JP2592688B2 - Direct positive image forming method - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a photographic image forming method, and more particularly, to a direct positive image forming method that provides a high maximum image density (Dmax) and a low minimum image density (Dmin).

[Conventional technology]

It is well known that an internal latent image type silver halide emulsion which has not been fogged in advance is subjected to fogging after image exposure or surface development while performing fogging to directly obtain a positive image.

Here, the internal latent image type silver halide photographic emulsion is
A silver halide photographic emulsion having a photosensitive nucleus mainly inside silver halide grains and forming a latent image mainly inside the grains upon exposure.

Various techniques are known in the art. For example, U.S. Pat.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 direct positive image, see, for example, “The Theory of the Photographic Process” by TH James.
ss), 4th edition, Chapter 7, pages 182 to 193 and U.S. Pat.
No. 1,276.

In other words, due to the surface desensitization effect caused by the so-called internal latent image generated inside the silver halide by the first imagewise exposure, fog nuclei are selectively generated only on the surface of the silver halide grains in the unexposed areas, Then, a photographic image (direct positive image) is formed on the unexposed area by performing a normal so-called surface development process.
Is believed to be formed.

As described above, as a means for selectively generating a fog nucleus, a method of giving a second exposure to the entire surface of a photosensitive layer, which is generally called a "light fogging method" (for example, British Patent No. 1,151,363)
Nucleating agent called “chemical fogging method”
ng agent) is known. For the latter method, see, for example, “Research Disclosure, Vol. 151, No. 15162 (19)
Issued on Nov. 76) on pages 76-78.

In order to directly form a positive (color) image, after performing a fogging process on the internal latent image type silver halide photosensitive material or performing a surface developing process while performing the fogging process, then (bleaching), fixing (or ( (Bleaching) can be achieved by fixing.
After the (bleaching) fixing process, a washing and / or stabilizing process is usually performed.

[Problems to be solved by the invention]

Hydrazine compounds are well known as nucleating agents used in the "chemical fogging method".

The hydrazine-based nucleating agent generally has a maximum image density (Dma
x) and the minimum image density (Dmin) are large and are the best in terms of discrimination.
It has the disadvantage of requiring a pH (pH> 12).

Heterocyclic quaternary ammonium salts are known as nucleating agents that act even at low treatment pH (pH ≦ 12), for example, US Pat. Nos. 3,615,615, 3,719,494, 3,734,738,
3,759,901, 3,854,956, 4,094,683, 4,3
No. 06,016, British Patent 1,283,835, JP-A-52-3,426 and JP-A-52-69,613. In particular U.S. Patent 4,1
The propargyl- or butynyl-substituted heterocyclic quaternary ammonium salt compounds described in US Pat. No. 15,122 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 example, for the purpose of spectral sensitization, the sensitizing dye and the heterocyclic quaternary ammonium nucleating agent
Competitive adsorption to silver halide emulsions occurs, so it is necessary to add a large amount of a quaternary salt nucleating agent with low adsorptivity, especially in the case of multilayer color light-sensitive materials, which may cause uneven density and loss of color balance. Yes, it could not be said to show 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, the introduction amount of the adsorbing group reduces the amount of addition necessary to obtain a sufficient Dmax,
The reduction in Dmax is said to be improved, but this effect was not at a satisfactory level.

As another method for solving the above problem, Japanese Patent Application Laid-Open No.
06656, -401480, -60449, -121842,-
226652, -239438, -231448, JP-A-64-70743
No.-65551, No.-65543, JP-A-1-93739, No.-96
645, -102556, -147450, -150133, -1
No. 54056, -145646, etc., are reported to give a high Dmax and a low Dmin using a compound that can be adsorbed to silver halide, but this is not sufficient, especially regarding the method of giving a low Dmin. There was none.

Accordingly, it is an object of the present invention to provide a direct positive photographic material which provides a high maximum image density and a low minimum image density, especially a low minimum image density.

An object of the present invention is to provide a photosensitive material having at least one internal latent image type direct positive silver halide photographic emulsion layer on a support after imagewise exposure, fog processing, or development processing while performing fog processing. In the direct positive image forming method, the development processing is performed in the presence of the following general formula (I).

General formula (I) Wherein, X is -O -, - S-, represents NR ^2, R ² is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, an aryl group, an amino group, an acylamino group, a heterocyclic group Express. R ¹ represents a heterocyclic group.

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

Hereinafter, the general formula (I) will be described in detail. R ² is a hydrogen atom substituted or unsubstituted alkyl group (for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, dimethylaminoethyl group, n-decyl group, etc.), alkenyl group ( For example, allyl group, butenyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, etc.), cycloalkyl group (eg, cyclohexyl group, 2-methylcyclohexyl group, etc.), aryl group (eg, phenyl group, naphthyl group, 4-methylphenyl group, 4-methoxyphenyl group, 3-ethoxycarbonylphenyl group, 3-carboxyphenyl group, etc.), amino group, acylamino group (for example, acetylamino group, propionylamino group, methoxypropionylamino group,
Etc.) and a heterocyclic group (for example, 4-pyridyl group, 2-pyridyl group, 2-thienyl group, 2-furyl group, 2-tetrahydropyranyl group, etc.).

R ¹ is a substituted or unsubstituted heterocyclic group (eg, 2
-Pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-
Methyl-4-pyridyl group, 4-quinolyl group, 2-thienyl group, 2-furyl group, 2-pyrrolyl group, 1-methyl-2
-Indolyl group, 4-hydroxy-2-quinolyl group, 2
-Tetrahydrothienyl group, 2-pyrrolidinyl group, 2-
Morpholinyl group, 2-imidazolyl group, 5-tetrazolyl group, 2-triazinyl group, 4-piperidinyl group, etc.)
Represents

M represents a hydrogen atom, an alkali metal atom (eg, a sodium atom, a potassium atom, etc.), an ammonium group (eg,
A trimethylammonium group, a dimethylbenzylammonium group, etc.) and a group which can be M = H or an alkali metal atom under alkaline conditions (eg, an acetyl group, a cyanoethyl group, a methanesulfonylethyl group, etc.).

In formula (I), X is preferably -O- or -S-, R ¹ is a pyridyl group, a furyl group, or an imidazolyl group, and M represents a hydrogen atom or an alkali metal atom.

Hereinafter, specific examples of the compound represented by formula (I) of the present invention are shown, but the compound of the present invention is not limited thereto.

The compound of the general formula (I) used in the present invention is a compound of the formula: Berichte der Deutschen Chemischen Gesellschaf
t) 28 , 77 (1875), JP-A-50-37436, JP-A-51-3231,
U.S. Pat. No. 3,295,976, U.S. Pat. No. 3,376,310, Berichte der Deutschen Chemischen Gesellschaft
22 , 568, (1889), 29 , 2483 (1896), Journal of Chemical Society (J. Chem. Soc.) 193
2 , 1806, Journal of the America Chemical Society (J. Am. Chem. Soc.) 71 , 4000 (1949),
U.S. Pat. Nos. 2,585,388 and 2,541,924, Advances in Heterocyclic Chemistry (Advances
in Heterocyclic Chemistry) 9 , 165 (1968), Organic synthesis IV, 569 (19)
63), Journal of the American Chemical
J. Am. Chem. Soc. 45, 2390 (1923), Chemische Berichte 9, 465 (187)
6), JP-B-40-28496, JP-A-50-89034, U.S. Patent
3,106,467, 3,420,670, 2,271,229, 3,13
7,578, 3,148,066, 3,511,663, 3,060,028
Nos. 3,271,154, 3,251,691, 3,598,599,
3,148,066, JP-B-43-4135, U.S. Patent 3,615,616
No. 3,420,664, 3,071,465, 2,444,605,
The compounds can be synthesized according to the methods described in JP-A-2,444,606, JP-A-2,444,607, JP-A-2,935,404, and the like, and the synthesis examples shown below.

