JPH0430164A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain good dot reproducibility by incorporating specific compds. into at least one layer of silver halide emulsion layers having the same spectral sensitivity. CONSTITUTION:At least one layer of the silver halide emulsion layers having the same spectral sensitivity contain at least one of the compds. expressed by formula I and at least one of yellow couplers and at least one of the compds. expressed by formula II are incorporated into the silver halide emulsion layers and/or the adjacent layers thereof. The good dot quality is thereby obtd. In the formulas, Z is the nonmetal atom group forming a nitrogenous heterocycle; the ring formed by Z may have a substituent; X is a hydrogen atom, the group which can be removed by reaction with the oxidant of a color developing agent; R is a hydrogen atom or substituent. In the formulas, R<1>, R<2> are a hydrogen atom or <=8C alkyl group, alkoxy group, alkylthio group or alkylamide group; R<3> is a hydrogen atom or <=11C alkyl group; the total of the carbon atoms of R<1>, R<2>. R<3> is >=8 and <=22.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a color photographic material with improved color tone;
In particular, the present invention relates to a silver halide color photographic material used to prepare a color proof image (color proof) from a plurality of black and white halftone dot images obtained by color separation and halftone dot image conversion in a color plate making/printing process.

[Conventional technology]

Conventionally, in the process of color plate making and printing, the method of obtaining color proofs from multiple black and white halftone images obtained by color separation and halftone image conversion has traditionally been to convert color images using photopolymers or diazo compounds. An overlay method and a sublint method are known.

The overlay method is very simple, has low production costs, and has the advantage that it can be used for proofing by simply overlapping film sheets of four colors (primary colors of subtractive color mixture and black), but it is difficult to overlay film sheets. It has the disadvantage that it produces a rather glossy texture, which results in a texture that is different from that of printed matter.

The sub-print method is a method of superimposing colored images on one support, and this method uses the adhesiveness of a photopolymerized material to obtain a colored image by toner development, as described in U.S. Special Fraud No. 3.582. .327, 3.607.2
No. 64 and No. 3,620.726.

Another method is to create a color proof by transferring a photosensitive colored sheet to a support, forming an image through exposure and development, then layering another colored sheet on top of this and repeating the same process. Special Public Service
441 and JP-A-56-501217.

In addition, a method has been developed in which each colored image obtained by exposing and developing a corresponding color separation film using a photosensitive colored sheet is formed on one support by transfer.
It is known as No. 97140. As the toner and coloring agent for the colored sheet forming these images, there is an advantage that the same coloring material as the ink used in printing can be used, so the color tone of the obtained color proof is similar to that of the printed matter.

However, these methods have the disadvantage that images must be superimposed or transferred in the process of creating a color proof, which requires time and production costs.

In order to overcome these drawbacks, a method for preparing a color proof using a silver salt color photographic material having a white support is disclosed in JP-A-56-113139 and JP-A-56-104335. However, since the colors of the yellow, magenta and cyan single layers obtained by color separation exposure and development of the silver salt color photographic material are different from the yellow, magenta and cyan colors of the printing ink, the colors of the printing ink cannot be changed. It is extremely difficult to reproduce.

Therefore, when using a negative color photosensitive material among subtractive full-color photosensitive materials as a color proofing material, exposure is required to make the color development of each halftone image of yellow, magenta, and cyan approximate the color of printing ink. The wavelength components of the light of time are controlled by filters, etc., and 1
In contrast to the two halftone images, the yellow color of the color photographic material,
U.S. Pat. No. 4,188,111 shows that the optimum color tone can be obtained by appropriately mixing magenta and cyan.
Known by the number.

However, when creating color proofs using this method, it has been found that as the size of the halftone dots becomes smaller, there is a large variation in the tone of the halftone dots, which impairs the role of the color brief, so it is not recommended as a countermeasure. It is enough.

In addition, in the method of creating a color proof by exposing a positive color photographic light-sensitive material from a black-and-white dot positive image, the method of controlling the wavelength components of the light during exposure involves the development of the yellow magenta and cyan colors of the color photographic light-sensitive material. It was difficult to adjust the ratio of amounts to approximate the color tone of printing ink, and it took a lot of time to adjust the color tone.

Therefore, as in Japanese Patent Application No. 63-306569, for magenta, where the difference in color tone between printing inks is particularly noticeable, a technique has been proposed in which a yellow coupler is mixed in the same layer as the magenta coupler-containing layer to bring the color tone closer to that of the ink. Are known.

On the other hand, in color proofing, halftone reproducibility is required to be as important as color tone.

For color proofing in photographic light-sensitive materials, it is essential that the so-called leg gradation be high contrast, and as a means for achieving this, a hydroquinone compound described in JP-A No. 62-239153 etc. is included in the photographic constituent layer. There are known techniques to do this.

However, it has been found that if the above-mentioned hydroquinone compound is added to the technique of Japanese Patent Application No. 63-306569, the halftone dot quality will be different from the small dots and the large fish, and therefore a sufficiently satisfactory halftone dot quality cannot be obtained.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a silver halide color photographic material for use 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, which has good halftone dot reproduction. An object of the present invention is to provide a silver halide color photographic light-sensitive material for color proofing, which provides a color tone similar to that of printing ink.

[Structure of the invention]

An object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which at least one silver halide emulsion layer having the same spectral sensitivity has the following formula - CM-I) and at least one yellow coupler, and in the silver halide emulsion layer and/or
Alternatively, the present invention can be achieved by a silver halide color photographic material containing at least one compound represented by formula (1) in an adjacent layer.

-Formula CM-I) In the formula, 2 represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by 2 may have a substituent.

X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.

Moreover, R represents a hydrogen atom or a substituent.

- Formula (I) i In the formula, Hl and R1 represent a hydrogen atom or an alkyl group having 8 or less carbon atoms, an alkoxy group, an alkylthio group, or an alkylamido group, and R3 represents a hydrogen atom or an alkyl group having 11 or less carbon atoms. . The total number of carbon atoms in RI RIR8 is 8 or more and 22 or less.

The compound represented by formula CM-I) will be explained in detail below.

