JPH05165138A - Direct positive silver halide color photographic sensitive material and image forming method by using same - Google Patents

Abstract

PURPOSE:To enhance the maximum density of a direct positive image obtained by exposure and development and to reduce its minimum density by incorporating a specified spectral sensitizing dyestuff and a specified dye and an internal latent image type silver halide emulsion. CONSTITUTION:A red-sensitive layer contains the spectral sensitizing dyestuff represented by formula I and a photosensitive layer or nonsensitive hydrophilic colloidal layer contains the dye represented by formula II, and the total silver amount is regulated to <=0.7g/m<2>. In formulae I and II, each of Y1 and Y2 is an atomic group necessary to form a benzothiazole ring or the like; each of R12 and R13 is alkyl; R11 is alkyl or aryl; X1 is an anion; n is 1 or 2; L is -CONH- or the like; R21 is alkyl or the like; each of R22 and R23 is H, alkyl or the like; R24 is H or alkyl, and each of R25 and R26 is alkyl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a direct positive color photographic light-sensitive material and a direct positive image forming method using the same.

More specifically, the present invention relates to a direct positive color photosensitive material suitable for producing a proof color image (color proof) for promptly confirming the final color and tone of a color print in the printing industry. And a direct positive image forming method using the same.

[0003]

2. Description of the Related Art A method is known in which a direct positive image is obtained by using an internal latent image type silver halide emulsion which has not been fogged in advance and performing surface development after fog processing after image exposure or while performing fog processing. ing. The internal latent image type silver halide photographic emulsion means a type of silver halide photographic emulsion having a photosensitive nucleus mainly inside the silver halide grain and a latent image is mainly formed inside the grain upon exposure. ..

Various techniques have been known so far in this technical field. For example, US Pat.
Nos. 2466957, 2497875, 25
No. 88982, No. 3317322, No. 3761266
Nos. 3,761,276, 3,796,577 and British Patent Nos. 1,153,163, 1,150,553, 1,
No. 011062 is mainly described in each specification and the like. By using these known methods, a photographic light-sensitive material having a relatively high sensitivity as a direct positive type can be produced.

The details of the mechanism for forming a direct positive image are described in T. H. James, The Theory of the Photographic Process
of the Photographic Process), 4th Edition, Chapter 7, 1
82 to 193, U.S. Pat. No. 3,761,276, and the like. That is, the fog nuclei are selectively generated only on the surface of the silver halide grains in the unexposed portion due to the surface desensitizing effect caused by the so-called internal latent image generated inside the silver halide by the first imagewise exposure, Then, a usual so-called surface development process is performed to form a photographic image (direct positive image) on the unexposed portion.

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, described in British Patent No. 1151313). Method) and a method using a nucleating agent called "chemical fogging method" are known. This latter method is described, for example, in "Research Disclosure".
151, No. 15162 (1976)
Issued Nov., pp. 76-78.

To directly form a positive color image, an internal latent image type silver halide light-sensitive material is subjected to fog treatment,
Or, while performing the fog treatment, perform surface color development processing,
Then, it can be achieved by bleaching and fixing (or bleach-fixing). After the bleaching / fixing treatment, washing and / or stabilization treatment is usually performed.

By the way, the color printed matter is prepared by a process of color-separating a color original and converting it into a halftone dot image to form a transmission type black and white halftone dot image. A printing plate is made from the obtained transmission type black and white halftone image, but prior to this, a color image for proofing (color proofing) is provided in order to easily know the finish of the final printed matter (main printing) and perform necessary proofing. ) Is being produced. When a color proof is created, the proofing process can be speeded up and costs can be reduced as compared with a case where a printing plate is prepared and a test printing is performed.

As a method of creating a color proof,
A surprint method and a surprint method using a photopolymer, a diazo method, a photoadhesive polymer and the like are known.
(For example, it is described in US Pat. No. 3,582,327, JP-A-56-501217, and JP-A-59-97140). However, in all of these methods, it is necessary to superimpose and transfer images, so that the process is complicated and time-consuming and expensive.

In contrast to these methods, a method for producing a color proof using a color photographic light-sensitive material (JP-A-56-1).
No. 04335) has a great advantage in terms of simplicity of the process and low cost, and has characteristics such as excellent tone reproduction. According to this method, a silver halide color photographic light-sensitive material of a coloring method having continuous gradation is used, and magenta color, cyan color,
A color proof is created by sequentially exposing each of the yellow and black ink plates to a normal color paper so that the color negatives are printed. The method using this color photographic light-sensitive material is also characterized in that it is easier to automate than the various methods described above.

Although various kinds of silver halide color photographic light-sensitive materials that can be used for color proof are conceivable, the transmission type black-and-white halftone image used in the production process of color printed matter is often positive type. A positive-positive type photosensitive material is particularly suitable. Among them, the direct positive type color photographic light-sensitive material as described above is most suitable for the purpose of color proof because of its simple processing.

In the direct positive image formation using the optical fogging method or the chemical fogging method, the developing speed is slower and the processing time is longer than that in the case of a normal negative type. Alternatively, a method of increasing the liquid temperature to shorten the processing time has been used. But generally pH
Has a problem that the minimum image density of the direct positive image obtained increases. Further, under high pH conditions, the developing agent is likely to be deteriorated by air oxidation, and the carbon gas in the air is easily absorbed to lower the pH, so that there is a problem that the developing activity is significantly lowered.

As means for increasing the developing speed in the direct positive image formation, a method using a hydroquinone derivative (described in US Pat. No. 3,227,552) and a method using a mercapto compound having a carboxylic acid group or a sulfonic acid group ( JP-A-60-170843) is known, but the effect of using these compounds is small, and a technique for effectively increasing the maximum density of a direct positive image has not been found. In particular, it has been required to obtain a high maximum image density without increasing the minimum image density.

A color proof image formed by halftone dots has a larger area ratio of a white background portion than a normal color image, and the hue of the white background greatly affects the quality of the entire image quality.

[0015]

When a direct positive color photographic light-sensitive material is subjected to a fogging treatment to obtain a color proof image, the whiteness is out of a preferable region, the impression is greatly different from that of the printed matter, and the evaluation is often erroneous. It was For this reason, there has been a demand for a direct positive color image forming method in which the whiteness is stable and a preferable whiteness close to that of a printed matter is obtained.

Therefore, a first object of the present invention is to provide a direct positive color light-sensitive material which has a low minimum image density and a high maximum image density. A second object of the present invention is to provide a direct positive color image forming method having good whiteness and excellent color reproducibility. A third object of the present invention is to provide a method for producing a color proof image in which the whiteness is a preferable hue and the fluctuation is small.

[0017]

The above object of the present invention has been achieved by the direct positive color photographic light-sensitive material described in (1) below. Preferred embodiments are the direct positive color photographic light-sensitive material of (2) and the direct positive color image forming method of (3) and (4).

(1) Each of at least one of a blue light-sensitive layer, a green light-sensitive layer, a red light-sensitive layer and a non-light-sensitive hydrophilic colloid layer containing an internal latent image type silver halide emulsion which has not been fogged in advance, is formed on a support. In a direct positive color photographic light-sensitive material provided, the red light-sensitive layer contains a spectral sensitizing dye represented by the general formula (I), and a light-sensitive layer or
A direct positive color photographic light-sensitive material comprising a non-photosensitive hydrophilic colloid layer containing a compound represented by the general formula (II) and having a total silver amount of 0.7 g / m ² or less. General formula (I)

[0019]

[Chemical 13]

In the formula, Y ₁ and Y ₂ each represent an atomic group necessary for forming a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring or a naphthoselenazole ring, and R ₁₂ and R ₁₃ respectively represent It represents an alkyl group, and R ₁₁ represents an alkyl group or an aryl group. However, R ₁₂ and R
_At least one of ₁₃ represents an alkyl group substituted with a sulfo group or a carboxyl group. X ₁ ⁻ represents an anion, and n represents 1 or 2. General formula (II)

[0021]

[Chemical 14]

However, L represents --CONH--, --NHCO-- or --NHCONH--, R ₂₁ represents an alkyl group or an aryl group, R ₂₂ represents a hydrogen atom, an alkyl group or a halogen atom, and R ₂₃ represents a hydrogen atom. Represents an alkyl group or an acylamino group (R ₂₂ and R ₂₃ may combine with each other to form a ring), R ₂₄ represents a hydrogen atom or an alkyl group, and R ₂₅ and R ₂₆ each represent an alkyl group. (R
₂₅ and R ₂₆ may combine with each other to form a ring). The substituents of the above groups do not include a sulfo group or a carboxy group. The total number of carbon atoms in R _{21 to} R ₂₆ is determined by the above general formula (II).
Is large enough to be diffusion resistant.

