JPH0367251A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color reproducibility and the light fastness of a magenta dyestuff image by forming a green-sensitive silver halide emulsion layer contg. a specified compd. and a specified magenta coupler on a support. CONSTITUTION:At least one green-sensitive silver halide emulsion layer contg. a compd. represented by formula I and a magenta coupler represented by formula II is formed on a support. In the formula I, each of R1 and R2 is H or alkyl, each or R3 and R4 is H, alkyl, etc., each or R5 and R6 is H, alkylacyl, etc., X is a divalent group having C as a constituent atom of the 6-membered ring and n is 0, 1 or 2. In the formula II, Z is a group of nonmetallic atoms required to form an N-contg. hetero ring, X is H or a group which is released by a reaction with the oxidized product of a color developing agent and R is a substituent bonding to the N-contg. hetero ring through C bonding to H. Color reproducibility is improved and the fading of a magenta bye image due to light is prevented.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, the present invention relates to a silver halide color photographic light-sensitive material, in which a dye image is stable against heat and light, and the occurrence of staining is prevented. This invention relates to silver color photographic materials.

[Prior art]

Conventionally, when a silver halide color photographic light-sensitive material is imagewise exposed and color developed, an oxidized product of an aromatic primary amine color developing agent and a coloring agent undergo a coupling reaction, resulting in the production of, for example, indoenol, indoenol, and indoenol. It is well known that aniline, indamine, azomethine, phenoxazine, phenazine, and similar dyes can be used to form color images. In such photographic systems, a subtractive color reproduction method is usually adopted, and color forming agents having additional colors, namely yellow magenta and magenta, are added to blue-sensitive, green-sensitive and red-sensitive light-sensitive silver halide emulsion layers, respectively. A silver halide color photographic material containing a coupler that develops cyan color is used.

Examples of couplers used to form the yellow image include acylacetanilide couplers, and examples of couplers used to form magenta images include pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, and indacilone couplers. is known, and as a coupler for forming a cyan image, for example, a phenol or naphthol coupler is generally used.

It is desired that the dye image obtained in this way does not change color or fade even if it is exposed to light for a long time or stored under high temperature and high humidity. It is also desired that the uncolored areas of silver halide color photographic materials (hereinafter referred to as color photographic materials) do not turn yellow (hereinafter referred to as Y stain) due to light or moist heat.

However, in the case of magenta couplers, fading by light in uncolored areas, Y-stain due to wet heat, and fading of color in dye image areas by light is much greater than with yellow couplers or cyan couplers, and this often poses a problem.

Couplers commonly used to form magenta dyes are 5-pyrazolones. The dye formed from this magenta coupler of 5-pyrazolones has a wavelength of 550 nm.
In addition to the main absorption in the vicinity, a major problem is that it has a secondary absorption in the vicinity of 430 na+, and various studies have been conducted to solve this problem.

Magenta couplers having an anilino group at the 3-position of 5-pyrazolones have small side absorption and are particularly useful for obtaining color images for printing. For details on these techniques, see, for example, U.S. Patent No. 2,343,703 and British Patent No. 1.
, No. 059,994, etc.

However, the above-mentioned magenta coupler has the disadvantage that the image storage property, particularly the fastness of the dye image to light, is extremely poor, and the Y-stain in the uncolored area is large.

As another means for reducing the side absorption near 430 nIl of the above magenta coupler, British Patent No. 1.047.
Pyrazolobenzimidazoles described in U.S. Pat. No. 612, indasilones described in U.S. Pat. No. 3,770,447, and U.S. Pat.
IH- described in No. 2.418 and No. 1,334,515
Pyrazolo[5,1-cl-1,2,4-triazole type coupler Research Disclosure
arch Disclosure) 24531 (19
IH-pyrazolo[1,5-b]-1,2 described in 84)
, 4-triazole coupler, Re5earch D
IH-pyrazolo[1,5-cl-1,2,3-triazole type coupler described in ISCLOSURE 24626 (1984), JP-A-59-162548, Re5
H(-imidazo[1,2-b]pyrazole type coupler, Re5earch Disclosure 24531 (above))
24230 (1984), IH-pyrazolo[1
,5-b] Pyrazole coupler Re5search
Magenta couplers such as 1) 1-pyrazolo[1,5-d1 tetrazole couplers described in Disclo-sure 24220 (1984) have been proposed. Among these, IH-pyrazolo[5゜1-cl-1,2,4-triazole type coupler IH-pyrazolo[1,5-b]
-1,2,4-triazole type coupler IH-pyrazolo[L5-cl-1,2,3-triazole type coupler) 1-imidazo[1,2-bl pyrazole type coupler
The dye formed from the 111-pyrazolo[1,5-b] pyrazole coupler and the IH-pyrazolo[1,5-dl tetrazole coupler has a subabsorption near 430 nm that is 5-pyrazolo[1,5-b] having an anilino group at the 3-position. It is significantly smaller than pigments formed from pyrazolones, which is preferable in terms of color reproduction, and furthermore, it has the advantage that the occurrence of Y-stin in uncolored areas is extremely small when exposed to light, heat, and humidity.

