JPS6128948A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color reproducibility and color image fastness by dispersing at least one kind of the magenta coupler expressed by formula I in coexistence with at least one of a high boiling solvent expressed by formula II into a silver halide emulsion layer. CONSTITUTION:At least one kind of the magenta coupler expressed by formula I is dispersed in coexistence with at least one kind of the high boiling solvent expressed by formula II into the silver halide emulsion layer. In formula I, R<1> and R<2> denote a hydrogen atom or substituent, X denotes the group which can be eliminated by the coupling reaction with the oxidant of an arom. primary amine developing agent and Z denotes a nitrogen atom or carbon atom. In formula II, R<3>, R<4> and R<5> denote respectively an alkyl group, cycloalkyl group, alkenyl group or aryl group, where the total sum of the carbon atoms of the groups expressed R<3>R<4> and R<5> is 12-60. The color reproducibility and color image fastness are thus improved by using the pyrazoloazole coupler.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic material having improved color reproducibility and color image sharpness. This invention relates to silver color photographic materials.

(Prior Art) In silver halide color photographic light-sensitive materials, newly developed dye-forming couplers (hereinafter simply referred to as couplers) are used to form dyes by reacting with light-sensitive silver halide emulsions and aromatic-grade amine-developed mulberry oxides. abbreviated) t- method is often used. Similarly, in color photographic materials, a combination of a yellow coupler, a cyan coupler, and a magenta coupler is usually used.

Among these, terpyrazolone couplers, which are frequently used as magenta couplers, have sub-absorption near 30 nm and have poor tail cutting on the long wavelength side.
This was a big problem in terms of color reproduction.

Therefore, in order to solve these drawbacks, a pyrazoloazole-based magenta coupler was developed, and the magenta dye obtained by coupling this family of couplers with an oxidized product of an aromatic-grade amine developer was prepared in an ethyl acetate bath. It is known that the liquid exhibits a highly pure magenta color with no sub-absorption near ≠30 nm and a good absorption tail on the long wavelength* side. However, the transmission or reflection absorption spectrum of a film or photographic paper obtained by color development of a light-sensitive material in which this pyrazoloazole magenta coupler is dispersed in a silver halide emulsion layer using a high boiling point gA bath medium is Problems have been that the edge cutting on the long wavelength side is not necessarily good, the color reproducibility is not sufficiently improved, and the optical clarity of the color image is also not sufficient.

(Objective of the Invention) The first object of the present invention is to improve color reproducibility by forming a magenta color image of an excellent hue with a well-cut edge of absorption on the long wavelength side using a pyrazoloazole coupler. An object of the present invention is to provide an improved silver halide color photographic material.

A second object of the present invention is to provide a silver halide color photographic material with improved color image consistency in a system using a pyrazoloazole coupler.

(Means for solving the problem) The above object is to provide a silver halide color having at least seven silver halide emulsion layers on a support.
- A photographic light-sensitive material, wherein at least one magenta coupler represented by the following general formula CI) coexists in the silver halide emulsion layer and at least one high boiling point solvent represented by the following general formula (II). Dispersion is low.
This was achieved by using a photosensitive material with the following characteristics: General formula (1) (wherein 1 and R2 represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of an aromatic-grade amine development system. Z
represents a nitrogen atom or a carbon atom, and when Z is a carbon atom, a t substituent other than a hydrogen atom may be bonded to this carbon atom.

Here, kLl, R2 or X may be used to entirely form a multilayer of two or more layers, and when Z is a carbon atom, the carbon $ atom may be used to form a multimer of two or more layers.

1. In formula (1), a multimer means one having at least one group represented by the general formula [I] in seven molecules, and includes bis-forms and polymer couplers. It will be.

Here, the polymer coupler may be a homopolymer consisting only of a monomer having a moiety represented by the general formula (I) (preferably one having an ethylenically unsaturated group, hereinafter referred to as vinyl monomer), or an aromatic Copolymers may be made with non-chromogenic ethylene-like monomers that do not couple with the oxidation products of the -grade amine developer. ) General formula [[] 054 (In the formula, R3, 几4 and 5 each represent an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. However, the group represented by B 3 , B 4 and R5 The total number of carbon atoms is 7.2 to to.

) The compound represented by the general formula [I] is /H-imidazo(/
, J-b) pyrazoles and /H-bicycloC',"
) ('121≠) triazoles, each represented by the general formula [■]& and [■].Among these, particularly preferred are compounds represented by the general formula [■].

(III) (■) General formula (III
) Refinery (IV, t substituent of l, R2 and 1 are also hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group) , acyloxy group, carbamoyloxy group, silyloxy7 group, sulfonyloxy group, acylamino group, ainilino group, ureido group, imide group, sul7amoylamino group, carbamoylaminohiko, alkylthio group, arylthio group, peterocyclic thio group, Alkoxycarbonylamino group, aryloxycarbonylamino group 7
group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, a 7-aryloxycarbonyl group, and X is a hydrogen atom.

Represents a group that is decoupled by a halogen atom, a carboxy group, or a group that is bonded to the carbon at the coupling position via an oxygen atom, nitrogen atom, or sulfur atom.

It also includes the case where kLl, Bj, 6 or X is a divalent group and forms a bis body. Furthermore, when the moiety represented by the general formulas [river] and (IV) is included in the vinyl monomer, 几1, 几2 or R6 represents a simple bond or linking group, and through this, the general formula ( III) The moiety represented by (IV) and the ethylenically unsaturated group are bonded.