(2) The direct positive color photographic light-sensitive material is a yellow coupler represented by the general formula (Y), a general formula (M)
The direct positive color photographic light-sensitive material as described in (1), which contains at least one of the magenta coupler represented by the formula (1) and the cyan coupler represented by the general formula (C). General formula (Y)

[0024]

[Chemical 15]

In the formula, R ₃₁ represents an alkyl group, a cycloalkyl group or an aryl group, R ₃₂ represents an alkyl group, a cycloalkyl group, an acyl group or an aryl group, and R ₃₃ represents a group capable of substituting on the benzene ring. Represent n represents 0 or 1. X
₃ represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidized product of a color developing agent, and Y ₃ represents an organic group. General formula (M)

[0026]

[Chemical 16]

In the formula, R ₄₁ represents a hydrogen atom or a substituent, and X ₄ represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine developing agent; Za, Zb. And Zc are = CH- and = C, respectively.
R ₄₂ - (R ₄₂ represents a hydrogen atom or a substituent), = N-
Or -NH-, which represents a Za-Zb bond and a Zb-Zc
One of the bonds is a double bond and the other represents a single bond; R ₄₁ and R ₄₂ have a Hammett's substituent constant σ _p of either group of −2.00 or more and −0.41 or less. Or
Alternatively, the sum of Hammett's substitution constants σ _p of these groups is −2.00 or more and −0.41 or less; when Zb-Zc is a carbon-carbon double bond, Zb-Zc is another aromatic group. May form part of a ring; may form a dimer with R ₄₁ , R ₄₂ or a divalent linking group of X; and R ₄₁
Alternatively, ₄₂ may be a polymer which is a divalent linking group and is linked to the polymer main chain via this. General formula (C)

[0028]

[Chemical 17]

In the formula, R ₅₁ is a hydrogen atom, a halogen atom or an alkyl group, R ₅₂ is an alkyl group, an aryl group or a heterocyclic group, and R ₅₃ is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an aryloxy group. Group or carbonamido group, X ₅ represents a hydrogen atom or a coupling-off group.

(3) Direct positive color image formation characterized by subjecting the direct positive color light-sensitive material described in (2) to a bleach-fixing treatment in the presence of at least one compound represented by the general formulas (VI) to (XII). Method. General formula (VI)

[0031]

[Chemical 18]

In the formula, R ₆₁ and R ₆₂ may be the same or different and each is a hydrogen atom or an alkyl group (preferably having 1 to 5 carbon atoms,
A methyl group, an ethyl group and a propyl group are particularly preferable) or an acyl group (preferably having a carbon number of 1 to 3, such as an acetyl group and a propionyl group), and n is an integer of 1 to 3. General formula (VII)

[0033]

[Chemical 19]

In the formula, R ₇₁ and R ₇₂ are R _{61 of} the general formula (VI),
Synonymous with R ₆₂ . n is an integer of 1 to 3. General formula (VIII)

[0035]

[Chemical 20]

General formula (IX)

[0037]

[Chemical 21]

General formula (X)

[0039]

[Chemical formula 22]

In the formula, R ₈₁ is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), an amino group, a lower alkyl group (preferably having a carbon number of 1 to 5, particularly a methyl group, an ethyl group, a propyl group). Preferred) and an amino group having an alkyl group (such as a methylamino group, an ethylamino group, a dimethylamino group, and a diethylamino group). General formula (XI)

[0041]

[Chemical formula 23]

In the formula, R ₈₂ and R ₈₃ may be the same or different and each is a hydrogen atom, an alkyl group (preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group), a phenyl group or a heterocyclic group. R ₈₄ represents a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, etc., preferably 1 to 3 carbon atoms), wherein R _{82 to} R ₈₃
Examples of the substituent possessed by are a hydroxyl group, a carboxyl group, a sulfo group, an amino group, a lower alkyl group and the like.
R ₈₅ represents a hydrogen atom or a carboxyl group. General formula (XII)

[0043]

[Chemical formula 24]

In the formula, R ₈₆ , R ₈₇ and R _{88, which} may be the same or different, each represents a hydrogen atom or a lower alkyl group,
X ₈ represents an amino group, a sulfonic acid group or a carboxyl group which may have a substituent (eg, a lower alkyl group such as a methyl group, an alkoxyalkyl group such as an acetoxymethyl group).

(4) A development-processed plate-making film having a black-and-white halftone image is adhered to the direct positive color light-sensitive material,
The method for forming a direct positive color image according to item (3), wherein the plate-making film is exposed with each light that has passed through respective filters of red, green and blue, and exposed three times successively.

The present invention will be described in more detail below. First, the sensitizing dye represented by formula (I) used in the direct positive silver halide photographic light-sensitive material of the present invention will be described in detail. In formula (I), the rings represented by Y ₁ and Y ₂ may be the same or different, and specifically, benzothiazole, naphtho (1,2-d) thiazole, naphtho (2,1)
-D) thiazole, naphtho (2,3-d) thiazole,
Benzoselenazole, naphtho (1,2-d) selenazole, naphtho (2,1-d) selenazole, naphtho (2,
3-d) Rings such as selenazole may be mentioned, and the preferable one is benzothiazole ring.

The above ring may have one or more various substituents. Preferred examples of such a substituent include a hydroxy group, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an unsubstituted and substituted alkyl group (eg, methyl, ethyl, propyl, isopropyl, hydroxyethyl, carboxymethyl, Ethoxycarbonylmethyl, trifluoromethyl, chloroethyl, methoxymethyl groups, etc.), aryl groups or substituted aryl groups (eg phenyl, tolyl, anisyl, chlorophenyl, 1
-Naphthyl, 2-naphthyl, carboxyphenyl group, etc.), heterocyclic group (for example, 2-thienyl, 2-furyl, 2
-Pyridyl), an aralkyl group (eg, benzyl, phenethyl, 2-furylmethyl, etc.), an alkoxy group (eg, methoxy, ethoxy, butoxy, etc.), an alkylthio group (eg, methylthio, ethylthio, etc.), a carboxy group,
An alkoxycarbonyl group (eg methoxycarbonyl,
Examples thereof include ethoxycarbonyl, butoxycarbonyl, etc.), an acylamino group (eg, acetylamino, propionylamino, benzoylamino group, etc.), or a methylenedioxy group or a tetramethylene group in which two adjacent groups are bonded.

Specific examples of the substituted or unsubstituted alkyl group represented by R ₁₂ and R ₁₃ include methyl, ethyl, propyl, isopropyl, pentyl, hexyl, 2-hydroxyethyl, 3-hydroxypropyl and 2-. (2-Hydroxyethoxy) ethyl, ethoxycarbonylmethyl, 2-phosphonoethyl, 2-chloroethyl, 2,2
2-trifluoromethyl, 2,2,3,3-tetrafluoropropyl, 2-carbamoylethyl, 3-carbamoylpropyl, methoxyethyl, ethoxyethyl, methoxypropyl, benzyl, phenethyl, p-sulfophenethyl, m-sulfophenethyl , P-carboxyphenethyl and the like groups.

At least one of R ₁₂ and R ₁₃ is an alkyl group substituted with a sulfo group or a carboxyl group,
Examples of the alkyl group substituted with a carboxyl group include a carboxymethyl group, a 2-carboxyethyl group, a 3-carboxypropyl group and the like. Examples of the alkyl group substituted with a sulfo group include 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 2-hydroxy-3-sulfopropyl, 2- (3-sulfopropyloxy) ethyl and 2-sulfatoethyl. , 3-sulfatopropyl group and the like. The alkyl group substituted with these sulfo groups or carboxyl groups preferably has 5 or less carbon atoms. X ₁ ^- as an anion represented by halogen, an inorganic acid or include anions such as organic acids.

