JP2909645B2 - Silver halide color photographic materials - Google Patents

Description

Description: BACKGROUND OF THE INVENTION The present invention relates to a color photographic light-sensitive material having an improved color tone, and more particularly to a plurality of black and white screens obtained by color separation and halftone image conversion in a color plate making and printing process. The present invention relates to a silver halide color photographic light-sensitive material used for producing a color image for correction (color proof) from a point image.

[Conventional technology]

Conventionally, in the process of color plate making and printing, as a method of obtaining a color proof from a plurality of black and white halftone images obtained by color separation and halftone image conversion, conventionally, a color image using a photopolymer or a diazo compound is used. The overlay method and the surprint method for forming are known.

The overlay method is very simple, has low production cost, and has the advantage that it can be used for proofreading only by stacking four color (subtractive primary color and black) film sheets. Produces gloss,
For this reason, there is a disadvantage that the printed material has a different texture.

The surprint method is to superimpose a colored image on one support, and as this method, a method of obtaining a colored image by toner development utilizing the tackiness of a photopolymerizable material is disclosed in U.S. Pat.No. 3,582,327, Nos. 3,607,264 and
Known in 3,620,726.

Also, transferred to a support using a photosensitive colored sheet,
A method for forming a color proof by forming an image by exposure and development, laminating another colored sheet thereon, and repeating the same process is disclosed in JP-B-47-2744.
No. 1 and JP-A-56-501217.

Further, a method of forming each colored image obtained by exposing and developing each corresponding color separation film using a photosensitive colored sheet on a single support by transfer is disclosed in
Known as 97140. As a toner for forming these images and a coloring agent for the colored sheet, there is an advantage that a coloring material similar to the ink used for printing can be used, and thus the color tone of the obtained color proof is close to that of a printed matter.

However, these methods have the drawbacks that in the step of producing a color proof, images must be superimposed or transferred, which requires a long operation time and high production cost.

As a solution to such a disadvantage, a method of producing a color proof by using a silver halide color photographic light-sensitive material having a white support has been disclosed in JP-A-56-113139 and JP-A-56-10.
No. 4335, the color of each single layer of yellow, magenta and cyan obtained by subjecting the silver halide color photographic light-sensitive material to color separation exposure and development is different from the yellow, magenta and cyan colors of the printing ink. Therefore, it is extremely difficult to reproduce the color of the printing ink.

Therefore, when a negative color photographic light-sensitive material is used as a color proofing material among the full-color photographic light-sensitive materials of the subtractive color method, exposure is performed to approximate the color development of each of the halftone images of yellow, magenta and cyan to the color of the printing ink. The wavelength component of the light at the time is controlled by a filter, etc.
It is known from U.S. Pat. No. 4,188,111 that an optimum color tone can be obtained by appropriately mixing yellow, magenta and cyan of a color photographic light-sensitive material with respect to one halftone image.

However, if you create a color proof this way,
When the size of a halftone dot is small, there is a disadvantage that the color tone of the halftone dot varies greatly, and in Japanese Patent Application No. 63-306569,
For example, a method has been disclosed in which a magenta coupler and a yellow coupler are incorporated in a layer having the same photosensitivity, but there are still disadvantages to be solved for practical use.

That is, if at least two couplers having different spectral absorptions are contained in the same photosensitive layer, the production conditions change. For example, if the stagnation time of the emulsion coating solution at the time of production changes, the color tone may change, or the sensitivity may change due to storage. The problem that performance fluctuates arises.

[Object of the invention]

An object of the present invention is a silver halide color photographic light-sensitive material used in a method for creating a color proof from a plurality of black and white halftone images obtained by color separation and halftone image conversion, and has a large dot and a small dot. The object of the present invention is to stably provide a silver halide color photographic light-sensitive material for color proof which can provide a color tone similar to the above.

Another object of the present invention is to provide a silver halide color photographic light-sensitive material for color proof, which has a small change in sensitivity depending on storage conditions.

[Configuration of the invention]

An object of the present invention is to provide a silver halide color photographic light-sensitive material having a photographic component layer including at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer has the following general formula [I] to At least one silver halide emulsion layer containing at least one compound represented by [IV] and having the same spectral sensitivity, comprises at least one compound represented by the following general formula [MI]; This is achieved by a silver halide color photographic material containing at least one yellow coupler and having a calcium atom content of 15 mg / m ² or less in the photographic component layer.

General formula [MI] In the formula, Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent.

 R represents a hydrogen atom or a substituent.

 Hereinafter, the present invention will be described in more detail.

In the present invention, the silver halide emulsion layer having the same spectral sensitivity may be a single emulsion layer,
It may comprise one or more silver halide emulsion layers. In the case of two or more silver halide emulsion layers,
It means that these are combinations of silver halide emulsion layers in which the difference between the wavelengths showing the maximum values of the spectral sensitivities is 30 nm or less.

In the present invention, it means that at least one silver halide emulsion layer having the same spectral sensitivity contains at least one of the compounds represented by the above general formula [MI] and at least one of yellow couplers. When the silver halide emulsion layer is a single layer, the silver halide emulsion layer contains at least one compound of the formula [MI] and at least one yellow coupler. When there are a plurality of the silver halide emulsion layers, the compound represented by the general formula [MI] may be contained in any of the plurality of the silver halide emulsion layers, and the yellow coupler is also used in the plurality of the silver halide emulsion layers. It may be contained in any of the silver emulsion layers. To give an example of a preferred embodiment, the general formula [M-
The compound of the formula (I) and a yellow coupler may be contained. In still another preferred embodiment, one of the two silver halide emulsion layers having the same spectral sensitivity contains the compound [MI] and the other layer contains the yellow coupler. It may be.

The silver halide color photographic light-sensitive material of the present invention contains a compound represented by the following general formula [MI].

General formula [MI] In the general formula [MI], Z represents a group of nonmetallic atoms necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent.

 R represents a hydrogen atom or a substituent.

The substituent represented by R is not particularly limited, but typically includes groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl. Atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl,
Carbamoyl, sulfamoyl, cyano, alkoxy,
Aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups And spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

As the aryl group represented by R, a phenyl group is preferable.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkyl component and the aryl component in the alkylthio group and the arylthio group represented by R include the alkyl group and the aryl group represented by R.

The alkenyl group represented by R has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, particularly 5 carbon atoms.
To 7 are preferable, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R has 3 carbon atoms.
~ 12, especially 5-7 are preferred.