However, the light fastness of azomethine dyes formed from these couplers is extremely low, and in addition, the dyes are easily discolored by light, which significantly impairs the performance of color photographic materials, especially printed color photographic materials. .

Furthermore, in JP-A No. 59-125732, IH -pyrazolo [5,
A technique has been proposed to improve the light fastness of the magenta dye image obtained from lyazole type magenta force puller force).

However, it has been recognized that even the above techniques are still not sufficient to prevent the magenta dye image from fading due to light, and moreover, it is almost impossible to prevent discoloration due to light.

[Purpose of the invention]

The present invention has been made in view of the above problems, and a first object of the present invention is to provide a color photographic material with excellent color reproducibility and significantly improved light fastness of magenta dye images. It is in.

A second object of the present invention is to provide a color photographic material having a magenta dye image that is less discolored by light.

A third object of the present invention is to provide a color photographic material in which the occurrence of Y-stin in areas that are not colored by light is prevented.

[Structure of the invention]

The above object of the present invention is to provide at least one green-sensitive silver halide emulsion layer containing a compound represented by the following general formula [T] and a magenta coupler represented by the following general formula (M-1) on a support. This is achieved by a silver halide color photographic light-sensitive material characterized by having the following characteristics.

General formula [T] In the formula, R1 and R3 represent a hydrogen atom or an alkyl group, R3
, R- is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, R6, Ra is a hydrogen atom, an alkyl group, an aryl group, an acyl group, or an alkoxycarbonyl group, and X is a constituent atom of the 6-membered ring. A divalent group having a carbon atom,
n represents 0.1 or 2.

General Formula [M-I] In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing hetero, 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.

R is bonded to one hydrogen atom. Alternatively, it represents a substituent that is bonded to the nitrogen-containing heterocycle through a carbon atom that is not bonded to a hydrogen atom.

The compound represented by the general formula [T] will be explained in detail below.

The alkyl group represented by R3 or R1 is preferably a methyl group.

The alkyl group represented by R3-R6 has 1 to 4 carbon atoms.
The aryl group is preferably a phenyl group.

The heterocyclic group represented by R1 or R is preferably a thienyl group.

The alkoxycarbonyl group represented by R,, R1 is preferably one having 2 to 19 carbon atoms, and the acyl group is preferably an acetyl group or a benzoyl group.

Each prefecture represented by R3-R6 includes those having a substituent, and when R,, R, is phenyl, preferred substituents include a halogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, and a cyclohexyl group. group, an alkoxy group having 1 to 18 carbon atoms, a phenylalkyl group having 7 to 9 carbon atoms, and a hydroxyl group. When R6゜R6 is an alkyl group, preferred substituents include a hydroxyl group, a phenyl group, and a carbon B
Examples thereof include a 1-12 alkoxy group, a benzoyloxy group, and an alkylcarbonyloxy group having 2 to 18 carbon atoms.

Preferred divalent groups represented by X) C=NN
) l-anru.

Here, R7 is a hydrogen atom, alkyl having 1 to 4 carbon atoms, Rm
is a hydrogen atom, methyl group, phenyl group, P (OXO dealle), (alkyl has 1 to 4 carbon atoms), allyloxy group, benzyloxy group, alkoxy group with 1 to 12 carbon atoms, Rm is a hydrogen atom, OR , allyloxy group, benzyloxy group, alkoxy group having 1 to 12 carbon atoms, acyloxy group, acylamino group, R1° is a hydrogen atom, an acyl group, R1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, CH
, OR, , R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and RI4 represents a hydrogen atom or an acyl group.

Examples include an acyloxy group represented by R5, an acyl group in an acylamino group, an acyl group represented by R, , R, , and a C═NNH-acyl group represented by X.

Here, R1-Ra, n has the same meaning as above, the acyl group is a benzoyl group, aQ having 2 to 18 carbon atoms, m is 0 or l, m≧Q, and R13 is alkylcarbonyl. In addition to groups, preferable examples include simple bonds, divalent bonding groups (for example, alkylene groups having 1 to 14 carbon atoms (p is 0
or l) group, R5 is a hydrogen atom, an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms), an acyl group, an alkoxyoxalyl group, a sulfonyl group, a carbamoyl group, R
16, Rlt is a hydrogen atom, an alkyl group, an aryl group,
R16 is water, R+7 has the same meaning as above, and Ro represents -R2+ atom and 1 alkyl group. ) represents.

Specific examples of the compound represented by the general formula [T] 13 4 30 -31 The compound represented by the general formula [T] can be made into synthetic leather by a known method. For example, a method of acylating a 4-hydroxytetrahydrothiobilane compound with an acid chloride, and a method of reacting a 4-ketotetrahydrothiobilane compound with a diol to produce a 1,5-dioxa-9-thiaspiro[5,5]-undecane compound. , a method for obtaining a 1,4-dioxa-8-thia-spiro[4,5]-decane compound, etc. can be used.

