JPH08160575A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To obtain the silver halide color photographic sensitive material high in sensitivity and good in preservability of a raw stock by incorporating 2 kinds of specified compounds in a photographic constituent layer. CONSTITUTION: At least one of constituent layers of red-, green-, and blue- sensitive silver halide emulsion layers and nonphotosensitive layer contains at least one kind of compounds represented by formulae I and II and the compound represented by formula III. In formulae I-III, each of R1 , R2 , Q1 , and Q2 is an aliphatic group and each of the total carbon number of R1 and R2 and that of Q1 and Q2 is >=8; each of R3 and Q3 is an optionally substituted group; each of (n) and (m) is 0 or 1; X is an H atom or a -OR group; Y is an H atom or a -OQ group; each of R and Q is an aliphatic or aromatic or heterocyclic group; Z is a -COOR11 , -CONR11 R12 , -SO2 NR11 R12 , -SO2 R11 , or -COR11 group; and each of R11 and R12 is an H atom or an alkyl, alkenyl, alkynyl, aryl, or heterocyclic group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having high sensitivity and good storability of raw samples.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material is exposed and then color-developed, whereby a paraphenylenediamine color-developing agent and a coupler react with each other to form a dye, thereby forming a color image.

Generally, in this photographic method, a color reproduction method by a subtractive color method is used to form yellow, magenta, and cyan color images.

Typical examples of cyan dye-forming couplers (cyan couplers) are phenols and naphthols. Among them, naphthols are capable of sufficiently long-wavelength and have high coupling reactivity, so that they are color negative films. Used for.

So far, naphthols substituted with a carbamoyl group at the 2-position have been used, but cyan dyes of this type are susceptible to reductive bleaching, and when treated with a fatigued bleaching solution, there is a problem that the color density is reduced.

On the other hand, the 2-arylcarbamoyl-1-naphthol compounds described in US Pat. No. 3,488,193 etc. have the advantage that the reduction of the color density due to the fatigue bleaching solution does not easily occur, but on the other hand, they have a high color density. In the range, the maximum absorption wavelength (λmax) of the image remarkably shifts to the short wavelength side, which is a disadvantage in terms of color reproducibility.

Japanese Laid-Open Patent Publication No.
The 2-arylcarbamoyl-1-naphthol-based compounds described in 62-83747 and the like have a characteristic that the maximum absorption wavelength does not easily shift to the short wave side even in the high coloring dye concentration range. In the general color negative color development processing, the maximum absorption wavelength thereof is often longer than 700 nm, and from the preferable maximum absorption wavelength 685 to 700 nm, it is a little too long and unfavorable for color reproduction, and also the recent high sensitivity. However, there is a problem in that the color developability is still insufficient.

Recently, a photographing unit (film with lens)
With the popularization of such a simple system, the film can be used under harsh conditions that have never been anticipated.
Storage has started to take place.

Conventionally, silver halide color photographic light-sensitive materials have a tendency to cause fog due to the presence of nuclei that can be developed even if they are not exposed to light. In many cases, reduction or deterioration of gradation is caused.

It is known to add an antifoggant, a stabilizer, or the like to a silver halide emulsion because it is desirable to reduce such an undesirable phenomenon as much as possible. For example, U.S. Patents 2,403,927 and 3,80
1-Phenyl-5-described in 4,633, Japanese Patent Publication No. 39-2825, etc.
Mercaptotetrazoles or 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene have been used as fog inhibitors.

However, these compounds are not always sufficient in the effect of suppressing fog during storage over time, and there are drawbacks such as lowering of sensitivity and softening of gradation, which are not satisfactory.

Further, in the case of a color light-sensitive material, an antifoggant used for the purpose of improving the storability over time is adsorbed to a silver halide emulsion more strongly than necessary, and as a result, the spectral sensitivity is impaired, or There were many adverse effects such as delaying the developability and desilvering property in the development process.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity and good storage stability of raw samples.

[0014]

The above object of the present invention is to provide one or more red-sensitive silver halide emulsion layers, green-sensitive silver halide emulsion layers, blue-sensitive silver halide emulsion layers and non-sensitive layers on a support. In a silver halide color light-sensitive material having at least a photosensitive layer as a constituent layer, at least one selected from compounds represented by the following general formula [I] and general formula [II] in at least one of the constituent layers. And a compound represented by the following general formula [A], and a silver halide color photographic light-sensitive material.