A preferable coupler as a magenta dye-forming coupler to be contained in the magenta image forming layer of the silver halide color photographic light-sensitive material of the present invention is a pyrazoloazole type coupler, and the coupler is represented by the following formula (M-I). Ru.

General formula (M-1) In general formula CM-1), 2 represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by 2 may have a substituent. .

X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.

Moreover, R represents a hydrogen atom or a substituent.

The substituent represented by R is not particularly limited, but typically includes six groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl. Atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfonyl Also included are the six groups famoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, and heterocyclic thio, as well as spiro compound residues, bridged hydrocarbon metal residues, and the like.

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

The aryl group represented by R is preferably a phenyl group.

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.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkylthioaryl group represented by R above.

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

The cycloalkenyl group represented by R has 3 to 3 carbon atoms.
12, especially those of 5 to 7 are preferred.

Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and aryloxyphosphonyl groups. , arylphosphonyl group, etc.; As an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc.; As a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc.; As a sulfamoyl group, an alkylsulfamoyl group,
Arylsulfamoyl groups, etc.; Acyloxy groups include alkylcarbonyloxy groups, arylcarbonyloxy groups, etc.; carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc. ; As the sulfamoylamino group, an alkylsulfamoylamino group or an arylsulfamoylamino group is preferred; as the heterocyclic group, a 5- to 7-membered one is preferable, and specifically, a 2-furyl group, a 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.; as the heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferred, for example 3.
4.5.6-tetrahydrobilanyl-2-oxy group, l
-Phenyltetrazole-5-oxy group; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1, 3,5-)'Riazole-6-thio group, etc.: Siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide group includes succinimide group, 3-heptadecylsuccinimide group, 7 Thalimide group, glutarimide group; spiro compound residues include spiro [3,3]hebutan-1-yl; bridged hydrocarbon compound residues include bicyclo [2゜2,
l] Heptan-1-yl, tricyclo [3°3.1.
1''.7] decane-1-yl, 7.7-dimethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxycarbonylamino , aryloxycarbonylamino,
carboxyl, heat (R1' has the same meaning as R above, 2' has the same meaning as 2 above, R1', R, and I represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group) #lr Preferred examples include halogen atoms, particularly chlorine atoms.

Examples of the nitrogen-containing heterocycle formed by 2 or 2' include a pyrazole ring, an imidazole ring, a triazole ring, or a tetrazole ring, and examples of the substituents that the ring may have include those described for R above. can be mentioned.

What is represented by general formula (M-1) is further represented by, for example, the following formulas (M-11) to [M-■].

General formula CM-1) General formula (M-111) General formula % formula %) General formula (M-V) General formula % formula %) General formula [M-■] Above - Formula CM-11) ~ [M- ■] in R3-R
1 and X have the same meanings as R and X above.

Also, among the -formula CM-I), preferred is the one represented by the following -formula [M-■].

- Formula [M-■] In the formula, R, , X and 2. - R in formula CM-1),
It has the same meaning as X and 2.

Among the magenta couplers represented by the above-mentioned formulas CM-11) to [M-■], particularly preferable ones are those represented by the general formula (M-11).
) is a magenta coupler.

In addition, when used for positive image formation, - formula (M-1) ~ [M
Regarding the substituents on the heterocycle in -■], in formula (M-I), R is also -formula CM-11)
~ In [M-■], it is preferable that R1 satisfies the following condition 1, more preferable is the case that the following conditions 1 and 2 are satisfied, and particularly preferable is the case that the following conditions 1.2 and 3 are satisfied. It is.

Condition 1: The root atom directly connected to the heterocycle is a carbon atom.

Condition 2: Only one hydrogen atom or no hydrogen atom is bonded to the carbon atom.

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

The most preferred substituents R and R3 that satisfy the above conditions are those represented by the following formula CM-n).

Formula CM'-II) In the formula, Re, R+e and Ro each have the same meaning as R above. Moreover, the above-mentioned R*, Rr. and R11, for example, R1 and R8° may be bonded to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and Rll is further bonded to the ring. It may also constitute a bridged hydrocarbon compound residue.

- Among formulas (M-X), (i) l to R are preferable.
When at least two of 3l are alkyl groups, (u)
One of Re-R11, for example, R11, is a hydrogen atom, and the other two, R9 and R1. combine to form a cycloalkyl together with the root carbon atom.

Furthermore, among (i), 2 among R9 to R0 is preferable.
One is an alkyl group, and the other is a hydrogen atom or an alkyl group.

In addition, - a substituent which the ring formed by Z in formula (M-1) and - a ring formed by Zl in formula [M-■] may have, and - formulas (M-1) to ( M-
R1-R1 in Vl) is the following - formula CM-X
) is preferred.

Formula CM-X) -R'-S OM-R'' In the formula, R1 represents an alkylene group, and Ht represents an alkyl group, a cycloalkyl group, or an aryl group.

The alkylene group represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and it does not matter whether the alkylene group is straight chain or branched.

The cycloalkyl group represented by R3 is preferably a 5- to 6-membered one.

In addition, when used for negative image formation, -Math CM-I)~
Regarding the substituents on the heterocycle in [M-■],
-Formula CM-1), R is also -Formula (M-1)
In ~[M-■], it is preferable that R satisfies the following condition 1, and more preferably the case that the following conditions 1 and 2 are satisfied.

Condition 1: The root atom directly connected to the heterocycle is a carbon atom.

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

The most preferred substituents R and R1 that satisfy the above conditions are those represented by the following formula CM-n).

General formula (M-n) R+* CHx- In the formula, Rtg has the same meaning as R above.

Preferred R1ff1 is a hydrogen atom or an alkyl group.

Typical specific examples of the compounds according to the present invention are shown below.

(M-4) (M-5) (M-7) (M CH.

(M-9) (M (M-11) (M-12) C1 Hatake H31 (M-13) CH.

CM-17) (M 1g) (M (M-23) (M (M-26) C@Hls (M-29) (M-30) (M-31) (M-32) (M-34) (M-35) (M-40) (M-42) CH.

CH.

CH.

C,,H,.