The compound represented by the general formula [T] is added to the green-sensitive silver halide emulsion layer together with the magenta coupler, and the method for adding it is described in US Pat.
, No. 170, No. 2,801.171, No. 2,272,
191 and No. 2,304,940, it is preferable to dissolve it in a high boiling point solvent, optionally in combination with a low boiling point solvent, disperse it, and add it to the hydrophilic colloid solution. If necessary, there is no problem in using a coupler hydroquinone derivative, an ultraviolet absorber, or a known dye image fading preventive agent.
Examples include compounds described in No. 1, etc. At this time, there is no problem even if two or more kinds of compounds of the present invention are mixed.

The amount of the compound represented by the general formula [T] added is 1.
The amount is preferably 5 g or less, particularly preferably 0.01 to 0.6 g.

In the general formula [M-1), there are no particular limitations on the substituent Ro that the ring formed by 2 may have, but
Typically, alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio,
Six groups include alkenyl, cycloalkyl, etc.
In addition, (n) chloroalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, anlu, carbamoylalkoxy, aryloxy, heterocyclicoxy, siloxy, acyloxy, carbamoyl oxine, amino, alkylamino, imide, ureido , sulfamoylamino,
Also included are the six groups of 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 Ro preferably has 1 to 32 carbon atoms, and may be linear or branched.

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

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

Examples of the sulfonamide group represented by Ro 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 Ro include the alkyl group and aryl group represented by R above.

The alkenyl group represented by Ro has 2 to 32 carbon atoms.
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 carbon atoms.
-12, especially 5-7 are preferred.

Sulfonyl groups represented by Ro include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and aryloxyphosphonyl groups. , arylphosphonyl group, etc.; As an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc.; As a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc.; As a sulfamoyl group, an alkylsulfamoyl group,
Arylsulfamoyl groups, etc.; Acyloxy groups include alkylcarbonyloxy groups, arylcarbonyloxy groups, etc.; carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc. : Examples of the sulfamoylamine group include alkylsulfamoylamine 7 groups, arylsulfamoylamino groups, etc.; As the heterocyclic group, 5- to 7-membered ones are preferable, and specifically, 2-furyl group, 2-thienyl group, etc. group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.; as the heterocyclic oxy group, those having a 5- to 7-membered heterocycle are preferred, for example 3.
4,5.6-tetrahydropyranyl-2-oxy group, 1
-Phenyltetrazole-5-oxy group, etc.; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-penzothiazolylthio group, 2.4-diphenoxy- 1,3,5-1 lyazole-6 monothio group, etc.: Siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide group includes succinimide group, 3-heptadecylsuccinimide group , 7-talimide group, glutarimide group, etc.; spiro compound residues include spiro[3,31-hebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo[2°2.1
] Hebutane-! -yl, tricyclo [3,3゜1.1
Examples include 3,11 decane-1-yl, 7,7-dimethyl-bicyclo[2,2,I]heptane-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, acyloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyl. Oxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy,
Alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl, (R1' is the same as the above Ro 2/ has the same meaning as 2 above, and R, / and R, / represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group.), but preferably a halogen atom, Especially the chlorine atom.

Examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, imidazole ring, triazole ring, and tetrazole ring.

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

General formula [M ■] In the above general formulas [M-1 to [M-■], R5 is the above R
and R2-R6 and X have the same meanings as Ro and X above.

Also, preferred among the general formulas [M-I] are those represented by the following general formula [M-■].

τ space ~ jiniyuy General formula [M-■] In the formula, R, , X and Zl are general formula [M-1] j: 8 R
, X and 2.

Among the magenta couplers represented by the general formulas [:M-4) to [M-■], particularly preferred ones are those represented by the general formula [M-'f
It is a magenta coupler represented by f).

The most preferred substituents R and R3 on the heterocycle are those represented by the following general formula [M-■].

General formula [M-■] R.

R1゜-C- Ro where Rs, R+. and Ro each have the same meaning as R above.

Also, the above R,,R,. and R1, for example R9
and R1° may be bonded to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R1, may be bonded to the ring to form a bridged hydrocarbon compound residue. You may.

Among the general formulas [M-I, (j) Rt~
When at least two of R0 are alkyl groups, (ii) one of Rs to R0, for example R11, is a hydrogen atom, and the other two, R5 and R3o, combine to form a cycloalkyl group with the root carbon atom. When forming, it is.

Furthermore, it is preferable among (i) that two of R9 to R are alkyl groups and the other one is a hydrogen atom or an alkyl group.

In addition, the substituents that the ring formed by 2 in the general formula [M-I] and the ring formed by Zl in the general formula [M-■] may have, and the general formula % formula % the following general formula [ Those represented by M-X) are preferred.

General formula [M-X] R1□-302-R.

In the formula, RI2 represents an alkylene group, and R1 represents an alkyl group, a cycloalkyl group, or an aryl group.

The alkylene group represented by R12 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and it does not matter whether the straight chain has one branch or not.

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

-3 of the magenta coupler shown below as [:M-I) -6 C. H mouth I3 -14 5 6- 2 CH3 7 8 9 0 5 6 CH.

CH.

CH.