As the sulfonyl group represented by R, an alkylsulfonyl group, an arylsulfonyl group, or the like; As the sulfinyl group, an alkylsulfinyl group, an arylsulfinyl group, or the like; As the phosphonyl group, an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group An acylcarbonyl group such as an alkylcarbonyl group or an arylcarbonyl group; a carbamoyl group such as an alkylcarbamoyl group or an arylcarbamoyl group; a sulfamoyl group such as an alkylsulfamoyl group or an arylsulfamoyl group; As an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc .; As a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc .; a ureido group Such as alkyl ureido groups and aryl ureido groups; sulfamoylamino groups such as alkylsulfamoylamino groups and arylsulfamoylamino groups; and heterocyclic groups having 5 to 7 members are preferred. Is a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group or the like; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, and for example, 3,4,5,6 -Tetrahydropyranyl-2-oxy group, 1-phenyltetrazol-5-oxy group, etc .; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, a 2-pyridylthio group, a 2-benzothiathio group. Zolylthio group, 2,4-diphenoxy-1,3,5-triazole-6-thio group, etc .; siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutyl Proxy group or the like; succinimide imide group as a group, 3-heptadecyl succinic acid imide group, a phthalimide group, a glutarimide group and the like; spiro [3.3] As a spiro compound residue heptane -
1-yl and the like; bicyclo [2.2.1] as an organic hydrocarbon compound residue
Heptan-1-yl, tricyclo [3.3.1.1 ^3,7 ] decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptane-1-yl and the like.

Examples of the group capable of leaving by reaction with an oxidized form of the color developing agent represented by X include, for example, a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, etc.), alkoxy, aryloxy,
Heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl,
Alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring linked by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl , (R ₁ ′ has the same meaning as R, Z ′ has the same meaning as Z, and R ₂ ′ and R ₃ ′ each represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group.) And preferably a halogen atom, particularly a chlorine atom. Examples of the nitrogen-containing heterocyclic ring formed by Z or Z ′ include a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring. Examples of the substituent that the ring may have include those described above for R. Is mentioned.

The compound represented by the general formula [MI] is more specifically represented by the following general formulas [M-II] to [M-VII].

General formula [M-II] General formula [M-III] General formula [M-IV] General formula [MV] General formula [M-VI] General formula [M-VII] In the general formulas [M-II] to [M-VII], R _{1 to} R ₈
And X have the same meanings as R and X described above.

Among the general formulas [MI], preferred are those represented by the following general formula [M-VIII].

General formula [M-VIII] In the formula, R ₁ , X and Z ₁ have the same meanings as R, X and Z in the general formula [MI].

Among the magenta couplers represented by the general formulas [M-II] to [M-VII], those particularly preferred are those represented by the general formula [MI]
I] is a magenta coupler represented by

When used for positive image formation, the general formulas [MI] to
As for the substituent on the heterocyclic ring in [M-VIII], R in the general formula [MI] is the same as that in the general formula [M
-II] to [M-VIII], it is preferable that R ₁ satisfies the following condition 1, more preferably, the following conditions 1 and 2
Is particularly preferable, and the following conditions 1 and 2 are particularly preferable.
And 3 are satisfied.

Condition 1 A root atom directly connected to a heterocyclic ring is a carbon atom.

Condition 2 One or no hydrogen atom is bonded to the carbon atom.

Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds.

Most preferred as the substituents R and R ₁ satisfying the above conditions are those represented by the following general formula [M-IX].

General formula [M-IX] In the formula, R ₉ , R ₁₀ and R ₁₁ have the same meanings as R described above.

Further, two of R ₉ , R ₁₀ and R ₁₁ , for example, R ₉ and R ₁₀
May be combined with each other to form a saturated or unsaturated ring (eg, cycloalkane, cycloalkene, heterocycle), and R ₁₁ may be bonded to the ring to form a bridged hydrocarbon compound residue. Good.

Preferred among Formula [M-X] is, (i) R ₉ ~
When at least two of R ₁₁ are alkyl groups, (ii) R 11
One example R ₁₁ in the ₉ to R ₁₁ is a hydrogen atom, a, if the other two R ₉ and R ₁₀ form a cycloalkyl together with the root carbon atom bonded.

Further, among (i), preferred are two of R _{9 to} R _11.
One is an alkyl group and the other is a hydrogen atom or an alkyl group.

Moreover, the general formula (M-I) formed by Z in the ring and Formula [M-VIII] ring has optionally substituents also formed by Z ₁ in, and Formula [M-II] ~
R _{2 to} R ₈ in [M-VI] are represented by the following general formula [M-VI
X] is preferred.

The general formula [M-X] -R ¹ -SO ^₂ -R ₂ Formula wherein R ¹ is an alkylene group, R ² represents an alkyl group, a cycloalkyl group or an aryl group.

The alkylene group represented by R ¹ preferably has 2 or more straight-chain carbon atoms, more preferably 3 to 6 carbon atoms, and may be straight-chain or branched.

The cycloalkyl group represented by R ² preferably have 5-6 membered.

When used for forming a negative image, the general formulas [MI] to
As for the substituent on the heterocyclic ring in [M-VIII], R in the general formula [MI] is the same as that in the general formula [M-VIII].
In [II] to [M-VIII], R ₁ preferably satisfies the following condition 1, more preferably the following conditions 1 and 2:
Is satisfied.

Condition 1 A root atom directly connected to a heterocyclic ring is a carbon atom.

Condition 2 At least two hydrogen atoms are bonded to the carbon atom.

The most preferred substituents R and R ₁ satisfying the above conditions are those represented by the following general formula [M-XI].

General formula [M-XI] R ₁₂ —CH ₂ — wherein R ₁₂ has the same meaning as R described above.

Preferred as R ₁₂ is a hydrogen atom or an alkyl group.

 Hereinafter, typical specific examples of the compound according to the present invention will be shown.

In addition to the representative examples described above, among the compounds described on pages 66 to 122 of Japanese Patent Application No. 61-9791, No. 1
~ 4,6,8 ~ 17,19 ~ 24,26 ~ 43,45 ~ 59,61 ~ 104,106 ~ 121,
Compounds represented by 123 to 162,164 to 223 can be mentioned.

The coupler is also available from the Journal of the Chemical Society,
Perkin I (1977), 2047-2052, U.S. Patent
No. 3,725,067, JP-A-59-99437, JP-A-58-42045, and JP-A-5-42045
9-162548, 59-171956, 60-33552, 60-
Nos. 43659, 60-177292 and 60-190779 can be synthesized.

The coupler of the present invention is generally used in an amount of 1 per mol of silver halide.
× 10 ^-3 mol to 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10
It can be used in the ^-1 molar range.

The above couplers can be used in combination with other types of magenta couplers.

In the present invention, a preferred yellow coupler contained in a silver halide emulsion layer having the same photosensitivity as that containing the compound of the general formula [MI] is represented by the following general formula [Y-
I].

Particularly preferred among the couplers represented by the general formula [Y-I], when combined with the magenta coupler represented by the general formula [MI], the pKa of the coupler represented by the [MI] to be combined Couplers having a pKa value no less than 3 or more below the value are preferred.

General formula [Y-I] In the general formula [Y-I], R ₁ represents a halogen atom or an alkoxy group.

R ₂ represents a hydrogen atom, a halogen atom or an optionally substituted alkoxy group. R ₃ is an acylamino group optionally having a substituent, an alkoxycarbonyl group, an alkylsulfamoyl group, an arylsulfamoyl group,
Represents an arylsulfonamide group, an alkylureido group, an arylureido group, a succinimide group, an alkoxy group or an aryloxy group.