[0015]

[Chemical 4]

[Wherein, R ₁ and R ₂ represent an aliphatic group (provided that the total number of carbon atoms of R ₁ and R ₂ is 8 or more)). R
₃ represents a substitutable group, and n represents 0 or 1. X represents a hydrogen atom or -OR, and R represents an aliphatic group, an aromatic group or a heterocyclic group. ]

[0017]

Embedded image

[In the formula, Q ₁ and Q ₂ represent an aliphatic group (provided that the total number of carbon atoms of Q ₁ and Q ₂ is 8 or more). Q
₃ represents a substitutable group, and m represents 0 or 1. Y represents a hydrogen atom or -OQ, and Q represents an aliphatic group, an aromatic group or a heterocyclic group. ]

[0019]

[Chemical 6]

[In the formula, Z is --COOR ₁₁ , --CONR ₁₁ R ₁₂ , --S
O ₂ NR ₁₁ R _12, represents -SO ₂ R ₁₁ or -COR _11, R _11, R ₁₂
Each represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. The present invention will be specifically described below.

First, the compound represented by the general formula [I] will be described.

In the general formula [I], examples of the aliphatic group represented by R ₁ and R ₂ include a linear, branched or cyclic alkyl group, alkenyl group and alkynyl group, which have a substituent. The aliphatic group represented by R ₁ is preferably an alkyl group having 4 to 20 carbon atoms,
Butyl group, isobutyl group, pentyl group, neopentyl group, isopentyl group, hexyl group, cyclohexyl group,
Octyl group, 2-ethylhexyl group, decyl group, dodecyl group, 2-methyloctyl group, 2-butyloctyl group, 2-hexyldecyl group, 5,7-dimethyloctyl group, 3,5,5-trimethylhexyl group, Hexadecyl group and the like can be mentioned. R ₂
The aliphatic group represented by is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, and the groups described above for R ₁ . The total carbon number of R ₁ and R ₂ is 8 or more, but the total carbon number is preferably 10 to 32, and at least one of them is particularly preferably a branched alkyl group.

R ₃ represents a substitutable group, and examples of the substitutable group are an aliphatic group (for example, a C _{1 to} C ₃₀ alkyl group), an aromatic group (for example, a phenyl group, a naphthyl group, etc.), and a halogen. Atom, hydroxyl group, amino group, carbonamido group, sulfonamide group, ureido group, acyloxy group, aliphatic oxy group (for example, C _{1 to} C ₃₀ alkoxy group), aromatic oxy group (for example, phenoxy group,
Naphthoxy group, etc., aliphatic thio group (eg C ₁ -C _30).
Alkylthio group), aromatic thio group (eg, phenylthio group, naphthylthio group, etc.), sulfamoylamino group and the like.

The aliphatic group represented by R in the general formula [I] is preferably a linear, branched, cyclic or substituted alkyl group having 1 to 30 carbon atoms, and a substituted alkyl group having 2 to 30 carbon atoms. Is particularly preferable. Examples of the substituent of the substituted alkyl group include a carboxyl group, an aliphatic oxycarbonyl group (for example, an alkoxycarbonyl group), an aliphatic oxy group (for example, a C _{1 to} C ₃₀ alkoxy group), an aromatic oxy group (for example, a phenoxy group). , Naphthoxy group, etc.), aliphatic thio group (eg C ₁ -C ₃₀ alkylthio group etc.), aromatic thio group (eg phenylthio group, naphthylthio group etc.), sulfonyl group, acyl group, carbamoyl group, sulfamoyl group, acylamino Group, sulfonamide group, halogen atom, ureido group, urethane group, acyloxy group, carbamoyloxy group, urethane group, hydroxyl group, aromatic group (eg, phenyl group, naphthyl group, etc.), heterocyclic group (eg, at least one 5 to 6-membered heterocyclic group including O, N, S), cyano group, nitro , An amino group, an oxalyl group, etc. oxamide group.

The aromatic group represented by R is preferably a substituted or unsubstituted phenyl group or naphthyl group, and particularly preferably a substituted phenyl group having 6 to 30 carbon atoms. Examples of the substituent of the substituted phenyl group include the groups described above as examples of the substituent of the substituted alkyl group of the aliphatic group of R.

