JPH05249633A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance color reproducibility and lightfastness of a processed image and to improve resistance to variation of dyes due to heat and moisture. CONSTITUTION:The silver halide photographic sensitive material having at least one of photosensitive layer and nonphotosensitive layer on a support contains at least one kind of magenta coupler in the photosensitive layer and at least one kind of ultraviolet absorber in at least one of the photosensitive layer or the nonphotosensitive layer and a weight ratio of a high-boiling organic solvent to this ultraviolet absorber in this layer is regulated to 0.3-0. This photosensitive material is processed with a color developing solution within 30sec.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material which is excellent in color reproducibility and light resistance of a dye image and in which color fluctuation due to heat and humidity is prevented.

[0002]

BACKGROUND OF THE INVENTION Recently developed 1H-pyrazolo- [1,
The 5, b] -1,2,4-triazole magenta coupler is different from the conventionally used 5-pyrazolone magenta coupler in that it has excellent color reproducibility because the coloring dye has no side absorption around 430 nm. Although characteristic, magenta dyes obtained from this type of coupler are known to have poor light resistance. Against this drawback, for example, JP-A-60-262159 describes that a phenol or phenyl ether compound is used to improve light resistance, but the effect is not yet satisfactory. Further improvements are desired.

Attempts to improve the light resistance have been made from the viewpoint of the structure of the coupler, for example, JP-A-63-307453.
No. 64-66646, JP-A-2-161430.
No. 2,296,241, No. 2-111943, No. 3-138644, etc., and the above-mentioned 1H-pyrazolo- [1,5, b] -1, having a bulky substituent at the 6-position.
The 2,4-triazole type magenta coupler is known as a coupler excellent in light resistance, but its effect is not yet satisfactory and further improvement is desired. In addition, although the color fading of the color-forming dyes obtained from these couplers due to heat and humidity is reduced, on the contrary, the density easily rises after storage, and the density balance with other yellow images and cyan images shifts, so images after image storage However, there was a problem that the initial good color balance deteriorated to a completely different color balance.

Further, in recent years, in the photographic industry, a silver halide photographic light-sensitive material capable of rapid processing, high image quality, and always maintaining stable performance has been demanded. That is, the silver halide photographic light-sensitive material is usually processed continuously by an automatic processor provided at each developing station, but as a part of improving the service to users, within the day when the development is accepted. It is required to process the image and return it to the user, and more recently, it has been required to return the image within a few hours from the reception, and the necessity for the rapid process is increasing more and more. Furthermore, shortening the processing time improves the production efficiency,
Rapid processing is also required because it enables cost reduction.

Although the above-mentioned magenta coupler has improved color reproducibility, there has been a problem in that the density of a color-developed image in a rapid process such as this is increased by the heat and humidity after storage. Therefore, as a result of various studies by the present inventors, not only good color reproducibility and light resistance can be obtained by using a specific coupler and an ultraviolet absorber layer, but also storage stability against heat and humidity is improved. The present invention has been discovered and the present invention has been achieved.

[0006]

OBJECTS OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in color reproducibility and light fastness of a processed image and in which color variation of dye image with respect to heat and humidity is improved. is there.

[0007]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive layer and at least one non-light-sensitive layer on a support. Formulas [IA], [IB], [IC], [I
D], [IE], [IF-1] or at least one of the compounds represented by [IF-2], and at least 1
The photosensitive layer or the non-photosensitive layer of the layer contains at least one ultraviolet absorber, and the ratio of the high boiling point organic solvent-containing weight in the ultraviolet absorber-containing layer to the ultraviolet absorber-containing weight is 0.3. It is achieved by a silver halide photographic light-sensitive material characterized by being 0 to 0.

General formulas [IA], [IB], and
[IC], [ID], [IE], [IF-1] or [I
The following can be used as the compound represented by F-2].

[0009]

[Chemical 10]

[In the formula, A represents a residue obtained by removing R ₂ or R ₃ from a pyrazolotriazole magenta coupler represented by the following general formula [II], and L represents a divalent linking group.
Y represents a nonmetallic atom group necessary for forming a 5- or 6-membered heterocycle with a nitrogen atom, and R ₁ represents a substituent. n represents an integer of 0 to 4.

[0011]

[Chemical 11]

In the formula, R ₂ and R ₃ represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidation product of a color developing agent. More preferably, the magenta coupler represented by the general formula [IA] described in (1) above is represented by the following general formula [IA-1], and is a silver halide color photographic light-sensitive material.

[0013]

[Chemical 12]

[In the formula, L ¹ represents a divalent linking group having a main chain having a chain length of 5 or less, and R ₁ and R ₂ represent a substituent.
Y represents a nonmetallic atom group necessary for forming a 5- or 6-membered heterocycle with a nitrogen atom, and n represents an integer of 0 to 4. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ]

[0015]

[Chemical 13]

[Wherein R ₁ , R ₂ and R ₄ represent a substituent, Y represents a group of non-metal atoms necessary to form a 5-membered or 6-membered heterocycle with a nitrogen atom, and n represents 0 to 4
Represents the integer. m represents 1 or 2. X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ]

[0017]

[Chemical 14]

[Wherein A is the general formula [I
I] represents a residue obtained by removing R ₂ or R ₃ from the pyrazolotriazole magenta coupler represented by I], L _B represents a divalent linking group or a simple bond, R _B represents an alkylene group, and Y represents It represents a group of non-metal atoms necessary for forming a 5- or 6-membered heterocycle with a nitrogen atom. ]

[0019]

[Chemical 15]

[Wherein A is the general formula [I
I] represents a residue obtained by removing R ₂ or R ₃ from a pyrazolotriazole magenta coupler represented by I], L _C represents a divalent linking group or a simple bond, and E represents —CO— or —SO.
_{-, - SO 2 -, -} N (R 16) -SO 2 -, - N
(R ₁₆₎ -CO -, - represents a O-CO-, R ₁₆ represents a hydrogen atom or a substituent, Y is nonmetallic atoms necessary to form a 5- or 6-membered heterocyclic ring together with the nitrogen atom Represents a group. ]

[0021]

[Chemical 16]

[Wherein A is a pyrazolotriazole magenta coupler represented by the general formula [II] to R ₂ or R ₃
Represents a residue obtained by removing, L _D represents a divalent linking group or a simple bond, B represents —O—, —S—, —SO ₂ —, —N
_{(R 16) -, - N} (R 16) 2 - represents, R _D represents a hydrogen atom or a _{substituent, R a, R b, R} c and R _d represents an alkyl group, Y _D is a 5- Alternatively, it represents a group of non-metal atoms necessary for forming a 6-member, one atom in the group of non-metal atoms represents bonding with B, and R ₁₆ represents a hydrogen atom or a substituent. ]

[0023]

[Chemical 17]

[Wherein A is the general formula [I
I] represents a residue obtained by removing R ₂ or R ₃ from a pyrazolotriazole magenta coupler represented by I], L _E represents a divalent linking group, R _E1 and R _E2 represent a hydrogen atom or a substituent, R _E1 and R _E2 may be the same or different, may be condensed with each other to form a 5- to 7-membered ring, k represents 0 or 1, and Z _E represents —O— or —S. - or -N (R ₁₆₎ - represents, R ₁₆ represents a hydrogen atom or a substituent. ]

[0025]

[Chemical 18]

[0026]

[Chemical 19]

[Wherein, L _a and L _b represent a divalent linking group or a simple bond, R _F represents an alkylene group or an arylene group, and Y is necessary for forming a 5- to 6-membered ring. A non-metal atom group, n _f represents 0 or 1, R _a1 ,
R _b1 , R _c1 , R _d1 and R _e1 represent a hydrogen atom or a substituent, and at least one of R _{a1 to} R _d1 is a hydroxyl group, an alkoxy group, an aryloxy group or

[0028]

[Chemical 20]

And X _f is --S--, --SO ₂ --or-
N (R ₁₆ ) _2- , R ₁₆ represents a hydrogen atom or a substituent, and two R ₁₆ may be the same or different;
Represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ]

The present invention will be described in more detail below. The general formulas [IA], [II], [IA-1], and [I
B], [IC], [ID], [IE], [IF-1],
In [IF-2], R ₁ , R ₂ R ₃ , R ₄ , _RD ,
The substituent represented by R _E1 , R _E2 , R _a1 , R _b1 , R _c1 , R _d1 and R _e1 is not particularly limited, but is typically alkyl, aryl, anilino, acylamino, sulfonamide, Examples include groups such as alkylthio, arylthio, alkenyl, and cycloalkyl. In addition to these, halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, Heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, each group such as heterocyclic thio, Na A spiro compound residue in beauty, bridged hydrocarbon compound residue and the like are also mentioned.

R ₁ , R ₂ R ₃ , R ₄ , R _D , R _E1 ,
Of the substituents represented by R _E2 , R _a1 , R _b1 , R _c1 , R _d1 and R _e1 , the alkyl group preferably has 1 to 32 carbon atoms and may be linear or branched. As an aryl group,
Phenyl is preferred. Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group. The alkyl component and the aryl component in the alkylthio group and the arylthio group are the above R ₁ , R ₂ R ₃ , R ₄ and
_Examples thereof include an alkyl group and an aryl group represented by R _D , R _E1 , R _E2 , R _a1 , R _b1 , R _c1 , R _d1 and R _e1 . The alkenyl group preferably has 2 to 32 carbon atoms and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group has 3 to 10 carbon atoms.
12, especially 5 to 7, are preferable. Examples of the sulfonyl group include an alkylsulfonyl group and an arylsulfonyl group. Examples of the sulfinyl group include an alkylsulfinyl group and an arylsulfinyl group. Examples of the phosphonyl group include an alkylsulfonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, and an arylphosphonyl group. Examples of the acyl group include an alkylcarbonyl group and an arylcarbonyl group.

Examples of the carbamoyl group include an alkylcarbamoyl group and an arylcarbamoyl group. Examples of the sulfamoyl group include an alkylsulfamoyl group and an arylsulfamoyl group. Examples of the acyloxy group include an alkylcarbonyloxy group and an arylcarbonyloxy group.

Examples of the carbamoyloxy group include an alkylcarbamoyloxy group and an arylcarbamoyloxy group. Examples of the ureido group include an alkylureido group and an arylureido group. As the sulfamoylamino group, an alkylsulfamoylamino group,
Examples thereof include an arylsulfamoylamino group.

The heterocyclic group is preferably a 5- to 7-membered one, and specific examples thereof include a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group and a 2-benzothiazolyl group. The heterocyclic oxy group is preferably one having a 5- to 7-membered heterocycle, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-
5-oxy group etc. are mentioned.

The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,
3,5-triazole-6-thio group and the like can be mentioned. Examples of the siloxy group include a trimethylsiloxy group, a triethylsiloxy group and a dimethylbutylsiloxy group.
Examples of the imide group include a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, and a glutarimide group.

As the spiro compound residue, spiro [3,
3] Heptan-1-yl and the like can be mentioned. As a bridged hydrocarbon compound residue, bicyclo [2,2,1] heptane-
1-yl, tricyclo [3,3,1,1 ³⁷ ] decane-1
-Yl, 7,7-dimethyl-bicyclo [2,2,1] heptan-1-yl and the like.

These R ₁ , R ₂ R ₃ , R ₄ , R _D ,
Each group represented by R _E1 , R _E2 , R _a1 , R _b1 , R _c1 , R _d1 and R _e1 includes one having a substituent. Examples of the group represented by X which can be removed by the reaction with the oxidized product of the color developing agent include a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy. Carbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, N
Examples thereof include nitrogen-containing heterocycles bonded by atoms, alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl groups, with halogen atoms being preferred, and chlorine atoms being particularly preferred.

When n is 2 or more, a plurality of R _1's may be the same or different, and a plurality of R ₁ 's may form a condensed ring. Also included in the present invention are polymer couplers and polymer couplers such as dimer couplers containing a pyrazolotriazole ring in R ₂ , R ₃ or X. Further, the present invention also includes a group represented by A in the general formula [IA] having a group obtained by removing A from the compound represented by the general formula [IA].

The above general formulas [IA], [IB] and [I]
C], [ID], [IE], [IF-1] and [IF-
In _{^{2], L, L 1, L B}} , L C, L D, L E, L
_Examples of the divalent linking group represented by _a and L _b include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, Acyl, carbamoyl, sulfamoyl, alkoxy, aryloxy, heterocyclic oxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonialamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl , A divalent group derived from each group such as heterocyclic thio, and a divalent group that can be formed by combining these divalent groups, preferably represented by the following general formula [X]. It is.

[0042]

[Chemical 21]

In the formula, the R ₁₃ side is bonded to the pyrazoloazole ring. R ₁₃ , R ₁₄ and R ₁₅ in the general formula [X] each independently represent an alkylene group having 1 to 12 carbon atoms, an arylene group, an alkylenearylene group or an aralkylene group. The alkylene group, which may be linear or branched, is, for example, a methylene group, a methylmethylene group, a dimethylene group, a decamethylene group, etc., and the arylene group is, for example, a phenylene group, a naphthylene group, etc., and an aralkylene group. As the alkylenearylene group,

[0044]

[Chemical formula 22]

And the like. The above R ₁₃ , R ₁₄ and R ₁₅
The alkylene group, arylene group, alkylenearylene group or aralkylene group represented by can have a substituent, and as the substituent, the above R ₁ , R ₂ , R ₃ and R _{4 can be used.}
Each substituent represented by Further, L, L ₂ and L ₃ in the general formula [X] are

[0046]

[Chemical formula 23]

Represents However, R ₁₆ represents a hydrogen atom, an alkyl group or an aryl group, and when two R ₁₆ are present,
Each R ₁₆ may be the same or different. p, q, r, s, t
And u represents an integer of 0 or 1.