Z ₂ represents a hydrogen atom, a monovalent organic group or a halogen atom which can be eliminated when coupling an oxidized form of a color developing agent.

Hereinafter, specific examples of the yellow coupler used in the present invention will be shown.

The ratio of the content of the magenta coupler to the content of the yellow coupler in the magenta image forming layer of the silver halide color photographic light-sensitive material of the present invention is such that the spectral absorption of the dye image obtained by the color development processing of the magenta image forming layer is magenta. What is necessary is just to determine so that it may approximate the spectral absorption of the printing image by printing ink. Specifically, the amount of the yellow coupler is preferably in the range of 0.02 to 0.5 mol per mol of the magenta coupler.

As the yellow coupler contained in the magenta image forming layer of the silver halide color photographic light-sensitive material of the present invention, a yellow coupler represented by the above general formula [Y-I] is preferably used.

In the present invention, a phenol-based or naphthol-based cyan dye-forming coupler is used as the cyan coupler contained in the cyan image forming layer.

Among them, a coupler represented by the following general formula [C-I] or [C-II] is preferably used.

General formula [C-I] In the general formula [C-I], R ₁ represents an aryl group, a cycloalkyl group or a heterocyclic group. R ₂ represents an alkyl group or a phenyl group. R ₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

Z ₁ represents a hydrogen atom or a group which can be eliminated by reaction with an oxidized form of an aromatic primary amine color developing agent.

General formula [C-II] In the general formula [C-II], R ₄ represents an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a nonyl group, and the like). R ₅ represents an alkyl group (for example, a methyl group, an ethyl group, etc.). R ₆ represents a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.) or an alkyl group (eg, methyl group, ethyl group, etc.). Z ₂ represents a hydrogen atom or a group which can be eliminated by a reaction with an oxidized form of an aromatic primary amine color developing agent.

These cyan couplers are described in U.S. Pat.
2,356,475, 2,362,596, 2,367,531, 2,3
69,929, 2,423,730, 2,474,293, 2,476,00
8, 2,498,466, 2,545,687, 2,728,660,
No. 2,772,162, No. 2,895,826, No. 2,976,146, No. 3,0
02,836, 3,419,390, 3,446,622, 3,476,56
No. 3, No. 3,737,316, No. 3,758,308, No. 3,839,044,
UK Patents 478,991, 945,542, 1,084,480,
Nos. 1,377,233, 1,388,024 and 1,543,040 and JP-A-47-37425, JP-A-50-10135, JP-A-50
-25228, 50-112038, 50-117422, 50-1
No. 30441, No. 51-6551, No. 51-37647, No. 51-52828
Nos. 51-108841, 53-109630, 54-48237
No. 54-66129, No. 54-131931, No. 55-32071,
Nos. 59-146,050, 59-31,953 and 60-117,249
It is described in each public information of the issue.

The coupler used in the present invention is generally used in each silver halide emulsion layer in an amount of 1 × 10 ^-3 mol to 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10 ^-1 mol, per mol of silver halide. Can be used.

The above coupler is usually dissolved in a high boiling point organic solvent having a boiling point of about 150 ° C. or higher using a low boiling point and / or a water-soluble organic solvent as necessary, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution. After emulsification and dispersion, it may be added to the target hydrophilic colloid layer. A step of removing the low boiling organic solvent at the same time as the dispersion or dispersion may be included.

In the present invention, the ratio of the high-boiling organic solvent and the low-boiling organic solvent according to the present invention is 1: 0.1 to 1:50, and further 1: 1 to 1:20.
It is preferred that

Any high-boiling organic solvent according to the present invention may be any compound having a dielectric constant of 6.0 or less. The lower limit is not particularly limited, but the dielectric constant is preferably 1.9 or more. For example, dielectric constant
Esters such as phthalic acid ester and phosphoric acid ester of 6.0 or less, organic acid amides, ketones, hydrocarbon compounds and the like. More preferred are phthalic acid esters or phosphoric acid esters.

In the present invention, the amount of calcium contained in the silver halide photographic light-sensitive material (value converted into calcium atom, the same applies hereinafter) mainly depends on the amount of calcium contained in gelatin used as a binder in the silver halide photographic light-sensitive material. I do.

16mg / m if no operation to remove calcium
^It usually contains ^two or more calcium.

In the present invention, the amount of calcium is
Any silver halide photographic light-sensitive material of 15 mg / m ² or less may be used.Specifically, a silver halide photographic light-sensitive material prepared by using all or a part of gelatin having a low calcium content by ion exchange resin or dialysis treatment is used. Materials are preferred.
Gelatin with low calcium content is generally 100 ppm
Say the following.

Calcium content of the silver halide photographic light-sensitive material of the present invention may be at 15 mg / m ² or less, but preferably 10mg /
m ² or less.

The silver halide photographic light-sensitive material of the present invention preferably contains at least one compound represented by the following general formulas [I], [II], [III] or [IV].

General formula [I] In the formula, R ₁₀ represents a lower alkylene group, and M represents a hydrogen atom, an alkali metal or an alkyl group. X is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group,
It represents a carboxyl group, amino group, hydroxyl group, sulfo group, nitro group or alkoxycarbonyl group. n represents 0 or 1, and m represents an integer of 1 to 5.

General formula (II) In the formula, R ₂₀ is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group, -CONHR (R is an alkyl group, an aryl group, an alkylthio group, an arylthio group, an alkylsulfonyl group,
Represents an arylsulfonyl group. ) Or a heterocyclic group. R ₃₀ and R ₄₀ represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a cyano group, an alkylthio group, an arylthio group, an alkylsulfoxide group, an alkylsulfonyl group, an alkylsulfinyl group, Further, R ₃₀ and R ₄₀ may be bonded to each other to form a benzene ring which may have a substituent.

General formula (III) In the formula, R ₅₀ and R ₆₀ represent a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 5 carbon atoms, or a hydroxymethyl group, and R ₇₀ represents a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms.

General formula (IV) In the formula, R ₈₀ represents a hydrogen atom, an alkyl group or an aryl group, and R ₉₀ represents a hydrogen atom, an alkyl group, an aryl group, a nitro group, a carboxyl group, a sulfo group, a sulfamoyl group, a hydroxy group, a halogen atom, an alkoxy group or Represents a thiazolyl group, and m represents 0 or 1. Z represents an atomic group constituting a thiazolyl ring.

In the general formula [I], examples of the lower alkylene group representing R ₁₀ include a methylene group, an ethylene group, and a propylene group. Examples of the halogen atom representing M include a chlorine atom,
A bromine atom and an iodine atom are exemplified. The alkyl group is preferably a linear or branched alkyl group having 1 to 8 carbon atoms. The cycloalkyl group is preferably a cycloalkyl group having 4 to 8 carbon atoms. As the aryl group, a phenyl group and a naphthyl group are preferable. The preferred carbon number of the alkoxycarbonyl group is 1-5.

