JPH0430165A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color reproducibility by incorporating the lipophilic fine particles obtd. by subjecting a soln. in which at least one kind of specific non- color developable compds. and at least one kind of dyestuff forming couplers coexist to emulsion dispersion into the above photosensitive material. CONSTITUTION:The photosensitive material contains the lipophilic fine particles obtd. by subjecting the soln. in which at least one kind of the non-color develop able compds. having >=2.5 hydrogen receptive parameter (pKHB) and at least one kind of the dyestuff forming couplers coexist to the emulsion dispersion. In addition, at least one kind of polymer compds. which are insoluble in water and are soluble in org. solvents are incorporated in combination into the lipophilic fine particles, by which the excellent color reproducibility is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material for color proofing with improved tone.

[Background of the invention]

In silver halide photographic materials, aromatic 1
A so-called dye-forming coupler is used, which reacts with an oxidized product of a grade amine developing agent to form an azomethine dye, and usually a combination of a yellow coupler, magenta coupler, and cyan coupler is used. However, the present situation is that the dyes produced from these couplers each have undesirable and unnecessary absorption compared to what is said to be ideal absorption.

In order to solve this problem, various improvements have been made in terms of coupler structure. For example, regarding magenta couplers, the couplers having a pyrazolo(5,1-C)-1,2,4-triazole skeleton are described in U.S. Pat. No. 3,725.067, and the couplers are described in U.S. Pat. No. 4,540.654. A coupler having a pyrazolo(1,5-b)-1,2,4-triazole bone core has been proposed, and for a yellow coupler, the color tone of the produced dye has been improved in JP-A-63-123047. Acylacetanilide couplers have been proposed. Regarding cyan couplers, the cyan coupler having an imidazole bone core described in Japanese Patent Application No. 1987-316997 and the Japanese Patent Application Laid-open No. 1-3
Cyan couplers having a 3-hydroxypyridine skeleton described in No. 15736 have been proposed. but,
All of these couplers have problems in that they are difficult to synthesize and increase manufacturing costs. In addition, the change in tone of the dye image produced by changing the coupler skeleton is generally large, which often causes inconvenience when trying to adjust the tone of the dye image to a certain desired tone. Provision of adjustment technology is desired.

On the other hand, JP-A-63-44658, JP-A-63-2
No. 50648, No. 64-537 and wo-88100
No. 723, etc., discloses a technique for emulsifying and dispersing a water-insoluble and organic solvent-soluble polymer together with a coupler.
Although it is known that color tone can be improved and adjusted by this method, the effect is insufficient.

In particular, in color proofing photosensitive materials used in the printing and plate making field, it is required that the color tone of the generated dye image be made close to that of the printing ink, but the azomethine dye produced in silver halide photographic materials is A shift in hue and a decrease in saturation occur in ink, and an effective tone adjustment technique for adjusting this is desired.

[Purpose of the invention]

A first object of the present invention is to provide a silver halide photographic material with excellent color reproducibility.

A second object is to provide a silver halide photographic light-sensitive material for color proofing that provides color reproducibility close to the color tone of printing ink.

A third object of the present invention is to provide a simple method for controlling the tone of image dyes produced in silver halide photographic materials.

[Structure of the invention]

The above object of the present invention is to provide a silver halide photographic material coated with at least one silver halide emulsion layer, in which a non-color-forming compound having a hydrogen acceptance parameter (1) KllB) of 2.5 or more is used. This was achieved by a silver halide photographic light-sensitive material characterized by containing lipophilic fine particles obtained by emulsifying and dispersing a solution in which at least one type of coupler and at least one type of dye-forming coupler coexist. Further, in the silver halide photographic material of the present invention, more remarkable effects can be obtained by containing at least one water-insoluble and organic solvent-soluble polymer compound in the lipophilic fine particles. The present invention will now be described in more detail.

Hydrogen acceptance parameter (hereinafter pKwm) in the present invention
It is abbreviated as ) is a parameter indicating the degree to which the substance accepts hydrogen bonds; R, W, Taft et al., J, 1m
+, Chem, Soc,, 91.4801 (196
9); M, T, Kamlet et al., J, Org; Ch.
ew,, 36.3853'(1971); J.
Mitsky et al., J. Am. Chem. Soc., 9
4.3438 (1972); M, T, Kamlet, J, Am, Chem, Soc, 95.5210
(1973) and many other documents. ^Physically,
Above, R, W, Taft, etc., J, Am, Che+m, S
oc., 91.4801 (1969). That is, using a hydrogen-donating p-fluorophenol as a base compound, the N of Fll of a hydrogen-bonding complex with a hydrogen-accepting compound in CCl2 is
From the equilibrium constant of complex formation determined from the MR shift value, p
The value of Kws is determined.

In the present invention, a non-color-forming compound with a pKIl of 2.5 or more (hereinafter referred to as a required high hydrogen-accepting compound) is used.
It is necessary to use a non-color-forming compound having a pKMm of 3.0 or more.

Typical examples of highly hydrogen-accepting compounds are listed below.
The present invention is not limited to these.

P K -1(n-CJ+s+rP-OP K2
(n-CaH+yTP-OPK-3(n
-Cal@CHCHhryP-0koC! 11゜P K 5 Cn-C5HtfNP-OP
K-6(CIHI02P-O P K-7((CHs)tNteTP-OPR8(n-
CJs woo-is.

PK-94-(dimethylamino)pyridine PK-1
0 pyridine-N-oxide P K 11 (n-
C4HsTsP -0 Next, the water-insoluble and organic solvent-soluble polymer compound (hereinafter referred to as a polymer, copolymer, etc.) according to the present invention will be explained.