[0048] -L _B -R _B in the general formula [IB] -,
-L _C in the general formula [IC] -, -L _D in the general formula [ID] -, -L _E in the general formula [IE] -, -L _a in the general formula [IF-1) and (IF-2] - and -L _b - chain length of the main chain of the divalent linking group is preferably atom having 15 or less represented by the case 10 or less but more preferably, there are cyclic moiety in the linking group wherein the The number of atoms in the portion is counted along the path with the smallest number of atoms, such as 3 for m-phenylene and 2 for o-phenylene.

R _B in the general formula [IB] has 1 to 32 carbon atoms.
The alkylene group may be linear or branched, and examples thereof include a methylene group, a methylmethylene group, a dimethylene group, and a decamethylene group. R _F in the general formulas [IF-1] and [IF-2] has 1 to 1 carbon atoms.
It represents 32 alkylene or arylene groups, and the alkylene group may be linear or branched, and examples thereof include methylene, methylmethylene, dimethylene, decamethylene groups, and the like.
Examples of the arylene group include phenylene and naphthylene groups.

The non-metal atom group represented by Y _D in the general formula [ID] is preferably saturated hydrocarbon or saturated hydrocarbon containing oxygen atom, nitrogen atom and / or sulfur atom. The alkyl group represented by R _a , R _b , R _c and R _d in the general formula [ID] preferably has 1 to 32 carbon atoms, and may be linear or branched, or cyclic. It may be saturated or unsaturated, and examples thereof include a methyl group, an ethyl group, an isopropyl group, a cyclohexyl group, and a vinyl group. Of these, a linear alkyl group is particularly preferable. General formulas [IF-1] and [IF-2]
In

[0051]

[Chemical formula 24]

A phenolic image stabilizer residue is shown below.
More preferably, it is represented by the general formula [FA] and the general formula [FB].

[0053]

[Chemical 25]

In the general formula [FA], R ₁₂₂ ,
R ₁₂₃ , R ₁₂₅ and R ₁₂₆ are each a hydrogen atom, a halogen atom,
Hydroxyl group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or acylamino group, of which alkyl group, an alkenyl group, an alkyl group described for the R ₁ for an aryl group, an alkenyl group,
The same as the aryl group can be mentioned. Further, examples of the halogen atom include fluorine, chlorine, bromine and the like.

Specific examples of the alkoxy group include methoxy group, ethoxy group, benzyloxy group and the like. Further, the acylamino group is R ₁₂₇ —CO
NH-, wherein R ₁₂₇ is an alkyl group (eg, methyl, ethyl, n-propyl, n-butyl,
n-octyl, tert-octyl, benzyl etc.), alkenyl group (eg allyl, octenyl, oleyl group), aryl group (eg phenyl, methoxyphenyl, naphthyl etc.) or heterocyclic group ( For example, each group of pyridinyl and pyrimidyl) can be represented.

In the above general formula [FA], R ₁₂₄
Represents an alkyl group, a hydroxyl group, an aryl group, an alkoxy group, an alkenyloxy group or an aryloxy group. Of these, the alkyl group and the aryl group are the same as those represented by R ₁ above. It can be specifically mentioned. The alkoxy group for R ₁₂₄ may be the same as the alkoxy group described for R ₁₂₂ , R ₁₂₃ , R ₁₂₅ and R ₁₂₆ .

R ₁₂₂ and R ₁₂₃ may be ring-closed to each other to form a 5-membered or 6-membered heterocycle, and R ₁₂₃ and R ₁₂₄ may be ring-closed to form a 5-membered or 6-membered ring. These rings may include those in which another ring is spiro-bonded. Typical representative examples of the phenolic image stabilizer residue represented by the general formula [FA] are shown below, but the invention is not limited thereto.

[0058]

[Chemical formula 26]

[0059]

[Chemical 27]

[0060]

[Chemical 28]

[0061]

[Chemical 29]

[0062]

[Chemical 30]

In the general formula [FB], R ₁₃₁ represents a secondary or tertiary alkyl group, a secondary or tertiary alkenyl group, a cycloalkyl group or an aryl group, and R ₁₃₂ represents a halogen atom, an alkyl group or an alkenyl group. , A cycloalkyl group or an aryl group, and n ² represents an integer of 0 to 3. When two or more R ₁₃₁ and R ₁₃₂ are present in the compound, each R ₁₃₁ and R ₁₃₂ may be the same or different. Y _B1 represents S, SO, SO ₂ or an alkylene group.

The secondary or tertiary alkyl group or secondary or tertiary alkenyl group represented by R ₁₃₁ is preferably one having 3 to 32 carbon atoms, particularly one having 4 to 12 carbon atoms, and specifically, Include groups such as t-butyl, s-butyl, t-amyl, s-amyl, t-octyl, i-propyl, i-propenyl, and 2-hexenyl.

The alkyl group represented by R ₁₃₂ is preferably one having 1 to 32 carbon atoms, and the alkenyl group is preferably one having 2 to 32 carbon atoms, and may be linear or branched. Specifically, groups such as methyl, ethyl, t-butyl, pentadecyl, 1-hexynonyl, 2-chlorobutyl, benzyl, 2,4-di-t-amylphenoxymethyl, 1-ethoxytridecyl, allyl and isopropenyl are Can be mentioned. The cycloalkyl group represented by R ₁₃₁ and R ₁₃₂ preferably has 3 to 12 carbon atoms, and examples thereof include groups such as cyclohexyl, 1-methylcyclohexyl and cyclopentyl.

The aryl group represented by R ₁₃₁ and R ₁₃₂ is preferably a phenyl group or a naphthyl group, specifically, phenyl, 4-nitrophenyl, 4-t-butylphenyl, 2,4-di-t-amyl. Phenyl, 3-hexadecyloxyphenyl, α-naphthyl and the like can be mentioned. Y _B1
The alkylene group represented by is preferably one having 1 to 12 carbon atoms, and specific examples thereof include groups such as methylene, ethylene, propylene, butylidene, and hexamethylene. Each group represented by R ₁₃₁ , R ₁₃₂ and Y _B1 may have a substituent.

Examples of the substituent which R ₁₃₁ , R ₁₃₂ and Y _B1 may have include a halogen atom and groups such as nitro, cyano, amide, sulfonamide, alkoxy, aryloxy, alkylthio, arylthio and acyl. Be done. Typical examples of the general formula [FB] are shown below, but the present invention is not limited thereto.

[0068]

[Chemical 31]

[0069]

[Chemical 32]

[0070]

[Chemical 33]

The above general formula [IA] and general formula [IA-
1], general formula [IB], general formula [IC], general formula [IF
-1], in the general formula [IF-2], as the non-metal atom group represented by Y,

[0072]

[Chemical 34]

It is preferable to contain R ₁₇ and R ₁₈ each independently represent a hydrogen atom, an alkyl group or an aryl group, and n ¹ represents an integer of 0-2. The above general formula [IA], general formula [IA-1], general formula [IB], general formula [IC], general formula [IF-1], general formula [IF-
2]

[0074]

[Chemical 35]

The 5- or 6-membered heterocyclic ring represented by may be saturated or unsaturated, but a saturated ring is preferable. Further, these heterocycles have R ₁ , R ₂ R ₃ , R ₄ , R _D ,
It may have a substituent represented by R _E1 , R _E2 , R _a1 , R _b1 , R _c1 , R _d1 and R _e1 . In the general formula [IA-1], L ¹ represents a divalent linking group having a main chain having a chain length of 5 or less, but in the case where a ring structure moiety is present in the linking group, The number of atoms is, for example, 3 for m-phenylene and 2 for o-phenylene, and is counted along the path with the smallest number of atoms.

The linking group represented by L ¹ is represented by the following general formula [X ₁ ]. Formula [X _{1] * 1 -A 1 -A 2 -A 3} -A 4 -A 5 - * 2 wherein, A ₁ to A ₅ are atoms or a single bond may have the valence of divalent or higher Each atom may be further substituted with a hydrogen atom or a substituent, * ₁ represents a position bonded to the pyrazolotriazole ring, and * ₂ represents a position bonded to the phenoxy group. ]

Atoms having a valence of two or more represented by A _{1 to} A ₅ are represented by the periodic table II _A , III _A , IV _A , V _A ,
An atom of Group VI _A , preferably a non-metal atom,
More preferred are carbon, nitrogen, oxygen, silicon, phosphorus, sulfur and selenium, and most preferred are carbon, nitrogen, oxygen, sulfur and phosphorus. In the general formulas [IF-1] and [IF-2], R _F is an arylene group and n _f is 1.
Linking groups La when it represents an even, most preferably represent a divalent linking group similarly chain length of main chain atoms of 5 or less and L ^1, La in this case is the same as L ^1. Preferred L ¹
Examples of L are shown below, but L ¹ is not limited thereto.

[0078]

[Chemical 36]

[0079]

[Chemical 37]

[0080]

[Chemical 38]

[0081]

[Chemical Formula 39]

[0082]

[Chemical 40]

[Wherein R ₁₀ , R ₁ , * ₁ , * ₂ , n, n
¹ is as described above, n ₁ represents 1 or 2, and n ₂
Is 1, 2 or 3, n ₃ is 0, 1, 2 or 3, n ₄
Represents an integer of 1 to 4, n ₅ represents an integer of 1 to 5, n ₆ represents 0 or 1, and n ₇ represents 0, 1 or 2. Typical examples of the magenta coupler according to the present invention are shown below, but the present invention is not limited thereto.

[0084]

[Chemical 41]

[0085]

[Chemical 42]

[0086]

[Chemical 43]

[0087]

[Chemical 44]

[0088]

[Chemical 45]

[0089]

[Chemical 46]

[0090]

[Chemical 47]

[0091]

[Chemical 48]

[0092]

[Chemical 49]

[0093]

[Chemical 50]

[0094]

[Chemical 51]

[0095]

[Chemical 52]

[0096]

[Chemical 53]

[0097]

[Chemical 54]

[0098]

[Chemical 55]

[0099]

[Chemical 56]

[0100]

[Chemical 57]

[0101]

[Chemical 58]

The pyrazolotriazole-based magenta coupler according to the present invention is a journal of the chemical
Society (Journal of the Che
medical Society), Perkin (Perki)
n); I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, 58-42045, 59-162548, 59.
-171956, 60-33552, 60-4
No. 3659, No. 60-172892, No. 60-190.
No. 779, No. 61-189539, No. 61-2417.
54, 63-163351, 62-15703.
It can be easily synthesized by those skilled in the art with reference to No. 1.

Next, typical synthesis examples of the pyrazolotriazole type magenta coupler according to the present invention will be shown below.

Synthesis Example 1 Synthesis of Exemplified Compound MA-1 The synthetic route is shown below.

[0105]

[Chemical 59]

[0106]

[Chemical 60]

10.0 g of compound (I), 9.2 g of potassium carbonate and ethyl (II) 1-α-bromolaurate
After adding 7.6 g to 250 cc of acetonitrile and heating under reflux for 10 hours, precipitated potassium bromide was filtered off by hot filtration. The filtrate was evaporated under reduced pressure, and the residue was washed with ethyl acetate 20
Extracted at 0 cc. After washing with water, it was dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The pale yellow residue was recrystallized from acetonitrile to give 15.2 g of compound (II
I) was obtained.

After dissolving 9.1 g of the compound (III) in 45 cc of ethyl alcohol, sodium hydroxide 1.
A solution prepared by dissolving 6 g in 50 cc of water was added, and the mixture was heated under reflux for 3 hours. After the reaction, the alkali was neutralized with diluted hydrochloric acid, ethyl alcohol was distilled off under reduced pressure, the mixture was extracted with ethyl acetate, washed with water, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The obtained oily substance was recrystallized from 300 cc of acetonitrile to obtain 7.2 g of white crystalline compound (IV).

Next, 1.4 g of p-nitrophenol and 20 cc of dioxane were added to 4.3 g of compound (IV), and after dissolution, dicyclohexylcarbodiimide (DCC) .2.
3 g was added, and the mixture was stirred at room temperature for 2 hours. After filtering the precipitate, the solvent was distilled off under reduced pressure, 50 cc of ethyl acetate was further added, and the solution was mixed with 50 cc of a 5% aqueous sodium carbonate solution to 3 cc.
After washing twice, it was dried over anhydrous magnesium sulfate.

The solvent was distilled off under reduced pressure to obtain 5.1 g of orange oily compound (V). Dimethylacetamide (60 cc) was added to this, and compound (VI) (2.2 g) was further added and dissolved by heating. Then, 150 cc of acetonitrile and 0.5 g of imidazole were added, and the mixture was heated under reflux for 4 hours. After distilling off the solvent acetonitrile under reduced pressure, ethyl acetate 300c
c and 200 cc of water were added for liquid separation. 5% organic phase
After washing with 100 cc of an aqueous sodium carbonate solution three times, it was dried over anhydrous sodium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography to obtain 5.0 g of white amorphous Exemplified Compound (MA-1). (The structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum.)