Each of the above groups may be substituted with an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, a sulfo group, a nitro group, an amino group, a cyano group, a carboxyl group, a phenyl group, or the like.

In the general formula [II], the alkyl group and the alkenyl group represented by R ₂₀ preferably have 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms. The cycloalkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. These alkyl group, alkenyl group, cycloalkyl group, aralkyl group, aryl group and heterocyclic group may have a substituent, and the substituent may be a halogen atom, nitro, cyano, thiocyano, aryl, alkoxy, aryl Oxy, carboxy, sulfoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, sulfo, acyloxy, sulfamoyl, carbamoyl, acylamino, diacylamino, ureido, thioureido, thioureido, urethane, thiourethane, sulfonamide, heterocyclic group, Arylsulfonyloxy, alkylsulfonyloxy, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylsulfinyl, arylsulfinyl,
It is selected from alkylamino, dialkylamino, anilino, N-alkylanilino, N-arylanilino, N-acylamino, hydroxy and mercapto groups.

The alkyl group representing R ₃₀ and R ₄₀ preferably has 1 to 18 carbon atoms, more preferably 1 to 9 carbon atoms. The cycloalkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms. These alkyl group, cycloalkyl group and aryl group may have a substituent, and as the substituent,
Examples include a halogen atom, a nitro group, a sulfone group, an aryl group, and a hydroxy group. When R ₃₀ and R ₄₀ form a benzene ring with each other, examples of the group substituted on the benzene ring include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a cyano group, and a nitro group.

In the general formula [III], R _50, R _60, hydroxymethyl group represented by lower alkyl group and R ₇₀ having 1 to 5 carbon atoms represented by R ₇₀ may have a substituent.

In the general formula (IV), R ₈₀ is preferably a hydrogen atom, R
₉₀ is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms,
An amino group, a nitro group, a sulfo group, a halogen atom, a hydroxy group, m is preferably 1, and the thiazolyl ring represented by Z is preferably It is.

Some of the compounds represented by the general formulas [I], [II], [III] and [IV] are known as preservatives for hydrophilic colloids for silver halide photographic materials.

Some of the compounds represented by the general formula [I] are disclosed in
No. 22847 and No. 63-257747. Some of the compounds represented by the general formula (II) are described in JP-A-54-27424,
Nos. 59-131929, 59-142543, 58-166343,
59-131929, 59-142543, 59-2263453, and the like.

Some of the compounds represented by the general formula [III] are disclosed in
Nos. -119547 and 62-231936. Some of the compounds represented by the general formula (IV) are disclosed in JP-A-63-274944.
And No. 60-263938.

However, none of the above-mentioned documents discloses a raw sample storage property at all.

Representative specific examples of the compounds represented by the general formulas [I], [II], [III] and [IV] are shown below, but the compounds of the present invention are not limited thereto.

In the present invention, one or more of these exemplified compounds can be selectively used.

These exemplified compounds are generally well known, and are commercially available from ICI Japan Co., Ltd., Dainippon Ink and Chemicals, Rohm and Hahn Japan Co., Ltd., San-Ai Oil Co., Ltd., and the like. .

The amount of the chemicals represented by the general formulas [I], [II], [III] and [IV] is not limited, but is preferably in the range of 1 × 10 ⁻⁴ to 1 × 10 ⁻⁴ g / m ² , It may be added to either the silver emulsion layer or the non-emulsion layer. The addition method is not particularly limited.

Next, the silver halide color light-sensitive material of the present invention will be described.

The silver halide emulsion used in the present invention includes silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide and silver chloride which are used in usual silver halide emulsions. Can be used. The structure of silver halide grains is
The particles may be uniform from the inside to the outside of the particles, or the inside and outside structures of the particles may be different. When the inside and outside compositions of the particles are different, the composition may change continuously or may be discontinuous.

The grain size of the silver halide grains is not particularly limited, but is preferably 0.2 to 1.6 μm, more preferably 0.25 to 1.2 μm, in consideration of other photographic properties such as rapid processing property and sensitivity.
m.

The particle size distribution of the silver halide grains may be polydisperse or monodisperse.

The silver halide emulsion used in the present invention may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at one time, or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing may be the same or different.

The type of reacting the soluble silver salt with the soluble halogen salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method and a combination thereof. Further, as one form of the double jet method, a pAg-controlled double jet method described in JP-A-54-48521 can be used.

If necessary, a silver halide solvent such as thioether may be used.

Any shape of silver halide grains can be used.

As the silver halide grains according to the present invention, grains having a single shape may be used, or grains having various shapes may be mixed.

The silver halide emulsion used in the present invention may be a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt, or a complex salt, a rhodium salt or a complex salt during the process of forming and / or growing silver halide grains. Metal ions can be added using an iron salt or a complex salt, and can be contained inside the particles and / or on the surface of the particles. By placing them in an appropriate reducing atmosphere, reduction sensitization can be performed on the inside of the particles and / or on the surface of the particles. A nucleus can be provided.

In the silver halide emulsion used in the present invention, unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or may be kept contained. When removing the salts, use Research Disclosure 17643
The method can be performed based on the method described in the item.

The silver halide emulsion used in the present invention may be a grain whose latent image is mainly formed on the surface, or may be a grain mainly formed inside the grain.

The silver halide emulsion used in the present invention is chemically sensitized by a conventional method. That is, a compound containing sulfur capable of reacting with silver ions, a sulfur sensitization method using active gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization using gold or another noble metal compound. Sensing methods or the like can be used alone or in combination.

In the present invention, for example, a chalcogen sensitization method can be used as the chemical sensitizer. The chalcogen sensitizer is a general term for a sulfur sensitizer, a selenium sensitizer, and a tellurium sensitizer, and a sulfur sensitizer and a selenium sensitizer are preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbazide, thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine. In addition, U.S. Patents 1,574,974, 2,410,689 and 2,278,94
No. 7, 2,728,668, 3,501,313, 3,656,955,
West German Application Publication (OLS) 1,422,869 JP-A-56-24937, 5
Sulfur sensitizers described in JP-A-5-45016 can also be used.

The addition amount of the sulfur sensitizer varies over a considerable range depending on various conditions such as pH, temperature, and the size of silver halide grains, but the standard is 10 ^-7 per mol of silver halide.
It is preferably from about ¹ mol to about 10 ^-1 mol.

Selenium sensitizers can be used in place of sulfur sensitization. Examples of selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, and selenocarboxylic acids. Salts and esters, selenophosphates, diethyl selenide, selenides such as diethyl diselenide can be used, and specific examples thereof are described in U.S. Pat.
Nos. 944, 1,602,592 and 1,623,499.

Further, reduction sensitization can be used in combination. The reducing agent is not particularly limited, and examples thereof include stannous chloride, thiourea dioxide, hydrazine, and polyamine.

A noble metal compound other than gold, for example, a palladium compound can also be used in combination.