The lipophilic microparticles of the present invention contain a high hydrogen-accepting compound, a dye-forming coupler, and preferably a mixture of the polymer compound, optionally containing a high-boiling organic solvent, a low-boiling organic solvent, and/or a water-soluble organic solvent. The surfactant of the present invention is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a dispersion means such as a stirrer, homogenizer, colloid mill, 70-jet mixer, and ultrasonic device. It may be added to the desired hydrophilic colloid layer. Low-boiling and/or water-soluble organic solvents may be removed from the prepared dispersion by distillation, noodle washing or ultrafiltration.

Examples of the low-boiling organic solvent include ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl ethyl ketone, methyl imbutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, and cyclohexanone. Further, examples of water-soluble organic solvents include methyl alcohol, ethyl alcohol, acetone, and tetrahydro-7-alcohol. These organic solvents can be used in combination of two or more types, if necessary.

As for the polymer compounds, those obtained by suspension polymerization, solution polymerization or bulk polymerization of the above-mentioned mono or copolymer heptamer components in the presence of a coupler and a high-boiling organic solvent and/or a high hydrogen-accepting compound are used. Alternatively, the method described in JP-A-60-107642, which involves dispersing in a hydrophilic binder in the same manner, may also be used.

In the present invention, as the magenta coupler, the above-mentioned -I]
A magenta coupler represented by is preferably used.

The substituent represented by R is not particularly limited, but typically includes alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, etc. In addition, halogen 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 polygroups such as 7 amoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, and heterocyclic thio, as well as spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by R preferably has a prime number of 1 to 32, 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 alkyl group and aryl 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.: Oxyphosphonyl group, arylphosphonyl group, etc.; Acyl group includes alkylcarbonyl group, arylcarbonyl group, etc.; Carbamoyl group includes alkylcarbamoyl group, arylcarbamoyl group, etc.; sulfamoyl group includes 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. : Examples of the sulfamoylamino group include an alkylsulfamoylamino group and an arylsulfamoylamino group; Preferably, the heterocyclic group is a 5- to 7-membered one, and examples of heterocyclic groups include a 2-furyl group and a 2-thienyl group. , 2-pyrimidinyl group, 2-benzothiazolyl group; the heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, for example 3.
4.5.6-tetoltetrahydrobilanyl-2-oxy group, l-phenyltetrazol-5-oxy group, etc.; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, such as a 2-pyridylthio group , 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5triazole-6-monothio group, etc.; Siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide group includes Succinimide group, 3-heptadecyl succinimide group, 7-talimide group, glutarimide replacement; spiro compound residues include spiro[3,3]heftan-l-yl; bridged hydrogenated compound residues is Bicyclo[2,2゜1
] Hellaph 9 Sea 1-i L,)! J cyclo[3,3
, 1,1''Idecane-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, Njl [nitrogen-containing heterocycle bonded with child, alkyloxycarbonyl amino, aryloxycarbonylamino, carboxyl, (R,' is the same as the above R, 2' is the same as the above Z, R2' and H, I are a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group) ), among which a halogen atom, particularly a chlorine atom, is preferable.

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.

More specifically, what is represented by the general formula CM-I) is represented by, for example, the following formulas CM-If) to [M-■].

General formula CM-1 [) General formula % Formula %) General formula CM-mV) General formula General formula CM -Vl) R8-R in the above - formulas [M-11) to [M-■]
8 and X have the same meanings as R and X above.

Also, among the formulas CM-1), preferred are those represented by the following formula [M-■].

In the formula, R, , X and zl are R in the general formula CM-I),
It has the same meaning as X and 2.

Among the magenta couplers represented by the above-mentioned formulas CM-11) to [M-■], particularly preferred ones are those represented by the general formula CM-1f.
It is a magenta coupler represented by :l.

Specific examples of the magenta coupler according to the present invention represented by the general formula CM-I are listed below, but the present invention is not limited thereto.

CH.

M-8 M-10 In addition to the above representative examples of compounds according to the present invention, specific examples of compounds according to the present invention include JP-A No. 62-1663.
Among the compounds described in No. 39, page 18, upper right llN-32, upper right column, No. 1-4.6.8-17゜19-24.26-43.45-59.61-104 ．．
Examples include compounds represented by 106-121°123-162.164-223.

Also, the coupler is described in the Journal of the Chemical
Society 4 (Journal of the Ch
chemicalSocity), Perkin
) I (1977), 2047-2052, U.S. Patent No. 3,725.067, JP-A-59-99437,
No. 58-42045, No. 59-162548, No. 5
No. 9-171956, No. 60-33552, No. 60-
No. 43659, No. 60-172982 and No. 60-1
It can be synthesized by referring to No. 90779 and the like.

These magenta couplers usually contain 1X10 to 5 moles per mole of silver halide, preferably 1X10-"
It can be used in the range of 1 mole to 1 mole.

These couplers can also be used in combination with other known magenta couplers (eg, 5-pyrazolone couplers, pyrazolopenzimidazole couplers).

In the present invention, in the case of a silver halide photographic light-sensitive material for color proofing, it is preferable that a yellow coupler is contained together with a magenta coupler in the magenta image forming layer in order to approximate the color tone of printing ink. When the magenta coupler in the magenta image forming layer is a coupler represented by the formulas [M to I], the effects of using the high hydrogen-accepting compound of the present invention and the polymer compound are more effectively exhibited. preferred.