The heterocyclic group for R is a 5- or 6-membered ring containing at least one hetero atom selected from nitrogen, oxygen and sulfur, or an aromatic ring (for example, benzene, naphthalene ring, etc.), hetero ring ( Fused rings with 5 to 6 membered heterocycles containing at least one O, N, S, etc.) are preferred, and these are further as described above as examples of the substituent in the substituted alkyl group of the aliphatic group of R. It may be substituted with an appropriate substituent.

R is preferably an aliphatic group or an aromatic group.

Among the compounds represented by the general formula [I], a compound represented by the following general formula [III] can be mentioned as a particularly preferred example.

[0029]

[Chemical 7]

In the formula, R ₄ , R ₅ , R ₆ and R ₇ each represent a linear or branched alkyl group (provided that the total number of carbon atoms of R _{4 to} R ₇ is 6 to 28). X is a hydrogen atom or O
R'represents a substituted alkyl group having 2 to 30 carbon atoms or a substituted phenyl group having 6 to 30 carbon atoms.

Examples of the substituent of the substituted alkyl group of R'and the substituted phenyl group include the groups described above as examples of the substituent of the substituted alkyl group of the aliphatic group of R of the general formula [I].

Next, the cyan coupler represented by the general formula [II] will be described.

In the general formula [II], the aliphatic group represented by Q ₁ and Q ₂ represents a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group and has a substituent. May be. As the aliphatic group represented by Q ₁ , an alkyl group having 4 to 20 carbon atoms is preferable, and a butyl group, an isobutyl group, a pentyl group, a neopentyl group, an isopentyl group, a hexyl group, a cyclohexyl group, an octyl group, 2- Ethylhexyl group, decyl group, dodecyl group, 2-
Examples thereof include a methyloctyl group, a 2-butyloctyl group, a 2-hexyldecyl group, a 5,7-dimethyloctyl group, a 3,5,5-trimethylhexyl group and a hexadecyl group. As the aliphatic group represented by Q ₂ , an alkyl group having 2 to 20 carbon atoms is preferable, a branched or cyclic alkyl group having 4 to 20 carbon atoms is more preferable, and a secondary butyl group, a tert-butyl group, and a tert-alkyl group are preferable. Liamyl group, 1,1,3,3-tetramethylbutyl group, cyclopentyl group, cyclohexyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-1-methylpentyl group, 1-hexyl-1-methylnonyl Group, bicyclooctyl group, adamantyl group and the like. The total carbon number of Q ₁ and Q ₂ is 8 or more, but the total carbon number is preferably 10 to 32.

Q ₃ represents a substitutable group, and examples of the substitutable group are an aliphatic group, an aromatic group, a halogen atom, a hydroxyl group, an amino group, a carbonamido group, a sulfonamide group, a ureido group and an acyloxy group. , An aliphatic oxy group,
Examples thereof include an aromatic oxy group, an aliphatic thio group, an aromatic thio group, and a sulfamoylamino group, which are represented by the general formula [I].
Is synonymous with R ₃ of.

The aliphatic group represented by Q in the general formula [II] is preferably a linear, branched, cyclic or substituted alkyl group having 1 to 30 carbon atoms, and a substituted alkyl group having 2 to 30 carbon atoms. Is particularly preferable. The substituent of the substituted alkyl group, a carboxyl group, an aliphatic oxycarbonyl group, an aliphatic oxy group, an aromatic oxy group, an aliphatic thio group,
Aromatic thio group, sulfonyl group, acyl group, carbamoyl group, sulfamoyl group, acylamino group, sulfonamide group, halogen atom, ureido group, urethane group, acyloxy group, carbamoyloxy group, urethane group, hydroxy group, aromatic, hetero Examples thereof include a ring group, a cyano group, a nitro group, an amino group, an oxalyl group, an oxamide group and the like, and these have the same meanings as R in the general formula [I].

The aromatic group represented by Q is preferably a substituted or unsubstituted phenyl group or naphthyl group, and particularly preferably a substituted phenyl group having 6 to 30 carbon atoms. Examples of the substituent of the substituted phenyl group include the groups described above as examples of the substituent of the substituted alkyl group of the aliphatic group of Q.

The heterocyclic group for Q is preferably a 5- or 6-membered ring containing at least one heteroatom selected from nitrogen, oxygen and sulfur, or a condensed ring thereof with an aromatic ring or heterocycle. Further, it may be substituted with a suitable substituent as described above as an example of the substituent in the substituted alkyl group of the aliphatic group of Q.

Q is preferably an aliphatic group or an aromatic group.

Among the compounds represented by the general formula [II], a particularly preferred example is a compound represented by the following general formula [IV].