[0111]

[Chemical formula 61]

[0112]

[Chemical formula 62]

[0113]

[Chemical 63]

[0114]

[Chemical 64]

[0115]

[Chemical 65]

[0116]

[Chemical 66]

[0117]

[Chemical 67]

[0118]

[Chemical 68]

[0119]

[Chemical 68]

[0120]

[Chemical 70]

[0121]

[Chemical 71]

The pyrazolotriazole-based magenta coupler according to the present invention is a journal of the chemical
Society (Journal of the Che
medical Society), Perkin (Perki)
n); I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, 59-171956, 60-43659, 60.
It can be easily synthesized by those skilled in the art with reference to Nos. 172892 and 60-190779.

Next, typical synthetic examples of the pyrazolotriazole type magenta coupler according to the present invention will be shown below.

Synthesis Example 2 Synthesis of Exemplified Compound MB-1 Synthetic Route

[0125]

[Chemical 72]

Synthesis of Intermediate B-3 To 30.7 g of Intermediate B-1 was added 150 ml of N, N-dimethylacetamide, 20 ml of morpholine was added, and the mixture was heated with stirring at 100 ° C. for 4 hours under a nitrogen stream. After cooling the reaction solution to room temperature, water (300 ml) and ethyl acetate (300 ml) were added for extraction, and the mixture was washed twice with 0.5N hydrochloric acid (50 ml),
The organic layer was dried and the solvent was distilled off under reduced pressure.

The obtained oily substance was purified by silica gel column chromatography (yield 18.8 g), the product was dissolved in 50 ml of ethanol, 150 ml of 2N aqueous sodium hydroxide solution was added, and the mixture was heated at 60 ° C. for 3 hours. It was stirred. The reaction solution was cooled at room temperature and neutralized with concentrated hydrochloric acid to precipitate white crystals. This was collected by filtration and washed with water to obtain 12.2 g of white crystalline intermediate B-3. ( ¹ HN
The structure was confirmed by MR, FD mass spectrum and IR spectrum. )

Synthesis of Exemplified Compound MB-1 5.7 g of Intermediate B-3 and 4.8 g of Intermediate B-4 were added as D.
It was dissolved in 30 ml of MF, 4.6 g of dicyclohexylcarbodiimide (DCC) was added, and the mixture was stirred at room temperature for 5 hours.
After filtering off the deposited precipitate, 150 m of water was added to the reaction solution.
1 and 250 ml of ethyl acetate were added for extraction. After drying the organic layer, the solvent was distilled off under reduced pressure, and the obtained product was purified by silica gel column chromatography to obtain 6.3 g of white amorphous MB-1. ( ¹ HN
The structure was confirmed by MR, FD mass spectrum and IR spectrum. )

Synthesis Example 3 Synthesis of Exemplified Compound MB-25 Synthetic Route

[0130]

[Chemical 73]

To 0.75 ml of a 40% formalin aqueous solution, 10 ml of acetic acid and 0.73 g of morpholine were added, and the mixture was stirred at room temperature for 1 hour, then 4.6 g of Intermediate B-5 was added, and the mixture was heated and stirred for 3 hours. 100 ml of ethyl acetate and 1 part of water in the reaction solution
After extraction with 100 ml of water and washing with 100 ml of a 3% aqueous sodium hydrogencarbonate solution twice, the organic phase was dried and the solvent was distilled off under reduced pressure. The obtained product was purified by silica gel column chromatography to obtain 2.2 g of pale yellow amorphous MB-25. ( ¹ HNMR,
The structure was confirmed by FD mass spectrum and IR spectrum. )

[0132]

[Chemical 74]

[0133]

[Chemical 75]

[0134]

[Chemical 76]

[0135]

[Chemical 77]

[0136]

[Chemical 78]

[0137]

[Chemical 79]

The pyrazolotriazole-based magenta coupler according to the present invention is a journal of the chemical
Society (Journal of the Che
medical Society), Perkin (Perki)
n); I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, 59-171956, 60-43659, 60.
It can be easily synthesized by those skilled in the art with reference to Nos. 172892 and 60-190779.

Next, typical synthesis examples of the pyrazolotriazole type magenta coupler according to the present invention will be shown below.

Synthesis Example 4 Synthesis of Exemplified Compound MC-7 The synthetic route is shown below.

[0141]

[Chemical 80]

C-1 (4.8 g) was dissolved by heating in 20 ml of N, N-dimethylacetamide, and then acetonitrile 100 was added.
ml and C-2 (7.7 g) were added, and the mixture was heated under reflux for 5 hours. After distilling off the acetonitrile under reduced pressure, the reaction solution was diluted with 200
It was poured into ml of water and the precipitated crystals were collected by filtration. The product was purified by silica gel column chromatography to obtain 4.4 g of white amorphous C-3. (
^The structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum. )

Further, C-3 4.2 g and C-4 1.4 g
Was dissolved in 50 ml of 1,4-dioxane, 1.7 g of dicyclohexylcarbodiimide (DCC) was added, and the mixture was stirred at room temperature for 2 hours. After separating insoluble matter by filtration, ethyl acetate 200
After adding ml to extract, washing with 50 ml of 0.5N hydrochloric acid,
It was washed with 50 ml of a 2% sodium hydrogen carbonate aqueous solution. After the organic layer was dried, the solvent was distilled off under reduced pressure, and the obtained product was recrystallized from acetonitrile to give white crystals of MC-
7 4.7 g were obtained. (The structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum.)

[0144]

[Chemical 81]

[0145]

[Chemical formula 82]

[0146]

[Chemical 83]

[0147]

[Chemical 84]

[0148]

[Chemical 85]

[0149]

[Chemical formula 86]

The pyrazolotriazole-based magenta coupler according to the present invention is a journal of the chemical
Society (Journal of the Che
medical Society), Perkin (Perki)
n); I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, 59-171956, 60-43659, 60.
-172892, 60-190779, Synthesis, 1984, 894 pages, 1984, 122 pages, 1984, 40 pages, 1981, JP-A-49-53574, British Patent No. 1,410,846, etc. It can be easily synthesized by those skilled in the art.

Next, typical synthesis examples of the pyrazolotriazole type magenta coupler according to the present invention will be shown below.

Synthesis Example 5 Synthesis of Exemplified Compound MD-1 A synthetic route is shown below.

[0153]

[Chemical 87]

D-1 (4.8 g) was dissolved by heating in 20 ml of N, N-dimethylacetamide, and then acetonitrile 100 was added.
ml and D-7.7g were added, and it heated and refluxed for 5 hours. After distilling off the acetonitrile under reduced pressure, the reaction solution was diluted with 200
It was poured into ml of water and the precipitated crystals were collected by filtration. The product was purified by silica gel column chromatography to obtain 4.5 g of white amorphous D-3. (
^The structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum. )

Furthermore, 4.2 g of D-3 and 1.2 g of D-4
100 ml of toluene and 3.0 of p-toluenesulfonic acid
g was added and the mixture was heated under reflux for 6 hours. The reaction solution was cooled at room temperature, washed with water, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 3.1 g of white amorphous MD-1. (The structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum.)

[0156]

[Chemical 88]

[0157]

[Chemical 89]

[0158]

[Chemical 90]

[0159]

[Chemical Formula 91]

[0160]

[Chemical Formula 92]

[0161]

[Chemical formula 93]

[0162]

[Chemical 94]

[0163]

[Chemical 95]

The pyrazolotriazole-based magenta coupler according to the present invention is a journal of the chemical
Society (Journal of the Che
medical Society), Perkin (Perki)
n); I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, 59-171956, 60-43659, 60.
-172892, 60-190779, New Experimental Chemistry Course, Vol. 14-III, pp. 1585-1594 (197).
7) Maruzen, Vol. 14-III, pp. 1576-1584 (1977) Maruzen, Helv. Chem. Acta. ，
36, 75 (1953), J. Am. Chem. So
c. 72, 2762 (1950), Drg. Syn
th. It can be easily synthesized by those skilled in the art with reference to Volume II, page 395 (1943) and the like.

Next, typical synthesis examples of the pyrazolotriazole type magenta coupler according to the present invention will be shown below.

Synthesis Example 6 Synthesis of Exemplified Compound ME-2 The synthetic route is shown below.

[0167]

[Chemical 96]

E-1 (4.8 g) was dissolved by heating in 20 ml of N, N-dimethylacetamide, and then acetonitrile 100 was added.
ml and succinic anhydride 2.0 g were added, and the mixture was heated under reflux for 5 hours. After distilling off the acetonitrile under reduced pressure, the reaction solution was mixed with 20
It was poured into 0 ml of water and the precipitated crystal was collected by filtration. The product was purified by silica gel column chromatography to obtain 4.6 g of white amorphous E-2. (
^The structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum. )

Furthermore, 4.5 g of E-2 and 3.6 g of E-3
Was dissolved in 50 ml of 1,4-dioxane, 3.1 g of dicyclohexylcarbodiimide (DCC) was added, and the mixture was stirred at room temperature for 4 hours. After separating insoluble matter by filtration, ethyl acetate 200
ml, 100 ml of water was added for extraction, and after washing with water,
The organic layer was dried and the solvent was distilled off under reduced pressure. The obtained product was purified by silica gel column chromatography to obtain 25.8 g of pale yellow amorphous ME-25.8.
(The structure was confirmed by ¹ HNMR, FD mass spectrum and IR spectrum.)

[0170]

[Chemical 97]

[0171]

[Chemical 98]

[0172]

[Chemical 99]

[0173]

[Chemical 100]

[0174]

[Chemical 101]

[0175]

[Chemical 102]

[0176]

[Chemical 103]

[0177]

[Chemical 104]

[0178]

[Chemical 105]

The pyrazolotriazole-based magenta coupler according to the present invention is a journal of the chemical compound.
Society (Journal of the Che
medical Society), Perkin (Perki)
n); I (1977), 2047-2052, U.S. Pat. No. 3,725,067, JP-A-59-99437, 58-42045, 59-162548, 59.
-171956, 60-33552, 60-4
No. 3659, No. 60-172892, No. 60-190.
No. 779, No. 61-189539, No. 61-2417.
54, 63-163351, 62-15703.
No. 1, Synthesys, 1984, p. 894, ibid.
122 pages, 984, 40 pages, 1981, JP-A-49-
53574, British Patent No. 1,410,846, New Experimental Chemistry Course 14-III, pp. 1585-1594 (1
977) Maruzen, Vol. 14-III, 1576-1584.
Page (1977) Maruzen, Helv. Chem. Act
a. 36, 75 (1953), J. Am. Che
m. Soc. 72, 2762 (1950), Dr.
g. Synth. It can be easily synthesized by those skilled in the art with reference to Volume II, page 395 (1943) and the like.

Next, typical synthesis examples of the pyrazolotriazole type magenta coupler according to the present invention will be shown below.

Synthesis Example 7 Synthesis of Exemplified Compound MF-1 The synthetic route is shown below.

[0182]

[Chemical formula 106]

[0183]

[Chemical formula 107]

Synthesis of Intermediate F-4 33.3 g of Intermediate F-1 was added with 1000 cc of ethyl acetate,
Sodium acetate (9.8 g) and water (200 cc) were added, and the mixture was ice-cooled to 5 ° C. Intermediate F was added to the reaction solution that was vigorously stirred.
-2 32.7 g of ethyl acetate solution was added dropwise over about 2 hours and then stirred at room temperature for 2 hours. The reaction solution was separated and further washed twice with 500 cc of 5% aqueous sodium hydrogen carbonate solution, and then the organic phase was dried and concentrated to dryness.

The obtained product was recrystallized from ethanol to obtain 51.8 g of intermediate F-3. Furthermore, the intermediate F-
3 51.5g with 2000cc of toluene and 15.0g
Phosphorus oxychloride was added and heated under reflux for 5 hours. The reaction solution was cooled to room temperature, washed with 500 cc of water three times, and toluene was distilled off under reduced pressure. The obtained brown oily substance was recrystallized from acetonitrile to obtain 42.6 g of Intermediate F-4. (The structure was identified by ¹ HNMR, FD mass spectrum and IR spectrum.)

Synthesis of intermediate F-7 Intermediate F-4 (42.5 g) was added to acetic acid (250 cc) and water (45 c).
c and sulfuric acid (45 cc) were added, and the mixture was heated under reflux for 4 hours. The reaction solution was ice-cooled, 300 g of ice and 500 cc of ethyl acetate were added for extraction, the organic phase was washed 5 times with 500 cc of 5% aqueous sodium hydrogen carbonate solution, dried and then concentrated to dryness.

