JP2557690B2 - Direct positive image forming method - Google Patents

Description

The present invention relates to a direct positive photographic light-sensitive material having on a support a layer containing at least one pre-fogged internal latent image type silver halide grain. The present invention relates to a direct positive image forming method in which development processing is performed after fogging or while performing fogging processing, and more particularly to a direct positive image forming method in which a sufficiently large D _max can be obtained even in low pH development processing.

(Prior Art) It is well known that a direct positive image is obtained by using an internal latent image type silver halide emulsion which has not been fogged in advance, and then performing a fogging process after image exposure or while performing a fogging process to obtain a surface image. Has been.

Here, the internal latent image type silver halide photographic emulsion is a type of silver halide photographic emulsion in which a silver halide grain has a photosensitive nucleus mainly inside and a latent image is mainly formed inside the grain by exposure. Say.

Various techniques have been known so far in this technical field. For example, U.S. Patent Nos. 2,592,250 and 2,466,9
No. 57, No. 2,497,875, No. 2,588,982, No. 3,317,322
Nos. 3,761,266, 3,761,276, 3,796,577 and British Patent Nos. 1,151,363, 1,150,553, 1,011,
The main thing is described in each specification of No. 062.

By using these known methods, a photographic photosensitive material having a relatively high sensitivity as a direct positive type can be produced.

For details of the mechanism for forming the direct positive image, for example,
The James of The Theory of the Phot (The Theory of the Phot)
Graphical Process), 4th Edition, Chapter 7, pp. 182-193 and U.S. Pat. No. 3,761,276.

That is, the fog nuclei are selectively generated only on the surface of the silver halide grains in the unexposed area due to the surface desensitizing action caused by the so-called internal latent image generated inside the silver halide by the first imagewise exposure, Then, it is considered that a photographic image (direct positive image) is formed on the unexposed portion by subjecting to a usual so-called surface development treatment.

As described above, as a means for selectively generating fog nuclei, a method of giving a second exposure to the entire surface of the photosensitive layer, which is generally called "photofogging method" (for example, British Patent No. 1,151,3630)
No.) and a nucleating agent called "chemical fogging" (unlcleat)
ing agent) is known. This latter method is described, for example, in “Research Disclosure”, Volume 151, No. 1516.
2 (issued in November 1976), pages 76-78.

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

Further, a heterocyclic quaternary ammonium salt is known as another nucleating agent, and for example, U.S. Patents 3,615,615 and 3,71
9,494, 3,734,738, 3,759,901, 3,854,956
No. 4,094,683, 4,306,016, British Patent No. 1,283,
No. 835, JP-A Nos. 52-3,426 and 52-69,613.

(Problems to be Solved by the Invention) Generally, the hydrazine-based nucleating agent has a large difference between the maximum concentration (Dmax) and the minimum concentration (Dmin), and is the best in terms of discrimination, but it is high in processing. pH (pH> 1
It has the drawback of requiring 2).

As the nucleating agent which acts even when the treatment pH is low (pH ≦ 12), there is the above-mentioned heterocyclic quaternary ammonium salt, and in particular, a propargyl- or butynyl-substituted heterocyclic ring described in US Pat. No. 4,115,122. The quaternary ammonium salt compound is an excellent nucleating agent in terms of discrimination in a direct positive silver halide emulsion.

However, when a sensitizing dye is added to the silver halide emulsion, for example, for the purpose of spectral sensitization, the sensitizing dye and the heterocyclic quaternary ammonium nucleating agent
Due to competitive adsorption on silver halide emulsions, it is necessary to add a large amount of quaternary salt nucleating agent, which has weak adsorptivity. Especially in the case of multi-layer color light-sensitive materials, uneven density or loss of color balance may occur. However, it could not be said that it showed sufficient performance. This tendency tends to be further increased by storage under high temperature and high humidity.

For the purpose of solving the above problems, US Pat. No. 4,471,044 reports an example of a quaternary salt nucleating agent having a thioamide AgX adsorption promoting group. Here, by the introduction of adsorption groups,
Although it is said that the amount of addition necessary for obtaining a sufficient Dmax is reduced and the reduction of Dmax at high temperature is improved, this effect was not at a sufficiently satisfactory level.

Therefore, it is a first object of the present invention to provide a direct positive image forming method which provides a high maximum image density and a low minimum image density.

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

(Means for Solving the Problems) The present invention relates to a direct positive photographic light-sensitive material having a layer containing at least one prefogged internal latent image-type silver halide grain on a support, after being fogged. Or a direct positive image forming method of developing while performing a fog treatment, wherein the fog treatment is carried out in the presence of a compound represented by the following general formula (I). Can be achieved.

General formula (I) In the formula, A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other represents a sulfonyl group or an acyl group, R ₁ represents an aliphatic group, an aromatic group, or a heterocyclic group, G ₁ is Carbonyl group, sulfonyl group, sulfoxy group, (R ₂ represents an alkoxy group or an aryloxy group), Or an iminomethylene group, X ₁ is a group capable of splitting the -G ₁ -X ₁ moiety from the residual molecule, and causing a cyclization reaction to form a cyclic structure containing the atoms of the -G ₁ -X ₁ moiety. Is. Here, at least _one of R _{1 and} X ₁ has a group capable of dissociating into an anion having a pKa of 6 or more, or an amino group.

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

In the general formula (I), A ₁ and A ₂ are each a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably substituted so that the sum of the substituent constants of the phenylsulfonyl group or Hammett is −0.5 or more). Phenylsulfonyl group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or the sum of Hammett's substituent constants is −0.
5 or more substituted benzoyl group), or a linear or branched or cyclic unsubstituted and substituted aliphatic acyl group (as a substituent, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, A hydroxyl group, a carboxy group, and a sulfonic acid group.),
Most preferably, both A ₁ and A ₂ are hydrogen atoms.

The aliphatic group represented by R ₁ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic represented by R ₁ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group.