When a direct positive image forming silver halide emulsion is employed as the silver halide emulsion, for example, an internal latent image type silver halide emulsion can be used.For example, a so-called conversion type halogen according to the conversion method described in U.S. Pat. Silver halide emulsion, or U.S. Pat.Nos. 3,206,316, 3,3
Silver halide emulsions having internally chemically sensitized silver halide grains described in U.S. Patent Nos. 3,271,157, 3,447,927 and
No. 3,531,291 describes a silver halide emulsion having silver halide grains containing polyvalent metal ions described therein, or a silver halide grain containing a dopant described in U.S. Pat. Weakly chemically sensitized silver halide emulsion, or JP-A-50-8524,
So-called core-shell type silver halide emulsions by a lamination method described in 38525 and 53-2408, and others described in JP-A-52-156614, JP-A-55-127549 and JP-A-57-79940. Silver halide emulsions can be used. In this case, it is particularly preferred that the internal latent image type silver halide emulsion is made of laminated type grains.

Such silver halide grains can be produced in the same manner as ordinary laminated silver halide grains. For example, JP-A Nos. 50-8524, 50-38525, 53-60222, and 55
No.-1524 and U.S. Pat. No. 3,206,313, etc., a method of forming silver chloride grains, adding bromide to convert them to silver bromide grains, and further laminating halides by adding silver nitrate, or a state in which excess halogen is small. To form silver iodobromide grains, and then sequentially stack silver chloride and silver bromide.

When an internal latent image type silver halide emulsion is used, the emulsion contains a stabilizer which is usually used to suppress the rear surface sensitivity as low as possible and to give a lower minimum density and more stable characteristics, for example, a compound having an azaindene ring. And a heterocyclic compound having a mercapto group.

As the compound having an azaindene ring, for example, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is preferable. Further, among the heterocyclic compounds having a mercapto group, as a nitrogen-containing heterocyclic compound, a pyrazole ring, 1,2,
4-triazole ring, 1,2,3-triazole ring, 1,3,4-
Thiadiazole ring, 1,2,3-thiadiazole ring, 1,2,4-
Thiadiazole ring, 1,2,5-thiadiazole ring, 1,2,3,4
-Tetrazole ring, pyritazine ring, 1,2,3-triazine ring, 1,2,4-triazine ring, 1,3,5-triazine ring and the like,
Further, a ring obtained by condensing two to three of these rings, for example, a triazolotriazole ring, a diazaindene ring, a triazaindene ring, a tetrazaindene ring, a pentazaindene ring and the like, a phthalazinone ring, an imidazole ring, and the like,
Particularly, 1-phenyl-5 mercaptotetrazole is preferable.

In the silver halide color photographic light-sensitive material of the present invention,
The following sensitizing dyes can be used to form at least three silver halide emulsion layers having different spectral sensitivities.

Useful sensitizing dyes used in blue-sensitive silver halide emulsion layers include, for example, West German Patent 929,080 and U.S. Pat.
No. 31,658, No. 2,493,748, No. 2,503,776, No. 2,519,00
No. 1, No. 2,912,329, No. 3,656,956, No. 3,672,897,
Nos. 3,694,217, 4,025,349, 4,046,572, British Patent 1,242,588, Japanese Patent Publication Nos. 4414030 and 52-24844, and the like. Also useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.Nos. 1,939,201, 2,072,908,
Typical examples thereof include cyanine dyes, merocyanine dyes and complex cyanine dyes as described in 739,149, 2,945,763 and British Patent No. 505,979. Further, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 234, No. 2,270,378, No. 2,442,710, No. 2,454,629
And cyanide dyes, merocyanine dyes and complex cyanine dyes as described in JP-A Nos. 2,776,280 and the like. Furthermore, cyanine dyes or composite cyanine dyes described in U.S. Pat. Nos. 2,213,995, 2,493,748, 2,519,001 and West German Patent 929,080 are advantageously used in green-sensitive silver halide emulsions or red-sensitive halogen emulsions. be able to.

These sensitizing dyes may be used alone or in combination. Especially the combination of sensitizing dyes
Often used for supersensitization. A typical example is
JP-B Nos. 434932, 434933, 43-4936, 44
-32753, 45-25831, 45-26474, 46-116
No. 27, No. 46-18107, No. 47-8741, No. 47-11114,
47-25379, 47-37443, 48-28293, 48
-38406, 48-38407, 48-38408, 48-412
No. 04, No. 48-41204, No. 49-6207, No. 50-40662,
No. 53-12375, No. 54-34535, No. 55-1569, JP
No. 50-33220, No. 50-33828, No. 50-38526, No. 51-1
07127, 51-115820, 51-135528, 51-151
No. 527, No. 52-23931, No. 52-51932, No. 52-104916
No. 52-104917, No. 52-109925, No. 52-110618
No. 54-80118, No. 56-25728, No. 57-1483, No.
58-10753, 58-91445, 58-153926, 59-
No. 114533, No. 59-11645, No. 59-116647, U.S. Patent
2,688,545, 2,977,229, 3,397,060, 3,52
2,052, 3,527,641, 3,617,293, 3,628,964
No. 3,666,480, 3,672,898, 3,679,428,
3,703,377, 3,769,301, 3,814,609, 3,8
37,862 and 4,026,707.

Examples of the dye used in combination with the sensitizing dye, which has no spectral sensitizing effect by itself, or a substance which does not substantially absorb visible light and exhibits supersensitization, include aromatic organic acid formaldehyde condensate ( For example, U.S. Pat.
473,510), cadmium salts, azaindene compounds, aminostil compounds substituted with nitrogen-containing heterocyclic groups (for example, those described in U.S. Pat. Nos. 2,933,390 and 3,635,721). U.S. Patent Nos. 3,615,613, 3,6
The combinations described in 15,641, 3,617,295 and 3,635,721 are particularly useful.

In the silver halide color photographic light-sensitive material of the present invention, commonly used additives can be used in addition to those described above.

Examples of the wetting agent include dihydroxyalkane and the like, and examples of the film property improving agent include, for example, a copolymer of alkyl acrylate or alkyl methacrylate and acrylic acid or methacrylic acid, styrene-
Suitable are water-dispersible fine particle polymeric substances obtained by emulsion polymerization of maleic acid copolymers, styrene maleic anhydride half-alkyl ester copolymers and the like, and as coating aids, for example, saponin, polyethylene glycol , Lauryl ether and the like. Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, and development speeds. The use of regulators, matting agents, anti-irradiation dyes and the like is optional.

Further, an ultraviolet absorber can be used to prevent discoloration of the dye image due to actinic rays having a short wavelength, and examples thereof include thiazolidone, benzotriazole, acrylonitrile, and benzophenone-based compounds.
It is advantageous to use 120, 320, 326, 327, and 328 (all manufactured by Ciba-Geigy) alone or in combination.

The image forming layer according to the invention may contain appropriate gelatin (including oxidized gelatin) and its derivatives depending on the purpose. Preferred gelatin derivatives include, for example, acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, esterified gelatin and the like.