[0050] Incidentally, X ₁ is the case where R ₁₂ or R ₁₃ to form a nitrogen atom and intramolecular salt on fused heterocyclic sulfonic group ^- may not be present. The alkyl group represented by R ₁₁ includes those having a substituent, and examples thereof include groups such as methyl, ethyl, propyl, benzyl and phenethyl. The aryl group represented by R ₁₁ is preferably a phenyl group. Specific examples of the sensitizing dye represented by formula (I) used in the present invention are shown below, but the present invention is not limited thereto.

[0051]

[Chemical 25]

[0052]

[Chemical formula 26]

[0053]

[Chemical 27]

In the present invention, an emulsion layer containing at least one kind of the spectral sensitizing dye represented by the general formula (I) is used as a red photosensitive layer, and the red photosensitive layer is at least one kind represented by the general formula (I). The above spectral sensitizing dye may be contained in an amount of 1.0 × 10 ⁻⁶ mol to 9.0 × 10 ⁻³ mol, and particularly 2.0 × 10 ⁻⁶ mol to 3.0 × per mol of silver halide. 1
0 ^-3 mol are preferred. The red photosensitive layer may contain two or more spectral sensitizing dyes represented by formula (I).

The compound represented by the general formula (II) of the present invention is known as the compound represented by the general formula (I) disclosed in JP-A-61-48854. Also in the present invention, the general formula (I) of JP-A-61-48854 is used.
The compound of can be preferably used.

The compound represented by the general formula (Y) of the present invention is known as the compound represented by the general formula (Y-I) disclosed in JP-A-3-238450. Also in the present invention, the compound of the general formula (Y-I) described in JP-A-3-238450 can be preferably used.

The pyrazoloazole coupler represented by formula (M) will be described in detail. The pyrazoloazole-based coupler represented by the formula (M) is known as a magenta coupler in a color photographic light-sensitive material for general use. However, this coupler has absorption on the shorter wavelength side than the magenta coupler which is usually used in a color image forming method for general use. For this reason, this coupler has practically not been used in a color image forming method for general use.

The present inventors have made a detailed study on the pyrazoloazole coupler represented by the formula (M). As a result, in the direct positive color image forming method, particularly in the production of a color proof, the above-mentioned ordinary negative type color image forming is carried out. It turned out that there were no problems with this coupler in the process. On the contrary, since the coloring property close to that of the printing ink is obtained due to the absorption on the short wavelength side, the use of this magenta coupler significantly improves the color reproducibility of the direct positive color image forming method. The effect of the present invention has not been expected at all in the usual negative type color image forming method. The magenta coupler represented by the general formula (I) is preferably a compound represented by the following formula (M
-II), (M-III), (M-IV), (MV), (MV)
I) or a pyrazoloazole-based short-wave magenta coupler represented by (M-VII).

[0059]

[Chemical 28]

[0060]

[Chemical 29]

[0061]

[Chemical 30]

[0062]

[Chemical 31]

[0063]

[Chemical 32]

[0064]

[Chemical 33]

General formulas (M-II), (M-III), (M-I)
V), (MV), (M-VI) and (M-VII), R ₄₁ , R ₄₆ , R ₄₇ , R ₄₈ , R ₄₉ , R ₄₁₀ , R ₄₁₁ and R ₄₁₂ are each a hydrogen atom. Or represents a substituent.

In the formula (M-II), R ₄₁ , R ₄₆ and R
Hammett's substituent constant of ₄₇ or group of sigma _p (hereinafter sigma _p
Is not less than −2.00 and not more than −0.41 or the sum of the values of σ _p of these groups is −2.0.
It is 0 or more and -0.41 or less. R in formula (M-III)
The value of σ _p of any of ₄₁ , R ₄₈ and R ₄₉ is -2.0.
It is 0 or more and −0.41 or less, or the sum of the values of σ _p of these groups is −2.00 or more and −0.41 or less. In the formula (M-IV), the value of σ _p of any group of R ₄₁ and R ₄₁₀ is −2.00 or more and −0.41 or less, or the sum of the values of σ _p of these groups is -2.00
It is above -0.41. In the formula (MV), R ₄₁
And the value of σ _p of any group of R ₄₁₁ is −2.00 or more and −0.41 or less, or σ _{p of} these groups is
The sum of the values is −2.00 or more and −0.41 or less. In the formulas (M-VI) and (M-VII), the value of σ _p of R ₄₁ is −2.00 or more and −0.41 or less. The value of σ _p of R ₄₁₂ is not particularly limited, but the smaller the value of σ _{p of} this group is, the more preferable.

The magenta coupler used in the present invention is more preferably of the formula (M-IV), (MV) or (MV).
It is a pyrazoloazole-based short-wave type magenta coupler represented by I). Most preferred is formula (M-IV).

R ₄₁ in the formulas (M-II) to (M-VII),
Examples of R _{46 to} R ₄₁₂ include a hydrogen atom, a halogen atom,
Alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, acylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, Carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group,
Silyloxy group, aryloxycarbonylamino group,
Examples thereof include an imide group, a heterocyclic thio group, a sulfinyl group, a phosphonyl group, an aryloxycarbonyl group and an acyl group.

X ₄ is a hydrogen atom, a halogen atom, a carboxyl group, or a group which bonds a carbon atom at the coupling position via an oxygen atom, a nitrogen atom, a carbon atom, a sulfur atom or the like, and is dissociated by the coupling. Represents a group. R ₄₁ , R _{46 to} R ₄₁₂ or X may be a divalent linking group to form a bis form. In addition, R ₄₁ , R _{46 to} R
_It may be a polymer in which any of ₄₁₂ becomes a divalent linking group and is linked to the polymer main chain via this. The compound represented by the general formula (M) of the present invention is disclosed in Japanese Patent Application No. 80551/1993.
Although disclosed in the specification, the following examples can be specifically mentioned.

[0070]

[Chemical 34]

[0071]

[Chemical 35]

[0072]

[Chemical 36]

[0073]

[Chemical 37]

[0074]

[Chemical 38]

[0075]

[Chemical Formula 39]

The phenolic cyan coupler represented by the general formula (C) will be described in detail below. In the general formula (C), R ₅₁ is a hydrogen atom, a halogen atom (fluorine, chlorine, bromine, iodine) or a total number of carbon atoms (hereinafter referred to as C number) 1 to 18 which may be substituted and is linear. ,
Represents a branched or cyclic alkyl. Here, examples of the substituent on the alkyl group include a halogen atom, an aryl group, an alkoxy group, and an aryloxy group.

In the general formula (C), R ₅₂ is a C number 1-36.
(Preferably 4 to 30), optionally substituted, linear, branched or cyclic alkyl group, C number of 6 to 3
6 (preferably 12 to 30) optionally substituted aryl group or C number of 2 to 36 (preferably 12 to 30)
Represents a heterocyclic group. Here, the heterocyclic group represents a 5 to 7-membered optionally condensed heterocyclic group having at least one hetero atom selected from N, O, S, P, Se and Te in the ring. 2-furyl, 2-cenyl, 2-
Examples include pyridyl, 4-pyridyl, 4-pyrimidyl, 2-imidazolyl, 4-quinolyl and the like.

As an example of the substituent of R ₅₂ , a halogen atom,
Cyano group, nitro group, carboxyl group, sulfo group, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl Group, acyl group,
Examples thereof include a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an imide group, a ureido group, an alkoxycarbonylamino group, and a sulfamoylamino group (hereinafter referred to as Substituent group A). Group, heterocyclic group, aryloxy group, alkylsulfonyl group, arylsulfonyl group or imido group.

In the general formula (C), R ₅₃ is a hydrogen atom, a halogen atom, an alkyl group having a C number of 1 to 16 (preferably 1 to 8), an alkoxy group having a C number of 1 to 16 (preferably 1 to 8), It represents an aryloxy group having a C number of 6 to 24 (preferably 6 to 18) or a carbonamido group having a C number of 1 to 24 (preferably 1 to 18). Here, the groups below the alkyl group may be substituted with a substituent selected from the above-mentioned substituent group A. In the general formula (C), X ₅ represents a hydrogen atom or a coupling-off group which can be released by a coupling reaction with an oxidized product of an aromatic primary amine developing agent.