The heterocycle of R ₁ is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of N, O, and S atoms, which may be a single ring, A condensed ring may be formed with an aromatic ring or a hetero ring.
The heterocyclic ring is preferably a 5- or 6-membered aromatic heterocyclic group, for example, a pyridine group, an imidazolyl group,
Quinolinyl group, benzimidazolyl group, pyrimidyl group,
Those containing a pyrazolyl group, an isoquinolinyl group, a thiazolyl group, and a benzothiazolyl group are preferred.

R ₁ may be substituted with a substituent. Examples of the substituent include the followings. These groups may be further substituted.

For example, alkyl group, aralkyl group, alkoxy group, aryl group, substituted 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, halogen atom, cyano group,
Examples include a sulfo group and a carboxyl group.

When possible, these groups may be linked to each other to form a ring.

Preferred as R ₁ is an aromatic group, more preferably an aryl group.

G ₁ is a carbonyl group, a sulfonyl group, a sulfoxy group, (R ₂ represents an alkoxy group or an aryloxy group), Alternatively, it represents an iminomethylene group, and a carbonyl group is most preferable as G ₁ .

X ₁ is a group represented by the general formula (a), the general formula (a) -L ₁ -Z ₁ expression in Z ₁ is nucleophilically attacked to G ₁ G ₁ -L ₁ -Z ₁ moiety the a group capable of splitting from the remainder molecule, L ₁ is G _1, L _1, Z ₁ ring structure can be generated by a divalent organic group and nucleophilic attack Z ₁ is to G _1. More specifically, Z ₁ easily nucleophilically attacks G ₁ when the hydrazine compound of the general formula (I) produces the next reaction intermediate due to oxidation or the like, R ₁ —N = N−G ₁ — L ₁ -Z ₁ R ₁ -N = is a group capable of splitting an N group from G ₁ , and specifically includes OH, SH, or NHR ₃ (R ₃ is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. , --COR ₄ or --SO ₂ R ₄ and R ₄
Represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or the like). It may be a functional group that reacts directly with G ₁ such as COOH (where OH, SH, NHR ₃ and --COOH are temporarily protected so that they are formed with these groups by hydrolysis of alkali etc. May be) or (R ₅ and R ₆ represent hydrogen atom, alkyl group, alkenyl group, aryl group or heterocyclic group) and react with G ₁ by reacting with nucleophile such as hydroxide ion or sulfite ion It may be a functional group that enables

The divalent organic group represented by L ₁ is an atom or atomic group containing at least one of C, N, S and O, and specifically, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, A heteroarylene group (these groups may have a substituent) -O-, -S-, (R ₇ represents a hydrogen atom, an alkyl group or an aryl group)-
N =, —CO—, —SO ₂ — and the like or a combination thereof, and preferably the ring formed by G ₁ , Z ₁ and L ₁ is a 5-membered or 6-membered ring.

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

General formula (b) In the formula, R _{8 to} R ₁₁ are hydrogen atoms, alkyl groups (preferably having 1 to 12 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms), aryl groups (preferably having 6 carbon atoms).
~ 12), etc., and may be the same or different. B
Is an atom necessary to complete a 5- or 6-membered ring which may have a substituent, m and n are 0 or 1, and (m
+1) is 0 or 1 when Z is COOH, and Z is OH, S
When H and NHR ₃ , it is 1 or 2. The 5- or 6-membered ring formed by B is, for example, a cyclohexene ring, a cycloheptene ring, a benzene ring, a naphthalene ring, a pyridine ring or a quinoline ring, and Z ₁ has the same meaning as in formula (a).

Among the general formula (b), preferred are those in which m = 0 and n = 1, and particularly preferred is that the ring formed by B is a benzene ring.

General formula (c) In the formula, R ₁₂ and R ₁₃ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a halogen atom or the like, and may be the same or different.

R ₁₄ represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

p represents 0 or 1, and q represents 1 to 4. R ₁₂ ,
R ₁₃ and R ₁₄ may combine with each other to form a ring as long as Z ₁ has a structure capable of intramolecular nucleophilic attack on G ₁ .

R ₁₂ and R ₁₃ are preferably a hydrogen atom, a halogen atom or an alkyl group, and R ₁₄ is preferably an alkyl group or an aryl group.

q preferably represents 1 to 3, and when q is 1, p is 1
When q is 2, p is 0 or 1, and when q is 3, p is 0
Or represents 1. Here, when q is 2 or 3, CR ₁₂
R ₁₃ may be the same or different.

Z ₁ has the same meaning as in formula (a).

As the substituent of X _1, the substituents listed for R ₁ can be applied, and for example, an acyl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group, a nitro group, or the like can be applied.

These substituents may be further substituted with these substituents. If possible, these groups may form a ring in which these groups are connected to each other.

R ₁ or X ₁ , especially R ₁ is a diffusion resistant group such as a coupler,
It preferably contains a so-called ballast group. The ballast group has at least 8 carbon atoms and is composed of a combination of one or more of an alkyl group, a phenyl group, an ether group, an amide group, a ureido group, a urethane group, a sulfonamide group and a thioether group.

R ₁ or X ₁ is a group Y ₁ L _{2 l} which promotes adsorption of the compound represented by formula (I) on the surface of silver halide grains.
May have. Here, Y ₁ is an adsorption promoting group to silver halide, and L ₂ is a divalent linking group. l is 0 or 1.

Preferable examples of the adsorption promoting group represented by Y ₁ on silver halide include a thioamide group, a group having a mercapto group disulfide bond, or a 5- to 6-membered nitrogen-containing heterocyclic group.

The thioamide adsorption promoting group represented by Y ₁ is 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. 5, No. 4,031,127, No. 4,080,207, No. 4,245,037,
No. 4,255,511, No. 4,266,013, and No. 4,276,364,
And "Research Disclosure" (Research
Disclosure) Volume 151, No. 15162 (November 1976), and Volume 176, No. 17626 (December 1978).