[0040]

Embedded image

In the formula, Q ₄ represents a linear, branched or cyclic alkyl group having 4 to 20 carbon atoms (for example, the groups mentioned above as examples of Q), and Q ₅ has 3 to 4 carbon atoms. Primary alkyl group (eg, tertiary butyl group, tertiary amyl group, 1,1,3,3-tetramethylbutyl group, 1-ethyl-1-methylpentyl group, 1-hexyl-1-methylnonyl group, bicyclooctyl group , Adamantyl group) or a 5- or 6-membered cyclic alkyl group (eg cyclohexyl group).

Y'represents a hydrogen atom or Q '. Q '
Is a substituted alkyl group having 2 to 30 carbon atoms or 6 to 30 carbon atoms
Represents a substituted phenyl group. Examples of the substituent of the substituted alkyl group of Q ′ and the substituted phenyl group include the groups described above as the examples of the substituent of the substituted alkyl group of the aliphatic group of Q of the general formula [II].

Typical examples of the compounds represented by the general formula [I] or the general formula [II] of the present invention are shown below.

[0044]

[Chemical 9]

[0045]

[Chemical 10]

[0046]

[Chemical 11]

[0047]

[Chemical 12]

[0048]

[Chemical 13]

[0049]

Embedded image

[0050]

[Chemical 15]

[0051]

Embedded image

[0052]

[Chemical 17]

[0053]

Embedded image

[0054]

[Chemical 19]

The general formula [I] and / or [II] of the present invention
The compound represented by (cyan coupler) is usually 1 × 10 ^-3 mol to 8 × 10 ^-1 mol, preferably 1 × 10 ³ per silver halide.
It can be used in the range of ^-2 mol to 8 × 10 ^-1 mol.

Next, the compound represented by the general formula [A] of the present invention will be explained.

[0057]

Embedded image

In the formula, Z is --COOR ₁₁ , --CONR ₁₁ R ₁₂ , --SO ₂
NR ₁₁ R ₁₂ , —SO ₂ R ₁₁ or —COR ₁₁ is represented, and R ₁₁ and R ₁₂ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Z is preferably -COOR ₁₁ -CONR ₁₁ R ₁₂ or -SO ₂ NR ₁₁ R ₁₂ , and more preferably -COOR ₁₁ or -CONR ₁₁ R ₁₂ .

In the general formula [A], examples of the alkyl group represented by R ₁₁ and R ₁₂ include methyl, ethyl, propyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl and octyl. , 2-
Each group such as ethylhexyl and dodecyl can be mentioned. These alkyl groups further include halogen atoms (eg chlorine, bromine, fluorine etc.), alkoxy groups (eg methoxy, ethoxy, 1,1-dimethylethoxy, hexyloxy, dodecyloxy etc.), aryloxy groups (eg phenoxy). , Naphthyloxy etc.), aryl groups (eg phenyl, naphthyl etc.), alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, 2-ethylhexylcarbonyl etc.) aryloxycarbonyl groups (eg phenoxycarbonyl, naphthyloxycarbonyl etc.) , Alkenyl groups (eg vinyl, allyl etc.), heterocyclic groups (eg 2-pyridyl, 3-pyridyl, 4-pyridyl, morpholyl, piperidyl, piperazyl, pyrimidyl, pyrazolyl, furyl etc.), alkynyl groups (eg propargyl) Amino group (e.g. amino, N,
N-dimethylamino, anilino, etc.), hydroxyl group, cyano group, sulfo group, carboxyl group, sulfonamide group (eg, methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, phenylsulfonylamino, etc.) May be done.

Examples of the alkenyl group represented by R ₁₁ and R ₁₂ include vinyl and allyl.

Examples of the alkynyl group represented by R ₁₁ and R ₁₂ include propargyl.

Examples of the aryl group represented by R ₁₁ and R ₁₂ include phenyl and naphthyl.

The heterocyclic group represented by R ₁₁ and R ₁₂ is
For example, a pyridyl group (eg, 2-pyridyl, 3-pyridyl, 4-
Pyridyl, etc.), thiazolyl group, oxazolyl group, imidazolyl group, furyl group, cenyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulforanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group and the like.

The above alkenyl group, alkynyl group, aryl group and heterocyclic group may be substituted with the same groups as the alkyl groups represented by R ₁₁ and R ₁₂ and the groups shown as the substituents of the alkyl group. it can.