More specifically, 几1, R2 and R6 are hydrogen atoms, halogen atoms (e.g. chlorine atom, bromine atom, etc.), alkyl groups (e.g. methyl group, propyl group, t-butyl group, trifluoromethyl group, tridecyl group). ,J-(2,F
-di-t-amylphenoxy)propyl group, -dodefluoroxyethyl group, 3-phenoxypropyl group, λ-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group, etc.), aryl group (e.g. Phenyl group, Hiro-
1-butylphenyl group, 21 μm di-t-7 milphenyl group, ≠-tetradecanamidophenyl group, etc.), heterocyclic groups (e.g. n, 27lyl group, λ-chenyl group, copyrimidinyl group, λ-benzothiazolyl group, etc.), cyano group, alkoxy group (e.g. methquine group, ethoxy group, 2
-methoxyethoxy group, codedecyloxyethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group (e.g., phenoxy group, λ-methylphenoxy7)
group, at-butylphenoxy group, etc.), heterocyclic group Φ
cy group (e.g., λ-benzimidazolyloxy group, etc.)
, acylox7 group (e.g., acetox7' group, hexadecanoylx7 group, etc.), carbamoyloxy group (e.g., N-phenylcarbamoyloxy group, N-ethylcarbamoyloxy group, etc.), silyloxyx7 group (e.g. ,
trimethylsilyloxy &, etc.), sulfonyloxy group (?lJ, tR, dodecylsulfonyloxy group, etc.)
, acylamide 7 groups (e.g., acetamide group, benzamide group, tetradeca/amide group, α-(2,≠-di-t
-amylphenoxy)butyramide group, r (3-t
--ethyl-≠-hydroxyphenoxy)butyramide group, α-(μm(Hiro-hydroxyphenylsulfonyl)
(phenoxy)tecanamide 4, etc.), anilino groups (e.g. phenylamino group, λ-chloroanilino group, cochrotortetradecanamide anilino group, cochchloro5-dodecyloxycarbonylanilino group, N-7 cetylanilino group, 27-chloro- ter(α-(3-1-butyl-Hiro-hydroxyphenoxy)dodecanamido)anilino group, etc.), ureido group (e.g., phenylureido group, methylureido group, N, N dibutylureido group, etc.), imide groups (e.g., N-succinimide group, 3-penzylhydantoynyl group, F-(,2-ethylhexanoylamino)phthalimide group, etc.), sulfamoylamino groups (e.g., N,N'-dipropyls), Rufamoylamine/m, N-methyl-N-decylsul7
amoylamino group, etc.), 1-rukylthio, i! i (for example, methylthio group, octylthio group, tetradecylthio group, cophenoxyethyl tertiary, J-phenoxyprovirthio group; tTj, 3-(methylphenoxy)propylthio group, *), arylthio groups (for example, phenylthio group, λ-butoxyj-t-octylphenylthio-6,1--z-ntadecylphenylthio group, λ-carboxyphenylthio group, μm tetradecanamidophenylthio group, etc.), heterocycle Thio group (e.g., λ-benzothiazolylthio group, etc.), alkoxycarbonyl amine 7
groups (eg, methoxycarbonyl 1-mino group, tetradecyloxy-7-carponylamino group, etc.), aryloxycarbonylamino groups (eg, phenoxycarbonylamino group).

) group, λ, 4t-di-tert-butylphenox7carbonylamino group, etc.), sulfonamide group (e.g. methanesulfonamide group, hexadecanesulfo/amide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecane sulfonamide group, comethyloxy-1-butylbenzenesulfonamide group
Cumoyl group, N.

N-dibutylcarbamoyl group, N-(,2-dodecylox7ethyl)carbamoyl group, N-methylhedodeflucarbamoyl group, he-(J-(J.

IA-')-tert-amylphenoxy)propyl)
carbamoyl group, etc.), acyl group (e.g., acetyl group, (co-, h-j-tert-7-milphenoxy)acetyl group, benzoyl group, etc.), sulfamoyl group (flJ
, t, N-ethylsulfamoyl group, N, N-dipropylsulfamoyl 4, N-(J-dodecyloxyethyl)sulfamoyl group, N-xf-N-dodecylsulfamoyl group, N.

N-diethylsulfamoyl group, etc.), sulfonyl group (
For example, methanesulfonyl group, oftance′″′″a
゛"74:/, X is a frozen candy atom, a compound atom (for example, a salt atom, a bromine atom, an iodine atom, etc.), a group connected by a carboxyl atom, a compound atom (for example, an acetoyloxy group, a pronotyloxy group, a benzoyl group) Oki'i
t, x *ψ-dichlorobenzoyloki 7 groups, ethoxy 7 groups
Oxaloyloxy group, pyruvinyloxy group, 7-namoyloxy group, phenoxy group, Hiro-77 no phenoxy group, ≠-methanesulfonamidophenoxy group, Hiro-methanesulfonylphenoxy group, α-naphthoxy group, 3-pentadecylphenoxy port , benzyloxycarbonyloxy group, ethoxy group, -monocyanoethoxy group, benzyloxy group, λ-) netethyloxy group, cophenoxyethoxy group, 5-enyltetrazolyloxy group, cobenzothiazolyloxy group, 4), a group linked via a nitrogen atom (for example, benzenesulfonamide 4, N-ethyltoluenesulfonamide group, heptafluorobutanamide group, etc.).