Specific examples of the acyclic thioamide group include, for example, thioureido group, thiourethane group and dithiocarbamic acid ester group, and specific examples of the cyclic thioamide group include
For example, 4-thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4
Triazoline-3-thione, 1,3,4-thiadiazoline-2-thione, 1,3,4-oxadiazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione and benzothiazoline- 2-thione and the like, which may be further substituted.

The mercapto group of Y ₁ is an aliphatic mercapto group, an aromatic mercapto group, or a heterocyclic mercapto group (when the carbon atom to which the --SH group is bonded is a nitrogen atom next to it, a cyclic thioamide having a tautomeric relationship with this) Synonymous with the group, and specific examples of this group are the same as those listed above).

Examples of the 5-membered to 5-membered to 6-membered nitrogen-containing heterocyclic group represented by Y ₁ include a 5-membered to 6-membered nitrogen-containing heterocyclic ring composed of a combination of nitrogen, oxygen, sulfur and carbon. 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 appropriate substituents.

Examples of the substituent include those described as the substituent for R ₁ .

Among those represented by Y ₁ , preferable ones are cyclic thioamide groups (that is, mercapto-substituted nitrogen-containing heterocycles, for example, 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group. , 2-mercapto-1,3,4-oxadiazole group, 2-mercaptobenzoxazole group, etc.) or nitrogen-containing heterocyclic group (for example, benzotriazole group,
Benzimidazole group, indazole group, etc.). Two or more Y ₁ L _{2 l} groups may be substituted and may be the same or different.

The divalent linking group represented by L ₂ is an atom or atomic group containing at least one of C, N, S and O. Specifically, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-, -NH-, -NR.
(R: monovalent substituent), —CO—, —SO ₂ — (these groups may have a substituent) and the like, alone or in combination.

Specific examples include, -CONH -, - NHCONH-, SO 2 NH -, - COO -, - NHCOO
-, _{-CH 2 -, CH 2 2,} CH 2 3, −NHCONHCH ₂ CH ₂ CONH−, _{-CH 2 CH 2 SO 2 NH -} , - CH 2 CH 2 CONH- , and the like.

These may be further substituted with appropriate substituents. Examples of the substituent include those mentioned as the substituent for R ₁ .

Among the substituents which can be dissociated into anions having a pKa of 6 or more and which are substituted for R ₁ or X ₁ in the general formula (I), preferably a substituent which can dissociate into anions having a pKa of 8 to 13 is neutral. Alternatively, it does not have to be a specific one as long as it hardly dissociates in a weakly acidic medium and sufficiently dissociates in an alkaline aqueous solution (preferably pH 10.5-12.3) such as a developing solution.

For example, a hydroxyl group, R ₁₅ SO ₂ NH- group represented by (R ₁₅ represents an alkyl group, an aryl group, a heterocyclic group and -L ₃ -Y ₁ (L ₃
Represents the same as the above L ₂ ), etc., and these groups may have a substituent), a mercapto group, a hydroxyimino group. An active methine group or an active methylene group (for example, --CH ₂ COOC ₂
H _5, -CH ₂ COCH _3, And the like.

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

Among those represented by the general formula (I), preferred are those represented by the general formula (II).

General formula (II) In the formula, R ₁₇ is a substituent (specifically, the same as the substituent of R _{1 in} the general formula (I)), L ₂ ) _l Y ₁ or a substituent capable of dissociating to an anion having a pKa of 6 or more. And k is 0, 1 or 2, and when k is 2, R ₁₇ may be the same or different. R ₁₆ is same as R ₁ of formula (I), or represents _{L 2 l} Y _1, preferably _{L 2 l} Y _1. (Wherein L ₂ , Y ₁ and l have the same meanings as described in the general formula (I)) G ₁ , X ₁ , A ₁ and A ₂ have the same meanings as the general formula (I), and more preferably R ₁₆ SO ₂ NH group is 0 or p to the hydrazino group.
It is replaced by the value.

Specific examples of the compound represented by formula (I) are shown below. However, the present invention is not limited to the following compounds.

The non-pre-fogged internal latent image type silver halide emulsion used in the present invention is an emulsion in which the surface of silver halide grains is not pre-fogged and has a latent image mainly inside the grains. , And more specifically,
A fixed amount of silver halide emulsion (0.5 to 3 g /
m ² ), and exposed to light for a fixed time of 0.01 to 10 seconds, and then at 18 ° C. in the following developer A (internal developer).
The maximum density measured by the usual photographic density measuring method when developed for 5 minutes was the same as the above, and the silver halide emulsion was exposed in the same manner as the following developing solution B (surface type developing solution).
Of the maximum density obtained when developed at 20 ° C for 6 minutes in
Preferred are those having a concentration of at least 5 times greater, more preferably those having a concentration of at least 10 times greater.

Internal developer A Metol 2g sodium sulfite (anhydrous) 90 g Hydroquinone 8g sodium carbonate (monohydrate) 52.5 g KBr 5 g KI 0.5 g Water to make 1 surface developer B Metol 2.5 g L-ascorbic acid 10g NaBO ₂ · 4H ₂ O 35g KBr 1g Water is added 1 Specific examples of the internal latent emulsion include, for example, US Pat.
Conversion type silver halide emulsions described in 2,250, U.S. Pat.Nos. 3,761,276, 3,850,637,
Same 3,923,513, same 4,035,185, same 4,395,478, same 4,504,
570, JP-A-52-156614, 55-127549, 53-6
0222, 56-22681, 59-208540, 60-10764
No. 1, No. 61-3137, Japanese Patent Application No. 61-32462, Research Disclosure No. 23510 (issued in November 1983) P236, the core / shell type silver halide emulsions described in the patent are disclosed. Can be mentioned.

The shape of the silver halide grains used in the present invention may be a regular crystal such as cubic, octahedral, dodecahedral or tetradecahedral, an irregular crystal shape such as spherical, etc. Plate-shaped particles having a thickness ratio of 5 or more may be used. Further, it may be an emulsion having a composite form of these various crystal forms, or an emulsion composed of a mixture thereof.