Specific examples of the compound represented by the general formula [A] are shown below, but the invention is not limited thereto.

[0066]

[Chemical 21]

[0067]

[Chemical formula 22]

The compound [A] of the present invention can be used in an amount of 1 × 10 ^-4 to 1 mol per mol of silver halide, preferably 1 × 10 ^{-3 to} 5 × 10 ^-1 mol. Is.
For layers other than the emulsion layer, 1 × 10 ^-5 to 1 × 10 per 1 m ^2
It is preferably used in the range of ^-1 mol, more preferably 1 x 10 ^-4 to 1 x 10 ^-2 mol.

General formula [I] and general formula [II] of the present invention
At least one selected from the compounds represented by the formula (A) and the compound represented by the general formula [A] (hereinafter, referred to as the compound of the general formula [I] and / or [II] and [A]) In order to do so, a conventional method, for example, a known dibutyl phthalate, a mixture of a high boiling point solvent such as tricresyl phosphate and butyl acetate, a low boiling point solvent such as ethyl acetate, or a solvent having only a low boiling point solvent of the general formula [ I] and / or [I
The compound [I] and the compound [A] are used alone or in combination and dissolved, and then mixed with an aqueous gelatin solution containing a surfactant,
Then, after emulsifying and dispersing by using a high-speed rotary mixer, a colloid mill or an ultrasonic disperser,
Alternatively, a method of directly adding to a layer other than the emulsion layer can be adopted. Further, after the above emulsified dispersion is set, it may be shredded, washed with water, and then added to the emulsion layer and / or a layer other than the emulsion layer.

The general formula [I] and / or [II] of the present invention
And the compound of [A] may be added separately to the emulsion layer and / or to a layer other than the emulsion layer by separately dispersing them by a high boiling point solvent and the above-mentioned dispersion method. I
I] and the compound of [A] are simultaneously dissolved and dispersed,
The method of adding to the emulsion layer is preferred. More preferably, in this method, the compound represented by the general formula [A] is dispersed alone and added to a layer other than the emulsion layer.

In the present invention, the silver halide emulsion may be chemically sensitized. In the present invention, preferable chemical sensitizers include sulfur sensitizers, selenium sensitizers and tellurium sensitizers.

Sulfur sensitizers applicable in the present invention include US Patents 1,574,944, 2,278,947 and 2,728,
The sulfur sensitizers described in No. 668, No. 3,656,955 and the like can be used.

Examples of the selenium sensitizer applicable in the present invention include, for example, US Pat.
No. 25832, etc.

Tellurium sensitizers and sensitizing methods applicable in the present invention are described in US Pat. Nos. 1,623,499 and 3,655,3.
No. 94, JP-A-4-204640 and the like.

The temperature of chemical ripening using a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like is preferably in the range of 40 to 90 ° C. More preferably, it is 45 ° C or higher and 80 ° C or lower. Also, p
H is preferably in the range of 4 to 9 and pAg is preferably in the range of 6 to 9.5.

The amount of the sulfur sensitizer, selenium sensitizer, tellurium sensitizer, etc. used varies depending on the compound used, silver halide grains, chemical ripening conditions, etc., but is generally 10 per mol of silver halide. ^-8 to 10 ^-4 mol is used. The addition method is, depending on the properties of the compound to be used, a method of adding it by dissolving it in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent, or a method of adding it by mixing with a gelatin solution in advance. However, the method disclosed in JP-A-4-140739, that is, the method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent may be used.

In the present invention, reduction sensitization may be used in combination. The reduction sensitization is preferably performed during the growth of silver halide grains. As the method of applying during the growth, not only the method of performing reduction sensitization while the silver halide grains are growing, but also the method of performing reduction sensitization with the growth of silver halide grains being interrupted and then performing the reduction sensitization Also included are methods of growing the perceived silver halide grains.

Next, the hydrophilic colloid layer will be described.

For the hydrophilic colloid layer in the present invention, it is usually advantageous to use gelatin.

For gelatin, lime-processed gelatin, acid-processed gelatin, Bull. Soc. Sci. Phot. Japan. No. 16, p. 30, (196
In addition to the enzyme-treated gelatin as described in 6), gelatin derivatives (eg gelatin include acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyamines, etc. Those obtained by reacting various compounds such as alkylene oxides and epoxy compounds) are included.