Examples of the coupling-off group are a halogen atom, a sulfo group and a C number of 1 to 36 (preferably 1 to 24).
An alkoxy group of C number 6 to 36 (preferably 6 to 24)
An aryloxy group having a C number of 2 to 36 (preferably 2 to 2)
4) acyloxy group, C-number 1-36 (preferably 1-)
24) alkylsulfonyl group, C-number 6 to 36 (preferably 6 to 24) arylsulfonyl group, C-number 1 to 36
(Preferably 2 to 24) alkylthio group, C number 6 to 3
6 (preferably 6 to 24) arylthio group, C number of 4 to
36 (preferably 4 to 24) imide group, C number of 1 to 36
A carbamoyloxy group (preferably 1 to 24) or a heterocyclic group bonded to the coupling active position with a nitrogen atom having a C number of 1 to 36 (preferably 2 to 24) (for example, pyrazolyl, imidazolyl, 1,2,4-). Triazol-1-yl, tetrazolyl). Here, the groups below the alkoxy group may be substituted with a substituent selected from the above-mentioned Substituent group A.

Examples of preferable groups for R ₅₁ , R ₅₂ , R ₅₃ and X _{5 in} formula (C) are shown below. R ₅₁ is preferably a fluorine atom, a chlorine atom, or an alkyl group substituted with at least one halogen atom, and particularly preferably a group represented by — (CF ₂ ) _q F or — (CF ₂ ) _r H. is there. Here, q and r each represent an integer of 1 to 16 (preferably 1 to 8). R ₅₂ is preferably an alkyl group, particularly preferably an aryloxy group at the 1-position,
It is an alkyl group substituted with an alkylsulfonyl group, an arylsulfonyl group, an imide group or a heterocyclic group.

R ₅₃ is preferably a hydrogen atom, a fluorine atom,
It is a chlorine atom, a methoxy group or an acetamide group, and particularly preferably a hydrogen atom. X ₅ is preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group,
It is an alkylthio group, an arylthio group or a heterocyclic thio group, and particularly preferably a hydrogen atom or a chlorine atom.
The following are R ₅₁ , R ₅₂ , R ₅₃ and X ₅ in the general formula (C).
A specific example of (Example of R ₅₁ ) -F, -Cl, -CF _3, -(CF ₂ ) ₂ F _, -(CF ₂ ) ₄ F
,-(CF ₂ ) ₆ F,-(CF ₂ ) ₈ F, -CF ₂ H,-(CF ₂ ) ₃ H,-(CF ₂ ) ₅
H,-(CF ₂ ) ₇ H,-(CF ₂ ) ₉ H, -CF ₂ Cl,-(CF ₂ ) ₃ Cl (Example of R ₅₂ )

[0083]

[Chemical 40]

[0084]

[Chemical 41]

[0085]

[Chemical 42]

[0086]

[Chemical 43]

[0087]

[Chemical 44]

[0088]

[Chemical 45]

[0089]

[Chemical 46]

[0090]

[Chemical 47]

(Example of R ₅₃ )

[Chemical 48]

(Example of X ₅ )

[Chemical 49]

[0093]

[Chemical 50]

[0094]

[Chemical 51]

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

[Chemical 52]

[0096]

[Chemical 53]

[0097]

[Chemical 54]

[0098]

[Chemical 55]

[0099]

[Chemical 56]

[0100]

[Chemical 57]

[0101]

[Chemical 58]

The cyan coupler represented by formula (C) is described in US Pat. No. 2,895,826 and JP-A-51-65.
It can be synthesized by the method described in each specification of No. 51 and No. 61-69065.

The non-pre-fogged internal latent image type silver halide emulsion used in the present invention contains silver halide grains in which the surface of the silver halide grains is not pre-fogged and the latent image is mainly formed inside the grains. More specifically, more specifically, a silver halide emulsion is coated on a transparent support in a fixed amount (0.5 to 3 g / m ² ) and a fixed time of 0.01 to 10 seconds is applied to this. When developed in the following developer A (internal type developer) at 20 ° C. for 6 minutes, the maximum density measured by a usual photographic density measuring method was applied in the same amount as above and exposed in the same manner. A silver halide emulsion having a concentration at least 5 times higher than the maximum concentration obtained when the silver halide emulsion is developed in the following developing solution B (surface type developing solution) at 18 ° C. for 5 minutes is preferable, and more preferably at least 10 times higher. concentration Is to have.

Internal Developer A Metol 2 g Sodium sulfite (anhydrous) 90 g Hydroquinone 8 g Sodium carbonate (monohydrate) 52.5 g KBr 5 g KI 0.5 g Water was added to 1 liter Surface developer B Metol 2.5 g L-ascorbin Acid 10g NaBO ₂ .4H ₂ O 35g KBr 1g Water added 1 liter

Specific examples of the inner latent type emulsion include, for example, conversion type silver halide emulsions described in the specification of US Pat. No. 2,592,250 and US Pat.
1,276, 3,850,637, 3,92
No. 3,513, No. 4,035,185, No. 4,39
5,478, 4,504,570, JP-A-52-
No. 156614, No. 55-127549, No. 53-5
0222, 56-22681, 59-2085
No. 40, No. 60-107641, No. 61-1337.
JP-A-62-215272,

Research Disclosure No. 23
510 (issued in November 1983), page 236, and US Pat. No. 478, which has a silver chloride shell.
No. 9627, JP-A-6-66, regarding a silver chlorobromide core-shell emulsion.
3-10160, 63-47766, Japanese Patent Application 1-
No. 2467 and the core / shell type silver halide emulsions described in JP-A-63-191145 and JP-A-1-52146 relating to emulsions doped with metal ions can be mentioned.

The internal latent image type core-shell silver halide emulsion has a silver halide molar ratio of the core to the shell of 20/1 or less 1
/ 100 or more is particularly preferable. In the present invention, Mn, Cu, and
At least one selected from the group consisting of Zn, Cd, Pd, Bi and metals belonging to Group VIII of the periodic table may be incorporated. Mn, Cu, Zn, Cd, P incorporated in the pre-fogged internal latent image type silver halide grains of the present invention
The amount of d, Bi or a metal belonging to Group VIII of the periodic table is preferably 10 ⁻⁹ to 10 ⁻² mol, and more preferably 10 ⁻⁷ to 10 ⁻³ mol, per mol of silver halide.

Of the above metals, the use of lead, iridium and bismuth and rhodium is especially preferred. These metals can be incorporated in the grains by allowing the metal ions to coexist in the form of an aqueous solution or an organic solvent solution when a silver halide solution is mixed with a silver ion solution to form silver halide grains. Alternatively, after forming the grains, the metal ions may be added in the form of an aqueous solution or an organic solvent solution, and then further covered with silver halide. The method of incorporating these metals is described in US Pat. Nos. 3,761,276, 4,395,478 and JP-A-59-216136.

The silver halide grains used in the present invention have a cubic shape, an octahedron shape, a dodecahedron shape or a tetradecahedron shape (Japanese Patent Application No. 1-43).
125), regular crystal forms such as 125), irregular crystal forms such as spheres, and JP-A-1-131547 and 1-1.
An emulsion in which tabular grains having a length / thickness ratio value of 5 or more, particularly 8 or more described in No. 58429 account for 50% or more of the total projected area of the grains 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, and the silver halide preferably used in the present invention contains no silver iodide or contains 3 mol% or less of salt. It is (iodo) silver bromide, (iodo) silver chloride or (iodo) silver bromide. The average grain size of the silver halide grains (the grain diameter in the case of spherical grains or grains close to spheres, and the vertical length in the case of cubic grains, the grain size is represented by the average based on the projected surface) is 1.5 μm or less. 0.1 μm or more is preferable, but 1.2 μm or less is particularly preferable.
It is 2 μm or more.

The particle size distribution may be narrow or wide, but in order to improve graininess, sharpness and the like, the number or weight of particles is within ± 40% of the average particle size, preferably within 30%, It is preferred to use a so-called "monodisperse" silver halide emulsion having a narrow grain size distribution so that 90% or more, particularly 95% or more of all grains are preferably within ± 20%.

Further, 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 emulsions having the same size in the emulsion layers having substantially the same color sensitivity are used. It is possible to mix a plurality of different particles in the same layer or to coat multiple layers in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or layered for use.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the surface of the grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc., alone or in combination. As the chemical sensitization method for core particles, the methods described in Japanese Patent Application Nos. 1-17488 and 1-17487 can be used. In the presence of a mercapto compound as described in JP-A-1-197742,
You may add thiosulfinic acid, a sulfinic acid, and a sulfite as described in 946, the same 2-69738, and Japanese Patent Application No. 1-95394. For specific examples, see Research Disclosure No. 17643-III (197
Issued December, 2012) See patent on page 23.