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

The average grain size of silver halide grains is 2 μm or less.
0.1 μm or more is preferable, but 1 μm or less and 0.15 μm or more is particularly preferable. The particle size distribution may be narrow or wide, but in order to improve graininess and sharpness, the number of particles or the weight thereof should be within ± 40% of the average particle size, preferably within ± 20% of 90% of all particles. So-called "monodisperse" silver halide emulsions with a narrow grain size distribution, such as> 100%, are preferably used in the present invention. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes or a plurality of emulsions having the same size but different sensitivities in emulsion layers having substantially the same color sensitivity. Can be mixed in the same layer or multi-layer coated in another layer. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and 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, precious metal sensitization, etc., alone or in combination. Specific examples are described in Patents such as Research Disclosure No. 17633-III (issued in December 1978) P23.

The photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye in a conventional manner. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above-mentioned strong sensitizer may be used in combination.
Specific examples are described in, for example, patents described in Research Disclosure Magazine No. 17643-IV (issued in December 1978) pp. 23-24.

The photographic emulsion used in the present invention may contain an antifoggant or stabilizer for the purpose of preventing fog during the production process of a light-sensitive material, storage or photographic processing, or stabilizing photographic performance. For specific examples, see Research Disclosure No. 17643-IV (19
(Published December 1978) and "Stabiliaution o" by EJBirr
f PhotographicSilver Hailde Emulsion "(Focal P
ress), 1974 etc.

Various color couplers can be used in the present invention to directly form a positive color image. A color coupler is a compound that forms a coupling or reactant with an oxidized form of an aromatic primary amine color developing agent to form or release a substantially non-diffusible dye. Preferably, it is a compound. Typical examples of useful color couplers are naphthol or phenol compounds, pyrazolone 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 described in "Research Disclosure" No. 17643 (December 1978) p25, VII-D, N.
No. 18717 (issued in November 1979) and Japanese Patent Application No. 61-32462 and the patents cited therein.

Card couplers, couplers in which the coloring dye has an appropriate diffusivity, achromatic couplers, and DIR couplers that release the development inhibitor along with the coupling reaction, in order to correct unnecessary absorption in the short wavelength region of the dye that is produced. 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.

Color fog inhibitors or color mixture inhibitors can be used in the light-sensitive material of the present invention.

Representative examples thereof are described in JP-A-62-215272, pages 185 to 193.

In the present invention, a color-enhancing agent can be used for the purpose of improving the color-forming property of the coupler. Representative examples of compounds are disclosed in
62-215272, pp. 121-125.

The light-sensitive material of the present invention includes dyes for preventing irradiation and halation, ultraviolet absorbers, plasticizers, optical brighteners, matting agents, antifoggants, coating aids, hardeners,
An antistatic agent, a slipperiness improving agent, etc. can be added.
Typical examples of these additives are Research Disclosure No. 17643, pp. VIII-XIII (published in December 1978), P25-2.
7 and 18716 (issued in November 1979) p647-651.

The present 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 at least one red-sensitive pore layer, green-sensitive emulsion layer, and blue-sensitive emulsion layer each on a support.
The order of these layers can be arbitrarily selected as necessary. The preferred order of layer arrangement is from the support side to red-sensitive, green-sensitive, and blue-sensitive or from the support side to green-sensitive, red-sensitive, and blue-sensitive.
Further, each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. . Usually, a cyan-forming coupler is contained in the red-sensitive emulsion layer, a magenta-forming coupler is contained in the green-sensitive emulsion layer, and a yellow-forming coupler is contained in the blue-sensitive emulsion layer, but different combinations can be used depending on circumstances.

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

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are described in Research Disclosure No. 17643 VVII (19).
Issued in December 1978) Those described in p28 and European patents 0,10
It is coated on a support described in JP-A No. 2,253 and JP-A No. 61-97655. Also, Research Disclosure No. 17643XV
The application method described on pages 28 to 29 can be used.

The present invention can be applied to various color light-sensitive materials.

Typical examples include color reversal films for slides or televisions, color reversal papers, and instant color films. It can also be applied to full-color copiers and color hard copies for storing CRT images. The present invention is also disclosed in Research Disclosure, No. 17123 (19
This is also applicable to black-and-white light-sensitive materials using a mixture of three-color couplers described in, for example, Jpn.

 Further, the present invention can be applied to a black and white light-sensitive material.

Black and white (B / W) photographic light-sensitive materials to which the present invention can be applied include B / W direct positive photographic light-sensitive materials described in JP-A-59-208540 and JP-A-60-260039 (for example, for X ray). Sensitive materials, duplicating sensitive materials, micro sensitive materials, photographic sensitive materials, printing sensitive materials) and the like.

Further, in the present invention, it is preferable to use a nucleation accelerator together with the engraving agent. The nucleation accelerator has substantially no function as an engraving agent, but is necessary for promoting 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. It is a substance that acts to accelerate the development time. As the nucleation accelerator, it is preferable to use the compound represented by the general formula (II) or (III).

General formula (II) In the formula, Q represents a group of atoms necessary to form a 5- or 6-membered heterocyclic ring. The heterocycle may be fused with a carbon aromatic ring or a heteroaromatic ring.

L represents a divalent linking group consisting of an atom or an atom group selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, and R ₁₈ represents a thioether group, an amino group, an ammonium group, an ether group or It represents an organic group containing at least one heterocyclic group.

n represents 0 or 1, and m represents 0, 1 or 2.

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

General formula (III) In the formula, Q'represents an atomic group necessary for forming a 5- or 6-membered heterocycle capable of forming iminosilver, and L, R ₁₈ , n and M have the same meanings as those in the above general formula (II). . m is 1 or 2
Represents

Further, [(L _n R ₁₈ ] m has the same meaning as that in the general formula (II).

 The general formulas (II) and (III) will be further described.