M-30 M, -31 -N-N 4 5 C++ *Hzs 7- Also, the coupler is described in the Journal of the Chemical
Society 4 (Journal of the Ch
chemical Society), Perk
in) I (1977), 2047-2052, U.S. Patent No. 3,725,067, JP-A-59-99437
No. 58-42045, No. 59-162548,
No. 59-171956, No. 60-33552, No. 6
No. 0-43659, No. 60-172982 and No. 60
- Synthetic leather can be made by referring to No. 190779 etc.

The couplers of the present invention typically have lX per mole of silver halide.
10-' mole - 1 mole, preferably l x 10-''
It can be used in a range of -8 mol x 10-' mol.

The couplers of the present invention can also be used in combination with other types of magenta couplers.

The high boiling point organic solvent used for dispersing couplers etc. has a boiling point of 15
Refers to an organic solvent having a temperature of 0°C or higher, and its type is not particularly limited, such as esters such as phthalate esters, phosphate esters, and benzoate esters, organic acid amides,
Examples include ketones and hydrocarbon compounds.

Among high boiling point organic solvents, the dielectric constant at 30°C is 6.
Those having a dielectric constant of 6.0 or less and 1.9 or more and a vapor pressure of 0.5+saHg or less at 100° C. are more preferable, and phthalate esters or phosphoric esters are particularly preferable.

Further, two or more types of high boiling point organic solvents may be used in combination.

Examples of phthalic acid esters advantageously used in the present invention include those represented by the following general formula (S-1).

General Formula (S-1) In the formula, R1 and R2 each represent an alkyl group, an alkenyl group, or an aryl group. However, the total number of carbon atoms in the groups represented by R1 and R2 is 12 to 32. More preferably, the total number of carbon atoms is 16 to 24, and still more preferably 18 to 24.

In the present invention, R1 and R2 of the general formula (S-1)
The alkyl group represented by may be linear or branched, such as butyl group, pentyl group, hexyl group, 2-ethylhexyl group, 3,5,51-limethylhexyl group, octyl group, nonyl group, decyl group, These include dodecyl group, tetradecyl group, hexadecyl group, and octadecyl group. R3
The aryl group represented by and R2 is, for example, a phenyl group,
Examples of the alkenyl group include a naphthyl group, and examples of the alkenyl group include a hexenyl group, a heptenyl group, and an octadecenyl group.

These alkyl groups, alkenyl groups and aryl groups are
Substituents for alkyl and alkenyl groups include, for example, halogen atoms, alkoxy groups, aryl groups, aryloxy groups, alkenyl groups, alkoxycarbonyl groups, etc. Examples of substituents of the group include halogen atoms,
Examples include alkyl groups, alkoxy groups, aryl groups, aryloxy groups, alkenyl groups, and alkoxycarbonyl groups.

In the above, R1 and R2 are preferably alkyl groups, such as 2-ethylhexyl group, 3,5.5-trimethylhexyl group, n-octyl group, n-nonyl group, etc.

Phosphoric esters advantageously used in the present invention include those represented by the following general formula C8-2).

General Formula (S-2) In the formula, R3R4 and R6 each represent an alkyl group, an alkenyl group, or an aryl group. However, R3R4 and R5
The total number of carbon atoms in the group represented by is 24 to 54,
Preferably it is 27 to 36.

The alkyl group represented by R3R' and Rs in general formula (S-2) is, for example, a butyl group, a pentyl group, a hexyl group, a 2-
Ethylhexyl group, heptyl group, nonyl group, decyl group,
Dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, nonadecyl group, etc.; examples of aryl groups include phenyl group, naphthyl group, etc., and examples of alkenyl groups include hexenyl group, heptenyl group,
Such as octadecenyl group.

These alkyl groups, alkenyl groups and aryl groups are
It also includes those having single or multiple substituents. Preferably R'R' and R% are alkyl groups, such as 2-ethylhex, sil, n-octyl, 3,5.5
-trimethylhexyl group, n-nonyl group, n-decyl group, 5ec-decyl group, 5ec-dodecyl group, t-octyl group, and the like.

Typical specific examples of high boiling point organic solvents preferably used in the present invention are shown below, but the present invention is not limited thereto.

-t -2 C,H.

S-5 ! 3-11 -7 CI(scHcJs C! H.

3 -14 -15 General formula (To) -17 -19 -21 Examples of the high-boiling organic solvent advantageously used in the present invention i:8 include those represented by the following general formula (To). , R, , R, and R3 each represent an alkyl group or an aryl group, and Q, m, and n each represent 0 or 1,
Q, m and n are never 1 at the same time.

The alkyl group represented by R, R2 and R3 in the above general formula (To) may be linear, branched or cyclic, and the alkyl group may have a substituent.

Examples of unsubstituted alkyl groups include alkyl groups having 1 to 20 carbon atoms, preferably 1 to 18 carbon atoms, such as ethyl group, butyl group, pentyl group, cyclohexyl group, octyl group, dodecyl group, heptadecyl group, octadecyl group, etc. .

Examples of the substituent of the substituted alkyl group include an aryl group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a sulfamoyl group.