Further, in the silver halide color photographic light-sensitive material of the present invention, in addition to gelatin,
Other hydrophilic binders can be included.

The hydrophilic binder can be added to a photographic constituent layer such as an emulsion layer or an intermediate layer, a protective layer, a filter layer, and a backing layer according to the purpose. Agents, lubricants and the like.

Further, the silver halide color photographic light-sensitive material of the present invention,
On the support, in addition to an emulsion layer forming an image-supporting layer, various photographic constituent layers such as a filter layer, an intermediate layer, a protective layer, an undercoat layer, a backing layer, and an antihalation layer are formed as necessary. You may. As a coating method of each layer, dip coating, air doctor coating, extrusion coating, slide hopper coating, curtain flow coating, or the like can be used.

In the present invention, when the image forming layer is composed of an internal latent image type silver halide color photographic light-sensitive material, any support can be used, and a typical support is, for example, if necessary. Examples thereof include a subbed polyethylene terephthalate film, a polycarbonate film, a porstyrene film, a polypropylene film, a cellulose acetate film, a baryta paper, a polyolefin lamy root paper such as polyethylene, and a polyethylene terephthalate film into which a white pigment is kneaded.

In the silver halide color photographic light-sensitive material of the present invention, at least three light-sensitive layers having different spectral sensitivities from each other, one of which is a blue-sensitive silver halide emulsion layer, and the other is green light by a sensitizing dye. On the other hand, a plurality of black and white halftone dots, such as a green-sensitive silver halide emulsion layer having a maximum sensitivity and a red-sensitive silver halide emulsion layer having a maximum sensitivity to red light with a sensitizing dye for the other layer. When an image is exposed to light having a different spectral distribution, it is preferable to provide a spectral sensitivity that hardly causes color mixing. Examples of preferred layer configurations including combinations of the above three layers of spectral sensitivity and image hue will be given.

The light-sensitive material of the present invention can be exposed using an electromagnetic wave in a spectral region where the emulsion layer constituting the light-sensitive material of the present invention has sensitivity. Light sources include natural light (daylight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser lights, light emitting diode light, electron beam, X-ray, γ-ray Any of known light sources such as light emitted from a phosphor excited by α-rays or the like can be used.

The silver halide color photographic light-sensitive material of the present invention has a structure having each of blue-sensitive, green-sensitive and red-sensitive color-sensitive layers of a normal color paper, and as a filter (optical filter), a three-color separation filter such as Wratten.
No. 25, No. 29, No. 58, No. 61, No. 47B can be used.

Exposure time is 1 millisecond, which is usually used for printers.
An exposure time of 10 seconds is of course shorter than 1 millisecond, for example, 100 microseconds to 1 microsecond using a cathode ray tube or a xenon flashlight.
Millisecond exposures can be used, and exposures longer than 10 seconds are possible.

The exposure may be performed continuously or intermittently.

The color developing agent used in the color developing solution of the present invention includes known ones widely used in various color photographic processes. These developers include aminophenol-based and p-phenylenediamine-based derivatives. These compounds are generally used in the form of a salt, for example, a hydrochloride or a sulfate, for stability in the free state. These compounds are generally used in a color developer 1
Is used at a concentration of about 0.1 to about 30 g, more preferably about 1 g to about 15 g for the color developing solution 1.

Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, and 5-amino-2.
-Oxytoluene, 2-amino-3-oxytoluene,
2-oxy-3-amino-1,4-dimethylbenzene and the like.

Particularly useful primary aromatic amino-based color developing agents are N, N-dialkyl-p-phenylenediamine-based compounds, wherein the alkyl group and the phenyl group may be substituted or unsubstituted. Among them, examples of particularly useful compounds include N, N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride,
N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5- (N-ethyl-N-dodecylamino) toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline Sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N, N-diethylaniline, 4-amino-N- (2-methoxyethyl) -N-ethyl-3- Methylaniline-p-toluenesulfonate and the like can be mentioned.

In the color developing solution applied to the processing of the silver halide photographic light-sensitive material of the present invention, a known developer component compound can be added in addition to the first aromatic amino-based color developing agent. For example, sodium hydroxide, sodium carbonate, alkali agents such as potassium carbonate, alkali metal bisulfite,
An alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softener, a thickener, and the like can be optionally contained.

The pH value of the color developing solution is usually 7 or more, most usually from about 10 to about 13.

Color development temperature is usually 15 ° C or higher, generally 20 ° C
In the range of ~ 50 ° C. For rapid processing, it is preferable to carry out at 30 ° C. or higher. The color development time is generally 20
It is preferably performed in the range of seconds to 60 seconds, more preferably 30 seconds to 50 seconds.

The silver halide photographic light-sensitive material of the present invention may contain these color developing agents in the hydrophilic colloid layer as the color developing agents themselves or as precursors thereof, and may be processed by an alkaline activation bath. A color developing agent precursor is a compound that can generate a color developing agent under alkaline conditions, and is a Schiff-based precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic imide derivative precursor,
Examples include a phosphoric acid amide derivative precursor, a sugar amine reactant precursor, and a urethane type precursor. The precursors of these aromatic primary amine color developing agents are described, for example, in U.S. Pat. Nos. 3,342,599 and 2,507,114.
Nos. 2,695,234 and 3,719,492, UK Patent 803,783, JP-A-53-185628, JP-A-54-79035, Research Disclosure (Research Disclos)
ure) 15159, 12146 and 13924.

These aromatic primary amine color developing agents or their precursors need to be added in such an amount that sufficient amount of color can be obtained by activation alone when activated. This amount varies greatly depending on the type of the light-sensitive material, but is generally in the range of 0.1 to 5 mol, preferably 0.5 to 3 mol per mol of silver halide. These color developing agents or precursors thereof can be used alone or in combination. For embedding in photosensitive material, it can be added by dissolving in an appropriate solvent such as water, methanol, ethanol, acetone, etc., and emulsification using a high boiling organic solvent such as dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc. It can also be added as a dispersion, and is available from Research Disclosure (Resear
(Ch. Disclosure) 14850, it can be added by impregnating a latex polymer.