In the general formula (II), Q is preferably an atom group necessary for forming a 5- or 6-membered heterocyclic ring composed of at least one atom of a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom. Represents The heterocycle may be fused with a carbon aromatic ring or a heteroaromatic ring.

Examples of heterocycles include tetrazole, triazole, imidazole, thiadiazole, oxadiazole, selenadiazole, oxazole, thiazole, benzoxazole, benzothiazole,
Examples include benzimidazoles and pyrimidines.

M is a hydrogen atom, an alkali metal atom (for example, sodium, potassium), an ammonium group (for example, trimethylammonium, dimethylbenzylammonium), M = H or a group which can be an alkali metal atom under alkaline conditions (for example, acetyl, cyanoethyl, methane). Sulfonylethyl).

Further, the heterocyclic ring is a nitro group, a halogen atom (eg chlorine, bromine), a mercapto group, a cyano group, a substituted or unsubstituted alkyl group (eg, methyl, ethyl, propyl, t-butyl, cyanoethyl), an aryl group. (Eg phenyl, 4-methanesulfonamidophenyl, 4-methylphenyl, 3,4-dichlorophenyl, naphthyl), alkenyl group (eg allyl), aralkyl group (eg benzyl, 4-methylbenzyl, phenethyl), sulfonyl group (Eg, methanesulfonyl, ethanesulfonyl, p-toluenesulfonyl), carbamoyl group (eg, unsubstituted carbamoyl, methylcarbamoyl,
Phenylcarbamoyl), sulfamoyl group (eg unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl), carbonamide group (eg acetamide, benzamide), sulfonamide group (eg methanesulfonamide, benzenesulfonamide, p-toluenesulfone) Amide), acyloxy group (eg acetyloxy, benzoyloxy), sulfonyloxy group (eg methanesulfonyloxy), ureido group (eg unsubstituted ureido, methylureido, ethylureido, phenylureido), thioureido group (eg unsubstituted Thioureido, methylthioureido), acyl groups (eg acetyl, benzoyl), oxycarbonyl groups (eg methoxycarbonyl, phenoxycarbonyl), oxycarphonylamido A group (eg, methoxycarbonylamino, phenoxycarbonylamino, 2-ethylhexyloxycarbonylamino), carboxylic acid or a salt thereof, sulfonic acid or a salt thereof, a hydroxyl group, or the like, but a carboxylic acid or a salt thereof, a sulfone It is preferred that the acid or its salt or the hydroxyl group is not substituted in terms of the nucleation promoting effect.

Preferred heterocycles 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. As the divalent linking group, for example, And the like.

These linking groups are A or a straight-chain or branched alkylene group (for example, methylene, ethylene, propylene, butylene, hexylene, 1-methyleneethylene) or a substituted or unsubstituted arylene group (phenylene) on the ring with a heterocycle described later. , Naphthylene).

R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ and R ₂₈ are each a hydrogen atom, a substituted or unsubstituted alkyl group (for example, methyl, ethyl, propyl, n-butyl), a substituted or unsubstituted aryl group (eg, phenyl, 2-
Methylphenyl) substituted or unsubstituted alkenyl group (eg, propenyl, 1-methylvinyl), or substituted or unsubstituted aralkyl group (eg, benzyl,
Phenethyl).

R ₁₈ is a thioether group, an amino group (including a salt form),
It represents an organic group containing at least one ammonium group, ether group or heterocyclic group (including salt form). Examples of such an organic group include a group in which a group selected from a substituted or unsubstituted alkyl group, an alkenyl group, an aralkyl group or an aryl group and the above group are combined, and a combination of these groups is used. Good. For example, dimethylaminoethyl group, aminoethyl group, diethylaminoethyl group, dibutylaminoethyl group, hydrochloride of dimethylaminopropyl group, dimethylaminoethylthioethyl group,
4-dimethylaminophenyl group, 4-dimethylaminobenzyl group, methylthioethyl group, ethylthiopropyl group, 4-methylthio-3-cyanophenyl group, methylthiomethyl group, trimethylammonioethyl group, methoxyethyl group, methoxyethoxyethoxy Ethyl group, methoxyethylthioethyl group, 3,4-dimethoxyphenyl group,
3-chloro-4-methoxyphenyl group, morpholinoethyl group, 1-imidazolylethyl group, morpholinoethylthioethyl group, pyrrolidinoethyl group, piperidinopropyl group, 2-pyridylmethyl group, 2- (1-imidazolyl)
Ethylthioethyl, pyrazolylethyl, triazolylethyl, methoxyethoxyethoxyethoxycarbonylaminoethyl and the like. n represents 0 or 1, and m represents 0, 1 or 2.

In the general formula (III), L, R ₁₈ , n, and M have the same meanings as those in the general formula (II), m represents 1 or 2, and Q ′ represents a 5-membered or 6-membered member which can form imino silver. Represents the group of atoms required to form a heterocycle. Preferably, it represents an atomic group necessary for forming a 5- or 6-membered heterocyclic ring selected from carbon, nitrogen, oxygen, sulfur and selenium. Further, this heterocycle may be condensed as a carbon aromatic ring or a heteroaromatic ring. The heterocycle formed by Q ′ includes, for example, indazoles, benzimidazoles, benzotriazoles, benzoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles, triazoles, tetrazoles, tetraazaindenes. , Triazaindenes, diazaindenes, pyrazoles, indoles and the like.

As the compound represented by the general formula (II), those represented by the following general formulas (IV), (V), (VI), and (VII) are preferably used.

General formula (IV) In the formula, M, R ₁₈ , L and n have the same meanings as in formula (II). X represents an oxygen atom, a sulfur atom or a selenium atom, preferably a sulfur atom.

General formula (V) In the formula, R ₂₉ 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, a methyl group, an ethyl group, Etc.), alkenyl group (eg, propenyl group, 1-methylvinyl group, etc.) Aralkyl group (eg, benzyl group, phenethyl group, etc.), aryl group (eg, phenyl group, 2-methylphenyl group, etc.), Alternatively, it represents L _n R ₁₈ .