(M-44) (M-46) Shiti3 (M-47) CM.

(M-51) (M-52) (M-53) (M-56) (M-57) (M-59) (M-60) (M-62) (M-63) (M to bar- N (M-66) (M-67) (M-68) (M-69) (M-73) In addition to the above representative examples, from page 66 of the specification of Japanese Patent Application No. 61-9791 Among the compounds described on page 122, No. l-4, 6, 8 to 17.19-24.2
6-43.45~59.61-104.106~121
．． Compounds represented by 123 to 162 and 164 to 223 can be mentioned.

Also, the coupler is described in the Journal of the Chemical
Society (Journal of the chem
icalSociety) + Perkin
) I (1977), 2047-2052, U.S. Pat.
-171956, 60-33552, 60-4
No. 3659, No. 6G-172982 and No. 60-19
It can be synthesized by referring to No. 0779 and the like.

The couplers of this invention typically have I/mole of silver halide.
X 10-” mol-1-t-ol, preferably lXl0-
It can be used in the molar range of '-8 x 10-' molar.

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

In the present invention, when a magenta coupler is used as a compound for forming a magenta image, a yellow coupler preferably contained in the same layer as the coupler is represented by the following formula (Y-
It is a coupler represented by 1).

Among the couplers represented by the general formula (Y-I), particularly preferred ones are - when combined with the magenta coupler represented by the formula (M-1), the pKa value of the coupler represented by the combined coupler CM-1) It is a yellow coupler having a pKa value not lower than 3 or more.

General Formula (Y-I) In General Formula (Y-I), %R1 represents a halogen atom or an alkoxy group.

R1 represents a hydrogen atom, a halogen atom, or an alkoxy group which may have a substituent. R8 is an acylamino group, an alkoxycarbonyl group, each of which may have a substituent;
Represents an alkylsulfamoyl group, an arylsulfamoyl group, an arylsulfonamide group, an alkylureido group, an arylureido group, a succinimide group, an alkoxy group, or an aryloxy group.

2 represents a hydrogen atom, a monovalent organic group or a halogen atom that can be separated when coupling an oxidized color developing agent.

Specific examples of yellow couplers used in the present invention are shown below.

(Y-1 (Y-2) (Y-4) (Y-5) (Y-6>I'11 (Y-7) (Y-8) (Y-9) (Y-10) (Y -13) (Y-14) (Y-15) (Y-16) (Y-17) (Y-18) (Y-19) (Y -20) (Y -21) (Y-22) (Y -23) (Y -24) (Y ShiH3 (Y -26) Hs (Y-27) (Y-28) (Y -31) (Y-32) (Y-33) (Y-34) (Y -36) (Y-37) (Y-38) (Y-40) (Y-41) (Y-42) (Y-43) (Y (Y-45) (Y-46) (Y-47) (Y (Y -49) (Y-51) (Y-52) (y-53) (Y-56) (Y-57) (Y -58) Magenta image of silver halide color photographic light-sensitive material of the present invention The content ratio of magenta coupler and yellow coupler in the forming layer is set such that the spectral absorption of the dye image obtained by the color development treatment of the magenta image forming layer approximates the spectral absorption of the printed image by magenta printing ink. Specifically, the amount of yellow coupler is usually 0.02 to 0.02 mole to 1 mole of magenta coupler.
A range of 5 moles is suitable.

As the yellow coupler contained in the magenta image forming layer of the silver halide color photographic light-sensitive material of the present invention, the yellow coupler represented by the above formula [Y-11] is preferably used.

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

Among these, couplers represented by the following formula [C-I] or [C-II] are preferably used.

- Formula [C-I] 1° General formula [In C-ll, R1 represents an aryl group, a cycloalkyl group, or a heterocyclic group. R1 represents an alkyl group or a phenyl group. R8 represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group.

Zl represents a hydrogen atom; or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

General formula [C-1[] In general formula [C-U], %R4 represents an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, nonyl group, etc.). R represents an alkyl group (eg, methyl group, ethyl group, etc.). R6 is a hydrogen atom, a hydrogen atom (
(eg, fluorine, chlorine, bromine, etc.) or an alkyl group (eg, methyl group, ethyl group, etc.).

Z! represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

These cyan couplers are described in U.S. Patent 2,306,41
No. 0, No. 2,356,475, No. 2,362.596
No. 2,367.531, No. 2,369.929, No. 2,423.730, No. 2,474゜293,
2,476.008, 2,498.466, 2,545゜687, 2,728.660, 2
, No. 772.162, No. 2,895°826, No. 2,
976.146, 3,002,836, 3,4
19°390, 3,446.622, 3,47
No. 6.563, No. 3,737゜316, No. 3,758
．． No. 308, No. 3,839.044, British Patent No. 478
．． No. 991, No. 945.542, No. 1,084.48
No. 0, same l.

377.233, 1,388.024 and 1
, 543,040 and JP-A-47-37
No. 425, No. 50-10135, No. 50-25228
No. 50-112038, No. 50-117422, No. 50-130441, No. 51-6551, No. 5
No. 1-37647, No. 51-52828, No. 51-1
No. 08841, No. 53-109630, No. 54-48
No. 237, No. 54-66129, No. 54-13193
No. 1, No. 55-32071, No. 59-146.050
No. 59-31,953 and No. 60-117,2
It is stated in each public relations issue of No. 49.

The couplers used in the present invention are usually present in each silver halide emulsion layer in an amount of IX 10-" to 1 mole, preferably IX 10-" to 8 moles per mole of silver halide.
It can be used in the range of XlO-' moles.

The couplers mentioned above are usually dissolved in a high boiling point organic solvent with a boiling point of about 150°C or higher, if necessary in combination with a low boiling point and/or water-soluble organic solvent, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution. After being emulsified and dispersed, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

In the present invention, the ratio of the high boiling point organic solvent and the low boiling point organic solvent according to the present invention is 1:0.1 to 1:50, more preferably 1:1.
The ratio is preferably 1 to 1:20.

The high boiling point 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. Examples include esters such as 7-talate ester and phosphate ester, organic acid amides, ketones, and hydrocarbon compounds having a dielectric constant of 6.0 or less. More preferred are heptatalic acid esters or phosphoric acid esters.