The obtained product was recrystallized from acetonitrile to obtain 30.9 g of intermediate F-5. Further, this was dissolved in 300 cc of ethanol, and then the intermediate F-6 24.
6 g and 8.6 g of potassium carbonate were added, and the mixture was heated under reflux for 4 hours. After filtering off the precipitated inorganic salt, ethanol was distilled off under reduced pressure to dissolve the product in 500 cc of ethyl acetate.
It was washed 3 times with 00 cc of water. After drying the organic phase, the solvent was distilled off under reduced pressure. The product was purified by column chromatography and further recrystallized with a mixed solvent of ethyl acetate and hexane to obtain 14.0 g of Intermediate F-7. ( ¹ HNMR, F
The structure was identified by D mass spectrum and IR spectrum. )

Synthesis of Exemplified Compound MF-1 14.0 g of Intermediate F-7 was dissolved in 300 cc of methanol, 2.0 g of palladium-carbon (support rate: 5%) was added, and contacted under a hydrogen gas atmosphere for 4 hours. The reduction was performed.
After removing palladium-carbon as a catalyst by filtration, the solvent methanol was distilled off under reduced pressure to obtain 13.5 g of Intermediate F-8.

Further, this was dissolved in 150 ml of n-butanol, 2.26 g of divinyl sulfone was added, and the mixture was heated under reflux for 3 hours. After concentrating the solvent n-butanol, it was purified by silica gel column chromatography, and further recrystallized with a mixed solvent of ethyl acetate-hexane to obtain 1
1.5 g of intermediate F-9 was obtained. Next, the intermediate F-9 1
1.5 g of the product was dissolved in 100 ml of chloroform and ice-cooled to 5 ° C., whereupon N-chlorosuccinimide 1.81 was added.
g was added in small portions over about 2 hours. The reaction solution was washed with water and dried, the solvent was distilled off under reduced pressure, and the obtained product was recrystallized from acetonitrile to give white crystals of MF-1.
10.8 g was obtained. (The structure was identified by ¹ HNMR, FD mass spectrum and IR spectrum.)

In addition to the above specific examples, magenta couplers used in the present invention are disclosed in JP-A-63-307453.
Presentation compounds (1) to (1) described on pages 6 to 7 of the publication.
5), the presentation compounds (1) to (31), (46) to (50) described on pages 8 to 14 of JP-A-64-7041.
(52) to (60), and the presentation compounds (I-1) to (I-2) described on pages 3 to 5 of JP-A No. 64-66646.
4), exemplary compounds (6) to (8), (10) and (12) to those described on pages 5 and 6 of JP-A-1-277236.
(15), (18), (20), JP-A-2-16023.
Exemplified compound (M-4) described on pages 11 to 18 of Japanese Patent Publication No. 3
~ (M-35), (M-37), (M-50) to (M-
53), exemplary compounds (M-1) to (M-89) described on pages 5 to 9 of JP-A-2-161430, JP-A-2-
Exemplified compounds described in pages 5 to 8 of 296241 (M
-1) to (M-6), (M-8) to (M-12), (M
-14) to (M-27), and Exemplified compounds (M-2) described on pages 5 to 7 and 35 of JP-A-3-138645.
To (M-29), (m-2) to (m-28), JP-A-HEI-3
Compounds (M-3) to (M-5), (M-7) to (M-12), described on pages 5 to 9 of JP-A-200413
(M-14), (M-16) to (M-30), Japanese Unexamined Patent Publication No. HEI 3
Exemplary compounds (M-1) to (M-38) described on pages 6 to 10 of JP-A-138644 can be mentioned.

The magenta coupler used in the present invention is
It can be synthesized according to the method described in the above publications and the like. The magenta coupler used in the present invention is usually used in an amount of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ^{−2 to} 7 × 10 ⁻¹ mol per mol of silver halide.

The yellow and cyan couplers used in the silver halide photographic light-sensitive material according to the present invention are coupled with an oxidant of a color developing agent to form a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm. Any compound capable of forming a substance can be used, but a particularly representative one is a wavelength range of 350 to 500.
A yellow coupler having a spectral absorption maximum wavelength in nm and a known cyan coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm are typical.

A yellow coupler which can be preferably used in the silver halide photographic light-sensitive material of the present invention is a coupler represented by the general formula [Y-I] described on page 8 of Japanese Patent Application No. 2-234208. Can be mentioned. Specific compounds are described in YC-1 on pages 9 to 11 of the specification.
To those listed as YC-9. Among them, YC-described on page 11 of the same specification
8 and YC-9 are preferable because they can reproduce a preferable yellow color.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material according to the present invention include general formulas [CI] and [C-II] described on page 17 of Japanese Patent Application No. 2-234208. ] The coupler represented by these can be mentioned. Specific compounds are described in the same specification 18 to 21.
Those described as CC-1 to CC-9 on the page can be mentioned as preferred. One of these cyan couplers preferably used is a 2-acylamino-5-ethylphenol cyan coupler, which is disclosed in JP-A-2-251845.
Compounds described on page 5, lower right, page 14 to page 6, upper left of the specification, and specific examples thereof include coupler No. 5 in the upper right column on page 6 to upper left column on page 7 of the above specification. II-1 to II
-20 can be mentioned.

Of these, the most preferred one is II
It is a compound represented by -4. Another type of cyan coupler preferably used is a 2,5 diacylaminophenol type cyan coupler, which is disclosed in JP-A-2-25.
No. 1845, the compound described in the 7th line to the 3rd line to the lower right line of the 3rd page from the left end, and specific examples thereof include the coupler in the upper left column on page 4 to the lower left column on page 5 of the above specification. No. II-1 to I-31 can be mentioned.
Of these, the compound represented by 1-2 is most preferably used.

When the oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material of the present invention, it is usually added to a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher. If necessary, a low boiling point and / or a water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After the dispersion, or at the same time as the dispersion, a step of removing the low boiling point organic solvent is preferably added.

As the high-boiling organic solvent which can be used for dissolving and dispersing the coupler (and the photographically useful organic compound such as the following ultraviolet absorber and color turbidity preventing agent), 1
A high boiling organic solvent having a vapor pressure of 0.5 mmHg or less at 00 ° C. is preferable, and a compound having a dielectric constant of 6.0 or less is preferable. The dielectric constant indicates the dielectric constant at 30 ° C.
Specific examples of the compounds include compound examples II-1 to II-9 and III- described in JP-A-63-103245.
1 to III-6, compound examples H-1 to H-22 described in JP-A No. 1-196048, and JP-A No. 64-6664.
Compound examples II-1 to II-38 described in No. 6 can be preferably used. Among these, phthalic acid esters such as dioctyl phthalate, dinonyl phthalate and diisododecyl phthalate, and phosphoric acid esters such as tricresyl phosphate are particularly preferably used.

Ethyl acetate is preferably used as the low boiling point organic solvent. As a preferred surfactant used at the time of dispersion, a compound having a hydrophobic group having 8 to 30 carbon atoms and -SO3M group or -OSO3M group (M represents a hydrogen atom or a cation) in one molecule is exemplified. You can Specific examples of preferable surfactants include anionic surfactants A-1 to A- described in JP-A 64-26854, pages 55 to 56.
11, more preferably A-11 and A-8 can be mentioned. A surfactant having a fluorine atom in the alkyl chain is also preferably used.

It is also preferable to add these surfactants to the coating solution. These dispersions are usually added to a coating solution containing a silver halide emulsion or the like and coated.
It is preferably added to the coating solution within 0 hours, more preferably within 3 hours, and most preferably within 20 minutes. For the purpose of shifting the absorption wavelength of the color-forming dye, the compound (d-
11) and compounds such as the compound (A′-1) described on page 35 of the same specification are preferably used. Besides, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

The coating amount of the coupler is not particularly limited as long as a sufficiently high concentration can be obtained, but it is preferably 1 × 10 ^{−3 to} 5 mol, and more preferably 1 × 1 mol per mol of silver halide. It is used in the range of 10 ^-2 to 1 mol. It is preferable to use an anti-fading agent together with the magenta coupler according to the present invention.

As this compound, one is disclosed in
Examples thereof include phenyl ether compounds represented by the general formula I and the general formula II described on page 3 of the specification of -66541. Specific examples of the compounds include the compounds I-1 to I-32 and II-1 to II-18 described in the above-mentioned pages 3 to 5 of the specification. Among these, more preferable compounds are the compounds represented by I-13 and II-9.

The second anti-fading agent preferably used in combination with the magenta coupler is a phenolic compound represented by the general formula IIIB described in Japanese Patent Application No. 1-203812. Compound II described in the above specification
I-1, III-12, III-13, and III-14 are more preferable, and the compound represented by III-14 is particularly preferable.

The third anti-fading agent preferably used in combination with the magenta coupler is an amine compound represented by the general formula A shown in Japanese Patent Application No. 64-90445. Specific examples of the compound include A-1 to A-15 described in the upper right of the above specification. Of these, the more preferred compound is A-3.

It is preferable to use an anti-fading agent in combination with the yellow coupler and the cyan coupler according to the present invention.
Among these, the preferred anti-fading agent is JP-A 1-1960.
Examples thereof include compounds represented by the general formula I ′ described on page 8 of No. 49 specification. More preferred compounds are the compounds represented by I-10 and I-13 described on page 9 of the above specification. The anti-fading agent used in combination with these magenta, yellow and cyan couplers is preferably added in the same oil oil droplet as the coupler in a proportion of 0.1 to 3 moles per 1 mole of the coupler, and more preferably 0. More preferably, it is added in a ratio of 5 to 1.5 mol.

As the anti-fading agent, it is preferable to use different kinds of compounds in combination, and a phenolic compound represented by the general formula [III-B] described in Japanese Patent Application No. 1-203812 and Japanese Patent Application Laid-Open No. 2-66541. The combined use of the phenyl ether compounds represented by the general formulas I and II described on page 3 of the above is mentioned as a preferable combined use. Also, Japanese Patent Application No. 1-30281
A combination of the phenolic compound represented by the general formula IIIB described in No. 2 and the amine compound represented by the general formula A represented by JP-A-64-90445 is also preferable.

Examples of the ultraviolet absorbent according to the present invention include compounds having a spectral absorption maximum wavelength in the ultraviolet region (400 nm or less) and a molecular extinction coefficient of 5000 or more. As preferred compounds, there may be mentioned the compounds represented by the general formula III-3 described in JP-A-1-250944 and the compounds represented by the general formula I described in Japanese Patent Application No. 2-102521.

Specific examples of preferable ultraviolet absorbers include, for example, III described in JP-A-1-250944.
c-1 to IIIc-17 and JP-A-64-666.
III-1 to III-24 described in Japanese Patent No. 46 and UV-1L described in Japanese Patent Application Laid-Open No. 63-187240.
To UV-22L and UV-1S described in the above specification.
To UV-19S and compounds I-1 to I-23 described in Japanese Patent Application No. 2-102521. Among them, preferred compounds include JP-A 1-25
Examples thereof include IIIc-7 and IIIc-12, which are described in the upper left of page 15 of the specification of 0944, and UV-23L, a liquid ultraviolet absorber described in JP-A-63-187240.

These UV absorbers are preferably added by the above-mentioned dispersion method, but in the present invention, the high boiling point organic solvent used in the UV absorber layer is 0.3% by weight ratio to the UV absorber. It is added at a rate of 0 to 0.
It is preferably added in a proportion of 0.1 to 0, most preferably 0. As the high boiling point organic solvent, the compound used for dispersing the coupler is preferably used. In the present invention, the ultraviolet absorber is preferably contained in the non-photosensitive layer. Further, a non-photosensitive intermediate layer further distant from the silver halide emulsion layer farthest from the support and a silver halide emulsion layer farthest away from the support and a second It is a non-light-sensitive layer intermediate between the silver halide emulsion layers which are distant from each other.

In the present invention, a hydroquinone compound may be added to the silver halide photosensitive layer in order to adjust the gradation. It is also preferable to add a hydroquinone compound to the non-photosensitive layer in order to prevent color turbidity during silver halide photosensitivity. Preferred examples of the hydroquinone compound added to the above-mentioned photosensitive layer and non-photosensitive layer include compounds represented by the general formula XII-1 described in Japanese Patent Application No. 2-39041 and Japanese Patent Application No. 256256/1990. Examples thereof include the compounds represented by the general formula II described in the specification.

Specific examples of preferable compounds include XII-1 described in Japanese Patent Application No. 2-39041;
Examples thereof include compounds represented by XII-37 to XII-42, and compounds represented by II-1 to II-14 described in Japanese Patent Application No. 2-256124. Particularly preferred compounds include XII-4 and XII-13 described in Japanese Patent Application No. 2-39041, and Japanese Patent Application No. 2-256.
The compound shown by II-8 and II-14 of the 124th specification is mentioned. Further, it is preferable to use a quinone compound which is an oxidant of these hydroquinone compounds in combination.

In the present invention, it is preferable to add a fine particle powder (so-called matting agent) to the layer and the surface layer which are most distant from the support. As the matting agent, compounds described in JP-A-2-73250, page 4, line 9 to line 20, are preferable, and crystalline or amorphous silica is most preferable. These can be used alone or in combination of two or more. The average particle size of the matting agent is preferably 1 to 10 micrometers, more preferably 2 to 7 micrometers.
A micrometer is more preferred. The coating amount of the matting agent is 0.021 to 0.1 g / m ² , and further 0.0
25 to 0.08 / m ² is more preferable.