3,ψ,! , 6-bentafluorobenzamide group, octanesulfonamide group, p-77 nonoenyl clade group, N, IN-diethylsul7 amoylamino group,
1-piperidyl group, S, S-dimethyl-2, ≠-dioquine chloride zolidinyl group, °l-penzyl ethoxy 7
-3-hydantoinyl group 5, ZN-/, /-dioxo-
J (2H)-oxo-/, cobenziisothiazolyl group, co-oxo/, λ-dihydro-7-pyridinyl group, imidazolyl group, pyrazolyl group, 3. j-diethyl-
l.

Co, l-triazole/-yl,! = or t-promobenzotriazol-/-yl, j'-methyl-/
, 2, 3. Hiro-triazol-l-yl group, benzimidazolyl group, 3-benzyl-7-hydantoynyl group, l
-Benzil-! -Hexadefluoroxy-3-hydantoynyl group, j-methoxyphenylazo group, Hiro-methoxyphenylazo group, Hiro-piparoylaminophenylazo group, Cohydrogyshihiro-probanoylphenylazo group 41) Groups linked by sulfur atom (For example, phenylthio group, cocalpoquinphenylthio group, λ-methoxy5
-t-octylphenylthio group, Hiro-methanesulfonylphenylthio group, ≠-octanesulfonaζ''dophenylthio group, λ-butoxyphenylthio group, co(2-hekibensulfonylethyl)-s-tert-octyl phenylthio group, benzylthio group, 1-S/7noethylthiolfi, /-ethoxycarbonyltridenruthio group,
Tafeniluko, 3. Hiroshi, tertetrazolylthio group,
λ-benzothiazolylthio, λ-dodecylthio5-
Thiophenylthio group, λ-phenyl-3-dodecyl group
, a, ta-1 riazolyl-! -thio group, etc.).

几 , 几 , 1 (or X becomes a divalent group and bis body t
- If we form this bivalent fund in more detail, we will explain in more detail that the substitution or no vIt servant's 1 Rukire 7 group (tlj, ta
, methylene group, ethylene group, /, 10-decylene group,
-CH2CH2-O-CH2CH2-1 etc., substituted or unsubstituted phenylene group (e.g. l, ≠-phenylene M, /, 3-phenylene group, -Ni((!Q-几2-
CONH- group (2 represents a substituted or unsubstituted alkylene group or phenylene group).

l (1, fL"t or kL
The linking group represented by 6 is an alkylene group (substituted or unsubstituted fullkylene group, for example, methylene group, ethylene group, 1.10-decylene group, -CH2C) 120CH2
C) 12-1 etc.), phenylene group (substituted or unsubstituted phenylene group, for example /, F-phenylene group, /,
3-Phenylene-CON)i-1-(J-1-0CO-) and an aralkylene group (for example, the group formed by combining the first group is included).

The ethylenically unsaturated group of the vinyl monomer A may have a substituent other than those represented by the general formulas [I■] and (IV). Preferred substituents are a hydrogen atom, a salt atom, or a lower alkyl group having 1-μ carbon atoms.

Examples of non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine development include acrylic carbon, α
- Chloroacrylics, α-alacrylic powders (e.g. methacrylic acid) and esters or amides fermented from these acrylics (e.g. acrylamide,
n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butylacrylate, t-butylacrylate), 1so-butylacrylate, 2-ethyl xyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy 7 methacrylate), methylene dibis acrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate) , acrylonitrile, methacrylaterile, aromatic vinyl compounds (e.g. styrene and its rust derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulphostyrene), itaconic acid, cytodiconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid, maleic acid,
Maleic acid ester, N-vinyl-2-pyrrolidone, N
-vinylpyridine, and 2- and Hiro-vinylpyridine, etc. The non-color-forming ethylenically unsaturated monomer used herein may also be used in combination with λ or more.

A method for synthesizing the compound V of the coupler having the above general formula (II[)t or (IV)] is described in the following. The compound of the general formula (IIIJ) is disclosed in Japanese Patent Application Shoj♂-, 23 Hiroshi et al., and the compound of the general formula (IV) is
The distance between the condyles is 1 ≠ Tata l λ, the same j ter λ 77 tAj, the same 5 ter hiro rtoi, the same 5 ter j 3 ≠ hiro 3 and the same 5 turf 0
/≠6, etc., respectively.

Specific examples of couplers represented by the general formula [■] or (IV) are shown below, but the couplers used in the present invention are not limited to these.

(M-≠) 2M-r) M-6) (M-/J) (M-/4t) (M-/j)' n 6MIB (M-/G) (M-/7) -C4Hg (M-/I) (M-/ri) (M-λO) (M-,2/) (M-Jj) (M-λHiroshi) Ha In kL3, R4 and about 5 of the general formula (II), The reason why the sum of the represented substituents is from 12 to 60 is because if the sum is outside this range, the desired effect of the present invention will be reduced. Furthermore, if the number of carbon curvature ridges exceeds 60, the ability to decompose the coupler is reduced, and the coupler may precipitate, which is not preferable. In the general formula ([1), the alkyl group represented by R, l-1 or 95 may be a straight-chain alkyl group or a branched alkyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group,
Hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexenyl group, hexenyl group, octadecyl group, nonadefur group, eicosyl group, etc. 6')' The cycloalkyl group represented by s ``3*fL''' or 几 is, for example, a methyl group, 7
These include the clohekiflu group. The aryl group expressed as ordinary, ordinary or ordinary means phenyl group, naphthyl group, etc.
Alkenyl groups include haftenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, dodecenyl group, octadecenyl group, etc. These alkyl groups, cycloalkyl groups, aryl groups, and alkenyl groups may have one or more it substituents. Examples of substituents for alkyl groups, cycloalkyl groups, and alkenyl groups include halogen atoms ( (e.g., fluorine atoms, hedge atoms, etc.), alkoxy groups (e.g., methoxy groups, ethoxy groups, etc.),
butoxy group, etc.), aryl group (e.g., phenyl group, tolyl group, naphthyl group, etc.), aryloxy group (e.g., phenoxy group, etc.), alkenyl group, alkoxycarbonyl group, etc. Substituents for the aryl group include the above-mentioned substituents. In addition to those listed as substituents for the alkyl group, cycloalkyl group, and alkenyl group, alkyl groups and the like may be mentioned. Preferably 几.