Next, the compound of general formula (1) will be explained.

- In formula (1), Rl and R1 are hydrogen atoms or alkyl groups having 8 or less carbon atoms (e.g. methyl, ethyl,
t-butyl, 5ea-hexyl, t-octyl), alkoxy groups (e.g. methoxy, ethoxy, butoxy, 2-
ethylhexyloxy), an alkylthio group (e.g. methylthio, butylthio, octylthio), an alkylamide group (e.g. methanamide, propanamide, 2-ethylpentanoylamide); methyl, n-propyl, 1so-propyl, heptyl, undecyl, 1-ethylpentyl, etc.), and the total number of carbon atoms in R1, R1, and R@ is 8 or more and 22 or less.

H+ and H* are preferably an alkyl group having 6 or less carbon atoms, and R3 is preferably an alkyl group having 7 or less carbon atoms.

Further, the total number of carbon atoms in R1, R2, and R3 is preferably 8 or more and 17 or less.

Specific examples of the compound of general formula CI) are listed below, but the present invention is not limited thereto.

I-(1) ■ R3 I'+3 I-(3) ■ r-(6) I-(7) ■ I-(9) ■ The amount of the compound represented by the general formula CI) is lXl0-
'mol/ml to lXl0-'mol/m!1 preferably l x 10-'moJ/II' to lXl0-
It is easily added to the emulsion layer and/or the layer adjacent thereto. .

- The compounds of the formula CI) can be used in combination of two or more types, or can also be used in combination with the following compounds.

In the formula, R4 and RI represent a hydrogen atom or an alkyl group having 8 or less carbon atoms, an alkoxy group, an alkylthio group, or an alkylamido group.

Next, the silver halide emulsion used in the photosensitive layer of the silver halide color photosensitive material of the present invention will be described.

The silver halide emulsion used in the present invention includes any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. can be used.

The structure of the silver halide grain may be uniform from the inside to the outside of the grain, or the structure inside and outside the grain may be different. Further, when the composition inside and outside the particle is different, the composition may change continuously or discontinuously.

There is no particular restriction on the particle size of the silver halide grains, but in consideration of other photographic performance such as rapid processability and sensitivity, it is preferably in the range of 0.2 to 1.6 μm, more preferably 0.25 to 1.2 μm. It is.

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 the acid method, neutral method, and ammonia method. The particles may be grown all at once, or after forming seed particles,
You can let it grow. The method of creating and growing the seed particles may be the same or different.

Further, the soluble silver salt and the soluble halogen salt may be reacted by any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof. Furthermore, as a type of simultaneous mixing method, I)A is described in JP-A No. 54-48521, etc.
The g-chondrold-double jet method can also be used.

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

Any shape of silver halide grains can be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

The silver halide emulsion used in the present invention includes cadmium salt, zinc salt, lead salt, thallium salt, iridium salt,
Alternatively, metal ions can be added to the interior of the particles and/or on the surface of the particles by using complex salts, rhodium salts, complex salts, iron salts, or complex salts, and metal ions can be included inside the particles and/or on the particle surfaces by placing them in an appropriate reducing atmosphere. /Or reduction sensitizing nuclei can be provided on the particle surface.

In the silver halide emulsion used in the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, please refer to Research Disclosure 1764.
This can be carried out based on the method described in No. 3.

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

The silver halide emulsion used in the present invention is chemically sensitized by a conventional method. In other words, sulfur sensitization using compounds containing sulfur that can react with silver ions or active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensitive methods and the like can be used alone or in combination.

In the present invention, for example, a chalcogen sensitization method can be used as a chemical sensitizer. The chalcogen sensitizer is a general term for sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, and sulfur sensitizers and selenium sensitizers are preferred. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbazide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine. Other U.S. Patents 1,574,974 and 2,410.68
No. 9, No. 2,278.947, No. 2,728,668
3,501,313, 3,656.955, OLS 1, 422, 869, JP 56-24937, JP 55-45016, etc. Sensitizers can also be used.

The amount of sulfur sensitizer added varies over a considerable range depending on various conditions such as pHx temperature and silver halide grain size, but as a guide, it is 1 O per mol of silver halide.
It is preferably about -7 mol to 10-' mol.

Selenium sensitizers can be used instead of sulfur sensitizers, but examples of selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas,
Selenides such as selenoketones, selenoamides, selenocarboxylic acid salts and esters, selenophosphates, diethylselenide, and diethylselenide can be used, and specific examples thereof can be found in US Pat. No. 1,574.
No. 944, No. 1,602.592, No. 1,623.4
No. 99 specification.

Furthermore, reduction sensitization can also be used together. The reducing agent is not particularly limited, but examples include stannous chloride, thiourea dioxide, hydrazine, and polyamine.

Further, noble metal compounds other than the total, such as palladium compounds, etc. can also be used in combination.

When a direct positive image forming silver halide emulsion is employed as the silver halide emulsion, an internal latent image type silver halide emulsion can be used, for example, as disclosed in US Pat. No. 3,592.
, 250, or US Pat. No. 3,200.
6.316, 3,317.322 and 3.36
Silver halide emulsions having internally chemically sensitized silver halide grains as described in U.S. Pat. No. 7.778, or U.S. Pat. Silver halide emulsions having silver halide grains incorporating polyvalent metal ions as described in US Pat. No. 3,761,276 or silver halide emulsions containing dopants as described in US Pat. Silver halide emulsions whose grain surfaces are weakly chemically sensitized, or JP-A Nos. 50-8524, 50-38525 and 53
So-called core-shell type silver halide emulsion produced by the lamination method described in No.-2408, and other JP-A-52-15
No. 6614, No. 55-127549 and No. 57-79
Silver halide emulsions such as those described in No. 940 can be used. In this case it is particularly preferred that the internal latent disc silver halide emulsion be made of laminated dust grains.