For the support according to the present invention, a cellulose ester film, a polyester film, a polycarbonate film and the like are preferably used, and a cellulose triacetate film, a polyethylene terephthalate film, a polyethylene naphthalate film and a polyparaphenylene terephthalamide film are particularly preferable.

In the present invention, the silver halide emulsion is used after physical ripening, chemical ripening and spectral sensitization.
Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 308119 (hereinafter abbreviated as RD17643, RD18716 and RD308119, respectively). The following shows the locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer 996 III-A Item 23 648 Spectral sensitizer 996 IV-A-A, B, C, D, E to J Item 23 -24 648-9 Supersensitizer 996 IV-AE, J section 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI In the present invention, a photographic constituent layer is known. Photographic additives are added.

Known photographic additives that can be used in the present invention are also described in the above-mentioned Research Disclosure.
The following shows the locations.

[Item] [Page of RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 VII-I item 25 650 Dye image stabilizer 1001 VII-J item 25 Whitening agent 998 V 24 UV absorber 1003 VIII- C, XIII C Item 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Antistatic agent 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Matting agent 1007 XVI Developer (included in light-sensitive material) Item 1011 XXB Various couplers can be used in the invention, and specific examples thereof are described in Research Disclosure above. ing. The relevant locations are shown below.

[Item] [Page of RD308119] [RD17643] Yellow coupler 1001 VII-D item VIIC-G item Magenta coupler 1001 VII-D item VIIC-G item Cyan coupler 1001 VII-D item VIIC-G item Colored coupler 1002 Item VII-G Item VIIG Item DIR coupler 1001 Item VII-F Item VIIF Item BAR coupler 1002 Item VII-F Other useful residues 1001 Item VII-F Release coupler Alkali-soluble coupler 1001 Item VII-E Additives used in the present invention Can be added by the dispersion method described in RD308119XIV.

In the present invention, the above-mentioned RD17643 page 28, RD1
8716 pp. 647 to 8 and auxiliary layers such as filter layers and intermediate layers described in RD308119, section XVII-K can be provided.

The light-sensitive material of the present invention is the above-mentioned RD308119VII-
Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in the section K can be adopted.

[0089]

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

Example 1 (Preparation of silver halide color light-sensitive material) Sample 101, which is a multilayer color light-sensitive material, was prepared by providing each layer having the composition shown below on a cellulose triacetate film support which was subjected to the following. .

[0091] The coating amount (Composition of photosensitive layer) The silver halide and colloidal silver, the amount expressed in terms of metallic silver in the unit of g / m ^2, also, the coupler, the additive g / m ² The amount expressed in units is also shown for the sensitizing dye in terms of the number of moles per mole of silver halide in the same layer.