The yellow coupler used in the present invention is preferably a yellow coupler represented by the following formula (Y).

General formula [Y] p.

In the formula, Rll represents an alkyl group, a cycloalkyl group, or an aryl group, R4 represents a hydrogen atom, a halogen atom, an aryloxy group, or an alkoxy group, and Rli represents a group that can be substituted on the benzene ring. a represents 0 or l. X1
1 represents a group that can be separated along with the connected oxygen atom upon coupling with an oxidized form of a developing agent, and Yll represents an organic group.

In formula (Y) above, the alkyl group represented by RII includes, for example, a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a dodecyl group, and the like.

Examples of the cycloalkyl group represented by R11 include a cyclopropyl group, a cyclohexyl group, and an adamantyl group.

Examples of the aryl group represented by R11 include a phenyl group.

These alkyl groups, cycloalkyl groups, and aryl groups represented by R11 include those having further substituents. Examples of substituents include halogen atoms, alkyl groups, cycloalkyl groups, aryl groups, alkoxy groups, and aryl groups. Examples include oxy group, alkylsulfonyl group, acylamino group, and hydroxy group.

R11 is preferably a branched alkyl group.

In general formula (Y), examples of the halogen atom represented by Rtx include a chlorine atom, a bromine atom, a fluorine atom, and the like, with a chlorine atom being preferred. Examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group, and the like, with a methoxy group being preferred. Examples of the aryloxy group include phenyloxy group.

In the general formula (Y), examples of groups that can be substituted on the penzene ring represented by R13 include halogen atoms (e.g. chlorine atom), alkyl groups (e.g. ethyl group, pent-propyl group,
t-butyl group), alkoxy group (e.g. methoxy group),
Aryloxy groups (e.g. phenyloxy groups), acyl oxy groups (e.g. methylcarbonyloxy groups, benzoyloxy groups), acylamino groups (e.g. acetamido groups, phenylcarbonylamino groups), carbamoyl groups (
For example, N-methylcarbamoyl group, N-phenylcarbamoyl group), alkylsulfonamide group (e.g. ethylsulfonamide group), arylsulfonamide group (fV
For example, phenylsulfonamide group), sulfamoyl group (
Examples include N-propylsulfamoyl group, N-7enylsulfamoyl group) and imide groups (for example, succinimide group and glutarimide group). a represents 0 or 1.

- In the formula (Y), Yll represents an organic group, and is preferably a group represented by the following formula [Y'], although it is not particularly limited.

General formula [Y'] 1 J-R 14 In the general formula [Y'], R8 represents an organic group containing one bonding group having a carbonyl or sulfonyl unit.

Groups having carbonyl units include ester groups, amide groups, carbamoyl groups, ureido groups, urethane groups, etc. Groups having sulfonyl units include sulfonyl groups, sulfonamide groups, sulfamoyl groups, aminosulfonamide groups, etc. can be mentioned.

Ls　　　　　　Rli represents an alkyl group, an aryl group, or a heterocyclic group.

Examples of the alkyl group represented by RIB include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and a dodecyl group. Furthermore, as the aryl group represented by RII,
Examples include phenyl group and s7tyl group.

These alkyl groups or aryl groups represented by R11 are
Those having substituents are also included. Substituents are not particularly limited, but typical examples include halogen atoms (chlorine atoms, etc.), alkyl groups (ethyl group, t-butyl group, etc.), aryl groups (phenyl group, p-methoxyphenyl group, etc.). group, naphthyl group, etc.), alkoxy group (ethoxy group, benzyloxy group, etc.), aryloxy group (phenoxy group, etc.), alkylthio group (ethylthio group, etc.), arylthio group (phenylthio group, etc.), alkylsulfonyl group (β
-hydroxyethylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, etc.), acylamino group [
For example, an alkylcarbonylamino group (such as an acetamido group), an arylcarbonylamino group (such as a phenylcarbonylamino group), a carbamoyl group (such as an alkyl group,
It also includes those substituted with aryl groups (preferably phenyl groups), specifically N-methylcarbamoyl groups,
N-7-enylcarbamoyl group, etc.], acyl group (e.g., alkylcarbonyl group such as acetyl group, benzoyl group, etc.)
7) Arylcarbonyl group, etc.), sulfonamide group (e.g., alkylsulfonamide group, arylsulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group [e.g., substituted with an alkyl group, aryl group (preferably phenyl group), etc. Including those that are
-methylsulfamoyl group, N-7xnylsulfamoyl group, etc.], hydroxyl group, and nitrile group.

In the general formula CY), Xll represents a group that can be separated along with the connected oxygen atom during the coupling reaction with the oxidized form of the developing agent.

Xll is preferably an aryl group or a heterocyclic group, including those having substituents. Substituents include those described above.

The yellow coupler represented by formula (Y) is R1.
, R. 3 or Y11 may be bonded to form a bis body.

These yellow couplers represented by the formula [Y] preferably contain IXIO-" per mole of silver halide.
mole-1 mole, more preferably IXIO-3 mole-8X
A range of 10-' moles can be used. These couplers can be used alone or in combination of two or more. Moreover, other couplers can also be used together.

Next, specific examples of the yellow coupler represented by the above-mentioned formula (Y) will be shown, but are not limited thereto. A cyan coupler represented by is preferred.

General formula (1) In the formula, R1 represents an alkyl group or an aryl group.

R1 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R1 represents a hydrogen atom, a halogen atom, an alkyl group or an amide group. Further, R1 may cooperate with R to form a ring. 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.