Such silver halide grains can be produced in the same manner as ordinary laminated silver halide grains.
No. 60222, No. 55-1524 and U.S. Patent No. 3,2
As described in No. 06.313, etc., silver chloride grains are formed, bromide is added to convert them to silver bromide grains, and halide is further added and laminated with silver nitrate, or iodobromide is carried out in a state with little excess halogen. Examples include a method of making silver particles and then sequentially stacking silver chloride and silver bromide.

When an internal latent image type silver halide emulsion is used, the emulsion contains a stabilizer that is commonly used, such as a compound having an azaindene ring, in order to suppress the backside sensitivity as low as possible and to impart a lower minimum density and more stable properties. and a heterocyclic compound having a mercapto group.

As the compound having an azaindene ring, for example, 4-hydroxy-6-methyl-1,3,3m,7-tetrazaindene is preferable. Among the heterocyclic compounds having a mercapto group, nitrogen-containing heterocyclic compounds include 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, l
.

2.5-thiadiazole ring, 1,2.3.4-tetrazole ring, biritazine ring, 1.2.3-) liazine ring,
1,2.4-triazine ring, 1.3.5-triazine ring, etc., and rings in which 2 to 3 of these rings are condensed, such as triazolotriazole ring, diazaindene ring, triazaindene ring, tetrazaindene ring , a pentazaindene ring, a 7-thalazinone ring, an imidazole ring, etc., and l-phenyl-5-mercaptotetrazole is particularly preferred.

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.

Examples of useful sensitizing dyes used in blue-sensitive silver halide emulsion layers include West German Patent No. 929,080, US Pat. No. 2,231,658, US Pat. No. 2,493,748,
2,503°776, 2,519.001, 2,912.329, 3,656°959, 3
, No. 672.897, No. 3,694.217, No. 4.
No. 025349, No. 4,046,572, British Patent 1
, No. 242.588, Special Publication No. 44-14030, No. 5
Examples include those described in No. 2-24844. Further, useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 1, No. 2,072,908, No. 2.739.149
No. 2,945.763, British Patent No. 505.979
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. Furthermore, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat. , No. 629, same 2
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 776, No. 280, etc. Furthermore, U.S. Pat. No. 2,213,995, U.S. Pat. No. 2,493,748, U.S. Pat.
Cyanine dyes or composite cyanine dyes such as those described in No. 1, etc. can be advantageously used in green-sensitive silver halide emulsions or red-sensitive halogen emulsions.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.

Typical examples are Special Publication No. 43-4932 and No. 43-49.
No. 33, No. 43-4936, No. 44-32753,
No. 45-25831, No. 45-26474, No. 46
-11627, 46-18107, 47874
No. 1, No. 47-11114, No. 47-25379,
No. 47-37443, No. 48-28293, No. 48
-38406, 48-38407, 48-38
No. 408, No. 4g-41204, No. 48-41204
No. 49-6207, No. 50-40662, No. 5
No. 3-12375, No. 54-34535, No. 55-1
No. 569, JP-A No. 50-33220, JP-A No. 50-338
No. 28, No. 50-38526, No. 51-107127
No. 51-115820, No. 51-135528, No. 51-151527, No. 52-23931, No. 52-51932, No. 52-104916, No. 52
-104917, 52-109925, 52-
No. 110618, No. 54-80118, No. 56-25
No. 728, No. 57-1483, No. 58-10753, No. 58-91445, No. 58-153926, No. 59-114533, No. 59-11645, No. 59
-116647, U.S. Patent No. 2,688,545, U.S. Patent No. 2,977.229, U.S. Patent No. 3,397,060, U.S. Patent No. 3
, No. 522.052, No. 3,527.641, No. 3,
No. 617.293, No. 3,62L964, No. 3,66
6.480, 3,672,898, 3,679
．． No. 428, No. 3,703.377, No. 3,769.
301, 3,814.609, 3,837,8
No. 62 and No. 4,026,707.

Examples of dyes that do not themselves have a spectral sensitizing effect, or substances that do not substantially absorb visible light and exhibit supersensitization, are used with sensitizing dyes, such as formaldehyde condensates of aromatic organic acids ( For example, U.S. Patent 3,
473,510), cadmium salts, azaindene compounds, aminostyl compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat. No. 2,933,390,
3,635.721). The combinations described in US Pat. Nos. 3,615,613, 3,615,641, 3,617.295, and 3,635.721 are particularly useful.

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

Examples of wetting agents include dihydroxyalkanes, and examples of film property improving agents include copolymers of alkyl acrylates or alkyl methacrylates and acrylic acid or methacrylic acid, styrene-maleic acid copolymers, and styrene. Water-dispersible particulate polymeric substances obtained by emulsion polymerization such as maleic anhydride half-alkyl ester copolymers are suitable, and examples of coating aids include saponin, polyethylene glycol, lauryl ether, etc. . Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, and development speed. The use of modifiers, matting agents, anti-irradiation dyes, etc. is optional.

Further, in order to prevent fading of the dye image due to short-wavelength actinic rays, ultraviolet absorbers can be used, such as thiazolidone, benzotriazole, acrylonitrile, benzophenone compounds, etc. In particular, Tinupin PS,
120, 320, 326, 327, 328 (
Both products (manufactured by Ciba Geigy) are advantageous to use alone or in combination.

The image forming layer in the present invention can 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,
Examples include esterified gelatin.

Further, in the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloid layer may contain other hydrophilic binders in addition to gelatin.

This hydrophilic binder can be added to photographic constituent layers such as an emulsion layer, an intermediate layer, a protective layer, a filter layer, and a backing layer depending on the purpose. It is possible to contain agents, lubricants, etc.

In addition, the silver halide color photographic light-sensitive material of the present invention may include, in addition to an emulsion layer forming an image-bearing layer on a support, a filter layer, an intermediate layer, a protective layer, a subbing layer, and a backing layer as necessary. ,
Various photographic constituent layers such as a sun protection layer may also be formed. As a coating method for each layer, dip coating, air doctor coating, extrusion coating, slide hopper coating, curtain 70-coating, etc. can be used.

In the present invention, even when the image-forming layer has an internal latent image formed of a silver halide color photographic light-sensitive material, any support can be used. Examples include polyethylene terephthalate film, polycarbonate film, polystyrene film, holoflopyrene film, cellulose acetate film, baryta paper, polyolefin laminate paper such as polyethylene, polyethylene terephthalate film kneaded with white pigment, etc. .

