensitive materials is 3
5 ml1/m2, and the ratio of the amount of washing water replenished to the amount of bleach-fix solution brought in was 9.1 times.

The composition of each treatment liquid was as follows.

Methylene phosphonic acid diethylene glycol benzyl alcohol potassium bromide sodium sulfite triethanolamine 4-aminoaniline sulfate potassium carbonate optical brightener (diaminostilbene type) 10 cubic meters 12.0 m1 1.60° 2.4 g e, ofI 30.3 g 1.0g Lithium dihydrate ethylenediaminetetraacetic acid F e (I [f ) 70
．． 0y ammonium dihydrate ammonium thiosulfate (700y#>18On
+fp-) Sodium luenesulfinate 20.0 g Sodium bisulfite 200 2-amino-5-mercap) -O,a,.

13.10.0g of 4-thiadiazole ammonium nitrate
゛ te
1000ml pH (25℃)
6.20 Fill tap water with the wood mother liquor and replenisher with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400). Water was passed through the mixed bed column to reduce the concentration of calcium and magnesium ions to 3 mg/e or less, and then 20 In!?/l of sodium isotheaterate dichloride and 1 to 1.5 g/Z of sodium sulfate were added. Yes, the pH of this liquid was in the range of 65 to 7.5.

Example 2 Color photographic paper was produced in the same manner as Sample No. 1 of Example 1 except that the nucleating agent shown in Table 2 was used. After storing this sample in an atmosphere of 45°C and 80% RH for 4 days, wedge exposure (5400KO 18 seconds, IOCMS)
, and perform processing step B.

The resulting cyan color image density was measured.

Table 2 Comparative Example-B Samples Nos. 19 to 13 using the nucleating agent of the present invention were preferable because the decrease in Dmax and the increase in D + *in due to incubation were smaller than those of Nos. and 14 of Comparative Example 1.

Processing step B Color development 110 seconds 38℃ Bleach-fixing 30 seconds 38℃ Washing with water 30 seconds 38℃ 30 38℃ *mol/A gmol [Color development] [Bleach-fix solution] Diethylenetriaminepentaacetic acid Diethyleneglycol Benzyl alcohol Sodium bromide Sodium chloride Sodium sulfite hydroxylamine sulfate 0.5g 8.0g 9.09 0.7g O,5° 2.0g 2.8° Potassium carbonate 30. h Fluorescent brightener (stilbene type) Add 1.0°
1oooIIlzpH10.50 t+H was adjusted with potassium hydroxide or hydrochloric acid.

Ammonium 1,000 sulfate Sodium bisulfite 40g Ethylenediaminetetraacetic acid 40.0g Iron (I
ll) Ammonium dihydrate ethylenediaminetetraacetic acid 4.0g Disodium dihydrate Add pure water to 10100O! p
H7,0 [Wash water] Using pure water (mother liquor - replenisher) Example 3 Produced in the same manner as in Example 1 except that the nucleating agent and nucleating accelerator were used as shown in Table 3. Wedge exposure of colored photographic paper (3200K, 0.2 seconds, 1oc
MS) The above treatment step A was performed. The magenta color image density was measured.

Table 3 Comparative example of addition amount 3.1x10-'mol/^gllI04.2xlO-
” n ^ Sample N using the nucleating agent of the present invention and further a nucleating accelerator
o, 15.16 18, 19, 21.22 No. 17.20.23 and comparative example No. 18, 19, 21.22 do not use nucleation accelerator,
Compared to Nos. 24 to 26, DI#ax was high and Dmin was low, which was preferable. Similar results were obtained for cyan and yellow color image densities.

Example 4 As shown in Table 4, color photographic paper was produced in the same manner as in Example 1 except that a nucleating agent and a nucleating accelerator were used. After storing these samples for 4 days at 60°C and 55% RH, they were exposed to wedge light (5400K, 0.2 seconds, 10C
After applying MS), the treatment step B was performed. The cyan color density of the obtained direct positive image was measured.

Table 4 1 Addition amount 5. IX 10-'mol/^g mol
"174.3X10-"n Sample No. 2 using the nucleating agent and nucleating accelerator of the present invention
7.28.30.31 is No. 2 without using nucleation accelerator
Compared to No. 9.32 and Comparative Examples Nos. 33 to 35, the decrease in Dmax and increase in Dmin due to incubation were small and preferred.

(Effects of the Invention) According to the present invention, even if a direct positive photographic light-sensitive material is developed at a low pH of 11 or less, the film remains sufficiently large.
ax can be obtained. And this is Example 1~
As shown in No. 4, a large 1XD wax can be obtained in all magenta, cyan, and yellow color image densities. Further, even if a direct positive photographic light-sensitive material is stored under high temperature and high humidity, image formation can be stably performed by the development process according to the present invention.

Agent: Patent Attorney (8107) Kiyotaka Sasaki (
3 others)

Claims (1)

[Scope of Claims] A direct positive photographic light-sensitive material having a layer containing at least one unfogged internal latent image type silver halide grains is formed on a support after or while being subjected to a fogging process. In a direct positive image forming method using development processing,
A direct positive image forming method, characterized in that the fogging treatment is carried out in the presence of a compound represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, A_1 and A_2 are both hydrogen atoms, or one is a hydrogen atom and the other is a sulfonyl group or an acyl group,
R_1 represents an aliphatic group, aromatic group, or heterocyclic group, G_1 represents a carbonyl group, sulfonyl group, sulfoxy group, ▲numerical formula, chemical formula, table, etc.▼ group (R_2 represents an alkoxy group or an aryloxy group) ), ▲There are mathematical formulas, chemical formulas, tables, etc.▼ group or iminomethylene group, and X_1 splits the -G_1-X_1 part from the remaining molecule to generate a cyclic structure containing the atoms of the -G_1-X_1 part. A group that causes a cyclization reaction. Here, at least one of R_1 or X_1 represents a group capable of dissociating into an anion having a pKa of 6 or more, or an amino group.