Further, it is preferable to add a high boiling point organic solvent to the surface layer. As a preferable high boiling point organic solvent to be added to the surface layer, a high boiling point organic solvent having a vapor pressure at 100 ° C. of 0.5 mmHg or less is preferable, and a compound having a dielectric constant of 6.0 or less is more preferable. The dielectric constant indicates the dielectric constant at 30 ° C. Specific examples of compounds include JP-A-63-63
-103245 described compound examples II-1 to II-
9 and III-1 to III-6, JP-A-1-19
Compound Examples H-1 to H-22 described in 6048, and Compound Examples II-1 to I described in JP-A No. 64-66646.
I-38 can be preferably used.

Among these, phthalic acid esters such as dioctyl phthalate, dinonyl phthalate and diisododecyl phthalate, and phosphoric acid esters such as tricresyl phosphate are particularly preferably used. The amount added is 1 mg
/ M ² to 100 mg / m ² , preferably 10 mg /
m ² to 50 mg / m ² .

In the present invention, it is preferable to add an oil-soluble dye. The oil-soluble dye means an organic dye having a solubility in water at 20 ° C. of 0.01 or less, and preferably a compound having a molecular absorption coefficient of 20000 or more at a maximum absorption wavelength at a wavelength of 400 nm or more. As a preferable compound, Japanese Patent Application No. 64-64
General formulas II and I shown on page 26 of the specification No. 1064
II compounds may be mentioned. Specific examples of preferable compounds include compounds 1 to 27 described on pages 29 to 32 of the above specification. Compound 4 among these
And 9 are particularly preferred. The oil-soluble dye is preferably added to the non-photosensitive layer, and is preferably added in an amount of 0.5 to 5 mg / m ² .

In the present invention, it is preferable to add a fluorescent whitening agent to the light-sensitive material. As a fluorescent whitening agent, Japanese Patent Application No.
Compounds represented by the general formula II described in the specification of -54396 are preferable. As specific compound examples, the above-mentioned specification 1
Compounds 1 to 6 described on pages 8 to 20 are mentioned. Of these, compound No. The compounds represented by 3, 1, and 5 are particularly preferable. These optical brighteners are preferably added to the non-photosensitive layer. The amount added is 0.001
0.3 mg / m ² is preferable, and further 0.1 to 0.2
More preferred is mg / m ² .

In the present invention, it is preferable to add a water-soluble polymer compound which complements the above-mentioned optical brightening agent and enhances the optical brightening effect. As preferred compounds, polyvinylpyrrolidone and polymers containing vinylpyrrolidone as a repeating unit are used. It is preferable that these are contained in the ultraviolet absorber-containing layer farthest from the support and / or in a layer further distant from the layer.

For the silver halide photographic light-sensitive material of the present invention, it is preferable to use water-soluble dyes having absorption in various wavelength regions for the purpose of preventing irradiation and halation. As a preferable anti-irradiation dye, a general formula I described in JP-A-62-253146 is used.
Compounds represented by I (specific examples of compounds include compounds II-1 to II described on pages 12 to 13 of the above specification)
-19), a compound represented by the general formula I described in JP-A No. 64-26850 (specific examples of the compound are the same as in the above specification 7).
Compound Nos. 1 to 85), the compound represented by formula I described in JP-A-2-97940 (specific examples of the compound are the same as above, page 5, lower columns to 9).
No. described in the upper part of the page Compounds represented by 1 to 103)
Can be mentioned.

Of these, particularly preferred compounds are No. 1 of the compounds represented by the general formula I described in JP-A No. 64-26850. 47, and JP-A-2-97
No. 940 of the compound represented by the general formula I shown in No. 940. The compound represented by 54. As the anti-irradiation dye, it is preferable to use dyes having different maximum absorption wavelengths in combination, a dye having a maximum absorption wavelength of 600nm to 700nm, a dye having a maximum absorption wavelength of 500nm to 600nm, and a maximum absorption wavelength of 400nm to 500nm. It is preferable to use a dye together. These dyes may be added to the outer layer, but are preferably added to the non-photosensitive layer. The addition amount, each of the compounds per preferably 1 to 100 mg / m ^2, still more preferably is 3~60mg / m ^2.

In the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder for dispersion and coating liquid. For how to make gelatin,
For example, T. H. James; The Thory o
f The Photographic Proccs
s, 4th cd. It is prepared by the description on pages 119,755 and pages 119 to 124, etc. of basic silver salt photography of photographic engineering. As raw materials, cow bone (ossein), cowhide (hide), pig skin (pig skin) are used. As the treatment, alkali treatment is preferably performed.

In the present invention, the isoelectric point of the alkali-treated gelatin is preferably 4.5 or more, more preferably 5 or more. Gelatin that has been subjected to post-ion exchange treatment is preferably used. It may be cation exchange, anion exchange, or both ion exchange, but a preferable treatment method is, for example, the method described in JP-A-63-296045, page 2, upper right, third line to lower left, tenth line. Further, gelatin which is post-treated with hydrogen peroxide is also preferably used. As for the composition of gelatin, it is more preferable that the low molecular weight component is small and that the high molecular weight component is large. For the measuring method of high-molecular weight and low-molecular weight components, see JP-A 1-2
The method described in No. 65247, page 2, lower left line 15 to page 3, upper left line 8 can be used. According to this method, it is more preferable that the high molecular weight component is 30% or more and / or the low molecular weight component is 40% or less.

The jelly strength of gelatin is preferably high, and more preferably 250 or more. Further, it is preferable that the content of ions, which are impurities contained in gelatin, is low.
It is more preferably ppm or less. Heavy metal ions such as iron and copper ions are 500 ppm or less in total, and 10 for each component.
ppm or less is preferable. Further, the sulfur component is preferably 3 ppm or less. Further, the higher the specific rotation of gelatin is, the more preferable it is, and the more preferable value is 150 or more. Also, it is naturally better that gelatin is less colored. 4 of a 16% by weight aqueous gelatin solution
The transmittance at 50 nm is preferably 50% or more.

In the present invention, a binder hardener is used. As a hardener, vinyl sulfone type hardener,
Chlorotriazine type hardeners are preferably used. As a vinyl sulfone type hardener, JP-A-61-24905 is used.
No. 4, page 25, upper right, line 13 to page 27, upper right 2
The compounds described in the line can be preferably used. Furthermore, the compound H-12 described on page 26 of the above specification is more preferable. As a chlorotriazine type hardener, Japanese Patent Laid-Open No. Sho 6
No. 1-245153, page 3, lower left, first line to page 3, lower right, lower line 4 and page 3, lower right, lower line 4 to 5
The compounds described in the lower left of the page are preferably used. Furthermore, the compound represented by XII-1 described on page 4 of the above specification is more preferable. These hardeners are preferably used in combination with different compounds and may be added to any layer. The hardener is
It is preferably used in an amount of 0.1 to 10% by weight based on the binder.

In the present invention, it is preferable to add an antifungal agent to either layer. As a preferable antifungal agent, a compound represented by the general formula II described on page 9 of Japanese Patent Application No. 1-298092 is preferable. Specific examples of the compound include the compound example No. 1 described on pages 69 to 70 of the above specification. 9 to 22. Of these, particularly preferred compounds are No. It is a compound represented by 9.

The silver halide grains according to the present invention may have any shape. One good example is
It is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756 and 4,225,666,
JP-A-55-26589 and JP-B-55-42737. The Journal of Photographic Science (J. Photogr. Sci) 21, 39 (1
973) and other methods described in the literature, etc.
Particles having a tetradecahedral shape, a dodecahedron shape, or the like can be prepared and used. Further, grains having twin planes may be used. The silver halide grain according to the present invention may be a grain having a single shape, or may be a mixture of grains having various shapes.

The grain size of the silver halide grain according to the present invention is not particularly limited, but considering other photographic performance such as rapid processing property and sensitivity, it is preferably 0.1 to 1.2 μm.
m, and more preferably 0.2 to 1.0 μm. The particle size can be measured by various methods commonly used in the technical field. As a typical method, Loveland's "particle size analysis method"
(ASTM Symposium on Right Microscopy, pp. 94-122, 1955) or "Theory of Photographic Processes, 3rd Edition" (co-authored by Mies and James, Chapter 2, published by Macmillan, Inc.). 1966).

This particle size can be measured by using the approximated diameter of the projected area of the particle. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The grain size distribution of the silver halide grains of the present invention may be polydisperse. It may be monodisperse. The coefficient of variation is preferably 0.22 or less, more preferably 0.1.
The number of monodisperse silver halide grains is 5 or less. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is defined by the following equation. Coefficient of variation = S / R (where S is the standard deviation of the particle size distribution, and R is the average particle size.)

The grain size as used herein means the diameter of a spherical silver halide grain, and the projected image of a cubic or non-spherical grain when converted into a circular image of the same area. Represents the diameter of. As a device and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method of making seed particles and the method of growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a double mixing method, a combination thereof, etc., but the one obtained by the double mixing method. Is preferred. Further, the pAg controlled double jet method described in JP-A-54-48521 may be used as one form of the simultaneous mixing method.

In addition, JP-A-57-92523 and 57-57.
-92524, etc., an apparatus for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition apparatus arranged in a reaction mother liquor, water-soluble silver described in German Published Patent 2,921,164, etc. Apparatus for adding salt and water-soluble halide salt aqueous solution with continuously changing concentration, Japanese Patent Publication No. 56-
An apparatus for forming grains while keeping the distance between silver halide grains constant by taking out the reaction mother liquor from the reactor described in No. 501776 and concentrating it by ultrafiltration may be used.

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

A publicly known method can be used for reduction sensitizing the silver halide emulsion according to the present invention. For example,
It is also possible to use a method of adding various reducing agents,
A method of aging under conditions of high silver ion concentration or a method of aging under conditions of high pH can be used.

As the reducing agent used for reduction sensitization of the silver halide emulsion according to the present invention, stannous chloride of stannous chloride,
Examples thereof include boranes such as tri-t-butylamine borane, sodium sulfite, sulfites such as potassium sulfite, reductones such as ascorbic acid, and thiourea dioxide. Among these, thiourea dioxide, ascorbic acid and its derivatives, and sulfite can be preferably used. Compared with the case where reduction sensitization is performed by controlling the silver ion concentration and pH during ripening, the method using a reducing agent as described above is excellent in reproducibility and is preferable.

These reducing agents are dissolved in a solvent such as water or alcohol and added to the silver halide emulsion for ripening, or they are added during the formation of silver halide grains to reduce and increase them simultaneously with grain formation. You may feel. The amount of these reducing agents to be added needs to be adjusted according to the pH of the silver halide emulsion, the silver ion concentration, etc., but generally 10 ^-7 to 10 ^-2 mol per mol of the silver halide emulsion. Is preferred.

After the reduction sensitization, a small amount of an oxidizing agent may be used to modify the reduction sensitizing nucleus or deactivate the remaining reducing agent. Examples of compounds used for such purposes include:
Examples thereof include potassium hexacyanoferrate (III), bromosuccinimide, p-quinone, potassium perchlorate, and hydrogen peroxide solution.

The silver halide emulsion according to the present invention can be reduction-sensitized and can be used in combination with a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer. As the chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and the sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and the like.

As the gold sensitizer applied to the silver halide emulsion according to the present invention, various gold complexes other than chloroauric acid, gold sulfide, gold thiosulfate and the like can be added. Examples of the ligand compound used include dimethylrhodnin, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used varies depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc.
It is preferably 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol. More preferably 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸
It is a mole.

The silver halide emulsion according to the present invention has the purpose of preventing fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reducing performance fluctuations during storage, and preventing fog that occurs during development. Known antifoggants and stabilizers can be used.

As an example of the compound which can be used for such purpose, there can be mentioned the compound represented by the general formula (II) described in JP-A-2-146036, page 7, lower column, and specific examples thereof are given. The compounds include (IIa-1) to (IIa-8) and (IIb-) described on page 8 of the publication.
1)-(IIb-7) compounds, 1- (3-methoxyphenyl) -5-mercaptotetrazole and the like can be mentioned.

These compounds can be added in a step such as a step of preparing silver halide emulsion grains, a step of chemical sensitization, the end of the chemical sensitization step, a step of preparing a coating solution, etc., depending on the purpose. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ⁻⁵ mol to 5 × 10 ⁵ mol per mol of silver halide.
It is preferably used in an amount of about ^-4 mol.

[0242] When added to the end of the chemical sensitization, the amount of 1 × 10 ^-6 mol to 5 × 10 ^-2 mol per mol of silver halide is preferred, 1 × 10 ^-5 mol to 5 × 10 ^{- 3} mol is more preferred. When it is added to the silver halide emulsion layer in the coating solution preparation step, the amount is 1 per mol of silver halide.
The amount is preferably in the range of × 10 ^-6 mol to 1 × 10 ^-1 mol.
It is more preferably x10 ^-5 mol to 1 x 10 ^-2 mol. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating solution coating is preferably about 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol.

When the silver halide photographic light-sensitive material according to the present invention is used as a color photographic light-sensitive material, it is spectrally sensitized in a specific region of a wavelength range of 400 to 900 nm by combining with a yellow coupler, a magenta coupler and a cyan coupler. A layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

Any known compound can be used as the spectral sensitizing dye used in the silver halide emulsion according to the present invention, and as the blue-sensitive sensitizing dye, Japanese Patent Application No. 2-5 can be used.
BS-1 to 108 described in No. 1124, pages 108 to 109
8 can be preferably used alone or in combination. As the green sensitizing dye, GS-1 to 5 described on page 110 of the same specification are preferably used. Examples of the red sensitizing dye include RS-described on pages 111 to 112 of the same specification.
1-8 are preferably used.