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, γ-rays, σ-rays, or the like.

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 that ordinary color paper has, and the filter (optical filter) is a three-color separation filter, such as Wratten N.
o, 25. No. 29. No. 58. No, 61, No
, 47B can be used.

The exposure time is 1 millisecond to 1 millisecond, which is normally used in printers.
Not only can exposure times be 0 seconds, but also exposures shorter than 1 millisecond, such as 100 microseconds or more using a cathode ray tube or xenon flash lamp.
Exposures of °l milliseconds can be used, and exposures longer than 10 seconds are also possible.

The exposure may be performed continuously or intermittently.

The color developing agent used in the color developing solution in the present invention includes known color developing agents that are widely used in various color photographic processes.

These developers include aminophenol and p-phenylenediamine derivatives. Since these compounds are more stable in the free state, they are generally used in the form of salts, such as hydrochlorides or sulfates. Also, these compounds are
Generally, the color developer 11 has a concentration of about 0.1 to about 309, more preferably the color developer Iff has a concentration of about 19 to about 309.
It is used at a concentration of about 159.

Examples of aminophenol-based developers include 0-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 amine color developers include N, N-
A dialkyl-p-phinidine diamine compound,
Alkyl groups and phenyl groups 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,N-
Dimethyl-p-7 22-diamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)toluene,
N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate, 4-amino-N
-Ethyl-N-(β-hydroxyethyl)aniline sulfate, 4-amino-3-methyl-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methyl Examples include aniline-p-)luenesulfonate, and 4-amino-N-ethyl-
N-(β-hydroxylethyl)aniline sulfate is preferred.

In addition to the first aromatic amino color developer, known developer component compounds can be added to the color developer applied to the processing of the silver halide photographic material of the present invention. For example, it may optionally contain alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, and thickening agents. can.

The pn value of the color developer is usually 7 or more, most commonly about lθ to about 13.

The color development temperature is usually 15°C or higher, numerically -20°C.
It is in the range of °C to 50 °C. For rapid processing, it is preferable to carry out the treatment at 30°C or higher. Further, the color development time is generally preferably carried out within a range of 20 seconds to 60 seconds, more preferably 30 seconds to 50 seconds.

The silver halide photographic material according to the present invention may contain these color developing agents in the hydrophilic colloid layer either as the color developing agent itself or as its precursor, and may be processed in an alkaline activation bath. A color developing agent precursor is a compound that can generate a color developing agent under alkaline conditions, and includes Schiff base type precursors with aromatic aldehyde derivatives, polyvalent metal ion complex precursors, heptallic acid imide derivative precursors, phosphoric acid amide derivative precursors, sugar amines, etc. Reactant precursors include urethane precursors. These aromatic primary amine color development main system precursors are:
For example, U.S. Pat. No. 3.342.599, U.S. Pat.
No. 114, No. 2,695.234, No. 3°719.4
No. 92, specifications of British Patent No. 803.783, Japanese Patent Application Laid-open Nos. 53-185628 and 54-79035,
Research Disclosure
Disclosure) No. 15159, No. 12146, and No. 13924.

It is necessary to add the aromatic primary amine color developing agent or its precursor in such an amount that sufficient color development can be obtained in the case of activation treatment. This amount varies depending on the type of photosensitive material, but is generally between 0.1 mol and 5 mol, preferably between 0.5 mol and 3 mol, per mol of silver halide. These color developing agents or their precursors can be used alone or in combination. In order to incorporate it into a photosensitive material, it can be added by dissolving it in an appropriate solvent such as water, methanol, ethanol, acetone, etc., or it can be added by emulsification using a high boiling point organic solvent such as dibutyl 7-talate, dioctyl 7-talate, or tricresyl 7-phosphate. It can also be added as a dispersion, and Research 0 Disclosure (Res.
They can also be added by impregnation into latex polymers as described in US Pat. No. 14,850.

When the image forming layer of the light-sensitive material of the present invention is an internal latent image-controlled silver halide emulsion layer and a positive image is directly formed using this layer, the main process is to form an internal latent image-controlled silver halide emulsion layer that has not been fogged in advance. After imagewise exposure of a silver photographic light-sensitive material, surface development is generally performed after or while performing fogging treatment. The fogging treatment can be carried out by providing uniform exposure over the entire surface or by using a fogging agent. In this case, it is preferable to use a fogging agent. A wide variety of compounds can be used as the fogging agent, and it is sufficient that the fogging agent is present during the development process. Although it may be included in the processing solution prior to the development process, it is better to include it in the internal latent image type silver halide photographic light-sensitive material (
Among them, the silver halide emulsion layer is particularly suitable.

Specific compounds of the fogging agent include the following formula [FA
-I] and [FA-Ill] are preferred.

[FA-11,・2... ([In FA-II, 2 represents a nonmetallic atom group necessary to form a 5- to 6-membered heterocycle, R11 is an aliphatic group, and R11 is hydrogen The atom, aliphatic group or aromatic group Z, R11, R1'' may be substituted, and R1'' may further be combined with the heterocyclic group completed by 2 to form a ring. , provided that at least one of the groups represented by R11R" and 2 contains an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or R11 and R
13 to form a 6-membered ring to form a dihydropyridinium skeleton.

Y is a counter ion for charge balance, and n is 0 or 1. FA-II group or an amino group, G is a carbonyl group, a sulfonyl group,
Sulfoxy group, phosphoryl group or iminomethylene group (I
N-C<), and 1jll and R'' are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group, an arylsulfonyl group, or an acyl group.

However, a hydrazone structure (>N-N-C<) may be formed by including G, R"IR" and hydrazine nitrogen. Further, the groups described above may be substituted with a substituent if possible. ) [FA-II type compounds and synthetic methods are described, for example, in Research Disclosure Magazine No. 22,534 (19
Published in January 1983, pp. 50-54), Japanese Patent Publication No. 55-138
742 amount, No. 60-11837, JP-A-2-9015
No. 4, U.S. Pat. No. 4.306.016 and U.S. Pat. No. 4.4.
71.044 etc.