Synthesis Example 1 (Synthesis Method of Exemplified Compound 1-3) Isonicotinic acid hydrazide 68.6 g and potassium hydroxide 33.
To 0 g, 700 ml of isopropyl alcohol was added and dissolved by heating. Then, 60 ml of carbon disulfide was added dropwise, and the mixture was heated under reflux for 4 hours. After cooling to room temperature, 700 ml of water and 44 ml of concentrated hydrochloric acid were added, and the precipitated crystals were collected by filtration and recrystallized from a mixed solvent of 300 ml of isopropyl alcohol and 300 ml of dimethylformamide to obtain the desired product.

Yield: 43.3 g Melting point: 258 ° C. Synthesis Example 2 (Synthesis of Exemplified Compound I-1) 68.6 g of isonicotinate hydrazide and methyl alcohol 5
After adding and dissolving 00 ml, 60 ml of carbon disulfide and 33.0 g of potassium hydroxide were added under ice cooling, and the precipitated crystals were collected by filtration. The obtained crystals were added to 300 ml of concentrated sulfuric acid while keeping the temperature at 5 ° C. or lower, and then 500 ml of water was added. When the pH was adjusted to 4 with a 1N aqueous sodium hydroxide solution, crystals were precipitated.

The precipitated crystals were collected by filtration and dimethylformamide 200 ml
To give the desired product.

Yield: 38.1 g Melting point: 256 ° C. The compound of the formula (I) can be contained in a light-sensitive material or a processing solution, but among the light-sensitive materials, an internal latent image type silver halide emulsion and other hydrophilic colloid layers ( In the intermediate layer and the protective layer. Particularly preferred is a silver halide emulsion or a phosphorus contact layer thereof.

The addition amount of the compound of the general formula (I) is preferably 10 ^-6 to 10 ^-2 mol, more preferably 10 ^-5 to 10 mol per mol of silver halide.
10 ^-2 moles.

When the compound of the general formula (I) is added to a processing solution, that is, a developing solution or a pre-bath thereof, 10 ^-8 to
It is preferably 10 ^-3 mol, more preferably 10 ^-7 to 10 ^-4 mol.

The compound of the general formula (I) of the present invention has the following general formula [N
When used in the presence of at least one nucleating agent represented by -I] and [N-II], the object of the present invention can be more remarkably achieved.

General formula [NI] (In the general formula [N-1], Z represents a group of nonmetal atoms necessary to form a 5- or 6-membered heterocyclic ring, R ¹¹ is an aliphatic group, R ¹² is a hydrogen atom, an aliphatic group or an aromatic group .Z, R ^11, R ¹² may be optionally substituted, also R ¹² is may form a ring by combining with heterocyclic ring further completed by Z. However R ^11, At least one of the groups represented by R ¹² and Z contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or forms a 6-membered ring with R ¹¹ and R ¹² to form a dihydropyridinium skeleton. Y is a counter ion for charge balance, and n is 0 or 1.

General formula [N-II] (In the general formula [N-II], R ²¹ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ²² represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, Or G represents an amino group, G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, or an iminomethylene group (HN =); R ²³ and R ²⁴ are both hydrogen atoms, or one of them is a hydrogen atom and the other is a hydrogen atom; an alkylsulfonyl group, an arylsulfonyl group or represents one one of the acyl group. However, G, may be formed hydrazone structure (N-N = C) in a form, including R ^22, R ²⁴ and hydrazine nitrogen.

Hereinafter, the general formulas [NI] and [N-II] will be described in detail.

In the general formula [NI], the heterocycle completed with Z is, for example, quinolinium, benzothiazolium, benzimidazolium, pyridinium, thiazolinium, thiazolium, naphthothiazolium, selenazolium, benzoselenazolium, imidazolium , Tetrazolium,
Indolenium, pyrrolium, acridinium, phenanthridinium, inquinolinium, oxazolium, naphthoxazolium and benzoxazolium nuclei. Examples of the substituent of Z include an alkyl group, an anenyl group, an aralkyl group, an aryl group, an alkynyl group,
Hydroxy group, alkoxy group, aryloxy group, halogen atom, amino group, alkylthio group, arylthio group, acyloxy group, acylamino group, sulfonyl group,
Sulfonyloxy group, sulfonylamino group, carboxyl group, acyl group, carbamoyl group, sulfamoyl group,
Examples thereof include a sulfo group, a cyano group, a ureido group, a urethane group, a carbonate group, a hydrazine group, a hydrazone group, and an imino group. As the substituent of Z, for example, at least one substituent is selected from the above-mentioned substituents, but when two or more substituents are present, they may be the same or different. The above substituents may be further substituted with these substituents.

Further, as a substituent of Z, it may have a heterocyclic quaternary ammonium group completed by Z via an appropriate linking group L.
In this case, a so-called dimer structure is adopted.

The heterocyclic ring completed by Z preferably includes a quinolinium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, and inquinolinium nucleus. More preferred are quinolinium and benzothiazolium, and most preferred is quinolinium.

The aliphatic groups represented by R ¹¹ and R ¹² are an unsubstituted alkyl group having 1 to 18 carbon atoms and a substituted alkyl group having 1 to 18 carbon atoms in the alkyl portion. Examples of the substituent include those described as the substituent for Z.

The aromatic group represented by R ¹² is one having 6 to 20 carbon atoms, such as phenyl group, and a naphthyl group.
Examples of the substituent include those described as the substituent of Z. R ¹² is preferably an aliphatic group, and most preferably a methyl group, a substituted methyl group, or a heterocyclic ring completed by Z to form a ring.

At least one of the groups represented by R ¹¹ , R ¹² and Z has an alkynyl group, an acyl group, a hydrazine group, or a hydrazine group, or forms a 6-membered ring with R ¹¹ and R ¹² , They form pyridinium skeletons, which may be substituted with the groups described above as substituents for the group represented by Z.

When at least one of the groups represented by R ¹¹ , R ¹² and Z or a substituent on the ring is an alkynyl group or an acyl group, or R ¹¹ and R ¹² are linked to form a dihydropyridinium skeleton The case is preferable, and the case where at least one alkynyl group is further included is preferable, and the propargyl group is particularly preferable.

The group represented by X ^1- (L ¹ ) _m is preferably used as the group for promoting adsorption to silver halide which the substituents of R ¹¹ , R ¹² and Z have. Here, X ¹ is an adsorption promoting group for silver halide, and L ¹
Is a divalent linking group, and n is 0 or 1.

Preferred examples of the group for promoting adsorption to silver halide represented by X ¹ include a thioamide group, a malcapto group and
And a 6-membered nitrogen-containing heterocyclic group.

These may be substituted by those described as substituents for Z. The thioamide group is preferably an acyclic thioamide group (for example, a thiourethane group, a thioureido group, etc.).

The mercapto group of X ^1, especially heterocyclic mercapto ring (e.g. 5-mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2-mercapto-1,3,4
Thiazoazole, 2-mercapto-1,3,4-oxadiazole and the like are preferred.

The 5- or 6-membered nitrogen-containing heterocycle represented by X ¹ is a combination of nitrogen, oxygen, sulfur and carbon, and preferably forms imino silver, and includes, for example, benzotriazole and aminothiatriazole. .

The divalent linking group represented by L ¹ is an atom or an 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-, -N
=, - CO -, - SO 2 - ( may have these groups the substituents), it is made of a single or a combination thereof and the like. Examples of combinations are: −SO ₂ NH−, -NHSO ₂ NH -, - (alkylene) − (Arylene) −SO ₂ NH −, − (arylene) -(Arylene) Are preferred.