The photographic emulsion used in the present invention contains an antifoggant or stabilizer for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. You can For specific examples, see Research Disclosure No. 1
7643-VI (issued in December 1978) and EJBi
rr "Stabiliaution of Photographic Silver Hailde
Emulsion "(Focal Press), 1974.

As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
-157638, 59-170840, and those described in International Application Publication (WO) 88/01402 are preferable.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 for the yellow coupler.
To 0.5 moles, magenta couplers 0.03 to 0.5 moles, and cyan couplers 0.00
2 to 1.0 mol. As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

A color fog preventing agent or a color mixing preventing agent can be used in the light-sensitive material of the present invention. Representative examples of these are described in JP-A No. 62-215272, pages 185 to 193. As the compound releasing a photographically useful group, compounds described in JP-A Nos. 63-153540, 63-259555, 63-212080, 1-64715 and 1-130986 are disclosed. Can be mentioned. In the present invention, a color-enhancing agent can be used for the purpose of improving the color-forming property of the coupler. A representative example of the compound is JP-A-62-2.
No. 15272, p.121-125 is mentioned.

The light-sensitive material of the present invention contains a dye for preventing irradiation or halation (eg, Japanese Patent Application No. 63-2.
No. 37985 and No. 63-240393 may be used. A solid microcrystal dispersion method may be used as the dispersion method of the dye. ), An ultraviolet absorber, a plasticizer, a fluorescent whitening agent, a matting agent, an air fog preventing agent, a coating aid, a film hardening agent, an antistatic agent, a slipperiness improving agent and the like can be added. Typical examples of these additives are Research Disclosure
No. 17643VII to XIII (issued in December 1978)
25-27, and 18716 (issued in November 1979), pages 647-651.

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 are usually red-sensitive emulsion layers on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as required. The preferred order of layer arrangement is red-sensitive, green-sensitive, blue-sensitive from the support side or green-sensitive, red-sensitive and blue-sensitive from the support side. 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. .. It is usual that the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but in some cases, the green-sensitive layer contains a yellow coupler and a magenta coupler. It is also possible to use different combinations such as mixed use.

In addition to the silver halide emulsion layer, the light-sensitive material of the present invention is preferably provided with an auxiliary layer such as a protective layer, an intermediate layer, a filter layer, an antihalation agent, a back layer and a white reflective layer. In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are No. Research Research Magazine. 17643VVII paragraph (issued December 1978) 2
Those described on page 8 and European patents 0,102,25
No. 3 and the support described in JP-A No. 61-97655. Research Disclosure No. 17
The coating method described in pages 64 to 29 of 643XV can be used.

The fogging treatment of the present invention is carried out by the following "light fogging method" and / or "chemical fogging method". The overall exposure in the "light fog method", that is, the fog exposure is performed after imagewise exposure, after color development processing or during color development processing. That is, the imagewise exposed light-sensitive material is exposed in a color developing solution or in a pre-bath of the color developing solution, or is taken out from these solutions and dried before being dried. Is most preferred.

In the present invention, the nucleating agent used when the so-called "chemical fogging method" is applied can be contained in the light-sensitive material or in the processing liquid for the light-sensitive material. It can be preferably contained in the light-sensitive material. Where "nucleating agent"
Is a substance which acts when the surface of an internal latent image type silver halide emulsion which has not been fogged in advance is subjected to a surface development treatment to directly form a positive image. In the present invention, it is particularly preferable to perform fogging treatment using a nucleating agent.

When it is contained in the light-sensitive material, it is preferably added to the inner latent type silver halide emulsion layer, but as long as it diffuses during coating or during processing and the nucleating agent is adsorbed on the silver halide. It may be added to other layers such as an intermediate layer, an undercoat layer and a back layer. When the nucleating agent is added to the processing solution, it may be contained in a developing solution or a low pH pre-bath as described in JP-A-58-178350. Also,
You may use together 2 or more types of nucleating agents.

Examples of the nucleating agent that can be used in the present invention include those described in "Research Disclosure", N.
o. 22534 (January 1983), pp. 50-54, ibid., No. 15162 (November 1976) 76-77
Page, same magazine, No. 23510 (November 1983) 346
Quaternary heterocyclic compounds and hydrazine compounds described on page 352.

Examples of the quaternary heterocyclic nucleating agent include US Pat. Nos. 3,615,615 and 3,719,494,
3,734,738, 3,759,901, 3,854,956, 4,094,683, 4,306,016, and British Patents 1,283,835.
No. 4, Japanese Patent Publication No. 49-38, 164, No. 52-19, 45
2, JP-A-52-47,326, JP-A-52-69,6.
No. 13, No. 52-3, 426, No. 55-138, 74
No. 2, 60-11, 837,

And the above-mentioned "Research Disclosure" magazine No. 22534; ibid. 23, 213 (198
Those described in, for example, pages 267 to 270 issued in August, 3rd year). Further, as a highly active quaternary salt compound, JP-A-63-63
-121042, 63-301942, JP-A-1
-191132, 2-101450, 2-79
Those described in No. 038 and No. 2-101451 can be used. Particularly, a quaternary heterocyclic nucleating agent represented by the following general formula (N) is preferable. General formula (N)

[0127]

[Chemical 59]

In the formula, Z represents a nonmetallic atom group necessary for forming a 5- to 6-membered heterocycle, and Z may be substituted with a substituent. R ¹ is an aliphatic group, and R ² is a hydrogen atom, an aliphatic group or an aromatic group. R ¹ and R ² may be substituted with a substituent. Further, R ² may be further bonded to the heterocycle completed by Z to form a ring. However,
At least one of the groups represented by R ¹ , R ² and Z contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or R ¹ and R ² form a 6-membered ring, and Form a pyridinium skeleton.

Further, at least one of the substituents of R ¹ , R ² and Z may have an adsorption promoting group for silver halide. Y is a counter ion for charge balance, and n
Is 0 or 1. Heterocycles completed with Z include, for example, quinolinium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, and isoquinolinium nuclei.
Quinolinium and benzothiazolium are more preferable, and quinolinium is most preferable.

As the substituent of Z, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkynyl group, a hydroxy group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylthio group, an arylthio group,
Acyloxy group, acylamino group, sulfonyl group, sulfonyloxy group, sulfonylamino group, carboxyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, ureido group, urethane group, carbonic acid ester group, hydrazine group, hydrazone group , Or imino group.

The substituent of Z may be via a suitable linking group. The aliphatic group of R ¹ and R ² preferably has 1 to 1 carbon atoms.
It is an unsubstituted alkyl group having 18 carbon atoms and a substituted alkyl group having 1 to 18 carbon atoms in the alkyl moiety. The aromatic group represented by R ² preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

Examples of the adsorption promoting group to silver halide which the substituents of R ¹ , R ² and Z may have include a thioamide group, a mercapto group and a 5- to 6-membered nitrogen-containing heterocyclic group. The thioamide group is preferably an acyclic thioamide group (eg, thiourethane group, thioureido group, etc.).

As the mercapto group, a heterocyclic mercapto group (for example, 5-mercaptotetrazole, 3-mercapto-1,2,4-triazole, 2-mercapto-1,3,4-thiadiazole, 2-mercapto-1,
3,4-oxadiazole) are preferred. The 5- or 6-membered nitrogen-containing heterocycle is composed of a combination of nitrogen, oxygen, sulfur and carbon, and preferably produces iminosilver, and examples thereof include benzotriazole and aminothiatriazole.

When a nucleating agent is used, it is preferable to use a nucleating accelerator for promoting the action of the nucleating agent. A nucleation accelerator does not substantially function as a nucleating agent,
It refers to a substance that promotes the action of a nucleating agent to increase the maximum density of a direct positive image and / or accelerates the development time required to obtain a constant direct positive image density.

Such nucleation accelerators include tetrazaindenes, triazaindenes and pentaazaindenes having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group. And the compounds described on pages 5 to 16 of JP-A-63-106656. In addition, JP-A-63
-226652, 63-106656, 63-
The compounds described in No. 8740 can be mentioned.