K4 and 几 are tolyl group, coethylhexyl group, 7
- methyloctyl group, cyclohexyl group, straight chain alkyl group having from J to II carbon atoms, and the like.

In the present invention, a high boiling point organic solvent refers to an organic solvent having a boiling point of /7/00 or more at 1 atm.

In the present invention, the high boiling point I achieved by the general formula C[[]
The amount of K solvent used may be any amount depending on the IUX of the magenta coupler represented by the general formula [I] and the user, but it has a high boiling point in terms of weight ratio; It is preferable that the ratio is OIO~20. Furthermore, the high boiling point M according to the present invention represented by general formula (11)
The boiling bath medium can also be used in combination with other conventionally known high boiling point organic solvents as long as the purpose of the present invention is not compromised. Examples of these high-boiling point solvents include dibutyl phthalate, 7
Notal ester thread bath media such as Cicoethylhexyl tarate, amide solvents such as N, i'J-diethyldodecanamide, fatty acid ester solvents, benzoin ester bath media, co-tert-tert-amylphenol Examples include phenolic solvents such as.

Specific examples of Sim point M machine bath media that are treated in one cycle (it) are shown below, but the present invention is not limited thereto.

0=P+0C4He once)3 (S-2) 0=P+(JCH2C)100Mc)ia )aC)i
a (S=J) 0=P+OC,)I engineering 3 once) 3 (S-Hiroshi) (S-j) (S-+) o=i'+oc8m, 7 once) 3 ((S
-r) (S-ta) (S-10) 0=P+0C8H□9 n)a (S-//) (8-lko) 0=P+OC1oH21-and)3 (S-/Hiroshi) (S-/ j) (S-/A) o=P+uc 1□H2,-U)3 (S-/7) ('S-/f) (S-koθ) U""P+OCx 4H29-U)3 0=P (-QC□5■13□-n) 3 (S-22) o=p+ocm6H33 once) 3 (S-2j) (J=P+0CH=CHC□6H33) 3 (S-2μ
) (S-2 Hiro) (S-Cotane 2H5 coupler color-forming dye is required to have a favorable hue in terms of color reproduction. Specifically, the main absorption wave color gamut is appropriate, and unnecessary absorption is small and bright colors are produced. Regarding the vividness of the color, the shape of the quetor, especially on the long wavelength side, gives a large shadow to the absorption spectrum of the dye.50% of the absorption maximum, 10
The smaller the difference between the absorption wavelength corresponding to the value of 2 or 2′i and the maximum absorption wavelength, the more intense the hue will be. It becomes a bright color with little color. In the present invention, the expression "1 absorbent hem cut" can also be expressed quantitatively by the above-mentioned 10 (1 & or 2 absorbent tentative width).

The magenta coupler and the high boiling point M bath medium according to the present invention can be dispersed and contained in at least one hydrophilic M colloid layer constituting the photographic photosensitive layer.

As a method for introducing a coupler into a silver halide emulsion layer, it is common to use a known method, for example as described in U.S. Pat. No. λ, J, 2.2.027. .

The phosphoric ester coupler bath medium used in the present invention generally has very good solubility for the coupler of the present invention, but because the coupler solvent/coupler ratio is made small, the coupler may not dissolve well. If sufficient, other Kabushi solvents such as phthalate Kab-t-81s can be used in combination. Moreover, in the present invention,
Before dissolving the coupler into the coupler solvent, the boiling point is approximately 30
~/! o 'C organic solvents, such as ethyl acetate, vinegar, lower alkyl acetate such as butyl, etc. Even if τ coexists, it is ↓.

Even when a coupler dissolved in a Kabucy solvent is introduced into a silver halide emulsion layer by these methods, for example, Japanese Patent Publication Shoj/-32. It is also possible to use a dispersion method using a steel metal as described in Japanese Patent Application Laid-open No. 5I-RRI-173.

If the coupler has an acid group, such as calphone or sulfone, it can also be introduced into the hydrophilic colloid as an alkaline water bath.

Emulsion of the photosensitive material of the present invention! Gelatin is advantageously used as the binder or VF, 1M colloid that can be used in the layer or intermediate layer, but other hydrophilic colloids can also be used alone or together with gelatin.

Uninventively, gelatin, even if it has been treated with lime, is
Either one processed using R may be used. Details of gelatin manufacturing method
It is described in Macromolecular Research (Stories of Gelatin, published by Academic Press, 6I1.).

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material based on the invention. Good performance...Silver iodide is silver iodobromide containing less than 1 mol of silver iodide (D silver iodide). Particularly favorable is silver iodobromide containing 1 mol or less of silver iodide. It is chemical silver.