Sample 1 First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound (SC-1) 0.14 High Boiling point solvent (OIL-2) 0.17 Gelatin 0.80 Third layer: low-sensitivity red sensitive layer Silver iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0.35 Sensitizing dye (SD-1) 2.0 × 10 ^-4 Sensitizing dye ( SD-2) 1.4 × 10 ^-4 sensitizing dye (SD-3) 1.4 × 10 ^-5 sensitizing dye (SD-4) 0.7 × 10 ^-4 cyan coupler (CA) 0.53 Colored cyan coupler (CC-1) ) 0.04 DIR compound (D-1) 0.025 High boiling point solvent (OIL-3) 0.48 Gelatin 1.09 4th layer: Medium-sensitive red sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD- 1) 1.7 × 10 ^-4 sensitizing dye (SD-2) 0.86 × 10 ^-4 sensitizing dye (SD-3) 1.15 × 10 ^-5 sensitizing dye ( SD-4)
0.86 × 10 ^-4 Cyan coupler (CA) 0.33 Colored cyan coupler (CC-1) 0.013 DIR compound (D-1) 0.02 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 Fifth layer: High sensitivity red Sensitive layer Silver iodobromide emulsion D 0.95 Sensitizing dye (SD-1) 1.0 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.0 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.2 × 10 ⁻⁵ Cyan coupler (CA) 0.14 Colored cyan coupler (CC-1) 0.016 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 Sixth layer: intermediate layer Compound (SC-1) 0.09 High boiling point solvent (OIL-2) 0.11 Gelatin 0.80 7th layer: low-sensitivity green-sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.38 Sensitizing dye (SD-4) 4.6 × 10 ^-5 Sensitizing dye (SD-5) 4.1 × 10 ^-4 Magenta Coupler (M-1) 0.14 Magenta Coupler (M-2) 0.14 Colored Magenta Coupler (CM-1) 0.06 High Boiling point solvent (OIL-4) 0.34 Gelatin
0.70 Eighth layer: Intermediate layer Gelatin
0.41 Ninth layer: Medium sensitivity green sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD-6) 1.2 × 10 ⁻⁴ Sensitizing dye (SD-7) 1.2 × 10 ^-4 Sensitizing dye (SD-8) 1.2 × 10 ^-4 Magenta coupler (M-1) 0.04 Magenta coupler (M-2) 0.04 Colored magenta coupler (CM-1) 0.017 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (OIL-4) 0.12 Gelatin 0.50 10th layer: High sensitivity green sensitive layer Silver iodobromide emulsion D 0.95 Sensitizing dye (SD-6) 7.1 × 10 ^-5 Sensitizing dye ( SD-7) 7.1 × 10 ^-5 Sensitizing dye (SD-8) 7.1 × 10 ^-5 Magenta coupler (M-1) 0.09 Colored magenta coupler (CM-1) 0.011 High boiling point solvent (OIL-4) 0.11 Gelatin 0.79 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling point solvent (OIL-2 0.19 gelatin
1.10 12th layer: low-sensitivity blue-sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.24 Silver iodobromide emulsion C 0.12 Sensitizing dye (SD-9) 6.3 × 10 ^-5 Sensitizing dye ( SD-10) 1.0 × 10 ^-5 Yellow coupler (Y-1) 0.50 Yellow coupler (Y-2) 0.50 DIR compound (D-4) 0.04 DIR compound (D-5) 0.02 High boiling point solvent (OIL-2) 0.42 gelatin 1.40 13th layer: high sensitivity blue-sensitive layer silver iodobromide emulsion C 0.15 silver iodobromide emulsion E 0.80 sensitizing dye (SD-9) 8.0 × 10 -5 sensitizing dye (SD-11) 3.1 × 10 - ⁵ Yellow coupler (Y-1) 0.12 High boiling point solvent (OIL-2) 0.05 Gelatin 0.79 14th layer: 1st protective layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.065 High boiling point solvent (OIL-1) 0.07 High boiling point solvent (OIL-3) 0.07 Gelatin 0.65 15th layer: 2nd protective layer Al Potassium soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm) 0.04 Lubricant (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, coating aid SU-1 and dispersion aid SU
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggant AF-1, two types of AF-2 having an average molecular weight of 10,000 and an average molecular weight of 1,100,000, and preservative DI-1 were added.

The emulsions used in the above samples are as follows. The average particle size is shown as a particle size converted into a cube.
Further, each emulsion was optimally subjected to gold / sulfur sensitization.

[0094]

[Table 1]

[0095]

[Chemical formula 23]

[0096]

[Chemical formula 24]

[0097]

[Chemical 25]

[0098]

[Chemical formula 26]

[0099]

[Chemical 27]

[0100]

[Chemical 28]

[0101]

[Chemical 29]

[0102]

Embedded image

[0103]

[Chemical 31]

[0104]

Embedded image

[0105]

[Chemical 33]

In the above-mentioned Sample 1, instead of the cyan coupler C-A added to the fifth silver halide emulsion layer, the comparative couplers C-B, C-C, C-D, RC-1, RC- were used.
2, RC-3 and the cyan coupler of the present invention are shown in Tables 2, 3,
4 as well as the compound represented by the general formula [A] as shown in Tables 2, 3 and 4, in the same manner as in Sample 1, Samples 2 to 80 shown in Tables 2 to 5 Was produced.

Samples 1 to 80 were each divided into two parts, I and II. I was subjected to wedge exposure according to a conventional method, and immediately subjected to development processing according to the following processing step I. Also, II is 45 ℃,
After leaving in an atmosphere of 80% RH for 7 days, the same wedge exposure as in I was performed and the same development processing was performed. However,
At this time, I and II were exposed to red light by a filter operation.

The sensitivity of I was evaluated. For the sensitivity of each sample, the sensitivity of the red-sensitive emulsion layer was measured (fog density +0.15
Reciprocal of the exposure dose that gives the optical density of 10), I sample No. 11 to 10
The relative value was set to 0. Also, the raw storage fog was represented by a relative value with the fog difference between the red-sensitive emulsion layers II to I taken as 100, and the fog difference of Sample No. 11 as 100 (the higher the value, the worse the deterioration. Indicates that). The results are shown in Tables 2-5
Shown in

(Processing step I) Processing step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ℃ 780ml Bleach 45 seconds 38 ± 2.0 ℃ 150ml fixation 1 minute 30 seconds 38 ± 2.0 ℃ 830ml stability 60 seconds 38 ± 5.0 ℃ 830ml Dry 1 minute 55 ± 5.0 ℃ － * Replenishment amount is the value per 1m ² of photographic material.