Known photographic additives that can be used in the present invention are the above-mentioned Research Disclosure No. 17643.
(Dec. 1978) and No. 18716 (197).
(November 1997), and the relevant parts are summarized in the table below.

Additive type RD17643 RD18716 1 Chemical sensitizer, page 23, page 648, right column 2 Sensitivity enhancer, same as above 3 Spectral sensitizer, supersensitizer, page 23 to page 648, right column to page 649, right column 4 increase White agent 24 pages 5 Antifoggants, stabilizers 24 to 25 pages 649 right column 6 Light absorbers, filters 25 to 26 pages 649 right column ~ Dyes, UV absorbers 650 left column

7 Anti-Staining Agent, page 25, right column, page 650, left to right column, 8 dye image stabilizer, page 25, 9 hardener, page 26, page 651, left column 10 binder, page 26, same as 11 plasticizer, lubricant, page 27, page 650, right Column 12 Coating aids, surface active agents, pages 26-27, ibid. 13 Static inhibitor, page 27, ibid.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are flexible supports generally used for photographic light-sensitive materials such as plastic films, papers and cloths, or rigid supports such as glass, ceramics and metals. Applied to the body. What is useful as the flexible support is a film made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate complex acid, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, a baryter layer or an α-olefin. Polymer (eg polyethylene, polypropylene, ethylene / butene copolymer)
It is a paper coated or laminated with the above. The support may be colored with a dye or pigment.

For coating the silver halide photographic emulsion layer and other hydrophilic colloid layers, various known methods such as dip coating method, roller coating method, curtain coating method and extrusion coating method can be used. .. Also, if necessary, US Pat. Nos. 2,681,294 and 276179.
Multiple layers may be simultaneously coated by the method described in No. 1, No. 3526528, No. 3508947, or the like.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Aminophenol compounds are also useful in this color development process, but p-phenylenediamine compounds are preferably used, and a typical example thereof is 4-amino-N-ethyl-N.
-Hydroxyethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 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 -Toluene sulfonate. Two or more kinds of these compounds can be used in combination depending on the purpose. Especially 4-amino-N-ethyl-
N-hydroxyethylaniline is 50% of the total developing agent
It is preferable to use at least a molar amount.

The photographic 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. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. 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), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, and other various conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture an
d Television Engineers Volume 64, p248-253
(May 1955 issue).

In the present invention, a bleach-fixing bath or its pre-bath,
Alternatively, the bleaching accelerator contained in the light-sensitive material is selected from compounds having a mercapto group or a disulfide bond, a thiazolidine derivative, a thiourea derivative and an isothiourea derivative and has a bleaching promoting effect. However, those represented by the following general formulas (VI) to (XII) are preferable. In formula (VI), R ₆₁ and R ₆₂ may be the same or different and each is a hydrogen atom, a substituted or unsubstituted lower alkyl group (preferably having a carbon number of 1 to 5, especially a methyl group, an ethyl group, a propyl group). Is preferred) or an acyl group (preferably having a carbon number of 1 to 3, for example, acetyl group, propionyl group, etc.), and n is 1
Is an integer of ~ 3. R ₆₁ and R ₆₂ may combine with each other to form a ring. As R ₆₁ and R ₆₂ , a substituted or unsubstituted lower alkyl group is particularly preferable. Examples of the substituents possessed by R ₆₁ and R ₆₂ include a hydroxyl group, a carboxyl group, a sulfo group, an amino group and the like.

In formula (VII), R ₇₁ and R ₇₂ have the same meanings as R ₁ and R _{2 in} formula (I). n is an integer of 1 to 3. R ₇₁ and R ₇₂ may combine with each other to form a ring. As R ₇₁ and R ₇₂ , a substituted or unsubstituted lower alkyl group is particularly preferable. Here, the substituent which R ₇₁ and R ₇₂ have is a hydroxyl group,
A carboxyl group, a sulfo group, an amino group etc. can be mentioned. In the formula, R ₈₁ is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), an amino group, a substituted or unsubstituted lower alkyl group (preferably having 1 to 5 carbon atoms,
In particular, a methyl group, an ethyl group and a propyl group are preferable), and an amino group having an alkyl group (a methylamino group, an ethylamino group, a dimethylamino group, a diethylamino group, etc.) is represented. Here, _examples of the substituent that R ₈₁ has include a hydroxyl group, a carboxyl group, a sulfo group, and an amino group.

In formula (XI), R ₈₂ and R ₈₃ may be the same or different and each is a hydrogen atom or an alkyl group which may have a substituent (preferably a lower alkyl group such as a methyl group, An ethyl group, a propyl group), a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent (more specifically, at least a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom). A heterocyclic group containing one or more, for example, pyridine ring, thiophene ring, thiazolidine ring, benzoxazole ring, benzotriazole ring, thiazole ring, imidazole ring, etc.),
R ₈₄ represents a hydrogen atom or a lower alkyl group which may have a substituent (for example, a methyl group, an ethyl group and the like, preferably having 1 to 3 carbon atoms). Here, examples of the substituent that R _{82 to} R ₈₄ have include a hydroxyl group, a carboxyl group, a sulfo group, an amino group, and a lower alkyl group. R ₈₅ represents a hydrogen atom or a carboxyl group.

In formula (XII), R ₈₆ , R ₈₇ and R ₈₈ may be the same or different and each is a hydrogen atom or a lower alkyl group (for example, a methyl group, an ethyl group and the like, preferably having 1 to 1 carbon atoms). 3)). R
₈₆ and R ₈₇ or R ₈₈ may combine with each other to form a ring. X ₈ represents an amino group, a sulfonic acid group or a carboxyl group which may have a substituent (eg, a lower alkyl group such as a methyl group, an alkoxyalkyl group such as an acetoxymethyl group). R _{86 to} R ₈₈ are particularly preferably a hydrogen atom, a methyl group or an ethyl group, and X ₈ is preferably an amino group or a dialkylamino group. Specific examples of the compounds represented by formulas (VI) to (VII) are shown below.

[0148]

[Chemical 60]

[0149]

[Chemical formula 61]

[0150]

[Chemical formula 62]

[0151]

[Chemical 63]

[0152]

[Chemical 64]

[0153]

[Chemical 65]

[0154]

[Chemical 66]

[0155]

[Chemical 67]

[0156]

[Chemical 68]

[0157]

[Chemical 69]

[0158]

[Chemical 70]

Any of the above compounds can be synthesized by a known method. Particularly, for the compound of the general formula (VI), US Pat. No. 4,285,984, G. Schwarzenbac.
h et al., Helv. Chim. Acta., 38, 1147 (1955), ROClint
on et al., J. Am. Chem. Soc., 70, 950 (1948), compounds of general formula (VII) are described in JP-A-53-95630, compounds of general formulas (VIII) and (IX). For details, see JP-A-5
JP-A-51-68568 and JP-A-51-70763 for compounds of the general formula (X)
No. 53-50169, Japanese Patent Publication No. 53-9854, and Japanese Patent Application Laid-Open No. 59-84 for compounds of the general formula (XI).
With respect to the specification of No. 214855 and the compound of the general formula (XII), reference can be made to JP-A No. 53-94927.

When the compound having a mercapto group or disulfide bond in the molecule used in the present invention, the thiazoline derivative or the isothiourea derivative is contained in the bleaching solution or the bleach-fixing solution, the addition amount depends on the kind of the photographic material to be processed,
Although it varies depending on the treatment temperature and the time required for the intended treatment, 1 × 10 ^-5 to 10 ^-1 mol per liter of the treatment liquid is suitable, and preferably 1 × 10 ^{-4 to} 5 × 10 ^-2 mol. Is. To add the above-mentioned bleaching accelerator to the processing solution,
It is generally dissolved in water, an alkaline organic acid, an organic solvent or the like in advance and added, but even if it is directly added as a powder to a bleaching bath or a bleach-fixing bath, its bleaching promoting effect is not affected at all. ..