-Formula CI[] t! In the formula, R6 represents a ballast group. R1 has 2 or more carbon atoms
6 represents an alkyl group. 2. is a hydrogen atom or an aromatic first
Represents a group that can be separated by reaction with an oxidized product of a class amine color developing agent.

-Formula CI [[) X.

In the formula, A and B each represent an organic group bonded to the imidazole ring via a carbon atom, nitrogen atom, oxygen atom or sulfur atom.

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

General formula (IV) where R6 represents an aliphatic group, an aromatic group or a heterocyclic group,
R1 represents a group or atom that can be substituted on the pyridine ring, Y represents a divalent linking group containing at least one amide bond and/or ester bond, x2 represents a hydrogen atom or a coupling-off group, and n is Represents an integer between O and 2. When n is 2, the two R7s may be the same or different, and the two R7s may form a ring. Furthermore, a ring may be formed between R7 and R6.

In the cyan coupler represented by formula CI),
The alkyl group represented by R1 preferably has 1 to 32 carbon atoms, and these groups may be linear or branched, and include those having substituents.

The aryl group represented by R1 is preferably a phenyl group, including those having substituents.

The alkyl group represented by R2 preferably has 1 to 32 carbon atoms, and these alkyl groups may be linear or branched, and include those having substituents.

The cycloalkyl group represented by R2 has 3 to 1 carbon atoms.
2 is preferred, and these cycloalkyl groups also include those having substituents.

The aryl group represented by R2 is preferably a phenyl group, including those having substituents.

The heterocyclic group represented by R8 is preferably a 5- to 7-membered one, may have a substituent, and may be fused.

R3 represents a hydrogen atom, a halogen atom, an alkyl group, or an amide group, and the alkyl group and the amide group include those having a substituent.

Further, the ring formed jointly by R1 and R3 is preferably a 5- to 6-membered ring, such as -2. Groups that can be separated by reaction with the oxidized product of the color developing agent represented by are halogen atoms, alkoxy groups, aryloxy groups, acyloxy groups, sulfonyloxy groups, acylamino groups, sulfonylamino groups, alkoxycarbonyloxy groups, Examples include an aryloxycarbonyloxy group and an imide group (including those each having a substituent), but preferably a halogen atom, an aryloxy group, and an alkoxy group.

Among the cyan couplers represented by the formula CI), particularly preferred are the cyan couplers represented by the formula CI), in which R1 and R
1 together form a ring, and is represented by the following formula (IA).

General formula (1-A) H XA In formula, RAl represents a phenyl group substituted with at least one halogen atom or an alkyl group substituted with at least one halogen atom, and these groups are Including those with substituents. RA! has the same meaning as R3 in formula CI) above. XA represents a halogen atom, an aryloxy group, or an alkoxy group, including those having a substituent.

Typical specific examples of cyan couplers represented by general formula CI) are shown below.

Specific examples of the above-mentioned cyan couplers include A-16 to A-50 described in Japanese Patent Application No. 17896, page 7, upper right column to page 9, lower left column;
No. 5155, page 7, bottom left column to lO page bottom right column, JP-A-6
2,5-dianlyamino/uncoupler described in No. 0-222853, page 6, upper left column to page 8, lower right column and JP-A-59-185335, page 6, lower left column to page 9, upper left column can be synthesized according to the methods described in these specifications and publications.

In the present invention, the amount of cyan coupler added is preferably in the range of 2XIO to 8 x 10-' mol, particularly preferably in the range of 1 x 10-' to 5 x 10 mol, per mol of silver halide.

In the cyan coupler represented by formula (It) above, the alkyl group represented by R may be linear or branched,
It also includes those having substituents.

R1 is preferably an ethyl group.

The ballast group represented by R4 is an organic group having a size and shape that imparts sufficient bulk to the coupler molecule to substantially prevent the coupler from diffusing from the layer to which it is applied to other layers. be.

2 has the same meaning as Zl in formula CI) above.

Next, specific examples of couplers represented by the general formula CI+) General formula (I[)
No. 61-3142, 61-9652, 61-9653, 61-39045, 61-5
No. 0136, No. 61-99141, No. 61-1055
It is described in No. 45 etc.

The cyan dye-forming coupler represented by formula (If) is usually used in an amount of 1x10-'' mole per mole of silver halide.
1 mol, preferably lXl0-2 mol-8X 10-'
It can be used in a molar range.

The organic group represented by A and B in the formula (I [ 4-aminophenyl)propyl, allyl, 2-dodecyloxyethyl, 3-phenoxypropyl, 2-hexysulfonylethyl, 3(4-(4-F
tesyloxybenzene)sulfonamidophenyl]propyl, l-methyl-2-((2-octyloxy-5
-t-octylphenyl)sulfonamidophenyl]ethyl, l-methyl-2-[2-octyloxy-5-(
2-octyloxy-5-t-octylphenylsulfonamido) phenylsulfonamide]ethyl, 2-[2
-octyloxy-5-(2-octyloxy-5-1
-octylphenylsulfonamide) phenylsulfonamide]ethyl, etc.), aryl groups (e.g. phenyl,
naphthyl, 2,4-dichlorophenyl, 2-hydroxy-5-methylphenyl, 2-acetamidophenyl, 2
-Methanesulfonamidophenyl, 2-butaneamidophenyl, 2-(N,N-dimethylsulfamoylamino)
Phenyl, 2-(4-dodecyloxybenzenesulfonamido)phenyl, 2-(2-(2,4-di-t-amylphenoxy)hexanamido]phenyl, 2-(octyloxy-5-t-octylphenylsulfone) amido) phenyl, 4-carbamoylphenyl, 4-cyanophenyl, 4-carboxyphenyl, 4-ethoxycarbonylphenyl, etc.), heterocyclic groups (e.g., 4-pyridyl, 2-benzimidazolyl, etc.), cyano group, carboxy group, acyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, etc.