The average grain size of silver halide grains in a photographic emulsion (in the case of spherical or approximately spherical grains, it is the grain direct size; in the case of cubic grains, it is the principal t-rice grain size, and it is expressed as an average based on the projected area. ) is not particularly limited, but is preferably 3μ or less.

The particle size may be narrow or wide.

The silver halide grains in the photographic emulsion may have a regular crystal structure such as a cube or a helium, or may have a spherical or hemispherical shape.
It may have an irregular crystalline shape such as a plate shape, or it may have a composite shape of these crystalline shapes. It may also consist of a mixture of particles of various crystalline forms.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy to4 or more of the total projected area.

The silver halide grains may have different phases inside and on the surface. Also f! It may be a particle in which an image is mainly formed on the surface, or it may be a particle in which an image is mainly formed inside the particle.

The photographic emulsion used in the present invention is P, Glafkides.
Written by Chimie et Phyjique f'hot
ographique (published by Paul Monte1,
/ri 67), G, F.

f'photographic Emul by Duffin
sionChemistry ('i'he Foca
l Press, /P76 Yu2, V, L, Zelik
nnan e, 8□"JIMaking'an
dCoating Photographic Em
ulsion('l'he k”ocal Press
It can be adjusted using the method described in, e.g.

That is, any of the dispersion method, neutral method, ammonia method, etc. may be used, and the method for reacting the Loe static silver salt and the Loe bath halogen salt may include a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. Either of these may be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method of keeping pAgtl constant in a liquid phase in which silver halide is produced, that is, a so-called Chondrald double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more silver halide emulsions formed separately may be mixed and used.

Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. may be allowed to coexist during the process of silver halide grain formation or physical ripening. good.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example, H, 'rieser@'
aDie Grundlagender Photog
raphischen prozesse mit S eye be r-ha 1 ogen i den” (Aka
Demische Verlagsgesellsha
ft, /ri4ff) The method described on pages 47j to 73 can be used.

That is, a sensitization method using sulfur-containing compounds (e.g., thio (iHP, salts, thionyls, mercapto compounds, rhodanines) that can react with active gelatin or silver);
Reduction sensitization method using reducing substances (e.g. stannous salts, amines, hydrazine fermentation conductors, formamidine sulfinic acid, silane compounds); Noble metal compounds (e.g. total complex salts as well as Pt, Ir, Pd, etc.) Complex salts of metals in group ■ of the periodic table)
't-tributary metal sensitization methods can be used alone or in combination.

The photographic emulsion used in the present invention may be used during the manufacturing process of the light-sensitive material, during storage, or during photographic processing. Various compounds can be contained for the purpose of preventing or completely stabilizing photographic performance. In other words, azoles such as benzothiazolium salts, nitroimidazoles, nitrobeyzimidazoles, chlorobenzimidazoles,
Bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, pencitripzoles, nitrobenzotriazoles, mercaptotetrazoles (especially l-phenyl-j-mercaptotetrazole) ), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxadolinthion; azaindenes, such as triazaindenes, tetraazaindenes (particularly hydroxy-substituted (/, !, 3a), etc.);

7) Tetraazaindenes), Hunterazaindenes'
Many compounds classified as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, prevention of contact, and improvement of photographic properties (e.g.,
Various surfactants may be contained for various purposes such as development acceleration, contrast enhancement, sensitization, etc.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or accelerating development, for example, ren oxide in polyalcohol or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, etc. class anthonium salt compounds, urethane derivatives,
Gold may also be included, such as urea derivatives, imidazole derivatives, and 3-pyrazolidones.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or releasable synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability.

The photographic emulsion used in the invention contains methine dyes.
(Spectrally sensitized by other methods may be used. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine color patches, and holopolar dyes.
Cyanine dye, hemicyanine color patch, styryl dye υ and hemioquinol dye are used as ff1t. Particularly suitable dyes for M include cyanine dyes, merocyanine colorants, and complex merocyanine dyes. For these pigments, any of the nuclei commonly used in anine pigments can be used as a basic heteroartic ring nucleus. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, virol cedar, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei: and Nuclei in which aromatic hydrocarbon rings are fused to these nuclei, sokuchi, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadole nucleus, naphtho.

A xazole nucleus, a benzothiazole nucleus, a naphthothiazole cedar, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine colored pigments or composite merocyania pigments include nuclei having a ketomethylene structure, such as birazoline-ion nucleus, thiohydantoin nucleus, λ-thioki-length zolidine, ≠-dione nucleus, thiazolidine-, Hiro-dione cedar, rhodanine nucleus, Thiobarbir ell nucleus etc! ~ can be used for 3# ring nuclei with different members.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds containing tS with a nitrogen-containing heterocyclic group (for example, U.S. Patent
7 Co. No. 1), fragrance 1! j Organic acid formaldehyde condensates (for example, those described in US Pat. No. 3,703,110), cadmium salts, azaindenated compounds, etc. may also be included. The present invention provides at least λ
It can also be applied to multilayer, multicolor photographic materials having two different spectral sensitivities. Multi-I-natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer on a support. The order of these no's can be chosen arbitrarily as needed. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used in some cases. You can also do that.

In the same or other photographic emulsion layer or non-light-sensitive layer of the photographic light-sensitive material prepared using the dud #3At-, other dye-forming couplers, i.e. In the color development process, a compound that can be used to develop color by reactionary coupling with an aromatic primary amine (for example, phenylenediamine m4 form, aminophenol derivatives, etc.) may be used. For example, as a magenta coupler! -Pyrazolone coupler, pyrazolobenzimidazole coupler, pyrazolo [s, /-C)
(/.