R ₃₀ represents a hydrogen atom, an unsubstituted amino group or L _n R _18, and when R ₂₉ and R ₃₀ represent L _n R ₁₈ , they may be the same or different from each other.

However, at least one of R ₂₉ and R ₃₀ represents L _n R ₁₈ .

M, R ₁₈ , L, and n have the same meanings as those in formula (II).

General formula (VI) In the formula, R ₃₁ represents L _n R ₁₈ . However, M, R ₁₈ , L, and n have the same meanings as those in the general formula (II).

General formula (VII) In the formula, R ₃₂ and R ₃₃ 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 and R ₃₁ have the same meanings as those in formula (VI).

Specific compounds represented by formulas (III) to (VII) are shown below, but the compounds that can be used are not limited thereto.

The nucleation accelerator can be contained in the light-sensitive material or the processing solution. Among the light-sensitive materials, the internal latent image type silver halide emulsion layer and other hydrophilic colloid layers (intermediate layer, protective layer, etc.) It is preferable to contain them. Particularly preferred is a silver halide emulsion layer or its adjacent layer.

The addition amount of the nucleation accelerator is 10 ^-6 to 1 mol / mol of silver halide.
It is preferably 10 ^-2 mol, more preferably 10 ^-5 to 10 ^-2 mol.

When a nucleation accelerator is added to a processing solution, that is, a developing solution or a prebath thereof, the amount is preferably 10 ^-8 to 10 ^-3 mol, more preferably 10 ^-7 to 10 ^-4 mol per one. .

The color developer used for the development processing of the light-sensitive material of the present invention,
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent, but p-
A phenylenediamine compound is preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N.
-Β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methoxyethylaniline and their sulfates, hydrochlorides or p-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
9.5 to 11.5.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing distance) or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.

The silver halide color photographic light-sensitive material used in the present invention is
After the desilvering process, it is common to carry out a washing and / or stabilizing process. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, and the temperature of rinsing water, the number of rinsing tanks (number of stages), replenishment method such as countercurrent and forward flow, and various other conditions. It can be set in a wide range. Of these, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in the Journal of the Society of Motion Pictu
re and Televison Engineers Volume 64, p248-253 (195
May, May 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 accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents.

On the other hand, to develop a black and white photosensitive material in the present invention,
Various known developing agents can be used. That is, polyhydroxybenzenes such as hydroquinone, 2-chlorohydroquinone, 2-methylhydroquinone, catechol, pyrogallol and the like; aminophenols such as p-aminophenol and N-methyl-
p-aminophenol, 2,4-diaminophenol and the like;
3-pyrazolidones, such as 1-phenyl-3-pyrazolidones, 1-phenyl-4,4'-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5 -Dimethyl-1-phenyl-3-pyrazolidone and the like; ascorbic acids and the like,
A single or a combination can be used. Also, JP-A-58-
The developer described in No. 55928 can also be used.

For detailed examples of developers, preservatives, buffers and developing methods for black-and-white photosensitive materials and their use, refer to Research Disclosure No.17643 (1978
Published in December) XIX to XXI.

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

Example 1 A paper support laminated on both sides with polyethylene (thickness 10
(0 micron), the following 1st to 14th layers were multilayer-coated, and the 15th to 16th layers were coated on the back side to prepare a color photographic light-sensitive material. The polyethylene coated on the first layer contains titanium oxide as a white pigment and a slight amount of ultramarine as a bluing dye (the chromaticity of the surface of the support is 88 in L ^* , a ^* , b ^* system).
It was 0 and -0.20-0.75. ).

(Composition of photosensitive layer) The components and the coating amount (g / m ² unit) are shown below. For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer was produced according to the production method of Emulsion EM1. However, as the emulsion for the 14th layer, a Lippmann emulsion which was not surface-sensitized was used.