Examples of organic groups via a nitrogen atom include acylamino groups (e.g., acetamide, benzamide, 2゜4-di-t-
amylphenoxyacetamide, 2,4-dichlorobenzamide, etc.), alkoxycarbonylamino groups (e.g., methoxycarbonylamino, propoxycarbonylamino, t-butoxycarbonylamino, etc.), aryloxycarbonylamino groups (e.g., phenoxycarbonylamino), Sulfonamide groups (e.g. methanesulfonamide, octanesulfonamide, benzenesulfonamide, 4-dodecyloxybenzenesulfonamide, etc.), anilino groups (e.g. phenylamino, 2chloroanilino, 2-chloro-4-tetradecanamideanilino) ), ureido groups (e.g., N-methylureido, N
-butylureido, N-phenylureido, N,N-dibutylureido, etc.), sulf7amoylamino groups (e.g., N,N-diethylsulfamoylamino, N-phenylsulfamoylamino, etc.), amino groups (e.g., unsubstituted amino, N-methylamino, N,N-diethylamino, etc.), heterocyclic groups (eg, 3.5-dimethyl l-pyrazolyl, 2.6-dimethylmorpholino, etc.), and the like.

Examples of organic groups via an oxygen atom include alkoxy groups (e.g., butoxy, ethoxy, i-propoxy, butoxy, 2.2.2-trifluoroethoxy, 3,3.3-
trifluoropropoxy, 2-chloroethoxy, 2-cyanoethoxy, 2-butanesulfonylethoxy, etc.), aryloxy groups (e.g., phenoxy, 4-methoxyphenoxy, 2,4-dichlorophenoxy, 4-(2,4
-ethylhexaneamide) phenoxy, etc.), silyloxy groups (e.g., trimethyloxy, dimethylphenylsilyloxy, dimethyl-t-butylsilyloxy, etc.),
Examples include heterocyclic oxy groups (eg, tetrahydropyranyloxy, 3-pyridyloxy, 2-(1,3-benzimidazolyl)oxy, etc.).

Organic groups via a sulfur atom include alkylthio groups (e.g. methylthio, ethylthio, butylthio, 3-(
4-(4-dodecyloxybenzene)sulfonamidophenyl)propylthio, 4-(2-butoxy-5-t-
octylphenylsulfonamide) benzylthio, etc.),
Arylthio groups (e.g. phenylthio, 2-su7tylthio, 2.5-dichlorophenylthio, 4-dodecylphenylthio, 2-butoxy-5-t-octylphenylthio, etc.), heterocyclic thio groups (e.g. 2-pyridylthio) ,
2-(1,3-benzoxasilyl)thio group, l-hexadecyl 1.2.3.4-tetrazolyl-5-thio group,
1-(3-N-octadecylcarbamoyl)phenyl-
1,2,3,4-tetrazolyl-5-thio, etc.).

Here, at least one of A and B is preferably an aryl group.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by Xl include, for example, chlorogen atoms (chlorine, bromine,
fluorine, etc.) and hydroxyl, alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy,
Alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, mercapto, arylthio, heterocyclic thio, alkoxythiocarbonylthio, acylamino, substituted amino, nitrogen-containing heterocycle bonded by N atom, sulfonamide , alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl and the like, preferably a halogen atom, especially a chlorine atom.

Typical specific examples of the cyan coupler represented by the above-mentioned formula (I[[) are shown below, but the present invention is not limited thereto.

These cyan couplers are Hemi/7 Yu Perichte (C
Hemische Berichte), 34 volumes,
According to the method described on pages 639-642 (1901), and also in Japanese Patent Application No. 6X261488 and No. 62-13414.
No. 4, No. 62-211067, No. 62-227476
It can be synthesized according to the method described in No.

These couplers usually contain 2 per mole of silver halide.
X 10-3 to 8 x 10 qmol, preferably 1 x 10-
It can be used in a range of 2 to 5 x 10-' moles.

In the cyan coupler represented by formula (rV) above, the divalent linking group containing an amide bond or ester bond represented by Y is specifically R.

-So, -N-, etc. are mentioned. Here R1 and R9
represents a leaf atom, an aliphatic group-1 aromatic group or a heterocyclic group.

Y is preferably -NHCO-.

X2 is preferably a halogen atom, an optionally substituted aryloxy group, or an alkoxy group.

Specific examples of the cyan coupler represented by the above formula (IV) are shown below, but the present invention is not limited thereto.

IV-1 Q IV-3 0) I CsH+ +(t) IV-4 IV-7 IV-8 These cyan couplers can be synthesized according to the method described in JP-A-1-315736.

These cyan couplers usually contain l x 10-' to 5 mol per mol of silver halide, preferably l x 10-'
It can be used in a range of 1 mol to 1 mol.

In the silver halide emulsion used in the present invention, any silver halide may be used, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride. can.

The silver halide grains may be formed by any of the acid method, neutral method, and ammonia method, and methods known in the photographic field such as simultaneous mixing method, forward mixing method, back mixing method, and conversion method are used.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

Silver halide emulsions can be used either with a wide grain size distribution (polydisperse emulsion) or with a narrow grain size distribution (monodisperse emulsion), but preferably a monodisperse emulsion (with a standard grain size distribution). deviation/average particle size - coefficient of variation less than 0.2θ)
It is. The particle size is preferably 0.1-1.0 μm.