λ, Hiro] triazole couplers, pyrazolo pyrazole couplers, pyrazolotetrazole couplers, open chain acryl acetonitrile couplers, etc. 6411. As yellow couplers, acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides),
These include meji, cyan couplers, naphthol couplers, and phenol couplers. These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized. The coupler may be either equivalent or equivalent to silver ion. Further, a colored coupler having a color correction effect or a 2-(so-called 1)I coupler which releases a development inhibitor upon development may be used.

In addition to f) IR couplers, colorless DIs in which the product of the coupling reaction is colorless and release a development inhibitor;
It may also contain an R coupling compound.ゎ工、Ka7. −
A compound that releases an inhibitor may be included in the light-sensitive material.

The coupler of the present invention and the above-mentioned couplers must be of two or more types in order to satisfy the n4% property required for photosensitive materials.
It is also possible to use the same compound in combination with different fc2
Of course, it may be added to more than one layer.

The photographic light-sensitive material of the present invention may contain an inorganic or M-organic hardener in the photographic emulsion layer and other hydrophilic colloid layers.

For example, chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds vlJC/, 3. r-Triacryloyl-hexahydro-s-triazine, l
, 3-vinylsulfonyl-2-propanoluna, etc.), active halogen compounds (2,≠-dichloro-6-hydroxy V
-s-) riazine), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

2. When the photosensitive material produced using the present invention contains dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer,
They may be mordanted, such as by cationic polymers.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid # derivative, an ascorbic lily derivative, etc. as a color antifoggant.

In the photosensitive material made using the #JAt of the present invention, an ultraviolet absorber may be added to the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (e.g., those described in U.S. Pat. 3riλ.

6♂/No.), benzophenone compounds (e.g., those described in JP-A No. 6-27!), Kuich-related ester compounds (e.g., U.S. Pat. No. 3,7a!, TOS', No. 3,707) , 37 Jr.), butadiene compounds (e.g., those described in U.S. Pat.

O1/-j, 222), or the benzoxidol compound el (e.g., U.S. Pat. No. 3,700,
≠! (described in item j) can be used. A UV-absorbing coupler (for example, an α-7-tole cyan dye-forming coupler), a UV-absorbing polymer, or the like may be used. These ultraviolet absorbers may be mordanted in specific layers.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for the purpose of preventing irradiation or other bridging purposes. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes: hemioxonol dyes and melonanine dyes are useful.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxphenol derivatives, and hibisphenols.

Photographic processing of layers comprising photographic emulsions made using the present invention may include, for example, Research Disclosure No. 4 λ
Any of the more well-known methods and known treatment liquids described on pages 1 to 30 can be applied. The processing temperature is usually chosen between /r'c and ro'c, but /I
The temperature may be as low as 0C or above RO'C.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiocyanate and thiocyanate, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (for example, Hiro-
Amino-N, N-diethylaniline, 3-methyl-V-
Amino-N, N-diethylaniline, V-amino-N-
Ethyl-N-β-hydroxy-7-ether aniline, 3-methyl-V-amino-N-ethel-f--β-hydroxy-7-etheraniline/, 3-methyl-g-aminoheter-N-β-methanesulfamide ether Aniline, Hiro-amino-3-methyl-N-ethyl-N-β-methoxyetheraniline, etc.) can be used.

Besides this, above, A, Mason Photograph
hicProcessing (:hemistry(
f”oca Press, 1266) P226~
22, U.S. Pat.

3. O/Evening issue, same 2. ! Riλ, 36 Hiro issue, Tokukai Akihiro! -2 KoyJi issue etc. may be used.

Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or anticapri agents such as bromides, iodides, and organic anticapri agents. etc. can be included. If necessary, water softeners, preservatives such as hydroxylamine, organic layering agents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, color mark-forming couplers, and competitors may be added. It may also contain couplers, fogging agents such as sodium boron hydride, auxiliary development systems such as l-phenyl-3-pyrazolidone, tackifying agents, polycarboxylic acid chelating agents, antioxidants, and the like.

After color development, the photographic emulsion layer is usually bleached.

The bleaching treatment may be carried out simultaneously with the multilayer treatment, or may be carried out separately. As a whitening agent, for example, iron (I[
), compounds of polyvalent metals such as cobalt (■), chromium (■), copper ([), peracids, quinones, nitroso compounds, etc. are used.

For example, ferricyanide, dichromate, iron CM) or organic complex salts of cobalt(III), such as ethylenediaminetetravinegar, nitrilotriacetic acid, /.

3-diamino-2-pro/7-minopolycarboxylic compounds such as nor40d or complex salts of organic acids such as citric acid, tartaric acid, and malic acid: persulfates, permanganates; nitronephenol, etc. are used. be able to. Among these, potassium ferricyanide, iron ethylenediaminetetraacetate (I
II) Sodium and ethylenediamine/four-fraud iron (II)
I) Ammonium is particularly useful. Ethylenediaminetetraacetic acid iron (III) complex salt also has -
It is also useful in bath whitening fixers.