The aryl group represented by R, , R, and R1 in the above general formula [T O) is a phenyl group or a naphthyl group, which may have a substituent, for example, a carbon number of 1 to 18
up to, preferably up to 1-12 alkyl groups, with 1 carbon number
-12 alkoxy groups, amino groups mono- or di-substituted with alkyl groups having 1 to 12 carbon atoms, 1 to 12 carbon atoms
These include amino groups, halogen atoms, hydroxy groups, and amino groups substituted with acyl groups.

Specific examples of the compound represented by the general formula (To) used in the present invention are shown below, and the present invention applies to these compounds (T.

(T.

(T.

(T.

(T.O. Shi8111 (To-10) (TO-11) (T O-20) (TO-12) (T.

13) (T.

22) (T.

14) (T O-15) (T.

24) (T.

16) (To-17) (T.

26) (T.O. 18) (T O-19) (T.

(T.

(To-7) (To-9) Shil! 11 wealth S (T.

21) (T O-23) (To-25) (T.

27) (T.

28) (T O-30) (T.

31) (T O-33) (To-41) (TO-42) (T O-43) (To-44) (T O-45) (T O-46) (T O-29) (T.

32) (T.

34) (T O-35) (TO-37) (T.

38) (To-39) (T O-40) (T O-47) (T.

48) (TO-49) (To-50) (To-51) (To-35) Shih3 (T.

52) (T O-53) (T.

54) (T O-55) (T O-56) (T.

65) CCsH+s'P-0 (T.

67) (T O-69) (C+.11□su "P-0 (T.

71) (CI211□k P -0 (T O-73) (T.O. 75) (T.

66) CCsH1r 5P-0 (To-68) (To-70) (i C+aH□tetP-0 (T.

72) CC+-H2m) "P-0 (T.O. 74) (TO-76) (T.

57) (T.

58) 1 (C11160CO(C1lz)+a:)rP 0C
tlL(T.

59) 1 ((C+H*)z NC0(CHz)a3'z P-O
C+zllxs(T.

60) (To-61) (T.

62) (C211s + rP = 0 (C, 111 "P=0 (T.

63) (T.

64) "nHJ"P-0 (CaH++chi “P-0 (T.

77) (T.O. 78) (T.

79) (T.

80) ((Czlls)2Nco(CHfte+o), P-0(
T.

81) (T.

82) (T.

83) 211° (To-84) (T.

85) (To-86) (T O-87) (T.O. 88) (T.

89) The amount of the high-boiling organic solvent used is preferably 0.1"10m+2, particularly preferably 0.1 to 5-5, per 1 g of coupler.

Examples of high-boiling organic solvents that may be used in combination with the above-mentioned high-boiling organic solvents include phenol derivatives that do not react with oxidized developing agents, phthalic esters, phosphoric esters, citric esters, benzoic esters, alkylamides, fatty acid esters, An organic solvent having a boiling point of 150°C or higher, such as trimesic acid ester, is used.

When the light-sensitive material of the present invention is used for multiple colors, examples of yellow couplers include acylacetanilide-based ones,
As the cyan coupler, phenol-based or naphthol-based couplers can be used.

The arrangement of each silver halide emulsion layer is a blue-sensitive silver halide emulsion layer containing a yellow coupler in order from the support side, and the blue-sensitive silver halide emulsion layer containing a yellow coupler in order from the support side. A silver halide emulsion layer, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a red-sensitive silver halide emulsion layer containing a cyan coupler are preferable. In order from the support side, a blue-sensitive silver halide emulsion layer containing a yellow coupler, a green-sensitive silver halide emulsion layer containing a compound represented by the general formula [T], and a magenta coupler represented by the general formula [M-1], a non-photosensitive intermediate layer containing an ultraviolet absorber, a red-sensitive silver halide emulsion layer containing a cyan coupler, a non-photosensitive layer containing an ultraviolet absorber,
Preferably, a protective layer is provided.

As the support, a resin-coated paper support or a polyethylene terephthalate support containing a white pigment is preferably used.

As the ultraviolet absorber, those represented by the following general formula (U-1) are preferred.

General formula (U) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nitro group, or a hydroxyl group, respectively.

The six groups represented by R1-R1 include those having substituents.

Among the groups represented by R8 and R1, hydrogen atoms, S alkyl groups, alkoxy groups, and aryl groups are preferred, and hydrogen atoms, alkyl groups, and alkoxy groups are particularly preferred.

Among the groups represented by R3, hydrogen atoms, halogen atoms, alkyl groups, and alkoxy groups are particularly preferred.

Among R1-R1, at least one is preferably an alkyl group, and more preferably at least two are alkyl groups. Moreover, it is preferable that at least one of Rl-Rs is a branched alkyl group.

A typical example is shown below.

2 In the above general formula Cu1t, R6Rz and R1 are preferably added in the amount of the compound represented by the general formula (U) from 0.1 to 300% by weight based on the binder of the layer to which the compound is added, and further 1 ~200% by weight is preferred.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any material used in emulsions can be used, but those with a silver chloride content of 90 mol % or more are particularly preferred, a silver bromide content of 10 mol % or less, and a silver iodide content of 0.
It is preferably 5% mole or less. More preferably,
It is silver chlorobromide with a silver bromide content of 0.1 to 2 mol%.