Specific examples of the compound represented by the general formula [FA-II are listed below, but the compound is not limited thereto.

(FA-I-1) (FA-I-2) (FA-1-3) (FA-I-4) 〇〇IClCl cn, c straw C1 (FA-I-5) CH, C=CH [FA -I+] type synthesis method is described in U.S. Patent No. 4.0
No. 30.925, No. 4.080.207, No. 4,
No. 276.364, No. 4.459.347, No. 4
．． 560.632, British Patent No. 4.560.638, British Patent No. 4.478.928 and British Patent No. 2. Oll, 39
No. 1B, JP-A-55-163533, JP-A No. 57-868
No. 29 and No. 60-179734, and in recent years, compound examples have been listed in JP-A No. 2-90154.

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

[FA-II-11 (FA-U-2) (FA-11-4) In the present invention, compounds represented by the general formulas [FA-I] and [FA-1] are contained in a photographic light-sensitive material When using water-miscible organic solvents such as alcohols (e.g. methanol, ethanol), esters (e.g. ethyl acetate), ketones (e.g. acetone), or
If it is water-soluble, it may be added to the hydrophilic colloid solution as an aqueous solution.

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

In the present invention, the fogging agents represented by the general formulas [FA-I] and [FA-1] may be contained in the hydrophilic colloid layer adjacent to the silver halide emulsion layer. Preferably, it is contained within.

The amount added varies depending on the characteristics of the silver halide emulsion actually used, the chemical structure of the fogging agent, and the development conditions, so it can vary over a wide range, but it is lXl0 per mole of silver in the silver halide emulsion. -'Mole may be about I X 1
A range of 0-'' moles is useful in practice, with a preferred range of 1.times.10-' to 1.times.10-f moles per mole of silver.

As the fogging agent of the present invention, [FA-I] is preferable, and among [FA-I], it is preferable that R'' is bonded to a heterocycle completed with 2 to form a ring.

In the present invention, a nucleation accelerator can be used to further promote the action of the fogging agent.

Nucleation accelerators include tetrazaindenes, triazaindenes, and pentazaindenes having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group, and JP-A-63-Sho. 10
Compounds described in Publication No. 6656 (pages 6 to 16) can be added.

The nucleation accelerator can be contained in the light-sensitive material or in the processing solution, but even in the light-sensitive material, it is used in internal latent image type silver halide emulsion layers and other hydrophilic colloid layers (intermediate layers, film-retaining layers, etc.). Preferably, it is particularly preferably contained in a silver halide emulsion layer or in a layer adjacent thereto.

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 can be directly formed by exposing the entire surface or developing it in the presence of a fogging agent after image exposure. The photosensitive material may be developed by any method, preferably a surface development method. This surface development processing method means processing with a developer substantially free of silver halide solvent.

In the present invention, a positive image (developed image) corresponding to the original image is obtained by subjecting the exposed silver halide color photographic light-sensitive material to processing using a processing solution having development processing and fixing ability.
It can be made concrete by forming the following.

The above-mentioned development processing includes not only color development processing but also a combination of black and white development and color development such as in reversal color processing.

It also includes full-surface exposure or development in the presence of a fogging agent, such as in the processing of internal latent image type silver halide photographic materials.

The black-and-white developer used in the development process is a so-called black-and-white developer used in the processing of color photographic light-sensitive materials, or a black-and-white developer used in the processing of black-and-white photographic materials. Various well-known additives added to developer solutions can be included.

Typical additives include l-722-3-pyrazolidone, developing agents such as metol and hydroquinone, preservatives such as sulfites, and promoters consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. Inorganic or w-organic inhibitors such as potassium bromide, 2-methylbenzimidazole and methylbenzthiazole, water softeners such as polyphosphates, and surface superfiltration consisting of trace amounts of iodides and mercapto compounds. Examples include development inhibitors.

After color development, the silver halide photographic material of the present invention is subjected to bleaching and fixing. Bleaching treatment may be performed simultaneously with fixing treatment. Many compounds are used as bleaching agents, among them iron (m), cobalt (■), and copper (II).
polyvalent metal compounds, especially complex salts of these polyvalent metal cations and organic acids, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylethylenediaminediacetic acid, malonic acid, tartaric acid, apple Acids, metal complex salts such as diglycolic acid and dithioglycolic acid, ferricyanates, dichromates, etc. may be used alone or in appropriate combinations.

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

After the fixing process, a washing process is usually performed.

In addition, as an alternative to washing with water, stabilization treatment may be performed, or both may be used in combination. can be done. These specific conditions are described in Japanese Unexamined Patent Publication No. 5
8.134636 etc. can be referred to.

To apply the present invention to a silver dye bleaching method, the difference in 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 spectral absorption property of the dye generated from the yellow coupler by color development to the printing ink. Therefore, it can be easily carried out in the same manner as in the case of silver halide photographic materials using the color development method described above.

〔Example〕

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

Example 1 Equimolar amounts of silver nitrate/aqueous solution and potassium bromide aqueous solution were simultaneously added to an aqueous gelatin solution at 50°C for 50 minutes using a double jet method to form cubic silver bromide particles with an average particle size of 0.3 μm. An emulsion was obtained.

To this emulsion were added 6.5 g of sodium thiosulfate and 3a+g of potassium chloroaurate per mole of silver, and the mixture was heated at 70°C to
After chemical ripening by heating for 0 minutes, this emulsion was further mixed with a silver nitrate aqueous solution and a sodium chloride-potassium bromide mixed solution (
molar ratio l:9) was added at the same time to give an average particle size of 0.45μ.
Cubic core consisting of silver bromide core and silver chlorobromide shell of intestine/
A shell emulsion was prepared. After washing and desalting, this emulsion contains 1 silver
2.0B sodium thiosulfate and 1.0+n per mole
g of potassium chloroaurate was added thereto, and chemical ripening was performed at 60° C. for 50 minutes to obtain a direct positive silver halide emulsion EM-1.