The color photographic emulsion layer forming the dye image layer according to the present invention is coated on a flexible support such as plastic film, paper, or cloth commonly used in photographic light-sensitive materials. Useful as flexible supports are films A consisting of semi-synthetic or synthetic polymers such as cellulose acetate, sululose acetate butyrate, polystyrene, polyethylene terephthalate, polycarbonate, etc.; , polypropylene), etc., Ijl cloth, or 2-laminated paper.The support may be colored using a dye or pigment.It may be made black for the purpose of blocking light.

C When these supports are used for reflective materials, it is preferable to add a white pigment to the support or laminate layer. White pigments include titanium dioxide, barium sulfate,
Zinc oxide, zinc sulfide, calcium carbonate, antimony trioxide, silica white, alumina white, titanium phosphorus, etc. can be mentioned, and titanium trioxide, barium sulfate, and zinc oxide are useful for this purpose.

The surface of these supports is generally treated with an undercoat to improve contact with photographic emulsions and the like. The surface of the support may be treated by corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the primer treatment.

When these supports are used for reflective materials, a hydrophilic colloid layer containing a high density of white pigment may be further provided between the support and the emulsion layer to improve the whiteness and sharpness of the photographic image. can.

In the reflective material having the magenta coupler of the present invention, the support is a paper support laminated with a polymer (paper support is often used, but if a synthetic resin film kneaded with a white pigment is used, smoothness, gloss and In addition to improving sharpness, photographic images with particularly excellent saturation and dark areas can be obtained, which is particularly preferable.In this case, the synthetic resin film raw material is polyethylene terephthalate, nv cellulose, and the white pigment is barium sulfate. , titanium oxide is particularly useful.

After processing and drying, the photographic material of the invention can be laminated with a two-snap layer on the front and back sides. Plastic films for lamination include boreolefin,
Polyesters, polyacrylic esters, polyvinyl acetate, polystyrene, butadiene-styrene copolymers, polycarbonates, and the like are useful, especially polyethylene terephthalate, copolymers of vinyl alcohol and ethylene, polyethylene, and the like.

(Example) The present invention will be described below with reference to Examples, but the present invention is not limited thereto.

Example 1 The following magenta dye obtained by reacting the exemplified coupler (M-4) and the following developer in the presence of ammonium persulfate and potassium carbonate was added to an equal weight of exemplified metal (S-7) with ethyl acetate. After settling and evaporating the ethyl acetate as a co-solvent, the solution was added to the visible absorption spectrum.

As a comparative example of developing agent maze/red dye, the visible absorption absorption torque of a color patch solution prepared by dissolving the above magenta dye in an isoelectric amount of dibutyl phthalate was measured (Comparative Example 1). A clear liquid dissolved in coulometric illustrative compound @ (S-7) (Comparative example) and a solution dissolved in dibutyl heptalate (comparative example)
Comparative Example 3) were prepared and their visible absorption spectra were measured.

The above absorption vector is shown in Figure 1.

Compare magenta dye from Figure 1! - There is no significant change in the absorption spectrum of the magenta dye of the picyclo-y coupler whether it is dissolved in the phosphate ester solvent of the present invention or in dibutyl phthalate, but the magenta dye of the pyrazoloazole coupler of the present invention When dibutyl phthalate vrc is dissolved in the phosphate ester solvent of the present invention, the absorption rate is lower than when dibutyl phthalate vrc is dissolved.

It can be seen that the edge breakage on the long wavelength side of the vector is greatly improved. Furthermore, since the magenta dye of the pyrazoloazole coupler of the present invention does not have sub-absorption on the short wavelength side, the absorption spectrum when this magenta dye is dissolved in the phosphate ester solvent of the present invention is small in color photographs. It can be seen that the color reproducibility has been improved.

(The visible absorption spectrum was measured using a Hitachi self-recording spectrophotometer 3aom.
Measured using ) Example 2 Example coupler (M-1) was used as the magenta coupler, and example compound (S-24A) was added to this coupler 101.
20 f, acetic acid: r-fk, 2 tmim mira, ro
Aqueous solution J containing gelatin/Of, sodium dobuflubenzenesulfonate/, and Of dissolved in oc by heating
oorra to obtain a fine emulsified dispersion using a mechanical method. The total amount of this emulsified dispersion is Br! Silver chlorobromide emulsion 100 consisting of Q moles? (Including Ag&,,!ri1)
In addition, as a hardening agent, λ-corresponding compound, Hiro-dihydroxy-6
-Chloro-S-) riazine sodium salt (10 mj) was added and coated on a paper support laminated with polyethylene on both sides so that the silver coating amount was 200 μ/m2,
A sample was prepared by providing a gelatin layer on top of this coating layer. This 7″L is designated as sample A.

Next, in place of the above-mentioned exemplified compound (S-2ψ), exemplified compound (S-7), Gikoetherhexyl phthalate,
Samples were prepared in the same manner using ethylphenol for Ko and Hiroji tert. These samples are called sample B.
, C, D.

- As the magenta coupler, the following comparative coupler was used instead of the coupler (M-4) of Example 1,
Sample E was prepared using exemplified compound (S-2, P) as a solvent.

These samples A-EK10oOCMS were subjected to wet exposure and processed with the following processing solution.