When the silver halide photographic light-sensitive material according to the present invention is exposed by a printer using a semiconductor laser, it is necessary to use a sensitizing dye having infrared sensitivity, and the infrared-sensitive sensitizing dye As for Japanese Patent Application No. 3-7361
The dyes of IRS-1 to 11 described in No. 9 specification, pages 12 to 14 are preferably used. Further, it is preferable to use the supersensitizers SS-1 to SS-9 described on pages 14 to 15 of the same specification in combination with these dyes.

When the silver halide photographic light-sensitive material according to the present invention is exposed using a laser, it is advantageous to use an exposure device using a semiconductor laser in terms of downsizing of the device. In scanning exposure, the exposure time per pixel corresponds to the exposure time actually received by the silver halide emulsion, but the exposure time per pixel is the luminous flux in the case of scanning exposure with laser light. In the spatial change in the intensity of the light flux, the outer edge of the light flux is defined as the point where the light intensity reaches the maximum value of 1/2, and the outer edge of the light flux and the line that is parallel to the scanning line and that passes through the point where the light intensity is the maximum. When the distance between two intersecting points is the diameter of the light beam, the (light beam diameter) / (scanning speed) can be considered as the exposure time per pixel. As the exposure time per pixel becomes shorter, the relationship between the exposure time and the color density tends to become more complicated, and the present invention is particularly effective when an apparatus having a short exposure time per pixel is used.

A laser printer device that is considered to be applicable to such a system is, for example, Japanese Patent Laid-Open No.
-4071, JP-A-59-11062, JP-A-63.
-197947, JP-A-2-74942, JP-A-2
No. 236538, Japanese Examined Patent Publication No. 56-14963, Japanese Examined Patent Publication No. 56-40822, European Wide Area Patent 77410, Department of Electronic Communication, Technical Research Report 80, No. 244, and Movie Television Technical Journal 1984/6 (382), 34-. Some are described on page 36.

As the reflective support according to the present invention, any material may be used, such as white pigment-containing polyethylene-coated paper, baryta paper, vinyl chloride sheet, white pigment-containing polypropylene, polyethylene terephthalate support and the like. Can be used. Above all, a support having a polyolefin resin layer containing a white pigment on its surface is preferable.

As the white pigment used in the reflective support of the present invention, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina, alumina hydrate, oxidation Examples thereof include titanium, zinc oxide, talc and clay. The white pigment is preferably barium sulfate or titanium oxide. The white pigment may be surface-treated with aluminum hydroxide, alcohol, a surfactant or the like.

The amount of the white pigment contained in the waterproof resin layer on the surface of the reflective support according to the present invention is preferably 10% by weight or more as the content in the waterproof resin layer,
Further, the content is preferably 13% by weight or more, and more preferably 15% by weight or more.

The degree of dispersion of the white pigment in the water resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, and more preferably 0.10 or less as the coefficient of variation described in the above publication. Is more preferable. The surface of the paper support is preferably smoother, and the center average roughness (SRa) is preferably 1.0 micrometer or less. The calculation method of SRa is calculated by the formula described on page 6 of the specification of Japanese Patent Application No. 3-2576.

The base paper used for the support according to the present invention is
It is selected from commonly used materials. That is, 1 natural pulp such as sulfite-bleached softwood pulp (NBKP), sulfite-bleached hardwood pulp (LBKP), alkali-processed sulfate-bleached softwood pulp (NBSP), and alkali-processed sulfate-bleached hardwood pulp (LBSP) You may use it in combination of 2 or more types. When used in combination, a desirable pulp blending ratio is a hardwood pulp / softwood pulp ratio of 95/5 to 60/40.

In the present invention, it is preferable to add various additives shown below to the base paper to enhance paper strength such as water resistance. For example, as the sizing agent, alkyl ketene dimer fatty acid salt, rosin, maleated rosin, alkenyl succinate,
Alkyl succinates, polysaccharides and the like are used, but kirketene dimer fatty acid salts are preferably used. It is preferable to use 0.2 to 2% of these per pulp. As the dry paper strengthening agent, cationized starch,
Cationized polyacrylamide, anionized polyacrylamide, carboxy-modified polyvinyl alcohol and the like are used, but cationized starch and anionized polyacrylamide are preferably used. Further, as the wet paper strength enhancer, melamine resin, urea resin, epoxidized polyamide resin, etc. are used, but epoxidized polyamide resin is preferably used.

Generally, the surface of the pulp is tub-sized or size-pressed with a liquid containing a water-soluble polymer additive. As the water-soluble polymer, cationized starch, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylamide, gelatin, etc. are used,
Preferred are cationized starch and polyvinyl alcohol. Further, as the inorganic electrolyte, salt, bowsho, etc. are used, but salt is preferable.

Glycerin, polyethylene glycol, etc. are used as the hygroscopic substance, hydrochloric acid, sodium hydroxide, sodium carbonate, etc. are used as the pH adjusting agent, and other dyes (preferably blue dye and ultramarine blue), optical brighteners, An additive such as an antistatic agent and an antifoaming agent is used in combination. After the pulp is appropriately crushed, it becomes a pulp slurry containing the above additives as required, and is made into paper by a paper machine such as a Fourdrinier paper machine and dried and supercalendered. Surface sizing is performed before or after this drying.

The support is preferably a base paper obtained as described above, coated on both sides with a polyolefin resin. Examples of the polyolefin resin include polyethylene,
It is a homopolymer of α-olefin such as polypropylene and a mixture of these polymers, and particularly preferable polyophylene is a high density polyethylene, a low density polyethylene, or a mixture thereof. The molecular weight of these polyophylenes is not particularly limited, but polyophylenes generally in the range of 20,000 to 200,000 are used.

The thickness of the polyolefin resin coating layer is not particularly limited, and is usually about 15 to 50 μm. When the support is a paper support, various forms of support can be used, for example, the support has a thickness of 80.
~ 180 micrometer thin base paper, utility model 64-
The peel-adhesive type and the thick base paper described in the specification of No. 29550 can also be used. When a support such as polypropylene or polyethylene terephthalate is used, it can be adjusted by adjusting the amount of white pigment applied to each of transparent, translucent and opaque types. The oxygen permeability of the support is 2.
It is preferably 0 ml / m ² · hr · atm or less.

The silver halide photographic light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment or the like on the support surface, if necessary, and then directly or undercoat layer (adhesiveness of the support surface, Applied through one or more undercoat layers for improving antistatic property, dimensional stability, abrasion resistance, hardness, antihalation property, friction property and / or other property) Good. When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. As a coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are particularly useful.

The produced print light-sensitive material is exposed through a processed negative film. Various types of negative films can be used. A preferred negative film that can be used with negative films having various spectral sensitivities is Konica Color Super DD100. More preferably, Konica Impress
a50, Fuji Riara. In addition, the exposure time is in a wide range from several tens of milliseconds to several tens of seconds. As the exposure method at this time, various methods which are usually carried out at a developing station can be used. As a device preferably used as a printer, for example, Konica Printer CRP-5N2,
SCP-8015, KCP-7N3, Gretag 314
1 printer, Agfa MSP printer, Kodak C
LAS35 printer etc. are mentioned. It is also preferable to produce a large-sized print using a stretcher or an enlarging machine.

In the image forming method of the present invention, the time from exposure to development may be any time, but a shorter time is preferable in order to shorten the overall processing time. The silver halide photographic light-sensitive material according to the present invention is
Even when the time from exposure to development is 30 seconds or less, the change in image density is small, and a high-quality image can be stably obtained, so that it can be advantageously used. As the aromatic primary amine developing agent used in the present invention. Known compounds can be used. The following compounds can be mentioned as an example of these compounds.

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-methyl-4- (N-ethyl-N- (β
-Hydroxyethyl) amino) aniline CD-6) 4-amino-3-methyl-N-ethyl-N
-(Β-Methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8) N, N-dimethyl-p-phenylenediamine CD-9) 4-amino-3-methyl-N-ethyl-N
-Methoxyethylaniline CD-10) 4-amino-3-methyl-N-ethyl-N
-(Β-Ethoxyethyl) aniline CV-11) 4-Amino-3-methyl-N-ethyl-N
-(Β-Butoxyethyl) aniline

The color developing agent used in the image forming method of the present invention may be used alone or in combination with other known p-phenylenediamine derivatives. In the image forming method according to the present invention, the compound used in combination with the compound represented by the general formula (I) is (CD-5),
(CD-6) and (CD-9) are preferred. These p-
The phenylenediamine derivative is generally used in the form of a salt such as sulfate, hydrochloride, sulfite, nitrate, p-toluenesulfonate.

The color developer according to the present invention may contain the following developer components in addition to the above components. As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, silicates, etc. may be used alone or in combination to cause precipitation. Without p
It can be used together within a range that maintains the H stabilizing effect. Further, disodium hydrogen phosphate, for the purpose of preparation or for the purpose of increasing ionic strength,
Various salts such as dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, borate and the like can be used.

If necessary, inorganic and organic antifoggants can be added. For the purpose of suppressing development, halide salt ions are often used,
In the image forming method according to the present invention, since it is necessary to finish development in a very short time, chloride ions are mainly used, and potassium chloride, sodium chloride, etc. are used.
The amount of chloride ion is approximately 3.0 × 10 ^-2 mol or more, preferably 4.0 × 1 per liter of the color developing solution.
It is 0 ^{-2 to} 5.0 x 10 ^-1 mol. Bromide ion can be used within a range that does not impair the effects of the present invention, but has a large effect of suppressing development, and is approximately 1.0 × 10 ⁻³ mol or less, preferably 5.0 per liter of color developing solution. It is preferably not more than × 10 ^-4 mol.

If necessary, a development accelerator can be used. Examples of development accelerators include various pyridinium compounds represented by US Pat. Nos. 2,648,604, 3,671,247 and JP-B-44-9503, other cationic compounds, and phenosafranine. Cationic dyes, neutral salts such as thallium nitrate, US Pat. Nos. 2,533,990 and 2,531,
No. 832, No. 2,950,970, No. 2,577,1
No. 27 and Japanese Patent Publication No. 44-9504, polyethylene glycol and its derivatives, nonionic compounds such as polythioethers, organic solvents, organic amines, ethanolamine, ethylenediamine, diethanolamine, and triethylamine described in Japanese Patent Publication No. 44-9509. Ethanolamine and the like are included. In addition, phenethyl alcohol described in U.S. Pat. No. 2,304,925 and others, acetylene glycol, methyl ethyl ketone, cyclohexanone, pyridine, ammonia, hydrazine, thioethers, amines and the like can be mentioned.

Further, in the color developing solution according to the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin and other Japanese Patent Publication No. 47-33378,
The compounds described in JP-A-44-9509 can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developing agent may be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol sulfate, phenidone, N, N'-diethyl-p-aminophenol sulfate, N, N, N ', N'-tetramethyl-p. -Phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually 0.01 to 1.0 per liter of a developing solution.
g used. Besides this, competing couplers if necessary,
Fogging agent, development inhibitor releasing coupler (so-called DI
R couplers), development inhibitor releasing compounds and the like can be added. Furthermore, various additives such as other stain preventing agents, sludge preventing agents, and multi-layer effect accelerators can be used.

Each component of the color developing solution can be adjusted by sequentially adding and stirring to a fixed amount of water. In this case, the component having a low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. In addition, more generally, a plurality of components obtained in stable coexistence are added to a concentrated aqueous solution, or in a solid state, those prepared in advance in a small container are added to water, and color development according to the present invention is performed by stirring. The liquid can also be adjusted.

In the present invention, the above color developing solution can be used in an arbitrary pH range, but from the viewpoint of rapid processing, it has a pH of 9.
It is preferably 5-13.0, more preferably p
It is used in the range of H9.8 to 12.0. The processing temperature for color development according to the present invention is preferably 35 ° C. or higher and 70 ° C. or lower. It is preferable that the temperature is higher because the treatment can be performed for a shorter time, but it is preferable that the temperature is not so high in view of the stability of the treatment liquid, and it is preferable that the treatment is performed at 37 ° C or higher and 60 ° C or lower.

The color development time is conventionally about 3 minutes and 30 seconds, but in the present invention, it is preferably 35 seconds or less, more preferably 20 seconds to 3 seconds.
The processing steps substantially consist of a color development step, a bleach-fixing step, and a water washing step (including a stabilization treatment as an alternative to water washing), but steps may be added or have the same meaning as long as the effects of the present invention are not impaired. Can be replaced with For example, the bleach-fixing step can be separated into a bleaching step and a fixing step, or the bleaching step can be performed before the bleach-fixing step.

As the processing step used in the image forming method of the present invention, it is preferable to provide a bleach-fixing step immediately after the color developing step. The bleaching agent that can be used in the bleach-fixing solution used in the image forming method of the present invention is not limited, but is preferably a metal complex salt of an organic acid. The complex salt is a polycarboxylic acid, aminopolycarboxylic acid or oxalic acid,
Organic acids such as citric acid are coordinated with metal ions such as iron, cobalt and copper. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes a polycarboxylic acid or an aminopolycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific examples of these compounds are described in JP-A-1
Compounds [2] to [20] described on page 58 to 59 of the specification of -205262 can be mentioned. These bleaching agents are used in an amount of 5 to 450 g, preferably 20 to 250 g, per liter of the bleach-fixing solution. As the bleach-fixing solution, a solution containing a silver halide fixing agent in addition to the bleaching agent as described above and, if necessary, a sulfite as a preservative is applied.