When the image forming layer of the light-sensitive material of the present invention is used as an internal latent image type silver halide emulsion layer and a positive image is directly formed using the same, the main steps are an internal latent image type halide which has not been fogged in advance. Generally, surface development is performed after or during fogging of a silver photographic light-sensitive material after image exposure. Here, the fogging treatment can be performed by giving uniform exposure over the entire surface or by using a fogging agent. In this case, the uniform exposure over the entire surface is preferably carried out by immersing or wetting the image-exposed internal latent image type silver halide photographic material in a developing solution or other aqueous solution, and then performing uniform exposure over the entire surface. . The light source used here may be any light within the photosensitive wavelength range of the internal latent image type silver halide photographic light-sensitive material, and it can be irradiated with high illuminance light such as flash light for a short time or weak. Light irradiation may be performed for a long time. The time of uniform exposure over the entire surface is the internal latent image type silver halide photographic material,
Depending on the development processing conditions and the type of light source used, it can be changed over a wide range so that the best positive image is finally obtained. Further, a wide variety of compounds can be used as the fogging agent. The fogging agent may be present at the time of development processing, for example, in an internal latent image type silver halide photographic light-sensitive material such as a silver halide emulsion layer or the like. Although it may be contained in a developing solution or a processing solution prior to the development processing, it is preferably contained in an internal latent image type silver halide photographic light-sensitive material (among them, particularly preferably in a silver halide emulsion layer).
The amount used can be varied widely according to the purpose. When added to the silver halide emulsion layer, a preferable addition amount is 1 to 1500 m per mol of silver halide.
g, particularly preferably from 10 to 1000 mg. Further, a preferable addition amount when added to a processing solution such as a developer is 0.01 to 5 g /
l, particularly preferably 0.08 to 0.15 g / l. Such fogging agents include, for example, U.S. Patent Nos. 2,563,785 and 2,588,982
Hydrazines described in US Pat.
The hydrazide or hydrazone compounds described in 227,552, and U.S. Patent Nos. 3,615,615, 3,718,470,
Heterocyclic quaternary nitrogen compounds described in 719,494, 3,734,738 and 3,759,901, etc., and further US Pat.
Acylhydrazinophenylthioureas described in No. 5; Further, these fogging agents can be used in combination. For example, Research Disclosure (Rese
Arch Disclosure No. 15162 describes that a non-adsorption type fogging agent is used in combination with an adsorption type fogging agent, and can be applied to the present invention.

Specific examples of useful fogging agents include hydrazine hydrochloride, phenylhydrazine hydrochloride, 4-methylphenylhydrazine hydrochloride, 1-formyl-2- (4-methylphenyl) hydrazine, 1-acetyl-2-phenylhydrazine , 1-acetyl-2- (4-acetamidophenyl) hydrazine, 1-methylsulfonyl-2-phenylhydrazine, 1-benzoyl-2-phenylhydrazine, 1-methylsulfonyl-2- (3-phenylsulfonamidophenyl) hydrazine And hydrazine compounds such as formaldehyde phenylhydrazine.

When the light-sensitive material of the present invention is embodied as an internal latent image type silver halide photographic light-sensitive material, a positive image is directly formed by exposing the whole image or developing it in the presence of a fogging agent after image exposure. However, an arbitrary developing method is adopted as a developing method of the photosensitive material, and a surface developing method is preferable. This surface development processing method means processing with a developer substantially free of a silver halide solvent.

In the present invention, the exposed silver halide color photographic light-sensitive material is subjected to development processing and processing with a processing solution having a fixing ability to form a positive image (visible image) corresponding to the original image. it can.

The above-described development processing includes a combination of black-and-white development and color development as in the reversal color processing, in addition to the color development processing. It also includes overall exposure or development processing in the presence of a fogging agent as in the processing of an internal latent image type silver halide photographic material.

The black-and-white developer used in the development processing is a so-called black-and-white first developer used in the processing of a generally known color photographic light-sensitive material, or the one used in the processing of a black-and-white photographic light-sensitive material. Various well-known additives to be added to the liquid can be contained.

Representative additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone;
Preservatives such as sulfites, accelerators composed of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate, and inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole and methylbenzthiazole Agents, water softeners such as polyphosphates, and surface overdevelopment inhibitors comprising a small amount of iodide or a mercapto compound.

The silver halide photographic light-sensitive material of the present invention, after color development,
Bleaching and fixing are performed. The bleaching process may be performed simultaneously with the fixing process. Many compounds are used as a bleaching agent. Among them, iron (III), cobalt (III), copper (I
Polyvalent metal compounds such as I), especially complex salts of these polyvalent metal cations with organic acids, for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylethylenediaminediacetic acid, malonic acid, tartaric acid; Metal complex salts such as malic acid, diglycolic acid and dithioglycolic acid, or ferricyanates and dichromates alone or in an appropriate combination are used.

As the fixing agent, a soluble complexing agent that solubilizes silver halide as a complex salt is used. Examples of the soluble complexing agent include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, thiourea, thioether and the like.

After the fixing process, a washing process is usually performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination. The stabilizing solution used for the stabilizing treatment may contain a pH adjuster, a chelating agent, a anti-blur agent and the like. These specific conditions are described in JP-A-58-134636.
Reference can be made.

In applying the present invention to the silver dye bleaching method, the difference in the spectral absorption characteristics of the yellow dye used in the silver dye bleaching method to the printing ink is similar to the difference in the dye formed from the yellow coupler by color development to the printing ink. Therefore, it can be easily carried out according to the case of a silver halide photographic light-sensitive material using the above-described color developing method.

〔Example〕

Hereinafter, specific examples of the present invention will be described, but embodiments of the present invention are not limited thereto.

Example 1 Equimolar silver nitrate aqueous solution and potassium bromide aqueous solution were added simultaneously to a gelatin aqueous solution at 50 ° C. for 50 minutes by a double jet method to obtain an emulsion composed of cubic silver bromide particles having an average particle size of 0.3 μm. Obtained.

To this emulsion was added 6.5 mg of sodium thiosulfate and 3 mg of potassium chloroaurate per mole of silver, and the mixture was heated at 70 ° C. for 70 minutes for chemical ripening, and then further added to an aqueous solution of silver nitrate and sodium chloride-bromide. Potassium mixed solution (molar ratio 1:
9) was added at the same time to prepare a cubic core / shell emulsion comprising a silver bromide core and a silver chlorobromide shell having an average particle size of 0.45 μm. After washing with water and desalting, this emulsion was added 2.0m per mole of silver.
g of sodium thiosulfate and 1.0 mg of potassium chloroaurate were added and chemically ripened at 60 ° C. for 50 minutes to directly obtain a positive silver halide emulsion EM-1.

Preparation of Blue-Sensitive Emulsion EM-B After color sensitization with sensitizing dye D-5 to EM-1, 600 mg of T-1 was added per mol of silver, and FA-1 was added at 8 mg / mol of silver.
× 10 ^-5 mol and FA-2 were added at 5 × 10 ^-4 mol per mol of silver to prepare a blue-sensitive emulsion.

Preparation of Green-sensitive Emulsion EM-G A green-sensitive emulsion was prepared in the same manner as the blue-sensitive emulsion except that sensitizing dye D-6 was added to EM-1 for color sensitization.

Preparation of Red-Sensitive Emulsion EM-R A red-sensitive emulsion was prepared in the same manner as the blue-sensitive emulsion except that sensitizing dye D-7 was added to EM-1 for color sensitization.

Using EM-B, EM-G, and EM-R, silver halide color light-sensitive materials having the composition shown in Table 1 were prepared.

The first to tenth layers were applied to the surface of a support laminated with polyethylene on both sides in the configuration shown in Table 1. In addition, SA-1 and SA-2 were used as coating aids, and H-1 was used as a hardening agent.