Preparation of blue-sensitive emulsion EM-H After color sensitizing with sensitizing dye D-5, 600 a+g of T-1 was added to EM-1 per mol of silver, and then FA-1-2 was added to EM-1 at 1 mol of silver.
A blue-sensitive emulsion was prepared by adding 8 x IO-'' moles per mole and F A-I-4 at 5 x 10-'' moles per silver mole.

Preparation of green-sensitive emulsion EM-G A green-sensitive emulsion was prepared in the same manner as the blue-sensitive emulsion except that EM-1 was color sensitized by adding sensitizing dye D-6.

Preparation of red-sensitive emulsion EM-R A red-sensitive emulsion was prepared in the same manner as the blue-sensitive emulsion except that EM-1 was color sensitized by adding sensitizing dye D-7.

Using the above EM-B, EM-G, and EM-R, silver halide color photosensitive materials having the configurations shown in Table 1 were prepared.

Table-1 (D -7') (D -6) (D -5) (SO-1) (As-1) (A-1) (A ■ (So-2) (A S -2) (ST -1) (T-1) (UV-1) (S T -2) (SA-1) (SA-2) The first to first θ layers were placed on the surface of a support laminated with polyethylene on both sides. Coating was performed using the following composition: 5A-1 and 5A-2 were used as coating aids, and H-1 was used as a hardening agent.

"a Table-2 Each of the obtained samples was subjected to the following exposure.Printer DSP-605F C (manufactured by Dainippon Screen Co., Ltd.)
Using a 0.075 step gray scale tablet and 150 lines/inch 1% to 5% net positive scale were brought into close contact and exposed to light passing through a Wratten filter No. 58 (green).

Next, remove the original film and use the Wratten Filter-47B.
(stomach) and similarly exposed to light through 25 (red).

The exposure conditions at this time were set to the minimum exposure time such that the color density of the portion corresponding to the white background was minimized.

After exposure, geography was performed according to the processing steps shown below to confirm the effects of the present invention.

It is shown in Table-3.

Processing process 1i (processing temperature and processing time) (1) Color development 35°C 2 minutes 30 seconds (4) Bleach fixing 35°C 1 minute (5) Stabilization treatment
25-30℃ 1 minute 30 seconds (6) Drying
78-80℃ 1 minute Asahi solution composition (color developing solution) Benzyl alcohol 15ml 12 Cerium sulfate 0.015g Ethylene glycol 8■a Potassium sulfite 2.5g Potassium bromide Sodium chloride Potassium carbonate Hydroxylamine sulfate Diethylenetriamine Pentaacetic acid 4-amino -N-Ethyl-N-(β-hydroxylethyl)aniline sulfate optical brightener (4,4'-diaminostilbendisulfonic acid derivative) Potassium hydroxide diethylene glycol potassium phosphate aqueous solution was added to bring the total amount to 1a, (bleach fixing) Liquid) Ferric ammonium ethylenediaminetetraacetate dihydrate Ammonium thiosulfate ethylenediaminetetraacetate (70% solution) Ammonium sulfite (40% solution) 1.0g 2.0g 5-a 8.0g Adjust to pH 10,50.

0.8g o・2g 25.0g O,1g 5.0g 2.0g 4.5g 0g 3g 100■a 27.5■a Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to bring the total amount to 11 shall be.

(Stabilizing liquid) 5-chloro-2-methyl-4-inchazolin-3-one 1.0 g ethylene glycol 10 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.5, bismuth chloride o, 2° magnesium chloride 0 .1g ammonium hydroxide (28% water, $11 liquid) 2.0g nitrilo-sodium acetate 1.0g Water is added to bring the total amount to Nl, and the pH is adjusted to 7.0 with ammonium hydroxide or sulfuric acid.

In addition, the stabilizing island structure is a two-tank countercurrent system.

Table 3 *l *2 Evaluation of magenta color tone: An appropriate density was determined, the color tone was compared with that of the printing ink, and a 5-level evaluation was made. The larger the value, the better the magenta tone.

Evaluation of gamma value in low concentration range 2Evaluation is performed using the formula expressed as below, *3 *4 (b is 1agE value when Fog + 0.50, mouse is Fog
The 1agE value at +0.02 and Fog are the fog density values. ) Comparison was made based on the ratio when the value of sample No. 1 was set as 100.

Evaluation of dot reproducibility = 150 lines/inch Halftone dot images of 1 to 5% were observed by 10 subjects using a magnifying glass, and the results of each evaluation of the reproduced halftone dot % were averaged.

Measurement was performed using a white background density dual densitometer PDA-65 (manufactured by Konica Corporation).

Example 2 After subjecting the sample of Example 1 to halftone exposure in the same manner, geography was carried out in the same manner except that the developing agent was changed to the following compound.

(1) 4-(N-ethyl-N-β-hydroxyethylamino]-2-methylaniline sulfate (2) N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-amino Aniline sulfate As a result, it was confirmed that it is more preferable to use 4-amino-N-ethyl-N-(β-hydroxylethyl)aniline sulfate in the present invention compared to the above two types of developing agents. .

〔Effect of the invention〕

As described above, the color tone was good and the halftone dot quality, especially the dot reproducibility, was clearly improved.

Claims (1)

[Scope of Claims] In a silver halide color photographic light-sensitive material having photographic constituent layers including at least one silver halide emulsion layer on a support, at least one silver halide emulsion layer having the same spectral sensitivity. contains at least one compound represented by the following general formula [M-I] and at least one yellow coupler, and contains a compound represented by the general formula [I] in the silver halide emulsion layer and/or in an adjacent layer. A silver halide color photographic light-sensitive material containing at least one of the compounds shown below. General formula [M-I] ▲ Numerical formulas, chemical formulas, tables, etc. It may have. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. Further, R represents a hydrogen atom or a substituent. ] General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R^1 and R^2 represent a hydrogen atom or an alkyl group, alkoxy group, alkylthio group, or alkylamido group having 8 or less carbon atoms. , R^3 represents a hydrogen atom or an alkyl group having 11 or less carbon atoms. R^1, R^2, R^3
The total number of carbon atoms is 8 or more and 22 or less. ]