Further, iron (III) ethylenediaminetetraacetate
A bleach-fixing solution having a composition in which a large amount of a halide such as ammonium bromide is added in addition to the acid bleaching agent and the silver halide fixing agent, and further ethylenediaminetetraacetic acid iron (I
II) It is possible to use a special bleach-fixing solution having a composition comprising a combination of an acid bleaching agent and a large amount of a halide such as ammonium bromide. As the halide,
In addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can be used.

The above-mentioned silver halide fixing agent contained in the bleach-fixing solution is a compound which reacts with silver halide as used in ordinary fixing processing to form a water-soluble complex salt, for example, potassium thiosulfate or thiosulfate. Typical examples thereof include thiosulfates such as sodium and ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, and thiocyanates such as ammonium thiocyanate, thiourea and thioether.

These fixing agents are used in an amount of 5 g or more per liter of the bleach-fixing solution in a range where they can be dissolved, but generally they are used in an amount of 70 to 250 g. In the bleach-fixing solution, various pH buffering agents such as borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide are used alone or in combination with 2. It is possible to include more than one species in combination. Further, various fluorescent whitening agents, antifoaming agents or surfactants may be contained. In addition, preservatives such as bisulfite adducts of hydroxylamine, hydrazine and aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohol and nitrates, organic compounds such as methanol, dimethyl sulfonamide and dimethyl sulfoxide. A solvent and the like can be contained as appropriate.

The bleach-fixing solution according to the present invention is described in JP-A-46 / 46
-280, Japanese Patent Publication No. 458506, 46-556.
No., Belgian Patent 770,910, Japanese Patent Publication No. 45-88
36, 53-9854, JP-A-54-71634.
And various bleaching accelerators described in JP-A-49-42349 and the like can be added.

The pH of the bleach-fixing solution is used at 4.0 or higher, but it is generally used in the range of pH 4.0 to 9.5.
It is preferably used at a pH of 4.5 to 8.5. Most preferably, it is used in the pH range of 5.0 to 8.5. The treatment is performed at a temperature of 80 ° C. or lower, preferably 55 ° C. or lower, while suppressing evaporation and the like. The processing time for bleach-fixing is preferably 3 to 45 seconds, more preferably 5 to 30 seconds.

In the developing treatment according to the present invention, the above-mentioned color development and bleach-fixing steps are followed by washing treatment with water.
Hereinafter, preferred embodiments of the water washing treatment will be described.
As the compound preferably used in the washing solution, a chelating agent having a chelate stabilization constant for iron ions of 8 or more is preferable. Here, the chelate stabilization constant refers to L. G.
Sillen, A .; E. Martell, "Stab
ility Constants of McTali
on Complcxes ", The Chemical
Society, London (1984) and S.S. C
haberck, A .; E. Martell, "Org
anic Sequestering Agent
s ", Wilcy (1959), etc., and generally known constants.

As chelating agents having a chelate stability constant of 8 or more with respect to iron ions, which are commonly used in washing solutions, organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds, etc. Is mentioned. The iron ion means ferric ion. Specific examples of the chelating agent having a chelate stability constant with ferric ion of 8 or more include JP-A 1-2
The compounds described in No. 05162, page 63, line 15 to page 64, line 17 can be mentioned. The amount of the chelating agent used is preferably 0.01 to 50 g, and more preferably 0.05 to 20 g, per liter of the washing liquid.

As a compound to be added to the washing solution, an ammonium compound is mentioned as a particularly preferable compound. These are supplied by ammonium salts of various inorganic compounds, and specific examples thereof include compounds described in JP-A-1-205162, page 65, line 5 to page 66, line 11. The addition amount of the ammonium compound is preferably 1.0 × 10 ⁻⁵ mol or more per liter of the washing liquid,
More preferably in the range of 0.001 to 5.0 mol,
More preferably, it is in the range of 0.002 to 1.0 mol.

[0281] Further, it is desirable that the washing solution contains sulfite within the range where bacteria are not generated. The sulfite salt contained in the washing solution may be any one such as an organic substance or an inorganic substance as long as it releases a sulfite ion, but is preferably an inorganic salt, and as a preferable specific compound,
Sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite, cartaraldehyde bis sodium bisulfite, succinic acid Aldehyde bis sodium bisulfite etc. are mentioned.

It is preferable that at least 1.0 × 10 ^-5 mol of the sulfite is added to 1 liter of the washing solution,
5 × 10 ^{−5 to} 1.0 × 10 ⁻¹ mol is more preferable. It may be added directly to the washing solution, but it is preferably added to the washing replenisher. The water-washing solution used in the present invention preferably contains a mildew-proofing agent, which can prevent sulfidation and improve image storability. Examples of the mildew-proofing agent that can be used in the washing solution according to the present invention include sorbic acid, benzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guadinine compounds, morpholine compounds, and quaternary phosphonium compounds. , Ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds, pyronone compounds and amino compounds.

Specific compounds are described in JP-A 1-20
The compounds described in No. 5162, page 68, line 10 to page 72, line 16 are mentioned. Among these compounds, particularly preferably used compounds are thiazole compounds, sulfamide compounds and pyronone compounds. The amount of the antifungal agent added to the washing liquid is 0.00 per 1 liter of the washing liquid.
It is preferably used in the range of 1 to 30 g, and more preferably 0.003 to 5 g.

The washing liquid according to the present invention preferably contains a metal compound in combination as a chelating agent. Such metal compounds include Ba, Ca, Cc, Co, In,
La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Z
Examples thereof include compounds of r, Mg, Al, and Sr.
These metal compounds can be supplied as an inorganic or organic salt such as a halide salt, a sulfate salt, a carbonate salt, a phosphate salt or an acetate salt, a hydroxide or a water-soluble chelate compound. The amount of these compounds added is preferably 1.0 × 10 ^{−4 to} 1.0 × 10 ⁻¹ mol per 1 liter of the washing liquid.
More preferably, it is 0 × 10 ^{−4 to} 2.0 × 10 ⁻² mol.

In addition to the above, a compound having an aldehyde group may be used as the one contained in the washing solution according to the present invention. Specific compounds include, for example, JP-A-1-20518.
No. 2 specification, exemplary compounds 1 to 73 described on pages 73 to 75
Exemplified compound 32 may be mentioned. The compound having an aldehyde group is 0.1 to 5 per 1 liter of washing water.
It is preferably used in the range of 0 g, especially 0.5
It is preferably used in the range of 10 to 10 g. Further, as the washing water according to the present invention, ion-exchanged water treated with an ion-exchange resin may be used.

The pH of the wash water applicable to the present invention is 5.
It is in the range of 5 to 10.0. As the pH adjuster applicable to the present invention, any of generally known alkali agents and acid agents can be used. The treatment temperature of the water washing treatment is preferably 15 ° C to 60 ° C, more preferably 20 ° C to 45 ° C. Further, the time of the water washing treatment is preferably 5 to 60 seconds, more preferably 5 to 50 seconds. When the water washing treatment is performed in a plurality of tanks, it is preferable that the earlier tank is treated in a shorter time and the latter tank is treated in a longer time. Especially 20% of the previous tank
It is preferable that the treatments are sequentially performed with the treatment time increased by 50%.

When the multi-tank counter flow current system is used as the method for supplying the washing treatment liquid in the washing treatment step according to the present invention, it is preferable that the washing treatment liquid is supplied to the post-bath and overflowed to the pre-bath. Of course, it can also be processed in a single tank.
As a method for adding the above compound, various methods such as adding as a concentrated solution to the washing tank or adding the above compound and other additives to the washing solution supplied to the washing tank and using this as a washing replenisher Is used. The amount of rinsing water in the rinsing step according to the present invention is 0.1 to 0.1 of the carry-in amount of the pre-bath (usually bleach-fixing solution or fixing solution) per unit area of the light-sensitive material.
50 times is preferable, and 0.5 to 30 times is particularly preferable.

The washing tank in the washing treatment according to the present invention is 1
˜5 tanks are preferable, and 1 to 3 tanks are more preferable. Further, it is preferable that the drying after the water washing treatment is performed at 50 ° C. to 90 ° C. for 40 seconds to 80 seconds. As a developing processing apparatus for the silver halide photographic light-sensitive material used in the image forming method of the present invention, any known apparatus may be used. Specifically, it may be a roller transboat type in which a photosensitive material is sandwiched between rollers arranged in a processing tank and conveyed, or an endless belt method in which a photosensitive material is fixed to a belt and conveyed, The tank is formed in a slit shape, a method of supplying the processing liquid to the processing tank and a method of conveying the photosensitive material, a spray method of spraying the processing liquid, a web method by contact with a carrier impregnated with the processing liquid, A method using a viscous treatment liquid can also be used.

In the present invention, a large amount of light-sensitive material is processed and run in these color development to drying steps to elute components from the light-sensitive material into the processing solution, contamination between processing tanks, and evaporation of the processing solution are saturated. The effect is particularly exerted when the treatment is performed after being stabilized. These processes of exposure to drying are processed by, for example, a color automatic developing machine for a large-scale laboratory. Specific examples of preferred devices include Noritz PRV2-406, PRV2-212, and PRV.
2-416. Further, it may be processed by a minilab system, and preferable devices include, for example, Konica Nice Print System NPS-602QA, Noritsu QSS-1401, Fuji FA-120 and the like.

The print sample thus obtained can be subjected to various post-treatments, but it is preferable to apply an ultraviolet-curing resin or laminate with a laminating material containing an ultraviolet absorber.

[0291]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A paper support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side on which the emulsion layer was coated, a molten polyethylene containing 15% by weight of surface-treated anatase type titanium oxide dispersed therein was laminated to prepare a reflective support. Each layer having the following constitution was coated on this reflective support to prepare a multilayer silver halide photographic light-sensitive material, Sample 101. The coating solution was prepared as follows.

First layer coating liquid 26.7 g of yellow color (Y-1), 10.0 g of dye image stabilizer (ST-1), dye image stabilizer (ST-
2) 6.67 g, stain inhibitor (HQ-2) 6.67
g and high boiling point organic solvent (DNP) 6.67 g, ethyl acetate 60 ml was added and dissolved, and this solution was 20%
10 containing 7 ml of surfactant (SU-1)
% Gelatin aqueous solution (220 ml) was also emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Further, as a hardening agent, (H-1) was added to the second and fourth layers, and (H-2) was added to the seventh layer. Surfactants (SU2) and (SU-3) were added as coating aids to adjust the surface tension.

[0295]

[Table 1]

[0296]

[Table 2]

[0297]

[Chemical 108]

[0298]

[Chemical 109]

[0299]

[Chemical 110]

[0300]

[Chemical 111]

[0301]

[Chemical 112]

[0302]

[Chemical 113]

[0303]

[Chemical 114]

[0304]

[Chemical 115]

(Preparation method for blue-sensitive silver halide emulsion) 4
The following (solution A) and (solution B) were added to 1000 ml of a 2% gelatin aqueous solution kept at 0 ° C. to obtain pAg = 7.3, p
Simultaneously added over 30 minutes while controlling H = 3.0, and further the following (solution C) and (solution D) were pAg = 7.3, pH =
Simultaneous addition was carried out over 180 minutes while controlling at 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) K ₂ IrCl ₆ 2 × 10 ^-8 mol / Mol Ag K ₄ Fe (CN) S 1 × 10 ⁻⁵ mol / mol Ag Sodium chloride 102.7 g Potassium bromide 1.0 g Water added 600 ml (D) Silver nitrate 300 g Water added 600 ml

[0307] After the addition is complete, Kao Atlas's Demol N
Of 5% aqueous solution of magnesium sulfate and 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous solution of gelatin to have an average particle size of 0.85 μm, a coefficient of variation of particle size distribution of 0.07, and a silver chloride content of 99. 5 mol% of monodisperse cubic emulsion EMP-1 was obtained. The following compounds were optimally chemically sensitized to the above EMP-1 at 50 ° C. to obtain a comparative blue-sensitive silver halide emulsion (EmB-1).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 8 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 4 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX

(Method for producing green-sensitive silver halide emulsion)
(A solution) and (B solution) addition time and (C solution) and (D solution)
A monodisperse cubic EMP-2 having an average particle size of 0.43 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained in the same manner as in EMP-1, except that the addition time was changed. EM above
P-2 was optimally chemically sensitized at 55 ° C. using the following compound to obtain a green-sensitive silver halide emulsion (EmG-1).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX increase Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX

(Method for producing red-sensitive silver halide emulsion)
(A solution) and (B solution) addition time and (C solution) and (D solution)
A monodisperse cubic EMP-3 having an average particle size of 0.50 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained in the same manner as in EMP-1, except that the addition time was changed. EM above
Using P-3, the following compounds were optimally chemically sensitized at 60 ° C. to obtain a red-sensitive silver halide emulsion (EmR-1).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX increase Dye-sensitizing agent RS-1 1 × 10 ⁻⁴ mol / mol AgX The sample thus obtained is referred to as Sample 101 (for comparison).