1st layer (anti-halation layer) Black colloidal silver ... 0.10 Gelatin ... 0.70 2nd layer (intermediate layer) Gelatin ... 0.70 3rd layer (low sensitivity red sensitive layer) With red sensitizing dye (ExS-1,2,3) Spectral sensitized silver bromide (average grain size 0.25μ, size distribution [variation coefficient] 8
%, Octahedron ... 0.04 Silver chlorobromide spectrally sensitized with red sensitizing dye (ExS-1,2,3) (5 mol% silver chloride, average particle size 0.40μ, size distribution)
10%, octahedron) ... 0.08 Gelatin ... 1.00 Cyan coupler (ExC-1,2,3 equivalent) ... 0.30 Anti-fading agent (Cpd-1,2,3,4 equivalent) ... 0.18 Stin inhibitor (Cpd- 5)… 0.003 Coupler dispersion medium (Cpd-6)… 0.03 Coupler solvent (Soly-1,2,3 equivalent)… 0.12 4th layer (high sensitivity red sensitive layer) Red sensitizing dye (ExS-1,2, Silver bromide spectrally sensitized in 3) (average grain size 0.60μ, size distribution 15%, octahedron) ...
0.14 Gelatin 1.00 Cyan coupler (ExC-1,2,3 equivalent) 0.30 Antifade agent (Cpd-1,2,3,4 equivalent) 0.18 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent ( Solv-1,2,3 equivalent) 0.12 Fifth layer (intermediate layer) Gelatin 1.00 Color mixing inhibitor (Cpd-7) 0.08 Color mixing inhibitor solvent (Solv-4,5 equivalent) 0.16 Polymer latex (Cpd) -8)… 0.10 6th layer (low-sensitivity green-sensitive layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4) (average grain size 0.25μ, size distribution 8%, octahedron)… 0.04 Silver chlorobromide spectrally sensitized with a green sensitizing dye (ExS-4) (5 mol% silver chloride, average grain size 0.40μ, size distribution)
10%, octahedron) 0.06 Gelatin 0.80 Magenta coupler (ExM-1,2 equivalent) 0.11 Anti-fading agent (Cpd-9) 0.10 Anti-stain agent (Cpd-10,11,12,13 10: (7: 7: 1 ratio) ...
0.025 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Colv-4,6 equivalents) ... 0.15 7th layer (high sensitivity green sensitive layer) Odor spectrally sensitized with green sensitizing dye (ExS-4) Silver halide (average grain size 0.65μ, size distribution 16%, octahedron) 0.10 Gelatin 0.80 Magenta coupler (ExM-1,2 equivalent) 0.11 Anti-fading agent (Cpd-3) 0.10 Anti-stain agent (Cpd) -10,11,12,13 in 10: 7: 7: 1 ratio) ...
0.025 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv-4,6 equivalents) 0.15 Eighth layer (intermediate layer) Same as fifth layer Ninth layer (yellow filter layer) Yellow colloidal silver ... 0.12 Gelatin ... 0.07 Anti-color mixing agent (Cdp-7) ... 0.03 Anti-color mixing agent solvent (Solv-4,5 equivalent) ... 0.10 Polymer latex (Cpd-8) ... 0.07 10th layer (intermediate layer) Same as 5th layer 11th Layer (low-sensitivity blue-sensitive layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5,6) (average grain size 0.40μ, size distribution 8%, octahedron) ... 0.07 Blue sensitizing dye ( ExS-5,6) spectrally sensitized silver chlorobromide (silver chloride 8 mol%, average grain size 0.60μ, size distribution)
11%, octahedron) 0.14 Gelatin 0.80 Yellow coupler (Exy-1) 0.35 Antifade agent (Cpd-14) 0.10 Antistain agent (Cpd-5,15 in 1: 5 ratio) 0.007 Coupler dispersion Medium (Cpd-6) ... 0.05 Coupler solvent (Solv-2) ... 0.10 12th layer (high-sensitivity blue sensitive layer) Silver bromide (average grain) spectrally sensitized with a blue sensitizing dye (ExS-5,6) Size 0.85μ, size distribution 18%, octahedron) 0.15 Gelatin 0.60 Yellow coupler (ExY-1) 0.30 Anti-fading agent (Cpd-14) 0.10 Stain inhibitor (Cpd-5,15 1: 5 ratio 0.007 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10 13th layer (ultraviolet absorbing layer) Gelatin 1.00 Ultraviolet absorber (Cpd-2,4,16 equivalents) 0.50 Color mixing inhibitor (Cpd-7,17 equivalent) 0.03 Dispersion medium (Cpd-6) 0.02 UV absorber solvent (Solv-2,7 equivalent) 0.08 Anti-irradiation dye (Cpd-18,1) 9,20,21 to 10:10:
13:15 ratio) 0.04 14th layer (protective layer) Fine silver chlorobromide (97 mol% silver chloride, average size 0.2μ)
… 0.03 Polyvinyl alcohol acrylic modified copolymer… 0.01 Polymethylmethacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) Equivalent ... 0.05 Gelatin ... 1.80 Gelatin hardening agent (H-1, H-2 equivalent) ... 0.18 15th layer (back layer) Gelatin ... 2.50 16th layer (back side) Protective layer) Polymethylmethacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) Equivalent ... 0.05 Gelatin ... 2.00 Gelatin hardening agent (H-1, H-2 equivalent) ... 0.14 How to make emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate is added to acetic acid. Octahedral bromide containing 1 x 10 ^-4 mol of lead per 1 mol of Ag and having an average particle size of 0.40μ, which was added simultaneously to a gelatin solution containing lead at 75 ° C for 15 minutes with vigorous stirring. Silver particles were obtained. 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione per mol of silver, 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) were sequentially added to this emulsion for 80 minutes at 75 ° C. The chemical sensitization treatment was performed by heating. Using the particles thus obtained as a core, the particles are further grown in the same precipitation environment as in the first time,
Finally, an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.7 µ was obtained. The coefficient of variation of particle size was about 10%. To this emulsion, 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) were added per mol of silver, and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion. Obtained.

The nucleating agent shown in Table 1 was used for each photosensitive layer. Furthermore, alkanol XC is used as an emulsion dispersion aid in each layer.
(Dupon) and sodium alkylbenzenesulfonate as succinate and Magefac as coating aids.
F-120 (manufactured by Dainippon Ink and Chemicals, Inc.) was used. Layers containing silver halide and colloidal silver can be used as stabilizers (Cpd-23,24,2
5) was used. This sample was designated as a sample number. The compounds used in the examples are shown below.

Solv-1 di (2-ethylhexyl) sebacate Solv-2 trinonyl phosphate Solv-3 di (3-methylhexyl) phthalate Solv-4 tricresyl phosphate Solv-5 dibutyl phthalate Solv-6 trioctyl phosphate Solv-7 di ( 2-Ethylhexyl) phthalate H-1 1,2-bis (vinylsulfonylacetamido) ethane H-2 4,6-dichloro-2-hydroxy-1,3,5-triazine Na
Salt The color photographic paper thus produced was subjected to wedge exposure (3200K, 0.5 seconds, 10 CMS) and then subjected to processing step A to directly obtain a positive image.

 The magenta color image density was measured.

Samples Nos. 1 to 7 using the nucleating agent of the present invention had a higher Dmax than those of Comparative Example No. 8 and were preferred. Similar results were obtained with cyan and yellow color image densities.

Treatment process A Treatment process time Temperature Color development 135 seconds 38 ℃ Bleaching and fixing 40〃 33〃 Washing (1) 40〃 33〃 Washing (2) 40〃 33〃 Drying 30〃 80〃 2), and the overflow solution of the washing bath (2) was introduced into the washing bath (1), which was a so-called countercurrent replenishment system. At this time, the amount of the bleach-fixing solution brought in from the bleach-fixing bath with the light-sensitive material to the washing bath (1) is
It was 35 ml / m ² , and the ratio of the replenishing amount with water washing to the carried-in amount of the bleach-fixing solution was 9.1.