The content of calcium in the photographic material was changed as shown in Table 2 by changing the mixing ratio between gelatin having a calcium content of 3000 ppm and gelatin having a calcium content of 100 ppm. In each sample, the same gelatin having the same mixing ratio was used from the first layer to the tenth layer.

After preparing the emulsion coating solution for the fifth green-sensitive layer,
A sample was prepared by coating at a temperature of 40 ° C. for 2 hours, and a sample was prepared by coating the remaining part at a temperature of 40 ° C. for 10 hours.

The following exposure was performed on each of the obtained samples. The blue light obtained by the color separation filter is irradiated on the entire surface at an exposure amount such that the color of the blue-sensitive layer is minimized, and then the red light obtained by the color separation filter is irradiated on the entire surface and red. Irradiation was performed at an exposure amount such that the color of the sensitive layer was minimized.

Next, processing was performed according to the processing steps described below, and the magenta density and the yellow density were measured for the image obtained by developing the green sensitive layer.

Processing step (processing temperature and processing time) (1) Color development 35 ° C 2 minutes 30 seconds (4) Bleaching and fixing 35 ° C 1 minute (5) Stabilization processing 25-30 ° C 1 minute 30 seconds (6) Drying 78-80 ℃ 1 minute Composition of processing solution (color developing solution) Benzyl alcohol 15 ml Cerium sulfate 0.015 g Ethylene glycol 8 ml Potassium sulfite 2.5 g Potassium bromide 0.8 g Sodium chloride 0.2 g Potassium carbonate 25.0 g T-1 0.1 g Hydroxylamine sulfate 5.0 g Diethylenetriaminepentaacetic acid 2.0 g 4-Amino-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Fluorescent whitening agent (4,4′-diaminostilbenzisulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Diethylene glycol 15 ml Potassium phosphate 8.0 g Add water to make the total volume 1 and adjust to pH 10.50.

(Bleaching and fixing solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjusted to pH 7.1 with potassium carbonate or glacial acetic acid and water To make the total amount 1.

(Stabilizing solution) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 10 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.5 g bismuth chloride 0.2 g magnesium chloride 0.1 g ammonium hydroxide ( (28% aqueous solution) 2.0 g Sodium nitrilotriacetate 1.0 g Add water to make the total amount 1 and adjust to pH 7.0 with ammonium hydroxide or sulfuric acid.

The stabilization treatment was of a two-tank countercurrent type. Table 3 shows the obtained results.

Here, the fluctuation (%) due to the stagnation of the density balance Y / M is the ratio of the yellow density to the magenta density (yellow density) / (magenta density) obtained by measuring each sample. Is the percentage of the 10-hour stagnation when the value at 2 hours is 100%, and the closer this value is to 100%, the smaller the color tone fluctuation of the green sensitive layer due to the stagnation of the coating liquid is, and the better. It is shown that it is. As is apparent from Table 3, the sample of the present invention
The value shows a value closer to 100%, indicating that the device has stable performance even when manufacturing conditions fluctuate.

Example 2 An aqueous solution of equimolar silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (KBr: NaCl = 70: 30 in molar ratio) were simultaneously added to an aqueous gelatin solution at 50 ° C. for 50 minutes by a double jet method. In addition, an emulsion composed of cubic silver chlorobromide grains having an average grain size of 0.48 μm was obtained.

To this emulsion, 6.2 mg of sodium thiosulfate and 3.0 mg of potassium chloroaurate per mole of silver were added and heated at 70 ° C. for 70 minutes for chemical ripening to obtain a negative silver halide emulsion Em-2.
I got

Preparation of Blue-Sensitive Emulsion EM-2B A blue-sensitive emulsion was obtained by sensitizing Em-2 with sensitizing dye D-5.
EM-2B was produced.

Preparation of green-sensitive emulsion EM-2G A sensitizing dye D-6 was added to Em-2 to perform color sensitization to prepare a green-sensitive emulsion EM-2G.

Preparation of Red-Sensitive Emulsion EM-2R A sensitizing dye D-7 was added to Em-2 to perform color sensitization to prepare a red-sensitive emulsion EM-2R.

Using the above EM-2B, EM-2G, and EM-2R, silver halide color photographic materials having the composition shown in Table 4 were prepared. Table-5
The content of calcium in the light-sensitive material was changed in the same manner as in Example 1 with the contents shown in Table 1, and a sample was prepared in which the compound shown in Table 5 was added to the third green-sensitive layer.

One part of the sample prepared by application was stored at 42 ° C. and 50% RH for 3 days, and then subjected to a raw sample storage test at 55 ° C. and 80% RH for 3 days. Table 6 shows the results of measuring the relative sensitivity of M by subjecting each of the obtained samples to wedge exposure and performing the same treatment as in Example-1.

As is clear from the results in Table 6, it is found that the sensitivity to storage is stable by containing the compounds of the general formulas [I] to [IV].

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 7/38 G03C 7/392 G03C 1/047

Claims (1)

(57) [Claims] 1. A silver halide color photographic light-sensitive material having a photographic component layer comprising at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer contains the following general formulas [I] to [I]. At least one silver halide emulsion layer containing at least one compound represented by the formula [IV] and having the same spectral sensitivity comprises at least one compound represented by the following formula [MI] and a yellow coupler Wherein the content of calcium atoms in the photographic constituting layer is 15 mg / m ² or less. General formula [I] [In the formula, R ₁₀ represents a lower alkylene group, and m represents a hydrogen atom, an alkali metal or an alkyl group. X is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group,
It represents a carboxyl group, amino group, hydroxyl group, sulfo group, nitro group or alkoxycarbonyl group. n represents 0 or 1, and m represents an integer of 1 to 5. The total number of carbon atoms in the formula [I] is 19 or less. General formula [II] [Wherein, R ₂₀ is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxy group, -CONHR (R is an alkyl group, an aryl group, an alkylthio group, an arylthio group, an alkylsulfonyl group,
Represents an arylsulfonyl group. ) Or a heterocyclic group. R ₃₀ and R ₄₀ represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a cyano group, an alkylthio group, an arylthio group, an alkylsulfoxide group, an alkylsulfonyl group, or an alkylsulfinyl group; Further, R ₃₀ and R ₄₀ may be bonded to each other to form a benzene ring which may have a substituent. General formula [III] [Wherein, R ₅₀ and R ₆₀ represent a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 5 carbon atoms, or a hydroxymethyl group, and R ₇₀ represents a hydrogen atom, a lower alkyl group having 1 to 5 carbon atoms. . General formula [IV] Wherein R ₈₀ represents a hydrogen atom, an alkyl group or an aryl group, and R ₉₀ represents a hydrogen atom, an alkyl group, an aryl group, a nitro group, a carboxyl group, a sulfo group, a sulfamoyl group, a hydroxy group, a halogen atom, an alkoxy group. Or, represents a thiazolyl group, and m represents 0 or 1. Z represents an atomic group constituting a thiazolyl ring. General formula [MI] [In the formula, Z represents a group of nonmetal atoms necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. R represents a hydrogen atom or a substituent. ]