[0161]

【Example】

Example 1 Preparation of Sample 101 A paper support (thickness 10) laminated on both sides with polyethylene.
(0 micron), the following 1st to 8th layers were multilayer-coated, and the 9th to 10th layers were multilayer-coated on the back side to prepare a color photographic light-sensitive material. Titanium oxide (4 g / m ² ) was used as a white pigment on the polyethylene coated on the first layer, and a slight amount (0.0
03 g / m ² ) of ultramarine blue as a bluing dye (the chromaticity of the surface of the support is 88.0 in the L ^* , a ^* , b ^* system, −0.
It was 20, -0.75. ).

(Photosensitive layer composition) The components and the coating amount (g /
m ² unit). However, the addition amount of the sensitizing dye is shown in mol per mol of silver. For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer is Emulsion E described below.
It was prepared by changing the particle size by changing the temperature according to the manufacturing method of M-1. However, as the emulsion for the eighth layer, a Lippmann emulsion which was not surface-sensitized was used.

First Layer (Antihalation Layer) Black Colloidal Silver ... 0.07 Color Mixing Inhibitor (Cpd-7) ... 0.05 Color Mixing Inhibitor Solvent (Solv-4, 5 Equivalent Amount) ... 0.12 Gelatin ... 0.70

Second Layer (Intermediate Layer) Gelatin ... 0.70

Third Layer (Red Sensitive Layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1 5.4 × 10 ⁻⁴ ) (average grain size 0.40 μ, grain size distribution 10%) , Octahedron) ... 0.40 Gelatin ... 1.00 Cyan coupler (ExC-1, 2, 3 at 1: 1: 0.2) ... 0.30 Anti-fading agent (Cpd-1, 2, 3, 4, 30 Equivalent amount) 0.18 Antistain agent (Cpd-5, 15 Equivalent amount) 0.003 Coupler dispersion medium (Cpd-6) 0.30 Coupler solvent (Solv-1, 3, 5 etc.) Amount) ... 0.12

Fourth Layer (Intermediate Layer) Gelatin ... 1.00 Color Mixing Inhibitor (Cpd-7) ... 0.08 Color Mixing Inhibitor Solvent (Solv-4, 5 Equivalents) ... 0.16 Polymer Latex (Cpd-) 8)… 0.10

Fifth Layer (Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-2 2.6 × 10 ⁻⁴ ) (average grain size 0.40 μ, grain size distribution 10%). , Octahedron) 0.20 Gelatin 0.80 Magenta coupler (ExM-1, 2 equivalents) 0.11 Yellow coupler (ExY-1) 0.03 Anti-fading agent (Cpd-9, 26, 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 in 10: 7: 7: 1 ratio) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Equivalent for Solv-4 and 6) 0.15

6th layer (intermediate layer) Same as 4th layer

Seventh Layer (Blue Sensitive Layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-3, 4 equivalents 3.5 × 10 ^{−4 in} total) (average grain size 0.60 μ, Particle size distribution 11%, octahedron) 0.27 Gelatin 0.80 Yellow coupler (ExY-2, 3 equivalents) 0.35 Antifading agent (Cpd-14) 0.10 Antifading agent ( Cpd-30) ... 0.05 Anti-staining agent (Cpd-5,15 in 1: 5 ratio) ... 0.007 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv-2) ... 0. 10

Eighth Layer (Ultraviolet Absorber-Containing Layer) Gelatin ... 1.00 Ultraviolet Absorber (Equivalent for Cpd-2, 4, 16) ... 0.50 Anti-Color Mixing Agent (Equivalent for Cpd-7, 17) ... 0.03 Dispersion medium (Cpd-6) ... 0.02 UV absorber solvent (Solv-2, 7 each equivalent) ... 0.08 Irradiation prevention dye (Cpd-18, 19, 20, 21, 27) At a ratio of 10: 10: 13: 15: 20) ... 0.05

Ninth Layer (Protective Layer) Fine grain silver iodobromide (99 mol% silver bromide, average size 0.05 μ) ... 0.03 Acrylic modified copolymer of polyvinyl alcohol (molecular weight 50,000). 01 Polymethylmethacrylate particles (average particle size 2.4 μ) and silicon oxide (average particle size 5 μ) Equivalent ... 0.05 Gelatin ... 1.80 Gelatin hardening agent (Equivalent for H-1 and H-2) ... 0.18

10th Layer (Back Layer) Gelatin ... 2.50 Ultraviolet Absorber (Equivalent for Cpd-2, 4, 16) 0.50 Dye (Equivalent for Cpd-18, 19, 20, 21, 27) )… 0.06

Eleventh Layer (Backside Protective Layer) Polymethylmethacrylate particles (average particle size 2.4 μ) and silicon oxide (average particle size 5 μ) Equivalent ... 0.05 Gelatin ... 2.00 Gelatin hardener (H- 1, H-2 equivalent amount) ... 0.14

Preparation of Emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution at 65 ° C. over 15 minutes with vigorous stirring,
Octahedral silver bromide grains having an average grain size of 0.23 μm were obtained. At this time, 0.3 g of 3,4-dimethyl-1,3 per mol of silver was used.
-Thiazolin-2-thione was added. 1 silver in this emulsion
Chemical sensitization was carried out by sequentially adding 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mol and heating at 75 ° C. for 80 minutes. Using the particles thus obtained as a core, the particles are further grown in the same precipitation environment as the first time,
Finally, an octahedral monodisperse core / shell silver bromide emulsion having an average grain size of 0.4 μ was obtained. Coefficient of variation of particle size is about 10%
Met. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver.
The mixture was heated at 0 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion.

ExZK-1 is used as a nucleating agent in each photosensitive layer.
And ExZK-2 are 10 ⁻³ for silver halide,
10 ^-2 % by weight, as a nucleation accelerator Cpd-22, 28,
29 were used at 10 ^-2 wt% each. Further, alkanol XC (Du Pont) and sodium alkylbenzene sulfonate were used as emulsification / dispersion aids in each layer, and succinate and Magefac F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. As a stabilizer for silver halide and colloidal silver-containing layers (equal amounts of Cpd-23, 24 and 25)
Was used. This sample was designated as sample number 101. The compounds used in the examples are shown below.

[0176]

[Chemical 71]

[0177]

[Chemical 72]

[0178]

[Chemical formula 73]

[0179]

[Chemical 74]

[0180]

[Chemical 75]

[0181]

[Chemical 76]

[0182]

[Chemical 77]

[0183]

[Chemical 78]

[0184]

[Chemical 79]

[0185]

[Chemical 80]

[0186]

[Chemical 81]

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

ExZK-1 7- (3-ethoxythiocarbonylaminobenzamido) -9-methyl-10-propargyl-1,2,3,3
4-Tetrahydroacridinium trifluoromethanesulfonate ExZK-2 2- [4- {3- [3- {3- [5- {3- [2-chloro-5- (1-dodecyloxycarbonylethoxycarbonyl) phenyl) phenyl Carbamoyl] -4-hydroxy-1
-Naphthylthio} tetrazol-1-yl] phenyl}
Ureido] benzenesulfonamide} phenyl] -1-
Formyl hydrazine

Processing Step A Time Temperature Color development 135 seconds 38 ℃ Bleaching and fixing 40 seconds 35 ℃ Washing with water (1) 40 seconds 35 ℃ Washing with water (2) 40 seconds 35 ℃ Drying 30 seconds 80 ℃

The composition of each processing liquid was as follows. [Color developer] D-sorbit 0.15 g sodium naphthalenesulfonate / formalin condensate 0.15 g nitrilotris (methylenephosphonic acid) pentasodium salt 1.8 g diethylenetriaminepentaacetic acid 0.5 g 1-hydroxyethylidene- 1,1-Diphosphonic acid 0.15 g Diethylene glycol 12.0 ml Benzyl alcohol 13.5 ml Potassium bromide 0.70 g Benzotriazole 0.003 g Sodium sulfite 2.8 g Hydroxylamine 1/2 sulfate 4.5 g Triethanolamine 6.0 g 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate / 1/2 hydrate 4.2 g Potassium carbonate 30.0 g Optical brightener (diaminostilbene type) 1. Add 3 g water to 1000 ml pH ( 5 ° C.) (pH adjusted with KOH or sulfuric acid) 10.35

[Bleach-fixing solution] [Tank solution] Ethylenediaminetetraacetic acid.2sodium.dihydrate 4.0 g Ethylenediaminetetraacetic acid.Fe (III) .Ammonium dihydrate 55.0 g Ammonium thiosulfate (750 g / liter) ) 168 ml sodium p-toluenesulfinate 30.0 g ammonium sulfite 35.0 g ammonium nitrate 10.0 g 1000 ml by adding water pH (25 ° C.) (pH adjustment with ammonia water or acetic acid) 6.20