Silver halide emulsions can be chemically sensitized (for example, sulfur sensitization, gold sensitization, selenium sensitization, reduction sensitization) and spectral sensitization (for example, cyanine dyes, merocyanine dyes, hemicyanine dyes, styryl dyes, Spectral sensitization using hemioxonol dyes) is possible. Also, fog suppressants or stabilizers known in the art (e.g., azaindenes,
mercapto heterocyclic compounds) can be added.

In the emulsion layer of the light-sensitive material, a diffusion-resistant coupler is used that forms a dye by coupling with an oxidized product of an aromatic primary amine compound (for example, p-phenylenediamine derivative or aminophenol derivative) during color development processing. It will be done.

A benzophenone-based or benzotriazole-based ultraviolet absorber may be added to the photosensitive material.

Particularly preferred are benzotriazole compounds, such as U.S. Patent No. 3,754.919, U.S. Pat.
Those described in No. 41572 and the like can be used.

The aqueous compounds such as the above-mentioned dye-forming couplers and ultraviolet absorbers are usually used in high-boiling organic solvents (e.g., phthalate esters, phosphate esters, phenol derivatives, alkylamides, etc.).
It is used after being dissolved in a cycloalkane) using a low-boiling point and/or water-soluble organic solvent if necessary, and emulsified and dispersed in a binder using a surfactant.

The binder used in the photographic constituent layer of the present invention includes:
Gelatin, albumin, agar, gum arabic, partially hydrolyzed, polyvinyl acetate, polyacrylamide, etc. can be used, and gelatin is particularly preferred.

The emulsion layer and auxiliary layer on the emulsion side may contain various photographic additives. For example, dye image stabilizers, color stain preventive agents, optical brighteners, antistatic agents, hardeners, etc. described in Research Disclosure No. 17643,
Surfactants, plasticizers, wetting agents, etc. can be used as appropriate.

As a coating method for the emulsion layer and the constituent layers, slide hopper coating, curtain coating, air doctor coating, etc. are useful, but simultaneous multilayer coating using a slide hopper is particularly preferred.

The exposure method used in the present invention includes a contact exposure method,
There are photographic exposure methods, enlargement exposure methods, and scanning exposure methods.
In particular, the contact exposure method is preferable from the viewpoint of halftone dot reproducibility for color proofs and dimensional reproducibility for originals.

Light sources used in the exposure of the present invention include natural light, tungsten electric lamps, fluorescent lamps, mercury lamps, halogen lamps, etc. Fluorescent lamps are particularly preferred because they generate less heat and can achieve miniaturization of exposure equipment in scanning exposure.

The color development process in the present invention is usually carried out in the order of a color development step, a bleach-fixing step, a water washing step, or a stabilization step known in the photographic industry. In addition, for direct positive color photosensitive materials, in addition to the above, there are also reversal processing methods such as fogging processing, and for reversal color photosensitive materials, a positive image can be obtained by combining with the first monochrome development processing.

Aromatic primary amines are typical color developing agents for the color sensitive material of the present invention, and known alkaline agents, preservatives, antifoggants, optical brighteners, etc. are used in the color developing solution. be able to. Known bleaching agents and fixing agents can be used in the bleach-fixing solution.

Next, the color developing agent used in the present invention will be described.

As the color developing agent, aromatic primary amines are preferred, and specific examples are shown below. A CD-2 color developing agent is preferred.

The amount of color developing agent added is 0, O1 mol/a or more,
Preferably it is 0.015 mol to 0.03 mol/12.

Known alkaline agents, preservatives, antifoggants, optical brighteners, antifoaming agents, color development accelerators, and the like can be added to the color developing solution.

The color development time is not particularly limited, but is usually 30 seconds to 4 minutes, and the temperature of the color developer is usually 20°C to 45°C.
It is.

〔Example〕

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

Example 1 Three types of silver halide emulsions shown in Table 1 were prepared by a neutral method and a simultaneous mixing method.

Table-1 2 mg per mole of silver halide added per mole of silver halide l 0.
After chemical sensitization, 4 mol of 5TB-1 shown below was added as an emulsion stabilizer per mol of silver halide to each silver halide emulsion containing 2 mmol.

D ■ D-2 SO3H-N(C2H6)3 D-3 TB-1 The following structure was placed on a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the other side. Each layer was coated on the side of the polyethylene layer containing titanium oxide to prepare a multilayer silver halide color photographic material 101. The coating solution was prepared as follows.

1st layer coating liquid Yellow coupler (YY-1) 26.7g, dye image stabilizer (sr-1) lo, Og, (ST-2)
6.67 g, 0.67 g of additive (HQ-1) and 6.67 g of high boiling point organic solvent (TPP), and 60 m of ethyl acetate.
Ω was added and dissolved, and this solution was mixed with 20% surfactant (SU-
1) 220mf of 10% gelatin aqueous solution containing 7mQ
f was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow Kabura dispersion.

This dispersion was mixed into blue-sensitive silver halide emulsion Em-1 (silver 10
g) to prepare a first layer coating solution.

The second to seventh layer coating solutions were also prepared in the same manner as the first layer coating solution.

In addition, (H-1) was added to the second layer and the fourth layer as a hardening agent.
Layer (H-2) was added.

As a coating aid teeth, surfactant (SU 2), (SU-3) Add The amount of silver halide emulsion added is shown in terms of silver.

M ■ Y-1 C Q C-2 ST-1 ST-2 ST-3 ST-4 ST-5 V-2 CH.