As the counter ion Y for charge balance, for example, bromine ion, chloride ion, iodine ion, p-toluenesulfonic acid, ethylsulfonic acid ion, perchlorate ion, trifluoromethanesulfonic acid ion, thiocyan ion, boron tetrafluoride Ion and phosphorus hexafluoride ion.

These compounds and their synthesis methods are described, for example, in Research
Research Disclosure Magazine No.22,5
No. 34 (issued in January 1983, pp. 50-54) and No. 23,213 (1
Issued in August 983, pages 267 to 270), JP-B-49-38,164, JP-B-52-19,452, JP-B-52-47,326, JP-A-52-69,613, JP-A-52,3,426, No. 55-138,742, No. 60-
No. 11,837, U.S. Pat. Nos. 4,306,016 and 4,471,044.

Specific examples of the compound represented by the general formula [NI] are shown below, but it should not be construed that the invention is limited thereto.

In the general formula [N-II], R ²¹ is preferably
It is an aromatic group, an aromatic hetero ring or an aryl-substituted methyl group, and more preferably an aryl group (for example, a phenyl group, a naphthyl group and the like). R ²¹ may be substituted by substitution, and examples of the substituent include the following. These groups may be further substituted. For example, alkyl group, aralkyl group, alkoxy group, alkyl or 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, Examples thereof include a sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, and a phosphoric amide group.

Of these, a ureido group and a sulfonylamino group are particularly preferred.

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

R ²² is preferably a hydrogen atom, an alkyl group (eg, a methyl group), an aralkyl group (eg, a 2-hydroxybenzyl group) or an aryl group (eg, a 2-hydroxymethylphenyl group), and particularly a hydrogen atom And an aryl group.

Examples of the substituent of R ^22, except that can be applied substituents listed for R ^21, for example, an acyl group, an acyloxy group, an alkyl- or aryloxycarbonyl group, an alkenyl group, even an alkynyl group or a nitro group apply. These substituents may be further substituted with these substituents. When possible, these groups may be connected to each other to form a ring.

R ²¹ or R ²² , among which R ²¹ , may contain a diffusion-resistant group such as a coupler, or may have a group X ² L ² _m2 which promotes adsorption to the surface of silver halide grains. At this time, it is particularly preferable to link with a ureido group or a sulfonylamino group.

Here, X ² has the same meaning as X ¹ in the general formula [NI], and is preferably a thioamide group, a mercapto group, or 5
And a 6-membered nitrogen-containing heterocyclic group. L ² represents a divalent linking group, the same meanings as L ¹ in the general formula [N-I]. m ² is 0 or 1.

More preferred X ² is an acyclic thioamide group (eg, thioureido group, thiourethane group, etc.), a cyclic thioamide group (ie, a mercapto-substituted nitrogen-containing heterocyclic ring such as 2-mercaptothiadiazole, 3-mercapto-1,
2,4-triazole, 5-mercaptotetrazole, 2
-Mercapto-1,3,4-oxadiazole, 2-mercaptobenzoxazole) or a nitrogen-containing heterocyclic group (eg, benzotriazole group, benzimidazole).

X ² is preferably a mercapto-substituted nitrogen-containing heterocycle or a nitrogen-containing heterocycle forming imino silver.

R ²³ and R ²⁴ are preferably hydrogen atoms. G is most preferably a carbonyl group.

As the general formula [N-II], those having an adsorptive group to silver halide and those having a ureido group or a sulfonylamino group are preferable.

In the synthesis method of [N-II], first, as examples of synthesizing a hydrazine-based nucleating agent having a silver halide adsorbing group, for example, U.S. Patent Nos. 4,030,925, 4,080,207, and 4,031,12
No. 7, No. 3,718,479, No. 4,269,929, No. 4,276,3
No. 64, No. 4,278,748, No. 4,385,108, No. 4,459,
No. 347, 4,478,928, 4,560,632, UK Patent 2,0
No. 11,391B, JP-A-54-74,729, JP-A-55-163533, JP-A-55-163533
Nos. 74536 and 60-179734.

Other examples of the synthesis of hydrazine-based nucleating agents include, for example, JP-A-57-86829, U.S. Patent Nos. 4,560,638 and 4,4
No. 78,928, and also Nos. 2,563,785 and 2,588,982
No.

Specific examples of the compound represented by the formula [N-II] are shown below, but the present invention is not limited thereto.

In the present invention, when the compounds represented by the general formulas [NI] and [N-II] are contained in a photographic light-sensitive material, alcohols (for example, methanol and ethanol),
A solution of an organic solvent miscible with water such as esters (eg, ethyl acetate) and ketones (eg, acetone) may be added to the hydrophilic colloid solution as an aqueous solution if it is water-soluble.

When it is added to a photographic emulsion, it may be added at any time from the start of chemical ripening to before coating, but preferably after chemical ripening.

In the present invention, the nucleating agents represented by the general formulas [NI] and [N-II] may be contained in the hydrophilic colloid layer adjacent to the silver halide emulsion layer. Is preferably contained. The addition amount may vary over a wide range because it varies depending on the characteristics of the silver halide emulsion actually used, the chemical structure of the nucleating agent and the development conditions, but about 1 × per mole of silver in the silver halide emulsion.
A range of 10 ^-8 moles to about 1 x 10 ^-2 moles is practically useful, preferably from about 1 x 10 ^-7 to about 1 x 10 ^-3 mole per mole of silver.

The nucleating agent of the present invention preferably [N-I], further if R ¹² Among the [N-I] to form a ring with a plurality ring completed by Z are preferred.

In the present invention, in order to further promote the action of the nucleating agent, the following nucleating accelerator can be used.

Further, the compound of the general formula (I) of the present invention has the following general formula (I)
When used in combination with at least one compound represented by I) and (III), discrimination of a high maximum concentration and a low minimum concentration can be more achieved.

General formula (II) General formula (III) In the formula, Q represents an atom group necessary for forming a 5- or 6-membered heterocyclic ring. Q 'represents an atom group necessary for forming a 5- or 6-membered heterocyclic ring capable of forming imino silver. The heterocyclic ring may be fused with a carbon aromatic ring or a heteroaromatic ring.

However, the case where the substituent on the heterocyclic ring of Q and Q 'is a heterocyclic group is excluded.

M is a hydrogen atom, an alkali metal atom, an ammonium group,
Or a group which is cleaved under alkaline conditions.

Hereinafter, the general formulas (II) and (III) will be described in detail.

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 heterocyclic ring may be fused with a carbon aromatic ring or a heteroaromatic ring.

As the heterocycle, for example, tetrazole, triazole, imidazole, thiadiazole, oxadiazole, selenadiazole, oxazole, thiazole, benzoxazole, benzthiazole, benzimidazole, pyrimidine and the like can give.

M represents a hydrogen atom, an alkali metal atom (eg, a sodium atom, a potassium atom, etc.), an ammonium group (eg,
A trimethylammonium group, a dimethylbenzylammonium group, etc.) and a group which can be M = H or an alkali metal atom under alkaline conditions (eg, an acetyl group, a cyanoethyl group, a methanesulfonylethyl group, etc.).