α Developer solution benzyl alcohol l! Gijie Terent Triaminta Vinegar m s tKBr
O, HirotNa280a
z yN a 2 CO3
J Of Hydroxyamine Sulfate 21 Hiro-1 Mino-
3-Methyl-N- /- (methanesulfonamide) Etheraniline・3/λH2SO4・H2O Hiromu,! ? Adjust to 1000 with water pH 10, / Kenshiro fixer ammonium thiosulfate (70wt%) / 10% Na 2803 rfN
a (Fe (EDTA)) ll0fE
DTA Hiro 1 Water/θ0
0 male pi-i 6. ff Four physical process temperature Time Developing solution 33°C 3 minutes 30 seconds Bleach-fixing solution 33°C 7 minutes 30 seconds Water Washing
2Ir ~ 3pm 00 3 minutes The color image of each sample thus obtained was attached to a Hitachi self-recording spectrophotometer Model 3 Hiro θ with an integrating sphere and λmax was 1. The reflection vector at O was measured and the results shown in Figure 2 were obtained (the reference side is magnesium oxide).

As a result, for the pyrazoloazole coupler of the present invention, the high boiling point phosphoric acid ester solvent of the general formula [II] of the present invention has desirable spectral absorption characteristics of the magenta color former for subtractive color photography. 600 nm or more), and there is no side absorption unlike pyrazolone couplers, and there is little absorption on the short wavelength side, giving a spectral absorption curve favorable for color reproduction.

Example 3 As described in Table I, the first layer (bottom layer) to the seventh layer (top layer) were coated on double-sided polyethylene laminated paper to prepare color photographic materials ~J.

The coating solution for each emulsion layer was prepared according to the method of Example 2 above.

These types of samples (F-J) were attached with a B-G-kL three-color separation filter and exposed and processed in the same manner as in Example 2.

Among the samples thus obtained, the IG color images were bright and highly saturated. However, other samples H,
I and J had low chroma, and sample H9 had a violet color tone, which was disadvantageous in terms of color reproducibility.

Example 4 Sample F'-JKB-G prepared in Example 3 was attached with a three-color separation filter, given the g element in the same manner as in Example 2, and subjected to the same treatment. The sample thus obtained was subjected to a fading test for 3 weeks using a fluorescent bleaching device (1,000 lux). The results are shown in Table ■.

As a result, it was found that the use of a high boiling point bath medium represented by the general formula ([1) for the pyrazoloazole compound of the present invention is also effective for improving the fastness of color images.

table "

[Brief explanation of the drawing]

FIGS. 1 and 2 show absorption spectra of maze/recolor development rates. In FIG. 1, the absorption spectra of Comparative Example λ and Comparative Example 3 almost overlap on the short wavelength side, even at the absorption maximum rainbow. Furthermore, in FIG. 2, A, B, and D almost overlap on the shorter wavelength side than the absorption maximum. Patent applicant: Fuji Photo Film Co., Ltd.
No change in content) Figure 1 0m Figure 2 0m Procedural amendment 1, matter □ Indication of cow Showa, ty year Patent application No. 110
No. 243 No. 2, Name of the invention Silver halide color photographic light-sensitive material 3, Relationship with the person making the amendment case Patent applicant contact information 10
6 Fuji Photo Film Co., Ltd., Tokyo Head Office, 2-26-30 Nishi-Azabu, Minato-ku, Tokyo Telephone: (406) 2537 4. Subject of amendment Description and drawings, contents of amendment Engraving of specification and drawings (no change in content) I will submit it. 1.Display of the incident Showa! 1st year patent application zo-2t
S No. 2, Name of the invention Silver halide color photographic light-sensitive material 3, Relationship with the case of the person making the amendment Patent applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Contact address 2-26-30 Nishiazabu, Minato-ku, Tokyo 106 4. Subject of amendment The description in column 5 of "Detailed Description of the Invention" of the description and the section of "Detailed Description of the Invention" of the description of contents of the amendment shall be amended as follows. 1) Insert "," before "sulfur atom" in the third line of page 1j. 2) Insert the following after (M-34) on page 11. (M-37) sHt formula t) (M-31r) (M-32) C8H near (t) (M-g0) 3) Correct with the chemical structural formula of the second page (S-da). 4) The chemical structural formula on page 22 (5--t) is corrected as follows. 5) Correct with the chemical structural formula on page 31 (S-/j). 6) Correct "wave color range" in the 7th line from the bottom of page 33 to "wavelength range". 7) Correct “lime treatment” in the first line of page 36 to “lime treatment”. 8) Insert "For photographic light-sensitive materials for photography" after "Good." in the ioth line of page 3. 9) Add the 3rd line on page 13 after "Silver halide." [For direct-view photographic materials such as color panels, preferred silver halide is chloride iodine containing 3 molt or less silver iodide. Silver bromide, silver iodochloride or silver iodobromide or silver chlorobromide. ” is inserted. 10) Page 33 Chemical structural formula of developer [Corrected as follows. 11) No. 1! ! Page Correct the chemical structural formula of magenta dye to [magenta dye H3]. 12) No. 12) Correct the chemical structural formula of the comparative magenta dye on page [Comparative magenta dye α].

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material comprising at least one silver halide emulsion layer provided on a support, wherein the silver halide emulsion layer contains a compound represented by the following general formula [I]. At least one type of magenta coupler represented by the following general formula [
1. A silver halide color photographic material characterized in that it is co-dispersed with at least one high-boiling point organic solvent represented by [II]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 and R^2 represent a hydrogen atom or a substituent, and Represents a group that can be separated by a coupling reaction. Z represents a nitrogen atom or a carbon atom, and when Z is a carbon atom, a substituent other than a hydrogen atom may be bonded to this carbon atom.) General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^3, R^4, and R^5 each represent an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. However, R^ 3. The total number of carbon atoms in the groups represented by R^4 and R^5 is 12 to 60.)