The silver halide grains of the present invention may be used alone, or
It may be used in combination with other silver halide grains having different compositions. Further, it may be used in combination with silver halide grains having a silver chloride content of 10 mol % or less.

In addition, in the silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more according to the present invention, the silver chloride content in the total silver halide grains contained in the emulsion layer is The proportion of silver chloride grains of 90 mol% or more is 60% by weight or more, preferably 80% by weight or more.

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

There is no particular restriction on the particle size of the silver halide grains of the present invention, but in consideration of other photographic performance such as rapid processability and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.2 μm to 1.6 μm.
It is in the range of 25 to 1.2 μm. The above particle size can be measured by various methods commonly used in the technical field. A typical method is Loveland's "Particle Size Analysis Method J (A, S, T, M, Symposium on Light Microscopy, 195
5, pp. 94-122) or “Theory of Photographic Process” (
Mies and James, 3rd edition, published by Macmillan (1966), Chapter 2).

The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.

Preferably, the silver halide grains are monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less in the grain size distribution. Here, the coefficient of variation is
This is a coefficient indicating the breadth of particle size distribution, and is defined by the following formula.

Here, rl represents the particle diameter of each particle, and nl represents the number thereof.

The grain size here refers to the diameter in the case of spherical silver halide grains, or the diameter when the projected image is converted into a circular image of the circumferential area in the case of grains with shapes other than cubic or spherical. represent.

The silver halide grains used in the emulsion of the present invention can be prepared by acidic method.
It may be obtained by either the neutral method or the ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced.

The method of creating the seed particle and the method of growing it may be the same or different.

The soluble silver salt and the soluble halogen salt may be reacted by any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but those obtained by a simultaneous mixing method are preferred. Furthermore, as a form of simultaneous mixing method,
It is also possible to use the pAg-chondrol double jet method described in No. 48521 and the like.

Furthermore, if necessary, a silver halide solvent such as thioether may be used. Further, compounds such as mercapto group-containing compounds, nitrogen-containing heterocyclic compounds, or sensitizing dyes may be added during the formation of silver halide grains or after the completion of grain formation.

Any shape of the silver halide grains according to the present invention can be used. One preferable example is a cube having (1001 plane) as a crystal surface.

Also, U.S. Patent Nos. 4,183,756 and 4,225,6
No. 66, JP-A-55-26589, JP-A-55-42
737, The Journal of Photographic Science (J, Photogr, Sci,), 2
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literature such as 1.39 (1973) and used. Furthermore, particles having twin planes may be used.

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

The silver halide grains used in the emulsion of the present invention may contain cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, Metal ions can be added to the interior of the particles and/or on the surface of the particles by using iron salts or complex salts, and reduction can be increased inside the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. Can give a sensitive core.

In the emulsion containing the silver halide grains of the present invention (hereinafter referred to as the emulsion of the present invention), unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or the unnecessary soluble salts may be left in the emulsion. . In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the emulsion of the present invention may be grains in which the m-image is mainly formed on the surface, or may be grains in which the m-image is mainly formed inside the grain. Preferably, the particles are particles on which latent images are mainly formed.

The emulsion of the present invention is chemically sensitized by conventional methods.

After exposure, the light-sensitive material of the present invention can be subjected to a process including at least a color development process and a desilvering process to give a dye image, but preferably, after exposure, a color development process is performed, and then a bleach-fixing process is performed. This treatment method involves washing with water or stabilizing.

In the color development process, a color developing agent is usually contained in a color developing solution, but some or all of the color developing agent is incorporated into a color photographic light-sensitive material, and color development with or without a color developing agent is carried out. It also includes processing with a developer.

The color developing agent contained in the color developing solution is an aromatic primary amine color developing agent, and includes aminophenol derivatives and p-phenylenediamine derivatives, with p-phenylenediamine derivatives being particularly preferred. These color developing agents can be used as salts of organic and inorganic acids;
For example, hydrochloride, sulfate, p-)luenesulfonate, sulfite, oxalate, benzenesulfonate, etc. can be used.

These compounds are generally about 0 for color developer 112.
．． Concentrations of from 1 to about 30 g, preferably from about 1 g to about 15 g per color developer 1a, are used.

Particularly useful primary aromatic amine color developers include N, N-
A dialkyl-p-phenylenediamine compound,
Alkyl groups and phenyl groups may be substituted or unsubstituted. Among them, examples of particularly useful compounds include N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, and 2-amino- 5-(N-ethyl N-dodecylamino)
-Toluene, N-ethyl-N-β-methanesulfonamidoethyl- aniline sulfate, N-ethyl-N-β-hydroxyethylaminoalinine, 4-amino-3-methyl-N,N-
Examples include diethylaniline, 4-amino-N-(2-methoxyethyl)-Nethyl-3-methylaniline-p-toluenesulfonate, and the like.