[Washing Water] Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

Samples 102 to 104 were prepared in the same manner as sample 101 except for the following changes. Compound I-1,
I-2 and II-1 are shown below. Sample 101 102 102 103 104 2nd layer-II-1 II-1 II-1 Compound II 1 1 1 (mg / m ² ) 3rd layer Red sensitizing dye ExS-1 I-1 I-2 I-1 / I-2 = ^1/1 (× 10 ^-4 mol / Ag mol) 5.4 5.4 5.4 Third layer silver amount 0.40 0.20 0.20 0.20 (g / m ² ) Fifth layer silver amount 0.20 0.20 0.20 0.20 (G / m ² ) Seventh layer Silver amount 0.27 0.27 0.27 0.27 (g / m ² ) Total silver amount 0.97 0.77 0.77 0.77 (g / m ² ) Relationship with the present application Comparative example The present invention The present invention

[0195]

[Chemical formula 82]

Wedge exposure (0.
After 2 seconds, 4800K, 100 CMS), treatment step A was performed. Maximum and minimum concentrations were measured. Maximum density Minimum density Sample No. Cyan Magenta Yellow Cyan Magenta Yellow 101 2.15 2.40 2.25 0.12 0.14 0.14 102 2.32 2.42 2.25 0.11 0.14 0.14 103 2.32 2.43 2.25 0.11 0.14 0.14 104 2.32 2.42 2.25 0.11 0.14 0.14 Samples 102 to 104 of the present invention are It was preferable that the maximum density was high and the minimum density was low compared to 101.

Example 2 The bleach-fixing time was shortened to 20 seconds, and the compound IX was added to the bleach-fixing solution.
Example except that 0.5 g / liter of (1) was added
1 was repeated and the amount of residual silver in the maximum density part was measured. Sample No. Residual silver amount 101 0.005 g / m ² 102 0.001 g / m ² or less 103 〃 104 〃 102 to 104 of the present invention had less residual silver amount than Comparative Example 101 and were preferable.

Example 3 Samples 101 to 104 were fine-contacted with a plate-making film having a halftone dot image using a fine checker FC850II manufactured by Fuji Photo Film Co., Ltd., and then red-exposed (SC-produced by Fuji Film Co., Ltd.
60 filters), green exposure (the same BPB-53 filter), and blue exposure (the same BPN-45, SC-42 filter) were successively performed. Then, the same processing step as the processing step A was carried out except that 0.5 g / liter of the compound IX- (1) was added to the bleach-fixing solution. The resulting color halftone image was observed with a magnifying glass of 100 times, and the minimum halftone dot area where formation of halftone dots of the cyan image was confirmed was examined. Sample No. Minimum halftone dot area 101 5% 102 2% 103 2% 104 2% Samples 102 to 104 of the present invention were preferable because they could reproduce halftone dots on the plate-making film to an area of 2%.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location G03C 7/32 7/42

Claims (4)

[Claims] 1. At least one layer of a blue light-sensitive layer, a green light-sensitive layer, a red light-sensitive layer and a non-light-sensitive hydrophilic colloid layer containing an internal latent image type silver halide emulsion which has not been fogged in advance is provided on a support. In the direct positive color photographic light-sensitive material thus obtained, the red light-sensitive layer contains the spectral sensitizing dye represented by the general formula (I), and the light-sensitive layer or
A direct positive color photographic light-sensitive material comprising a non-photosensitive hydrophilic colloid layer containing a compound represented by the general formula (II) and having a total silver amount of 0.7 g / m ² or less. General formula (I): In the formula, Y ₁ and Y ₂ each represent an atomic group necessary for forming a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring or a naphthoselenazole ring, and R ₁₂ and R 2
₁₃ represents an alkyl group, and R ₁₁ represents an alkyl group or an aryl group. However, at least one of R ₁₂ and R ₁₃ represents an alkyl group substituted with a sulfo group or a carboxyl group. X ₁ ⁻ represents an anion, and n represents 1 or 2. General formula (II) However, L is -CONH-, -NHCO- or -NHCO
Represents NH-, R ₂₁ represents an alkyl group, an aryl group, R ₂₂ represents a hydrogen atom, an alkyl group or a halogen atom, R ₂₃ represents a hydrogen atom, an alkyl group or an acylamino group (R ₂₂ and R ₂₃ are R ₂₄ may represent a hydrogen atom or an alkyl group,
R ₂₅ and R ₂₆ each represent an alkyl group (R ₂₅ and R ₂₆
May combine with each other to form a ring). The substituents of the above groups do not include a sulfo group or a carboxy group. The total number of carbon atoms in R _{21 to} R ₂₆ is large enough for the compound of the general formula (II) to have diffusion resistance. 2. The direct positive color photographic light-sensitive material contains at least one of a yellow coupler represented by the general formula (Y), a magenta coupler represented by the general formula (M), and a cyan coupler represented by the general formula (C). The direct positive color photographic light-sensitive material according to claim 1, wherein General formula (Y) In the formula, R ₃₁ represents an alkyl group, a cycloalkyl group or an aryl group, R ₃₂ represents an alkyl group, a cycloalkyl group, an acyl group or an aryl group, and R ₃₃ represents a group which can be substituted on the benzene ring. n represents 0 or 1. X ₃ represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidation product of a color developing agent, and Y ₃ represents an organic group. General formula (M) In the formula, R ₄₁ represents a hydrogen atom or a substituent, and X ₄ represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine developing agent; Za, Zb.
And Zc, respectively _{= CH -, = CR 42 -} (R 42 represents a hydrogen atom or a substituent), = N-or -NH-
And one of the Za-Zb bond and the Zb-Zc bond is a double bond and the other is a single bond; R ₄₁ and R ₄₂
Is the value of Hammett's substituent constant σ _p of any of the groups is −
2.00 or more and -0.41 or less, or the sum of Hammett's substitution constants [sigma] _p of these groups is -2.00 or more and -0.41 or less; Zb-Zc is a carbon-carbon double bond. In the case of, Zb-Zc may form part of another aromatic ring; R ₄₁ , R ₄₂ or X may be a divalent linking group to form a dimer; And R ₄₁ or R ₄₂ is 2
It may be a polymer which becomes a valent linking group and is linked to the polymer main chain via this. General formula (C) In the formula, R ₅₁ is a hydrogen atom, a halogen atom or an alkyl group, R ₅₂ is an alkyl group, an aryl group or a heterocyclic group,
R ₅₃ is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group or a carbonamido group,
₅ represents a hydrogen atom or a coupling-off group. 3. A direct positive color image forming method, which comprises subjecting the direct positive color light-sensitive material according to claim 2 to a bleach-fixing treatment in the presence of at least one compound represented by the general formulas (VI) to (XII). .. General formula (VI) In the formula, R ₆₁ and R _{62, which} may be the same or different, each represents a hydrogen atom, an alkyl group or an acyl group, and n is an integer of 1 to 3. General formula (VII): In the formula, R ₇₁ and R ₇₂ have the same meanings as R ₆₁ and R _{62 in} formula (VI). n is an integer of 1 to 3. General formula (VIII) General formula (IX) General formula (X) In the formula, R ₈₁ represents a hydrogen atom, a halogen atom, an amino group, a lower alkyl group or an amino group having an alkyl group. General formula (XI) In the formula, R ₈₂ and R _{83, which} may be the same or different, each represents a hydrogen atom, an alkyl group, a phenyl group or a heterocyclic group, and R ₈₄ represents a hydrogen atom or a lower alkyl group,
₈₅ represents a hydrogen atom or a carboxyl group. General formula (XII) In the formula, R ₈₆ , R ₈₇ and R _{88, which} may be the same or different, each represents a hydrogen atom or a lower alkyl group, and X ₈ represents an amino group, a sulfonic acid group or a carboxyl group. 4. A development-processed plate-making film on which a black and white halftone image is formed is adhered to the direct positive color light-sensitive material,
4. The direct positive color image forming method according to claim 3, wherein the plate-making film is exposed with each of the lights that have passed through the red, green, and blue filters, and is exposed three times in succession.