In addition, these heterocycles may be nitro group, halogen atom (eg, chlorine atom, bromine atom, etc.), mercapto group, cyano group, and substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, propyl group, t-group). Butyl group,
Methoxyethyl group, methylthioethyl group, dimethylaminoethyl group, morpholinoethyl group, dimethylaminoethylthioethyl group, diethylaminoethyl group, dimethylaminopropyl group, dipropylaminoethyl group, dimethylaminohexyl group, methylthiomethyl group, methoxyethoxy Ethoxyethyl group, trimethylammonioethyl group, cyanoethyl group, etc.), aryl group (for example, phenyl group, 4-methanesulfonamidophenyl group, 4-methylphenyl group, 3-methoxyphenyl group, 4-dimethylaminophenyl group, 3,4-dichlorophenyl group, naphthyl group, etc.), alkenyl group (eg, allyl group, etc.), aralkyl group (eg, benzyl group, 4-methylbenzyl group, phenethyl group, 4-methoxybenzyl group, etc.), Alkoxy groups (eg meth Si, ethoxy, methoxyethoxy, methylthioethoxy, dimethylaminoethoxy, etc., aryloxy (eg, phenoxy, 4-methoxyphenoxy, etc.), alkylthio (eg, methylthio, ethylthio, propylthio) Group, methylthioethyl group, dimethylaminoethylthio group, methoxyethylthio group, morpholinoethylthio group,
A dimethylaminopropylthio group, a piperidinoethylthio group, a pyrrolidinoethylthio group, a morpholinoethylthioethylthio group, an imidazolylethylthio group, a 2-pyridylmethylthio group, a diethylaminoethylthio group, etc., an arylthio group (for example, phenylthio Group, 4-dimethylaminophenylthio group, etc.), heterocyclic oxy group (for example, 2-pyridyloxy group, 2-imidazolyloxy group,
Etc.), a heterocyclic thio group (for example, 2-benzthiazolylthio group, 4-pyrazolylthio group, etc.), a sulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group, methoxyethylsulfonyl group, dimethyl Aminoethylsulfonyl group, etc.), carbamoyl group (for example, unsubstituted carbamoyl group, methylcarbamoyl group, dimethylaminoethylcarbamoyl group, methoxyethylcarbamoyl group, morpholinoethylcarbamoyl group, methylthioethylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl Groups (eg, unsubstituted sulfamoyl, methylsulfamoyl, imidazolylethylsulfamoyl, phenylsulfamoyl,
), A carbonamide group (eg, an acetamido group, a benzamide group, a methoxypropionamide group, a dimethylaminopropionamide group, etc.), a sulfonamide group (eg, a methanesulfonamide group, a benzenesulfonamide group, a p-toluenesulfonamide group, Etc.), acyloxy group (for example, acetyloxy group, benzoyloxy group,
), A sulfonyloxy group (eg, a methanesulfonyloxy group, etc.), a ureido group (eg, an unsubstituted ureido group, a methylureido group, an ethylureido group, a methoxyethylureido group, a dimethylaminopropylureido group,
A methylthioethylureido group, a morpholinoethylureido group, a phenylureido group, etc.), a thioureido group (for example, an unsubstituted thioureido group, a methylthioureido group,
Methoxyethylthioureido group, etc.), acyl group (eg, acetyl group, benzoyl group, 4-methoxybenzoyl group, etc.), oxycarbonyl group (eg, methoxycarbonyl group, phenoxycarbonyl group, methoxyethoxycarbonyl group, methylthioethoxycarbonyl group) Methoxyethoxyethoxyethoxycarbonyl group, dimethylaminoethoxycarbonyl group, morpholinoethoxycarbonyl group, etc.), oxycarbonylamino group (for example, methoxycarbonylamino group, phenoxycarbonylamino group, 2-ethylhexyloxycarbonylamino group,
Etc.), an amino group (eg, an unsubstituted amino group, a dimethylamino group, a methoxyethylamino group, an anilino group, etc.), a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a hydroxyl group, and the like.

In the general formula (III), M has the same meaning as that of the general formula (II). Q 'represents a group of atoms necessary for forming a 5- or 6-membered heterocyclic ring capable of forming imino silver, and is preferably a group consisting of at least one of carbon, nitrogen, oxygen, sulfur and selenium atoms. Represents an atom group necessary to form a 5- or 6-membered heterocyclic ring. Further, the heterocyclic ring may be condensed with a carbon aromatic ring or a heteroaromatic ring. Examples of the heterocyclic ring formed by Q ′ include indazoles, benzimidazoles, benzotriazoles, benzoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles,
Examples include triazoles, tetrazoles, tetrazaindenes, triazaindenes, diazaindenes, pyrazoles, indoles and the like. The groups which may be substituted on these heterocycles are the same as the above-mentioned substituents for Q.

Specific examples of the general formulas (II) and (III) are shown below, but the compounds of the present invention are not limited thereto.

The compounds represented by the general formulas (II) and (III) can be contained in a light-sensitive material or a processing solution. Among the light-sensitive materials, an internal latent image type silver halide emulsion and other hydrophilic colloid layers ( In the intermediate layer and the protective layer. Particularly preferred is a layer in or adjacent to a silver halide emulsion.

The amount of the general formulas (II) and (III) is 1
It is preferably 10 ^-6 to 10 ^-2 mol per mol, more preferably 10 ^-6 to 10 ^-2 mol.
^-5 to 10 ^-2 mol.

When the general formulas (II) and (III) are added to a processing solution, that is, a developing solution or a prebath thereof, 10 to 10
^{The amount} is preferably from ^-8 to 10 ^-3 mol, more preferably from 10 ^-7 to 10 ^-4 mol.

The non-pre-fogged internal latent image type silver halide emulsion used in the present invention is an emulsion containing silver halide in which the surface of silver halide grains is not pre-fogged and a latent image is mainly formed inside the grains. More specifically, a specific amount (0.5 to 3) of a silver halide emulsion is coated on a transparent support.
g / m ² ) and exposed to it for a fixed period of time of 0.01 to 10 seconds.
The maximum density measured by a usual photographic density measurement method when developed for 5 minutes at a temperature of 20 ° C. in a developing solution B (surface type developing solution) described below was coated in the same amount as described above and exposed in the same manner. Are preferably at least 5 times larger than the maximum density obtained when the development is carried out for 6 minutes, more preferably at least 10 times larger.

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 Add water. 1 Specific examples of internal latent image type emulsion
No. 1011062, U.S. Pat.Nos. 2,592,250 and 2,456,
The conversion type silver halide emulsion and the core / shell type silver halide emulsion described in the specification of JP-A No. 943 can be mentioned. Examples of the core / shell type silver halide emulsion are described in JP-A-47-32813, No. 47-32814, No. 52-134721
Nos. 52-156614, 53-60222, 53-66218, 5
3-66727, 55-127549, 57-136641, 58-7022
No. 1, No. 59-208540, No. 59-216136, No. 60-107641,
No. 60-247237, No. 61-2148, No. 61-3137, Special Publication No. 56-
No. 18939, No. 58-1412, No. 58-1415, No. 58-6935, No.
58-108528, Japanese Patent Application No. 61-36424, U.S. Pat.
3317322, 3761266, 3761276, 3850637,
No. 3923513, No. 4035185, No. 4395478, No. 4504570
And European Patent 0017148, Research Disclosure Magazine 16345 (November 1977) and the like.

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. Emulsions having a complex form of these various crystal forms or an emulsion composed of a mixture thereof may be used.

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

The average grain size of the silver halide grains is 2 μm or less.
The thickness is preferably 0.1 μm or more, and particularly preferably 1 μm or less and 0.15 μm or more. The particle size distribution may be either narrow or wide, but within ± 40% of the average particle size in terms of the number or weight of the particles to improve graininess and sharpness, etc.
It is preferred to use a so-called "monodisperse" silver halide emulsion having a narrow grain size distribution such that 90% or more of all grains fall within ± 20%. 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 a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the surface of the grains by sulfur selenium sensitization, reduction sensitization, noble metal sensitization or the like, alone or in combination. A detailed example is described in, for example, a patent described in Research Disclosure Magazine No. 17643-III (issued in December 1978) P23.

The photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye by a conventional method. 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 dyes and supersensitizers may be used in combination. Specific examples are described in, for example, Patents described in Research Disclosure Magazine No. 17643-IV (published on December 12, 1978 (pp. 23 to 24).

The photographic emulsion used in the present invention may contain an antifoggant or a stabilizer for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. Detailed examples are described in, for example, Research Disclosure Magazine No. 17643-VI (19
Published December 1978) and “Stabiliaution of
Photographic Silver Hailde Emulsin "(Focal Pres
s), published in 1974.

The fogging treatment of the present invention is performed by the following “light fogging method” and / or “chemical fogging method”. The front exposure in the “light fogging method” of the present invention, that is, the fog exposure, is performed after the imagewise exposure and during the development processing and / or during the development processing.
The image-exposed light-sensitive material is immersed in a developing solution or a pre-bath of the developing solution, or is exposed before being taken out of these solutions and dried, but is most preferably exposed in the developing solution.

As a light source for fogging exposure, a light source within the photosensitive wavelength of the photosensitive material may be used, and in general, any of a fluorescent lamp, a tungsten lamp, a xenon lamp, and sunlight can be used. These specific methods are described, for example, in British Patent 1,151,36.
No. 3, No. 45-12710, No. 45-12709, No. 58-6936,
JP 48-9727, JP 56-137350, JP 57-129438, JP 5
8-62652, 58-60739, 58-70223 (corresponding U.S. Pat.No. 4,440,851), 58-120248 (corresponding European patent 89101A)
No. 2). JP-A-56-13735 for photosensitive materials having photosensitivity in all wavelength ranges, for example, color photosensitive materials
A light source having a high color rendering property (as close to white as possible) as described in No. 0 or No. 58-70223 is preferred. Light illuminance is 0.01
2,000 lux, preferably 0.05-30 lux, more preferably 0.05-5 lux is suitable. A light-sensitive material using a higher-sensitivity emulsion preferably has a lower illuminance. The adjustment of the illuminance may be performed by changing the luminous intensity of the light source, by dimming with various filters, by changing the distance between the photosensitive material and the light source, or by changing the angle between the photosensitive material and the light source. Also, the illuminance of the fog light is continuously changed from low illuminance to high illuminance,
Alternatively, it can be increased stepwise.

The light-sensitive material is preferably immersed in a developing solution or a solution in a pre-bath thereof, and irradiated with light after the solution has sufficiently penetrated the emulsion layer of the light-sensitive material. The time from immersion in the liquid to light fogging exposure is generally 2 seconds to 2 minutes, preferably 5 minutes to 1 minute, more preferably 10 seconds to 30 seconds.

The exposure time for fogging is generally from 0.01 seconds to 2 minutes, preferably from 0.1 seconds to 1 minute, more preferably from 1 second to 40 seconds.

In the present invention, as the nucleating agent used when performing the so-called "chemical fogging method", the compounds of the above-mentioned general formulas [NI] and [N-II] can be mentioned.

Various color couplers can be used for directly forming a positive color image in the present invention. A color coupler is a compound that produces a coupling or a substantially non-diffusible dye by coupling reaction with an oxidized form of an aromatic primary amine-based color developing solution. Preferably, it is a compound. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open-chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are described in "Research Disclosure", magazine No. 17643 (published in December 1978), p.
No. 18717 (issued in November 1979) and Japanese Patent Application No. 61-32462, and the patents cited therein.

Above all, examples of the yellow coupler usable in the present invention include a yellow di-equivalent coupler of an oxygen atom releasing type and a nitrogen atom releasing type. In particular, an α-pivaloylacetanilide-based coupler is excellent in the fastness of a coloring dye, particularly in light fastness, while an α-benzoylacetanilide-based coupler is preferable because a high color density can be obtained.

The 5-pyrazolone-based magenta coupler preferably usable in the present invention is a 5-pyrazolone-based coupler in which the 3-position is substituted with an arylamino group or an acylamino group (among others, a sulfur atom-eliminating double-equivalent coupler).

More preferred are pyrazoloazole couplers, among which pyrazolo [5,1-c] [1,2,4] triazoles described in U.S. Pat.
The imidazo [1,2-b] described in U.S. Pat.No.4,500,630 in terms of low yellow side absorption and light fastness of the coloring dye.
Pyrazoles are even more preferred, U.S. Pat.
Pyrazolo [1,5-b] [1,2,4] triazole described in No. 4 is particularly preferred.

Cyan couplers that can be preferably used in the present invention include naphthol-based and phenol-based couplers described in U.S. Pat.Nos. 2,474,293 and 4,502,212, and an ethyl group or more at a meta position of a phenol nucleus described in U.S. Pat. And 2,5-diacylamino-substituted phenol couplers are also preferred in view of color image fastness.

Card couplers for correcting unnecessary absorption in the short wavelength range of the formed dyes, couplers having appropriate diffusibility of color forming dyes, non-color couplers, and DIR couplers that release a development inhibitor with the coupling reaction And polymerized couplers can also be used.

Typical amounts of color coupler used range from 0.001 to 1 mole per mole of photosensitive silver halide. Preferably, the amount is 0.01 to 0.5 mol for the yellow coupler, 0.03 mol to 0.5 mol for the magenta coupler, and 0.002 to 0.5 mol for the cyan coupler.

In the present invention, a color enhancer can be used for the purpose of improving the color developability of the coupler. Representative examples of compounds are disclosed in
62-215272, pages 374-391.

The coupler of the present invention is dissolved in an organic solvent having a high boiling point and / or a low boiling point, and is stirred in a gelatin or other hydrophilic colloid aqueous solution by high-speed stirring with a homogenizer or the like, by mechanical fineness of a colloid mill or by using ultrasonic waves. It is emulsified and dispersed by the technique described above, and this is added to the emulsion layer. In this case, a high boiling point organic solvent is not necessarily used, but it is preferable to use a compound described in JP-A-62-215272, pages 440 to 467.

The coupler of the present invention can be dispersed in a hydrophilic colloid by the method described in JP-A No. 62-215272, pages 468 to 475.

The light-sensitive material prepared by using the present invention may be used as a color fogging inhibitor or a color mixing inhibitor as a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, and a sulfonamide phenol. A derivative or the like may be contained. Representative examples of color antifoggants and color mixture inhibitors are disclosed in
-215272, pages 600 to 663.

Various fading inhibitors can be used in the light-sensitive material of the present invention. Examples of the organic discoloration inhibitor include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols, senderd phenols including bisphenols, gallic acid derivatives, methylenedioxybenzene. Kind,
Representative examples include aminophenols, hindered amines, and ether or ester derivatives in which the phenolic hydroxyl group of each of these compounds is silylated or alkylated. Further, metal complexes represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Compounds having both hindered amine and hindered phenol partial structures in the same molecule as described in U.S. Pat. No. 4,268,593 give good results in preventing deterioration of the yellow dye image due to heat, humidity and light. Further, in order to prevent deterioration of the magenta dye image, especially deterioration due to light, spiroindanes described in JP-A-56-159644, and hydroquinone diether or monoether described in JP-A-55-89835 were substituted. Chromans give favorable results.

Representative examples of these color mixture inhibitors are described in JP-A-62-215272, 401.
Pp. 440. These compounds can achieve their purpose by adding 5 to 100% by weight, based on the corresponding color coupler, to the photosensitive layer, usually by co-emulsifying the coupler with the coupler.

In order to prevent the cyan dye image from deteriorating due to heat and particularly to light, it is effective to introduce an ultraviolet absorber into both layers adjacent to the cyan coloring layer. Further, an ultraviolet absorber can be added to a hydrophilic colloid layer such as a protective layer. Representative examples of the compounds are described in JP-A-62-215272, pp. 391-400.