Further, the above color developing agents may be used alone or in combination of two or more. Further, the color developing solution may contain commonly used alkaline agents such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium metaborate, or borax, and may further contain various additives. agents, such as alkali metal halides, such as potassium bromide or potassium chloride,
Or development tJ! It may contain a binder such as citradinic acid, and a preservative such as hydroxylamine, polyethyleneimine, glucose or a sulfite such as sodium salt or potassium salt. Furthermore, various antifoaming agents and surfactants, methanol, N,N-dimethylformamide,
Although it can contain ethylene glycol, diethylene glycol, dimethyl sulfoxide, benzyl alcohol, etc., in the present invention, a color developing solution that does not substantially contain benzyl alcohol and contains sulfite in an amount of 2 x 10-'' mol/a or less is used. The sulfite concentration is preferably l x 10-4 to 1.7 x 10-
"mol/(t is more preferable, especially 5 X 10-3
~l x 10-" mole/Q is preferred. Also, "substantially free of benzyl alcohol" means that the concentration is 0.5 m12
It refers to less than #2, and it is preferable that it is not contained at all.

The pH of the color developer is usually 7 or higher, preferably about 9.
~13.

Also, the temperature of the processing solution in the color developing tank is preferably 10°C to 6°C.
The temperature is preferably 256°C to 45°C.

The developing time is preferably within 2 minutes and 30 seconds, more preferably within 2 minutes.

After color development, silver halide color photosensitive materials are usually bleached. The bleaching treatment may be performed simultaneously with the fixing treatment (bleaching and fixing) or separately, but it is preferable to use a bleach-fixing bath that processes bleaching and fixing in one bath. The pH of the bleach-fix solution is preferably 4.5 to 6.8, particularly preferably 4.5 to 6.0.

The bleaching agent that can be used in the bleach-fix solution is preferably a metal complex salt of an organic acid, particularly a complex salt of an organic acid such as aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid coordinated with a metal ion such as iron, cobalt or copper. Preferably.

Additives added to the bleach-fix solution include, in particular, alkali halides or ammonium halides, rehalogenating agents such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, metal salts, chelating agents, etc. It will be done.

In addition, p of borates, 1j-acids, acetates, carbonates, phosphates, etc.
Those known to be added to ordinary bleaching solutions, such as H buffering agents, alkylamines, and polyethylene oxides, can be added as appropriate.

Furthermore, the bleach-fix solution contains sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, and sodium metabisulfite, as well as boric acid, borax, and hydroxide. Contains one or more pH buffers selected from various salts such as sodium, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. be able to.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 A solution in which a coupler and optionally a dye image stabilizer and stain inhibitor were dissolved in a high-boiling organic solvent and ethyl acetate was added to an aqueous gelatin solution containing a dispersion aid and dispersed using an ultrasonic homogenizer. Gelatin liquid for coating is added to the obtained dispersion,
A photosensitive silver halide emulsion was added to prepare an emulsion layer coating solution.

Each layer having the structure shown in Table 1 is coated on a support laminated with polyethylene on one side of a paper support and polyethylene containing titanium oxide on the first layer side of the other side to prepare a multilayer silver halide color photographic light-sensitive material. Sample soil was prepared.

The silver halide emulsion used was prepared as follows.

[Preparation method of blue-sensitive silver halide emulsion The following (
AI) and (Bl) at pAg-6,5, pH-3,0
Simultaneously twist 21+7 L over 30 minutes while controlling
= 5.5 and simultaneously added over 180 minutes.

At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Liquid A) N a C (13,42 g K B r 0.03
Add gH, O 2(]00
ml2B liquid) A g N 03
10gH! add O
200mf+(C liquid) N a C12102,7g K B r
1. Add OgH,0
600m (2 (D liquid) A g N Os
Add 300gH,O
After the addition of 600+oQ, a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and 20% of magnesium sulfate were added.
% aqueous solution, and then mixed with gelatin aqueous solution to obtain an average particle size of 0.85 μm+, coefficient of variation (S
)=0.07, and a monodispersed cubic emulsion EMPl having a silver chloride content of 99.5 mol % was obtained.

The following compound was used for the above emulsion EMP-1, and the temperature was 50°C.
A blue-sensitive silver halide emulsion (
EmA) was obtained.

Sodium thiosulfate 0.8mg 1 mol 1 mol Auric acid 0.5mg/ :f:
AgX stabilizer 5B-56XlO-'mol 1 molA
gX sensitizing dye D l 5xlO-' mol 1 mol Agz [Preparation method of green-sensitive silver halide emulsion] (Liquid A)
Same as EMP-1 except for changing the addition time of (B solution) and (C solution) and (D solution), average particle size 0.43μ, coefficient of variation (S/r) - A monodisperse cubic emulsion EMP-2 with a silver chloride content of 99.5 mol% was obtained.

For EMP-2, the following compound was used at 120°C at 55°C.
Green-sensitive silver halide emulsion (EmB) after separation chemical ripening
I got it.

Sodium thiosulfate 1.5 mg 1 mol 1 mol A-auric acid 1.0 mg/mol Jl/
AgX stabilizer S B -56X 10-' mol 1 mol AgX sensitizing dye p-24, QXIQ-' mol 1 mol AgX [Preparation method of red-sensitive silver halide emulsion 1 (liquid A)
EMP-1-O, Oa, a monodisperse cubic emulsion with a silver chloride content of 99.5 mol% EMP- I got 3.