 The composition of each treatment liquid was as follows.

Color developer Mother liquor Ethylenediaminetetrakismethylenephosphonic acid 1.5g Diethylene glycol 10ml Benzyl alcohol 12.0ml Potassium bromide 1.60g Sodium sulfite 2.4g N, N-bis (carboxymethyl) hydrazine 4.0g Triethanolamine 6.0g N-ethyl-N- (Β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulphate 6.0g Potassium carbonate 30.3g Fluorescent brightener (diaminostilbene type) 1.0g Water added 100ml pH (25 ℃) 10.50 Bleach-fixer mother liquor Ethylenediaminetetraacetic acid / 2 sodium・ Dihydrate 4.0g Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ammonium ・
Dihydrate 70.0g Ammonium thiosulfate (700g /) 180ml Sodium p-toluenesulfinate 20.0g Sodium bisulfite 20.0g 2-Amino-5-mercapto-1,3,4-thiadiazole
0.6g Ammonium nitrate 10.0g Add water 1000ml pH (25 ℃) 6.20 Washing water Both mother liquor and replenisher are tap water with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion. Water was passed through a mixed bed column packed with exchange resin (Amberlite IR-400) to reduce the concentration of calcium and magnesium ions to 3 mg / or less, followed by sodium diisocyanurate dichloride 20 mg / and sodium sulfate 1.5 g. / Was added. The pH of this solution was in the range of 6.5-7.5.

Example 2 A color photographic paper was prepared in the same manner as in Sample No. 1 of Example 1 except that the nucleating agent was changed to that shown in Table 2. This sample was stored in an atmosphere of 45 ° C. and 80% RH for 4 days, then subjected to wedge exposure (5400K, 0.8 seconds, 10 CMS), and a treatment step B was performed. The resulting cyan color image density was measured.

Sample Nos. 9 to 13 using the nucleating agent of the present invention show that the decrease in Dmax and the increase in Dmin due to incubation are N of Comparative Example 1.
I liked it smaller than o.14.

Processing step B time Temperature color development 110 seconds 38 ℃ Bleach fixing 30 seconds 38 ℃ Water wash 30 seconds 38 ℃ Water wash 30 seconds 38 ℃ [Color development] Mother liquor Diethylenetriaminepentaacetic acid 0.5g 1-Hydroxyethylidene-1,1-diphosphonic acid 0.5g Diethylene glycol 8.0g Benzyl alcohol 9.0g Sodium bromide 0.7g Sodium chloride 0.5g Sodium sulfite 2.0g Hydroxylamine sulfate 2.8g 3-Methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate Salt 2.0 g 3-Methyl-4-amino-N-ethyl-N- (β-hydroxylethyl) -aniline sulfate 4.0 g Potassium carbonate 30.0 g Optical brightener (stilbene type) 1.0 g Pure water added 1000 ml pH 10.50 pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fixing solution] Mother liquor Ammonium thiosulfate 77g Sodium hydrogen sulfite 14.0g Ammonium ethylenediaminetetraacetate (III) dihydrate 40.0g Ethylenediaminetetraacetic acid disodium dihydrate 4.0g 2-Mercapto-1,3,4- Triazole 0.5 g Pure water was added to 1000 ml pH 7.0 [Washing water] Pure water was used (mother liquor = replenisher) Example 3 Implemented except that a nucleating agent and a nucleating accelerator were used as shown in Table 3. In the same manner as in Example 1, the color printing paper produced was subjected to the above-mentioned processing step A after wedge exposure (3200K, 0.2 seconds, 10 CMS). The magenta color image density was measured.

Sample using the nucleating agent of the present invention, and further a nucleating accelerator
No.15,16,18,19,21,22 No.17,2 without using nucleation accelerator
0,23 and No. 24-26 of the comparative example, Dmax is higher and D
min was low and was good. Similar results were obtained with cyan and yellow color image densities.

Example 4 A color photographic paper was produced in the same manner as in Example 1 except that a nucleating agent and a nucleating accelerator were used as shown in Table 4. These samples were stored in an atmosphere of 60 ° C and 55% RH for 4 days, then exposed to wedge (5400K, 0.2 seconds, 10CMS),
The processing step B was performed. The cyan color density of the obtained direct positive image was measured.

Nucleating agent of the present invention, sample No. 27 using the nucleation accelerator,
Nos. 28, 30 and 31 of Nos. 29 and 32, which do not use a nucleation accelerator, and comparative examples
Compared to Nos. 33-35, the decrease in Dmax and the increase in Dmin due to incubation were small and preferred.

(Effect of the Invention) According to the present invention, a sufficiently large Dmax can be obtained even if a direct positive photographic light-sensitive material is subjected to development processing at a low pH of 11 or less. Then, as can be seen from Examples 1 to 4, a large Dmax can be obtained at any of the magenta, cyan and yellow color image densities. Further, even if the positive photographic light-sensitive material is directly stored under high temperature and high humidity, the image formation can be stably performed by the development processing according to the present invention.

Claims (1)

(57) [Claims] 1. A direct positive photographic light-sensitive material having a layer containing at least one pre-fogged internal latent image type silver halide grain on a support is developed after or while being fogged. In the direct positive image forming method, the fog treatment is performed in the presence of a compound represented by the following general formula (I). General formula (I) In the formula, A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other represents a sulfonyl group or an acyl group, R ₁ represents an aliphatic group, an aromatic group, or a heterocyclic group, G ₁ is Carbonyl group, sulfonyl group, sulfoxy group, (R ₂ represents an alkoxy group or an aryloxy group), Or an iminomethylene group, X ₁ is a group capable of splitting the -G ₁ -X ₁ moiety from the residual molecule, and causing a cyclization reaction to form a cyclic structure containing the atoms of the -G ₁ -X ₁ moiety. Is. Here, at least _one of R _{1 and} X ₁ has _a group capable of dissociating into an anion having _a pK _a 6 or higher, or an amino group.