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

The photosensitive material of the present invention includes a dye for preventing irradiation and halation, an ultraviolet absorber, a plasticizer, a fluorescent brightener, a matting agent, an air fog inhibitor, a coating aid, a hardening agent,
An antistatic agent, a slipperiness improving agent and the like can be added.
Representative examples of these additives are described in Research Disclosure Magazine No. 17643VIII-XII (issued in December 1978), pp. 25-2.
7, and 18716 (issued in November 1979), pages 647 to 651.

The invention is also applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on a support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer, and one blue-sensitive emulsion layer on a support.
The order of these layers can be arbitrarily selected as needed. The preferred order of the layer arrangement is red sensitivity, green sensitivity, blue sensitivity or green sensitivity, red sensitivity, and blue sensitivity from the support side.
Each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, or a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. . Usually, the cyan-sensitive coupler is contained in the red-sensitive emulsion layer, the magenta-forming coupler is contained in the green-sensitive emulsion layer, and the yellow-forming coupler is contained in the blue-sensitive emulsion layer. However, depending on the case, different combinations may be used.

The following compounds can be added for the purpose of increasing the maximum image density, lowering the minimum image density, improving the storability of the light-sensitive material, or accelerating the development.

Hydroquinones (for example, US Pat. No. 3,227,552,
Nos. 4,279,987); chromans (for example, US Pat. No. 4,268,621, JP-A-54-103031, Research
Disclosure Magazine, No. 18264 (issued in June 1979) 33
Compounds described on pages 3-334; quinones (for example, Research
Disclosure Magazine, No. 21206 (December 1981) 433-4
Compounds described on page 34); amines (for example, US Pat. No. 4,15
Oxidants (for example, compounds described in JP-A-60-260039, Research Disclosure, No. 16936, issued May 1978), pp. 10-11. Catechols (for example, compounds described in JP-A-55-21013 and JP-A-55-65944); compounds that release a nucleating agent during development (for example, compounds described in JP-A-60-107029); thioureas (For example, compounds described in JP-A-60-95533); spiropisindanes (for example, JP-A-55-659)
No. 44).

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 Magazine No. 17643 VVII (19
Issued in December 1978) those described on page 28 and European patents 0,10
It is applied to a support described in 2,253 or JP-A-61-97655. Also, Research Disclosure Magazine No.17643XV page
The application method described on pages 28 to 29 can be used.

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

For example, a color reversal film for slides or a television, a color reversal paper, an instant color film and the like can be mentioned as typical examples. Also, the present invention can be applied to a full-color copying machine or a color hard copy for storing an image on a CRT. 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 black-and-white photographic light-sensitive materials.

Examples of black-and-white (B / W) photographic light-sensitive materials to which the present invention can be applied include photographic light-sensitive materials immediately after B / W poly described in JP-A-59-208540 and JP-A-60-260039. Timber,
(Dup sensitive material, micro sensitive material, photographic sensitive material, print sensitive material)
and so on.

The color developer used in the development of the photosensitive material of the present invention is
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.
Phenylenediamine compounds are preferably used, and typical examples thereof are 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 sulfates, hydrochlorides or p-toluenesulfonates thereof.
These compounds can be used in combination of two or more depending on the purpose.

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

The fixed emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing processing before bleach-fixing processing or bleaching processing after bleach-fixing processing can be arbitrarily performed according to the purpose.
Examples of the bleaching agent include iron (III), cobalt (III),
Compounds with increased polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include ferricyanide; iron dichromate; iron (II
Organic complex salts of I) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Use of aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid; persulfates; bromates; permanganates; it can. Among these, iron aminopolycarboxylates (II) including iron (III) complex salts of ethylenediaminetetraacetate
I) Complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. In addition, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching and bleach-fixing solutions. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodide.The use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. As the preservative of the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. 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 picture and T
It can be determined by the method described in elevision Engineers, Vol. 64, p. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Cause problems. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, a method of reducing calcium ions and magnesium ions described in Japanese Patent Application No. 61-131632 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. It is also possible to use bactericides described in "Sterilization, Sterilization and Antifungal Techniques of Microorganisms" edited by the Society of Sanitary Engineers, and "Encyclopedia of Antifungal and Antifungal Agents" edited by the Japan Society of Antifungals and Fungi.

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to 9
And preferably 5 to 8. The washing water temperature and the processing time can also be variously set depending on the characteristics of the photosensitive material, the application, etc., but in general, the range is 20 seconds to 10 minutes at 15 to 45 ° C, preferably 30 seconds to 5 minutes at 25 to 40 ° C. Is done. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilization process, Japanese Unexamined Patent Publication No.
-8543, 58-14834, and 60-220345 can all be used. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing solution for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline compounds described in U.S. Pat.No. 3,342,597, 3,342,599, Schiff base compounds described in Research Disclosures 14850 and 15159, aldol compounds described in 13924, and metals described in U.S. Pat.No.3,719,492 Salt complex, JP 5
Examples thereof include urethane compounds described in 3-135628.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-1154.
No. 38, etc.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to. Further, in order to save silver of the light-sensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

It is preferable that the replenishment amount in each processing step is small. The amount of the replenisher is preferably 0.1 to 50 times, more preferably 3 to 30 times, the amount of the pre-bath brought in per unit area of the photosensitive material.
It is twice.

On the other hand, to develop a black and white photosensitive material in the present invention,
Various known protagonists 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-58-5
The developer described in No. 5928 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.

The spectral sensitizing dye in the present invention is represented by the general formula (IV), but is preferably used in view of effects such as Dmax and Dmin.

(IV) In the formula, Z ₁ and Z ₂ are a thiazole nucleus, a thiazoline nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, an oxazole nucleus,
A benzoxazole nucleus, an oxazoline nucleus, a naphthoxazole nucleus, an imidazole nucleus, a benzimidazole nucleus, an imidazoline nucleus, a selenazole nucleus, a selenazoline nucleus, a benzoselenazole nucleus or a group of atoms necessary for forming a naphthoselenazole nucleus. It is preferable to have a benzoxazole nucleus.

R ₁ and R ₂ represent an alkyl group or a substituted alkyl group. However, at least _one of R ₁ and R ₂ has a sulfo group or a carboxy group.

L ₁ and L ₂ represent a substituted or unsubstituted methine group.

 n represents the integer of 0-2.

The nucleus formed by Z ₁ and Z ₂ may have a substituent introduced therein, as is well known in the field of cyanine dyes. Examples of the substituent include an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, an aralkyl group, and a halogen atom.

R ₁ and R ₂ may be the same or different.
The alkyl of R ₁ and R ₂ preferably has 1 to 8 carbon atoms.
Such as methyl, ethyl, propyl, butyl, pentyl, heptyl and the like. Examples of the substituent of the substituted alkyl group include a carboxy group, a sulfo group, a cyano group, a halogen atom (such as a fluorine atom, a chlorine atom, and a bromine atom), a hydroxy group, and an alkoxycarbonyl group (having 8 or less carbon atoms, such as methoxycarbonyl). Group, ethoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy group (having 7 or less carbon atoms, for example, methoxy group, ethoxy group, propoxy group, butoxy group,
A benzyloxy group or the like), an aryloxy group (for example, a phenoxy group, a p-tolyloxy group or the like), an acyloxy group (for example, having 3 or less carbon atoms, for example, an acetyloxy group or a propionyloxy group), or an acyl group (for example, having 8 or less carbon atoms). For example, acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (eg, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbamoyl group, piperidinocarbamoyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N , N-dimethylsulfamoyl group, morpholinosulfonyl group, etc.),
There are aryl groups (for example, phenyl group, p-hydroxyphenyl group, p-carboxyphenyl group, p-sulfophenyl group, α-naphthyl group, etc.). The preferred carbon number of the substituted alkyl group is 6 or less.