90°C at 60°C using the following compound for EMP-3.
After separation chemical ripening, red-sensitive silver halide emulsion (EmC)
I got it.

Sodium thiosulfate L8rmg1 mol AgX
Chloroauric acid 2.0 mg 1 mol 1 mol A fixative S B -56X LQ-' mol/mol A
gX sensitizing dye D-38,0 AO-1 T IV-1 IV-2 B Next, samples containing the third layer magenta coupler and dye image stabilizer (additive) in the combinations shown in Table 2 were prepared.

This sample was exposed to a wedge of green light in a conventional manner and then processed according to the following processing steps.

[Processing process 1 Temperature Development color development 3
5.0±0.3°O 45 seconds bleach fixing 35.0±0.
Stabilize at 5°C for 45 seconds Dry at 30-34°C for 90 seconds 60-80°C for 60 seconds [Color developer] Pure water 800mff Triethanolamine lOgN,N
-Diethylhydroxylamine 5g Potassium bromide 0.02g Potassium chloride 2g Potassium sulfite
0.3g 1-hydroxyethylidene-1,1 diphosphonic acid 1. O.

Ethylenediaminetetraacetic acid 1.0g Catechol-3,5-disulfonic acid disodium salt 1.0gN-
Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4 aminoaniline sulfate 4.5g optical brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g potassium carbonate
Add 27 g of water to bring the total volume to Iff, and adjust the pH to 10.10.

[Bleach-fix solution] Bleach-fix solution 1Q contains: 60 g of ferric ammonium ethylenediaminetetraacetic acid dihydrate, 3 g of ammonium thiosulfate (70% aqueous solution), 100 mQ, and 27.5 m4 of ammonium sulfite (40% aqueous solution). Adjust to pH=5.7 with potassium carbonate or glacial acetic acid.

[Stabilizing liquid 1 In stabilizing solution lQ, ) was measured.

Display results Shown in 2.

5-chloro-2-methyl-4-inchazolin 3-one 1.0 g ethylene glycol 1.0 g 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)
Contains 1.5g. pH with sulfuric acid or potassium hydroxide
Adjust to -7-0.

All samples with magenta dye images after processing were evaluated as follows.

[Light fastness test]: Initial concentration 1.0 when exposed to sunlight for 14 days using an underglass outdoor sunlight exposure table
The fading rate was determined.

Fading rate - (1,0-density after fading) x 100 Also, increase in blue light reflection density of white part (addition amount of stain: number of moles per mole of Kabra in the same surface layer Table-3 It is clear from Table-2 The compound of the present invention and the general formula [M
In combination with the coupler represented by -13, a synergistic effect of improving the fading rate and staining was observed.

Also, the magenta coupler of sample 6 is M-3, M-13, M
Each sample replaced with -28, 5-2 of sample 12 was replaced with S-5 and T
Samples replaced with weight mixtures such as O-66, S- of sample 13
The effects of the present invention were also observed for the samples in which 1/2 weight of 2 was replaced with TO-4 and TO-55.

Example 2 The 3rd NI magenta coupler dye image stabilizer and high-boiling organic solvent of Sample 1 of Example 1 were variously changed; Samples were prepared and the light fastness test was conducted in the same manner as in Example 1. It is shown in Table-3.

HBS: High boiling point organic solvent DBP: Diphthyl phthalate TCP: Tricresyl phosphate As is clear from Table 3, the compound of the present invention and the general formula [M-
In combination with the coupler shown in 1), the light fastness is significantly improved, especially the dielectric constant at 30°C6,
It can be seen that when a high boiling point organic solvent of θ or less is used, the effect is large.

Also, T-9 of sample 12 was changed to T-1, T-2, T-4゜T-
7, each sample in which T-14, T-16, and T-17 were replaced, sample in which T-9 of sample 12 was replaced with T-11, S of sample 19
Samples in which 1/21 of -5 was replaced with T 0-68, T 0-86, T-24 of sample 22 was replaced with T-20, T-29,
The effects of the present invention were also observed for each sample in place of T-31.

Claims (1)

[Scope of Claims] At least one green-sensitive silver halide emulsion layer containing a compound represented by the following general formula [T] and a magenta coupler represented by the following general formula [M-I] on a support. A silver halide color photographic material characterized by: General formula [T] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 are hydrogen atoms or alkyl groups, R_3 and R_4 are hydrogen atoms, alkyl groups, aryl groups, or heterocyclic groups, R_6 represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, or an alkoxycarbonyl group, X represents a divalent group having a carbon atom as a constituent atom of the 6-membered ring, and n represents 0, 1 or 2. ] General formula [M-I] ▲ Numerical formulas, chemical formulas, tables, etc. May have. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. R is bonded to one hydrogen atom. Alternatively, it represents a substituent that is bonded to the nitrogen-containing heterocycle through a carbon atom that is not bonded to a hydrogen atom. ]