PP OP NP IDP V.P. Triphenylphos 7ate Dioctyl phthalate dinonyl phthalate diisodecyl phthalate Polyvinylpyrrolidone Q-1 Q-2 B.S. ■ V-2 CsH++(t) 1M- to 503 50, K U-1 U-2 C,H.

Na03S -CHCOOCH, CHC, Hs CHzCOOCHzCHCaHs zHs U-3 NaOxS CHCOOCH*(CFzCFx)*H
GHzCOOCHz(CFxCFP)JC(CHzSO
*CH-CH2)a Next, samples 102- 110 was produced.

Next, these samples were exposed to light through a color negative film obtained by photographing and developing the scenes shown below, and were subjected to the processing steps shown below. 10 of the obtained scene exposure samples
It was submitted to human subjects and visual evaluations were conducted, especially regarding the color reproducibility of yellow.

(Scene A) Scenery of an amusement park (Scene B) Visual evaluation of the basket with fruits was performed by observing each print, and the color reproduction of yellow was excellent. (5 points) Somewhat excellent. (4 points) Average (3 points) Slightly inferior. (2 points) Inferior. (1 point) A five-level evaluation was performed, and the average value was determined. The results are shown in Table-2.

[Processing process] Temperature Time color development 35.0±0.3°C 45 seconds bleach fixing 35.0±0.5°C 45 seconds stabilization
Dry for 90 seconds at 30-34℃ 60-80℃ 60
Second color developer pure water
800m12 triethanolamine
logN, N-diethylhydroxyamine
5g potassium bromide 0.0
2g potassium chloride 2g potassium sulfite 0.3g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0g ethylenediaminetetraacetic acid II 1.0g catechol-3,5-disulfonic acid disodium salt 1.0g N-ethyl-N-β- Methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g Potassium carbonate
Add 27g of water to bring the total volume to N2, and adjust the pH to
Adjust to -10,10.

Bleach-fix solution Ferric ammonium dihydrate ethylenediaminetetraacetic acid 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100ml12 Ammonium sulfite (40% aqueous solution) 27.5mQ Add water to make Iff, pH with potassium carbonate or glacial acetic acid =
Adjust to 5.7.

Stabilizing liquid 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene 1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20% Aqueous solution) 3.0g ammonium sulfite 3.0g optical brightener (4,4'-diaminostilbendisulfonic acid derivative)
Add 1.5g of water to make 1I2, and add sulfuric acid or potassium hydroxide table *, ** Added amount is 0.40g/m" *** TPP:PK-4-1:2 (weight ratio) PP 1) Kum -1,73 As is clear from Table 2, all the samples using high hydrogen-accepting compounds other than those of the present invention show a remarkable improvement in yellow color reproducibility.Especially, the high hydrogen-accepting compounds It can be seen that the color reproducibility improvement effect is large in the sample in which a polymer compound is also used.

Example 2 An emulsion consisting of cubic silver bromide grains with an average grain size of 0.3 μm was prepared by simultaneously adding equimolar amounts of silver nitrate aqueous solution and potassium bromide aqueous solution to a gelatin aqueous solution at 50°C for 50 minutes using the double jet method. I got it.

To this emulsion, 6.5 mg of sodium thiosulfate and 3++ g of potassium chloraurate per mole of silver were added and heated at 70°C for 70 minutes to perform chemical ripening. A potassium bromide mixed solution (molar ratio 1:9) was added at the same time to reduce the average particle size to 0.45.
A cubic core/shell type emulsion consisting of a μ-shaped silver bromide core and a silver chlorobromide shell was prepared.

After washing with water and desalting, 2.0 mg of sodium thiosulfate and 1.0 mg of potassium chloroaurate were added to this emulsion per mole of silver, and chemical ripening was performed at 60°C for 50 minutes to directly form a positive silver halide emulsion. EM-1 was obtained.

Preparation of blue-sensitive emulsion EM-B After color sensitization with sensitizing dye D-5, 600 mg of T-1 per mole of silver was added to EM-1, and then FA-1 was added at a concentration of 8 X 10-' per mole of silver. A blue-sensitive emulsion was prepared by adding 5 x 10-' moles of FA-2 per mole of silver.

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-H 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.

A silver halide color photosensitive material having the structure shown in Table 3 was prepared using the above EM-B and EM-GlEM-R.

Table (D-7,) (D -6> (D -5) (YC-1) [MC (CC-2) (So-1 (so-2) (AS Ura H (AS -2) R H (A- (A ■ :)LlsK SO,a (A ■ (ST-A) (ST-B) (T- R (FA-1) (FA-2) (uv-1) (UV-2) C ,H Musu(SA-1 Js CH3α)OCH2C)I CaH*(SA-2) I2 One side of the double-sided polyethylene coated paper has a titanium dioxide content of 15% by weight and is a 30 g layer, and the double-sided polyethylene and paper Sample 201 was prepared by coating the first layer to the first O layer having the above structure on the titanium dioxide-containing polyethylene side of a support having a total thickness of 100 μι.5A- was used as a coating aid.
1 and 5A-2, and H-2 was used as a hardening agent.

Next, samples 202 to 218 were prepared by changing the yellow coupler and solvent of the seventh layer as shown in Table 4, and adding polymer compounds as shown in Table 4.