Examples of the substituted methine group for L ₁ and L ₂ include a lower alkyl group (eg, a methyl group, an ethyl group, a propyl group, etc.), a phenyl group, a benzyl group and the like.

 Specific examples of the sensitizing dye are shown below.

These cyanine dyes are all known compounds and can be easily obtained or synthesized.

The content of the sensitizing dye of the present invention represented by the general formula (I) is 1 × 10 ^-6 to 1 × 10 ^-2 mol, preferably 1 × 10 ^-5 to 1 × 10 ^-3 mol per mol of silver. And more preferably 5 × 10 ⁻⁵ or more.
1 × 10 ^-3 mol.

Two or more sensitizing dyes of the general formula (IV) of the present invention may be used in combination, or may be used in combination with other cyanine, merocyanine, polymethine dyes and the like.

〔Example〕

Example 1 A paper support laminated on both sides with polyethylene (thickness 10
A color photographic light-sensitive material was prepared by coating the following first to fourteenth layers on the front side (0 micron) and the fifteenth to sixteenth layers on the back side. Titanium oxide (4 g / m ² ) is used as a white pigment in the polyethylene on the first layer,
m including ² of ultramarine as a bluing dye (chromaticity of the surface of the support is L ^*, a ^*, b ^* system in 88.0, -0.20, was -0.75.).

(Composition of photosensitive layer) The components and coating amounts (g / m ² units) are shown below. For silver halide, the coating amount is shown in terms of silver. The emulsion used for each layer was prepared according to the method for preparing emulsion EM1. However, the emulsion of the 14th layer was a Lippmann emulsion which did not undergo surface chemical sensitization.

1st layer (antihalation layer) Black colloidal silver 0.10 gelatin ... 0.70 2nd layer (intermediate layer) gelatin ... 0.70 3rd layer (low-sensitivity red-sensitive layer) Red sensitizing dye (ExS-1,2, Silver bromide spectrally sensitized in 3) (average grain size 0.25μ, size distribution [coefficient of variation] 8)
%, Octahedral) 0.04 Gelatin ... 1.00 Cyan coupler (ExC-1, 2, 3 1: 1: 0.2) 0.30 Anti-fading agent (Cpd-1, 2, 3, 4 equivalents) ... 0.18 Anti-stain agent (Cpd-5) ... 0.003 Coupler dispersant (Cpd-6) ... 0.03 Coupler solvent (Solv-1, 2, 3 equivalents) ... 0.12 4th layer (highly sensitive red-sensitive layer) Red Silver bromide spectrally sensitized with sensitizing dye (ExS-1,2,3) (average grain size 0.60μ, size distribution 15%, octahedral) ... 0.14 gelatin ... 1.00 cyan coupler (ExC-1, 0.3, 1: 1: 0.2) 0.30 Anti-fading agent (Cpd-1, 2, 3, 4 equivalents) 0.18 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Solv-1, 0.12 Fifth layer (intermediate layer) Gelatin... 1.00 Color-mixing inhibitor (Cpd-7) ... 0.08 Solvent for color-mixing inhibitor (Solv-4, 5 equivalents) ... 0.16 Polymer latex ( Cpd-8) 0.10 6th layer (low-sensitivity green-sensitive layer) Silver bromide spectrally sensitized with green sensitizing dye (S-2) (average particle size 0.25μ, size distribution 8%, octahedron) ...... 0.04 gelatin 0.80 Magenta coupler (ExM-1, 2, 3 equivalents) ... 0.11 Anti-fading agent (equivalent to Cpd-9, 26) ... 0.15 Stain inhibitor (Cpd-10, 11, 12, 13 to 10) : 7: 7: 1 ratio) ...... 0.025 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv-4, 6 equivalents) ... 0.15 7th layer (highly sensitive green sensitive layer) Green sensitization Silver bromide spectrally sensitized with dye (S-2) (average grain size 0.65μ, size distribution 16%, octahedral)… 0.10 Gelatin… 0.80 Magenta coupler (ExM-1, 2, 3 equivalents) ... 0.11 Anti-fading agent (Cpd-9, 26 equivalents) ... 0.15 Stain inhibitor (Cpd-10, 11, 12, 13 in a 10: 7: 7: 1 ratio) ... 0.025 Coupler dispersion medium (Cpd) -6) ...... 0.05 Coupler solvent (So lv-4, 6 equivalents) ... 0.15 8th layer (intermediate layer) Same as 5th layer 9th layer (yellow filter layer) Yellow colloidal silver (particle size 100 mm) ... 0.12 Gelatin ... 0.70 Cpd-7) ...... 0.03 Solvent for color mixture inhibitor (Solv4, 5 equivalents) ...... 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 blue sensitizing dye (ExS-5, 6) (average grain size 0.40μ, size distribution 8%, octahedron)… 0.07 Gelatin… 0.80 Yellow coupler (ExY- 0.35 Discoloration inhibitor (Cpd-14) 0.10 Stain inhibitor (Cpd-5, 15 in a 1: 5 ratio) 0.007 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10 Layer 12 (high-sensitivity blue-sensitive layer) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average grain 0.15 Gelatin .... 0.60 Yellow coupler (ExY-1, 2 equivalents) ... 0.30 Anti-fading agent (Cpd-14) ... 0.10 Stain inhibitor (Cpd) 0.005 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-2) 0.10 13th layer (UV absorbing layer) Gelatin ... 1.00 UV absorbing layer (Cpd-2, 4, 16 equivalents) ...... 0.50 Color mixture inhibitor (Cpd-7, 17 equivalents) ... 0.03 Dispersion medium (Cpd-6) ... 0.02 Ultraviolet absorber solvent (Solv-2, 7 etc.) Amount) …… 0.08 Anti-irradiation dye (Cpd-18,19,20,21,27
10: 10: 13: 15: 20 ratio) ...... 0.05 14th layer (protective layer) Fine particle silver chlorobromide (97 mol% of silver chloride, average size 0.1μ) ...... 0.03 Acrylic-modified copolymer of polyvinyl alcohol (Molecular weight
50,000) …… 0.01 Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) equivalent: 0.05 gelatin: 1.80 gelatin hardener (equivalent to H-1, H-2) 0.18 15th layer (back layer) gelatin: 2.50 UV light Absorbent (Cpd-2, 4, 16 equivalents) ... 0.50 Dye (Cpd-18, 19, 20, 21, 27 equivalents) ... 0.06 16th layer (backside protective layer) Polymethyl methacrylate particles (average Particle size 2.4
μ) and equivalent amount of silicon oxide (average particle size 5μ) ... 0.05 gelatin ... 2.00 gelatin hardener (H-1, H-2 equivalent) ... 0.14 How to make emulsion EM-1 Potassium bromide and silver nitrate The aqueous solution was simultaneously added to the aqueous gelatin solution at 75 ° C. for 15 minutes with vigorous stirring to obtain octahedral silver bromide particles having an average particle size of 0.35 μm. At this time silver 1
0.3 g of 3,4-dimethyl-1,3-thiazoline-2 per mole
-Thion was added. To this emulsion, 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mol of silver were sequentially added, and heated at 75 ° C. for 80 minutes to perform chemical sensitization. Using the particles thus obtained as a core, the particles were further grown in the same precipitation environment as in the first experiment, and finally had an average particle diameter of 0.7 μm.
Octahedral monodispersed core / shell silver bromide emulsion was obtained. The coefficient of variation of the particle size was about 10%. To this emulsion, 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mole of silver were added, and heated at 60 ° C. for 60 minutes to perform chemical sensitization to obtain an internal latent image type silver halide emulsion. Obtained.