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and its replenishing solution were used.

Color developer and color replenisher developer Replenisher Replenisher Water 800 ml 800 ml Potassium carbonate 30 g 35 g Sodium hydrogen carbonate 2.5 g 3.0 g Potassium sulfite 3.0 g 5.0 g Sodium bromide 1.3 g 0.4 g Potassium iodide 1.2 mg-hydroxylamine sulfate Salt 2.5g 3.1g Sodium chloride 0.6g-4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5g 6.3g Diethylenetriaminepentaacetic acid 3.0g 3.0g Potassium hydroxide 1.2g 2.0 g Add 1 liter of water and use potassium hydroxide or 20% sulfuric acid to adjust the color developer to pH 10.06 and the replenisher to pH 10.18.
Adjust to.

Bleaching solution and bleach replenishing solution Bleaching solution Replenishing solution Water 700 ml 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125 g 175 g Ethylenediaminetetraacetic acid 2 g 2 g Sodium nitrate 40 g 50 g Ammonium bromide 150 g 200 g Glacial acetic acid 40 g 56 g Water Then, the bleaching solution is adjusted to pH 4.4 and the replenisher is adjusted to pH 4.0 using ammonia water or glacial acetic acid.

Fixer and fixer replenisher Fixer replenisher Replenisher Water 800 ml 800 ml Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g Ammonia water or glacial acetic acid was used as the fixer at pH 6.2, Adjust the replenisher to pH 6.5 and add water to make 1 liter.

Stabilizer and Stable Replenisher Water 900 ml Ethylene oxide 10 mol adduct of p-octylphenol 2.0 g Dimethylol urea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzisothiazolin-3-one 0.1 g Siloxane (UCC L-77 ) 0.1g ammonia water 0.5
After adding cc water to 1 liter, add ammonia water or 50
Adjust to pH 8.5 with% sulfuric acid.

[0115]

[Table 2]

[0116]

[Table 3]

[0117]

[Table 4]

[0118]

[Table 5]

[0119]

Embedded image

[0120]

Embedded image

As is clear from the results of Tables 2, 3, 4, and 5, the samples Nos. 30 to 80 of the present invention are highly sensitive to the comparative samples Nos. 1 to 30, and the fog is increased during raw storage. Is smaller, which means that the raw storage property is excellent.

Further, by adding the compound represented by the general formula [A] of the present invention to an emulsion layer and a layer other than the emulsion layer, the sensitivity is high and the fog increase in raw storage is small, which is excellent. You can see that

[0123]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having high sensitivity and good storage stability of raw samples.

Claims (1)

[Claims] 1. A halogenation having at least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, blue-sensitive silver halide emulsion layer and non-photosensitive layer as constituent layers on a support. In the silver color light-sensitive material, at least one selected from compounds represented by the following general formula [I] and general formula [II] in at least one of the constituent layers.
A silver halide color photographic light-sensitive material comprising a seed and a compound represented by the following general formula [A]. Embedded image [In the formula, R ₁ and R ₂ represent an aliphatic group (provided that the total number of carbon atoms of R ₁ and R ₂ is 8 or more). R ₃ represents a substitutable group, and n represents 0 or 1. X represents a hydrogen atom or -OR, and R represents an aliphatic group, an aromatic group or a heterocyclic group. ] [Chemical 2] [In the formula, Q ₁ and Q ₂ represent an aliphatic group (provided that the total number of carbon atoms of Q ₁ and Q ₂ is 8 or more). Q ₃ represents a substitutable group, and m represents 0 or 1. Y represents a hydrogen atom or -OQ, and Q represents an aliphatic group, an aromatic group or a heterocyclic group. ] [Chemical 3] [In the formula, Z is -COOR ₁₁ , -CONR ₁₁ R ₁₂ , -SO ₂ NR ₁₁ R ₁₂ ,
Represents —SO ₂ R ₁₁ or —COR ₁₁ , R ₁₁ and R ₁₂ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group,
It represents an aryl group or a heterocyclic group. ]