Also, the side opposite to the emulsion layer coating side is 1m as a back layer! 5g of gelatin per serving, 0. Olg's SA-1, 0.07g
A layer consisting of H-2 and 0.3 g of silica with an average particle size of 5 μm was applied. The sample was vacuum-adhered to a black-and-white transmission negative with 1-inch 175-line dots and the dot area varied from 0% to 100% and exposed. The light source during exposure was a fluorescent lamp, and the color separation filters were Kodak Latchin filters No. 47B, No. 47B, and Red, respectively.
61. No. 29 was used. Next, the following development treatment was performed.

Processing steps (processing temperature and processing time) (1) Color development 35°C 2 minutes 30 seconds (2) Bleach-fixing 35°C 1 minute (3) Stabilization treatment 25-30°C 1 minute 30 seconds (
4) Drying 78-80℃ 1 minute Asahi solution composition (color developer) Benzyl alcohol Cerium sulfate Ethylene glycol Potassium bromide Potassium chloride Sodium carbonate Hydroxylamine sulfate Diethylene triamine Pentaacetic acid 4-Amino-N-ethyl-N -(β-Hydroxyethyl)aniline sulfate fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) Potassium hydroxide diethylene glycol potassium phosphate aqueous solution is added to bring the total amount to la, and I) H is added.

(Bleach-fix solution) 1.0g 2.0g 15m (1 g Adjust to 10.50 15+12 0.015g 8 g 2.5g 0.8g 0.2g 25.0g O,1g 5.0g g 4.5g Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100mff Ammonium sulfite (40% solution) 27.5mQ Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid and add water to total volume 1m
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 g Bismuth chloride 0.2 g Magnesium chloride 0. 1g ammonium hydroxide (28% aqueous solution) 2.0g sodium nitrilotriacetate 1.0g water was added to bring the total amount to 14,
Adjust the pH to 7.0 with ammonium hydroxide or sulfuric acid.

The stabilization treatment was carried out using a two-tank countercurrent method.

Ten subjects visually evaluated the similarity of the yellow tone of the obtained sample to the printing ink. The visual evaluation was made into a 5-level evaluation similar to Tora Example-1, and the average value was calculated.

The results are shown in Table 4.

table Add the same molar amount as YC-1 of this sample 201.

* * 8.2+ag/dm” *
*Book 5.0+ag/da”DOP Nidioctyl 7-talate TCP: Tricresyl phos-7ate As is clear from Table 4, all samples using the high hydrogen-accepting compound of the present invention have a color tone similar to that of printing ink. It turns out that he has excellent sex.

Furthermore, a sample in which a high hydrogen-accepting compound and a polymer compound were used in combination had better effects. Furthermore, it can be seen that the effect of the present invention is greater in the sample using the yellow coupler preferably used in the present invention, which is represented by the above-mentioned formula [Y].

Example-3 Magenta coupler in the fifth layer of sample 201 of Example-2,
Samples 301 to 315 were prepared by changing the yellow coupler and solvent as shown in Table 51, and adding polymer compounds as shown in Table 5. Using the obtained sample, we investigated the similarity of the magenta color tone to printing ink.
Table C-3 a Same method as Example-2 As is clear from Table-5, all samples using the high hydrogen-accepting compound of the present invention showed an improvement effect in the approximation to the color tone of printing ink. It will be done. Among these, the effect is greater when the above polymer compounds are used in combination. Furthermore, the above-I
] It can be seen that the effect is more remarkable when using a magenta coupler represented by the following formula, and the color tone is highly similar to that of printing ink. When a yellow coupler is not used in combination with a magenta coupler, the color tone is poor in approximation to the printing ink, and the improvement effect of the present invention is also small.

Example-4 By changing the cyan coupler in the third layer of Samples 208 and 212 of Example-2 as shown in Table-6, Samples 401 to 4 were prepared.
20 were produced. Using the obtained sample, visual evaluation was performed in the same manner as in Example 2 to determine the similarity of the green color tone to that of printing.

The results are shown in Table-6.

As is clear from Table 6, all the samples using the high hydrogen-accepting compound of the present invention show an improvement effect in the approximation of color tone to printing.

Regarding cyan couplers, among the above formulas CI), the cyan couplers represented by the above formula [1-A] and the cyan couplers in which R1 and R8 in the above formula (1) jointly form a ring are more preferable. It can be seen that when a coupler is used, the approximation to the printed color tone is excellent, and the improvement effect of the present invention is large. In particular, a cyan coupler in which XA in formula CI-A) is a group substituted via oxygen has excellent effects. Furthermore, the formula (1[), (IIl
) and (IV) are particularly excellent in approximation to the printed color tone, indicating that the improvement effect of the present invention is remarkable.

〔Effect of the invention〕

According to the present invention, it was possible to provide a silver halide photographic material with excellent color reproducibility. In particular, it was possible to provide a silver halide photographic material for color proofing having a tone close to that of printing ink.

Claims (4)

[Claims] (1) In a silver halide photographic material coated with at least one silver halide emulsion layer, at least one non-color-forming compound having a hydrogen acceptance parameter (pK_M_■) of 2.5 or more, and A silver halide photographic material comprising lipophilic fine particles obtained by emulsifying and dispersing a solution containing at least one dye-forming coupler. (2) The silver halide photographic material according to claim 1, wherein the lipophilic fine particles contain at least one polymer compound that is insoluble in water and soluble in organic solvents. (3) Claim (1) characterized in that at least one silver halide emulsion layer of the silver halide photographic light-sensitive material contains a coupler represented by the following general formula [M-I].
) or the silver halide photographic material described in (2). General Formula [M-I] In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z 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. Further, R represents a hydrogen atom or a substituent. (4) The silver halide photographic material for color proofing according to claim (1), (2) or (3).