For each photosensitive layer, ExZK-1 and ExZK-2 were used as nucleating agents in an amount of 10 ^-3 and 10 ^-2 % by weight, respectively, based on silver halide. Further, each layer has an alkanol XC (Dupon
Co., Ltd.) and sodium alkylbenzenesulfonate, and succinic acid ester and MagefacF-120 (manufactured by Dainippon Ink and Chemicals, Inc.) as coating aids. (Cpd-23, 24, 25) was used as a stabilizer in the layer containing silver halide and colloidal silver.

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 (vinylsulfonylacetamide) ethane H-2 4,6-dichloro-2-hydroxy-1,3,5-triazine sodium salt ExZK-17- (3-ethoxy) Thiocarbonylaminobenzamide) -10-prohagyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate ExZK-2 2- [4- {3- [3- {3- [5-} 3-
[2-Chloro-5- (1-dodecyloxycarbonylethoxycarbonyl) phenylcarbamoyl] -4-hydroxy-1-naphthylthioditheolazol-1-yl]
Phenyl {ureido] benzenesulfonamido} phenyl] -1-formylhydrazine treatment process Time Temperature color development 135 seconds 38 ° C Bleaching and fixing 40〃 33〃 Rinse (1) 40〃 33〃 Rinse (2) 40〃 33〃 Dry 30〃 80〃 The composition of each treatment solution was as follows.

Color developer D-Sorbit 0.15 g Sodium naphthalenesulfonate / formalin condensate 0.15 g Ethylenediaminetetrakismethylenephosphonic acid 1.5 g Diethylene glycol 12.0 ml Benzyl alcohol 13.5 ml Potassium bromide 0.70 g Benzotriazole 0.003 g Sodium sulfite 2.4 g N, N-bis (Carboxymethyl) hydrazine 4.0 g D-glucose 2.0 g triethanolamine 6.0 g N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 30.0 g Fluorescent whitening agent (diaminostilbene) 1.0 g Add water 1000 ml pH (25 ° C) 10.25 Bleach-fix solution Ethylenediaminetetraacetic acid disodium dihydrate 2.0 g Ethylenediaminetetraacetic acid ・ Fe (III) ・ ammonium ・
Dihydrate 70.0 g Ammonium thiosulfate (700 g / l) 180 ml Sodium p-toluenesulfinate 45.0 g Sodium bisulfite 35.0 g 5-mercapto-1,3,4-triazole 0.5 g Ammonium nitrate 10.0 g Water was added to 1000 ml pH (25 ℃) 6.10 Rinse water Tap water is mixed into a mixed-bed column filled with H-type strongly acidic cation exchange resin (Rohm and Haas Amberlite IR-120B) and OH-type anion exchange resin (Amberlite IR-400). Water and water were passed to adjust the concentration of calcium and magnesium ions to 3 mg / l or less, and then 20 mg / l of sodium dichloride isocyanurate and 0.1 g / l of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

Sample No. 14 was prepared using the color photographic material prepared as described above.
And Samples Nos. 1 to 13 were prepared in the same manner as Sample No. 14 except that the compounds of the present invention were added to the sixth and seventh layers as shown in Table 1.

After incubating these samples at 60 ° C. and 30% RH for 3 days, they were subjected to wedge exposure (10 CMS, 0.1 ″, 3200 K, halogen lamp) and processed in processing step A. The magenta image density was measured and the results are shown in Table 1. .

Samples Nos. 1 to 12 using the compounds of the present invention are comparative examples.
Compared with No. 14, the increase in Dmin and the decrease in Dmax after incubation were small and preferred. In addition, the increase in Dmin after incubation was smaller than that of the comparative compound II-8, which was preferable.

The amount of the compound represented by formulas (1) and (II-8) is 2.
It was 5 × 10 ⁻⁴ mol / Ag mol.

Example 2 Samples 15 to 21 in which the compounds of the general formulas (I), (II) and (III) of the present invention were added to the sixth and seventh layers of the color light-sensitive material prepared in Example 1 as shown in Table 2 It was adjusted.

These samples were processed in the same manner as in Example 1, and the magenta image density was measured. The results shown in Table 2 were obtained.

The addition amounts of the compounds of the general formulas (I), (II) and (III) are 1.0 × 10 ⁻⁴ mol / Ag mol, 3.0 × 10 ⁻⁴ mol / Ag mol,
9.0 × 10 ⁻⁴ mol / Ag mol.

As is clear from Table 2, when the compounds of the general formulas (II) and (III) are used in combination with the compound of the general formula (I) of the present invention,
After incubation, showing higher Dmin but higher
It has been found that Dmax can be achieved.

Example-3 II-4 was added to the third, fourth, eleventh, and twelfth layers of Sample 19 of Example 2.
Was completely repeated except that 5.2 × 10 ⁻⁴ mol / Ag mol was added, and almost the same results were obtained.

〔The invention's effect〕

The present invention provides a direct positive image that provides a high maximum image density and a low minimum image density.

Claims (3)

(57) [Claims] 1. A method wherein a photosensitive material having at least one internal latent image type direct positive silver halide photographic emulsion layer on a support is imagewise exposed, subjected to fogging, or developed with fogging. In the method of forming a positive image, the developing treatment is performed in the presence of the following general formula (I). General formula (I) Wherein, X is -O -, - S-, represents NR ^2, R ² is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, an aryl group, an amino group, an acylamino group, a heterocyclic group Express. R ¹ represents a heterocyclic group. M represents a hydrogen atom, an alkali metal atom, an ammonium group or a group that can be cleaved under alkaline conditions. 2. The method according to claim 1, wherein said developing treatment is carried out in the presence of at least one compound selected from the compounds represented by the following general formulas [N-1] and [N-II]. The method for forming a direct positive image according to the above item 1). General formula [NI] (In the general formula [N-1], Z represents a group of nonmetal atoms necessary to form a 5- or 6-membered heterocyclic ring, R ¹¹ is an aliphatic group, R ¹² is a hydrogen atom, an aliphatic group or an aromatic group .Z, R ^11, R ¹² may be optionally substituted, also R ¹² is may form a ring by combining with heterocyclic ring further completed by Z. However R ^11, At least one of the groups represented by R ¹² and Z contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or forms a 6-membered ring with R ¹¹ and R ¹² to form a dihydropyridinium skeleton. Y is a counter ion for charge balance, and n is 0 or 1.) General formula [N-II] (In the general formula [N-II], R ²¹ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ²² represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, Or an amino group, G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, or an iminomethylene group (HN = C); R ²³ and R ²⁴ are both hydrogen atoms, or one is a hydrogen atom and the other is a hydrogen atom; There alkylsulfonyl group, an arylsulfonyl group or represents one one of the acyl group. However, hydrazone structure in a form including G, and R ^22, R ²⁴ and hydrazine nitrogen (N-N = C)
May be formed. 3. The developing process according to the following general formulas (II) and (II)
The method for forming a direct positive image according to claim 1, wherein the method is carried out in the presence of at least one compound selected from the compounds represented by I). General formula (II) General formula (III) In the formula, Q represents a group of atoms necessary to form a 5- or 6-membered heterocyclic ring. Q 'represents an atom group necessary for forming a 5- or 6-membered heterocyclic ring capable of forming imino silver. The heterocyclic ring may be fused with a carbon aromatic ring or a heteroaromatic ring. However, this excludes the case where the substituent on the heterocyclic ring of Q and Q 'is a heterocyclic group. M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group that cleaves under alkaline conditions.