[0313]

[Chemical formula 116]

[0314]

[Chemical 117]

In the preparation of Sample 101, the magenta coupler of the fourth layer and the high boiling point organic solvent of the ultraviolet absorber-containing layers of the fourth and sixth layers were changed and added as shown in Table 3 in the same manner as described above. Each sample was prepared. Each sample was exposed to a wedge of green light according to a conventional method and then developed in the following development process.

(Processing step) Processing step Temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C. 45 seconds 80 ml Bleach fixing 35.0 ± 0.5 ° C. 45 seconds 120 ml Water washing 30-34 ° C. 60 seconds 150 ml Dry 60-80 ° C. 30 seconds The composition of the development processing solution is shown below.

Color developer tank liquid Pure water 800 ml Tritylenediamine 2 g Diethylene glycol 10 g Potassium bromide 0.01 g Potassium chloride 3.5 g Potassium sulfite 0.25 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl -4-Aminoaniline sulfate 6.0 g N, N-diethylhydroxylamine 6.8 g Triethanolamine 10.0 g Diethylenetriaminepentaacetic acid sodium salt 2.0 g Optical brightener (4,4'-diaminostilbensulphonic acid derivative ) 2.0 g Potassium carbonate 30 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.10.

Color developer replenishing solution Pure water 800 ml Tritylenediamine 3 g Diethylene glycol 10 g Potassium sulfite 0.5 g N-Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulphate 10.0 g N , N-diethylhydroxylamine 6.0 g Triethanolamine 10.0 g Diethylenetriamine pentaacetic acid sodium salt 2.0 g Optical brightener (4,4'-diaminostilbensulphonic acid derivative) 2.5 g Potassium carbonate 30 g Water was added. Bring the total volume to 1 liter and adjust the pH to 10.60.

Bleach-fixing solution tank solution and replenishing solution Diethylenetriamine pentaacetate ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 5-Amino-1,3,4, -thiadiazole-2- Thiol 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Water is added to bring the total volume to 1 liter, and the pH is adjusted to 6.5 with potassium carbonate or glacial acetic acid.

Washing liquid tank liquid and replenishing liquid Orthophenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolone-3-one 0.02 g 2-Methyl-4-isothiazolone-3-one 0.02 g Diethylene glycol 1 .0g fluorescent brightener (Tinopal SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g BIC13 (45% aqueous _{solution) 0.65g MgSO 4 · 7H 2 0} 0.2g PVP ( polyvinylpyrrolidone) 1.0 g ammonia water (ammonium hydroxide 25% aqueous solution) 2.5 g nitriloacetic acid trisodium salt 1.5 g Water is added to bring the total volume to 1 liter, and pH is adjusted to 7.5 with sulfuric acid or ammonia water. The light resistance test of the obtained magenta color-developed sample, and the color change due to heat and humidity when stored in a dark place were measured as follows.

[Light resistance test] The PDA-65 densitometer (manufactured by Konica Corporation) was used to measure the green light reflection density before and after fading when each sample was exposed to sunlight for 30 days using an underglass outdoor exposure table. Was measured. The degree of fading due to light (fading rate) was determined as follows. Fading rate = 100 × (D-Do / Do) Do = density before photobleaching (1.0) D = density after photobleaching

[Heat and humidity resistance] Each sample was tested at 85 ° C. and 60% RH.
The sample was stored for 3 days under the conditions described above, and the green light reflection density before and after the storage was measured using a PDA-65 densitometer (manufactured by Konica Corporation). The degree of discoloration due to heat and humidity (rate of increase in density) was determined as follows. The closer to 100, the better. Color change rate = 100 × (D / Do) Do = Density before color change (1.0) D = Density after color change The results are shown in Table 3 below.

[0323]

[Table 3]

The silver halide photographic light-sensitive material according to the present invention not only has improved light resistance as compared with the comparative sample, but also
It can be seen that there is little discoloration due to the increase in concentration due to heat and humidity resistance.
In this way, the effect of improving the light resistance in rapid processing and the resistance to discoloration by heat and humidity is an effect not expected in the prior art.
Further, even in the case of the comparative sample containing the anti-fading agent, the sample of the present invention to which the anti-fading agent is not added has an effect that the light resistance is good and the discoloration resistance is also good.

(Example 2) In Example 1, two monodisperse emulsions having different grain sizes and different exposure performance characteristics were used as the blue, green and red sensitive emulsions.
The same test as in Example 1 was carried out except that the seeds were used in combination, and the same test as in Example 1 was carried out, and it was confirmed that the effect of the present invention was obtained more effectively with the sample of the present invention.

(Example 3) Using each of the light-sensitive materials obtained in Example 1, the same evaluation was performed using the equipment of the minilab system. The equipment is Konica Nice Print System 602AQ, and the treatment liquid is Konica Minilab Color Paper Process 2-20QA-M) (Deve
loper replenisher 20 P-1, D
develop Starter 20P-1S, Bl
each-fix & repairnisher 20P-
2, Super stabilizer & replen
washer20P-2) was used. The processed negatives include Konica Impreza 50 and SuperDD1.
00, Fuji Riara was used. Before the test, each print photosensitive material of the present invention was used for running processing until the total amount of replenisher liquid in each tank of the processor became three times the initial amount of each tank liquid.
Separately from this, a test in which running treatment was simultaneously performed using Konica Color QA Paper Type A5 was also conducted before the test. The same test as in Example 1 was conducted, and it was confirmed that the effect of the present invention was more effectively obtained with the sample of the present invention.

Example 4 The same process as in Example 2 was carried out except that the process time was changed as follows. Processing step time Color development 20 seconds Bleach fixing 20 seconds Water washing 60 seconds Dry 30 seconds Evaluation was carried out in the same manner as in Example 1 and it was confirmed that the effects of the present invention were effectively obtained.

Example 5 A sample was prepared by protecting the surface of each sample obtained in Example 3 with an ultraviolet curable resin containing an ultraviolet absorber and a laminating material. It has been found that the sample of the present invention can more effectively obtain the effects of the present invention.

Example 6 Next, the following samples were prepared, and the same exposure and treatment as in Example 1 were performed together with the samples prepared in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Table 4.
-1. (Samples 201 to 226) For samples evaluated at the same time, see Samples 101 to 126 of Example 1. On a support made of polyethylene-coated paper,
The following layers were sequentially coated from the support side to prepare a multi-color silver halide color photographic light-sensitive material.

First layer: Blue-sensitive silver chloride emulsion Yellow coupler (*) is 8 mg / dm ² , and blue-sensitive silver chloride emulsion (EmA) shown below is 3 mg / d in terms of silver.
m ² , high boiling point organic solvent (DNP) was coated at 3 mg / dm ^2, and gelatin was coated at a coating amount of 16 mg / dm ² .

Second layer: intermediate layer Hydroquinone derivative (Ex. No. HQ-4) 0.4
The coating amount was 5 mg / dm ² .

Third layer: green light-sensitive silver chloride emulsion layer Magenta coupler (EM-1) 4 mg / dm ² , green light-sensitive silver chloride emulsion (0.7 mg / dm ² in terms of silver), high boiling organic solvent. 4 mg / dm ² and gelatin 14 m
The coating was performed so that the coating amount was g / dm ² .

Fourth layer: intermediate layer An ultraviolet absorber (UV-A) shown below is added in an amount of 3 mg / d.
m ² , (UV-B) 3 mg / dm ² , high boiling point organic solvent 4 mg / dm ² and hydroquinone derivative (Ex. N
o. HQ-4) was applied at a coating amount of 0.45 mg / dm ² and gelatin at 9 mg / dm ² .

Fifth layer: Red-sensitive silver chloride emulsion layer Cyan coupler (*) is 4 mg / dm ² , high-boiling organic solvent (DOP) is 4 mg / dm ² , and red-sensitive silver chloride emulsion (Em. E) converted to silver, 3 mg / dm ² ,
And gelatin were coated so as to have a coating amount of 14 mg / dm ² .

Sixth layer: intermediate layer An ultraviolet absorber (UV-A) shown below was added at 2 mg / d.
m ² , (UV-B) 2 mg / dm ² , high boiling organic solvent (DNP) 2 mg / dm ² and gelatin 4 mg / dm ^2.
The coating was applied so that the coating amount was dm ² .

Seventh layer: protective layer Gelatin was coated so that the coating amount was 9 mg / dm ² . In addition, (*) in the 1st to 7th layers is shown in Table 3. Used silver halide emulsion Em. A to Em. E is as follows.

[0337]

[Chemical 118]

[0338]

[Chemical 119]

[0339]

[Table 4]

It can be seen that the sample produced here also exhibits the effects of the present invention as compared with the comparative sample. Further, the sample evaluated in Example 1 is more effective because the effect of the present invention appears more. In addition, the sample of the present invention manufactured in Example 1 is
It was excellent in other properties, and a clearer image was obtained for a long time even after storage.

[0341]

INDUSTRIAL APPLICABILITY According to the present invention, the color reproducibility and light fastness of the processed image are excellent, and the color fluctuation of the dye image due to heat and humidity is improved.

[Chemical 69]

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive layer and at least one non-light-sensitive layer on a support, wherein the light-sensitive layer has the general formula [IA],
[IB], [IC], [ID], [IE], [IF-
1] or [IF-2] is contained, and at least one photosensitive layer or non-photosensitive layer contains at least one ultraviolet absorber, and the ultraviolet absorption-containing layer A silver halide photographic light-sensitive material, characterized in that the ratio of the content of the high boiling point organic solvent to the content of the ultraviolet absorber in the above is 0.3 to 0. [Chemical 1] [In the formula, A represents a residue obtained by removing R ₂ or R ₃ from the pyrazolotriazole magenta coupler represented by the general formula [II], and L represents a divalent linking group. Y represents a nonmetallic atom group necessary for forming a 5- or 6-membered heterocycle with a nitrogen atom, and R ₁ represents a substituent. n represents an integer of 0 to 4. [Chemical 2] In the formula, R ₂ and R ₃ represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a color developing agent. ] [Chemical 3] [Wherein A is R ₂ or R from a pyrazolotriazole magenta coupler represented by the general formula [II] described in claim 2.
Represents a residue in which ₃ is removed, L _B represents a divalent linking group or a simple bond, R _B represents an alkylene group, and Y represents a 5- or 6-membered heterocycle together with a nitrogen atom. Represents the necessary non-metallic atomic group. ] [Chemical 4] [Wherein A is R ₂ or R from a pyrazolotriazole magenta coupler represented by the general formula [II] described in claim 2.
Represents a residue in which ₃ is removed, L _C represents a divalent linking group or a simple bond, and E represents —CO—, —SO—, —SO
_{2 -, - N (R 16} ) -SO 2 -, - N (R 16) -CO
R ₁₆ represents a hydrogen atom or a substituent, and Y represents a group of non-metal atoms necessary for forming a 5- or 6-membered heterocycle with a nitrogen atom. ] [Chemical 5] [In the formula, A represents a residue obtained by removing R ₂ or R ₃ from the pyrazolotriazole magenta coupler represented by the general formula [II], L _D represents a divalent linking group or a simple bond, and B represents is -O -, - S -, - SO 2 -, - N (R 16)
Represents —, —N (R ₁₆ ) ₂ —, R _D represents a hydrogen atom or a substituent, R _a , R _b , R _c and R _d represent an alkyl group, and Y _D represents a 5- or 6-membered group. It represents a group of non-metal atoms necessary for formation, one atom in the group of non-metal atoms represents bonding with B, and R ₁₆ represents a hydrogen atom or a substituent. ] [Chemical 6] [Wherein A is R ₂ or R from a pyrazolotriazole magenta coupler represented by the general formula [II] described in claim 2.
Represents a residue in which ₃ is removed, L _E represents a divalent linking group,
R _E1 and R _E2 represent a hydrogen atom or a substituent, and R _E1 and R _E2
May be the same or different, may be condensed with each other to form a 5- to 7-membered ring, k represents 0 or 1, and Z _E
Is -O -, - S- or -N (R ₁₆₎ - represents, R ₁₆ represents a hydrogen atom or a substituent. ] [Chemical 7] [Chemical 8] [In the formula, L _a and L _b represent a divalent linking group or a simple bond, and R _F represents an alkylene group or an arylene group,
Y represents a non-metal atom group necessary for forming a 5- to 6-membered ring, n _f represents 0 or 1, and R _a1 , R _b1 , R _c1 , R _d1.
And R _e1 represents a hydrogen atom or a substituent, and at least one of R _{a1 to} R _d1 is a hydroxyl group, an alkoxy group, an aryloxy group or In and, X _f is -S -, - SO ₂ - or -N (R _{16) 2}
And R ₁₆ represents a hydrogen atom or a substituent, and two R 2
₁₆ may be the same or different, and X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidant of a color developing agent. ] 2. The ratio of the content of the high-boiling-point organic solvent in the UV absorbent-containing layer to the weight of the UV absorbent-containing layer is 0.
The silver halide photographic light-sensitive material according to claim 1, which is 1 to 0. 3. The method of processing a silver halide photographic light-sensitive material according to claim 1, wherein the processing time with the color developing solution is 30 seconds or less.