EP0439069A2

EP0439069A2 - Silver halide photographic light-sensitive material

Info

Publication number: EP0439069A2
Application number: EP91100578A
Authority: EP
Inventors: Shinpei C/O Fuji Photo Film Co. Ltd. Ikenoue; Mamoru C/O Fuji Photo Film Co. Ltd. Tashiro; Junichi C/O Fuji Photo Film Co. Ltd. Yamanouchi; Keiichi C/O Fuji Photo Film Co. Ltd. Adachi; Toru C/O Fuji Photo Film Co. Ltd. Harada
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1990-01-19
Filing date: 1991-01-18
Publication date: 1991-07-31
Also published as: EP0439069A3; JPH03215844A

Abstract

A silver halide photographic light-sensitive material comprises at least one silver halide emulsion layer containing a silver halide emulsion subjected to chemical sensitized by a gold compound and a chalcogenide compound on a support. An amount of hydrogen cyanide released from 1 m² of the light-sensitive material in in a wet atmosphere at 75 C for two hours is 0.8 µm, or less, and the light-sensitive material is sealed in a closed vessel capable of maintaining a relative humidity constant.

Description

The present invention relates to a silver halide photographic light-sensitive material and, more particularly, to a silver halide photographic light-sensitive material in which photographic properties are not much degraded while the material is sealed in a closed vessel and stored.
A 135-formatted silver halide photographic light-sensitive material which is most often used by general users is normally sealed in a closed vessel and stored. In this manner, degradation in photographic properties caused by an external moisture or noxious gas can be reduced. The above storage condition of a light-sensitive material is very effective in an extremely high humidity atmosphere or in the presence of a gas noxious to a light-sensitive material. As a result of making various researches, however, it is found that a degree of degradation in photographic properties is smaller when a light-sensitive material is stored outside a closed vessel under the same humidity as in the closed vessel than when it is stored in the closed vessel. This fact indicates that a light-sensitive material is easily influenced by a noxious substance produced or released from the light-sensitive material itself when it is sealed in a closed vessel, thereby degrading its photographic properties. However, no references nor patents, which allow researchers to easily predict the type of noxious substance produced from a light-sensitive material, have been available.
WO No. 12847/89 and U.S. Patents 3,900,323 and 4,211,837 disclose that degradation in photographic properties of a light-sensitive material can be reduced when a heavy metal compound capable of scavenging a noxious substance produced by a carbon black used in a shading paper is contained in a shading poper. Assuming that the same noxious substance is produced by a carbon black and a light-sensitive material, it is expected that degradation in photographic properties of a light-sensitive material during storage can be reduced if a heavy metal compound is contained in the light-sensitive material. A serious problem of degradation in photographic properties, however, arises when heavy metal compounds such as silver, copper, platinum, palladium, zinc, cadmium, lead, iron, bismuth, and mercury disclosed in the above patents are added to a light-sensitive material. Even if the same noxious substance is produced from a carbon black and a light-sensitive material, therefore, it is very difficult to apply the technique disclosed in the above patents to a 135-formatted silver halide photographic light-sensitive material.
JP-A-62-168143 ("JP-A" means Published Unexamined Japanese Patent Application) discloses that degradation in photographic properties of a light-sensitive material during storage can be prevented by decreasing a humidity in a closed vessel. This patent specification, however, has no description which indicates that an influence of a noxious substance except for water produced from a light-sensitive material itself is reduced by means of decreasing a humidity. The present inventors, therefore, conducted experiments and found that degradation in photographic properties of a light-sensitive material during storage was reduced by decreasing the humidity in a closed vessel even in the case of the light-sensitive material which is assumed to release a noxious substance. When the humidity was decreased to be a value at which a satisfactory effect was obtained, however, a problem of, e.g., a static failure, and reduction in property of automatic loading of a film with respect to a camera caused by low curling tendency were posed. It is, therefore, found that the use of means of decreasing the humidity in a closed vessel has its limitation.
It is an object of the present invention to provide a silver halide photographic light-sensitive material in which a change in photographic properties is small when the material is stored in a closed vessel and, more particularly, to a silver halide photographic light-sensitive material in which a change in photographic properties is small when the material is stored in a closed vessel at around normal humidity, and especially to prevent an increase in fog and decrease in gradation (gamma).
The above object of the present invention is achieved by the following materials.

(1) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing a silver halide emulsion subjected chemical sensitization by a gold compound and a chalcogenide compound on a support, wherein an amount of hydrogen cyanide released from 1 m² of the light-sensitive material in a wet atmosphere at 75 C for 2 hours is 0.8 I'g or less, and the light-sensitive material is sealed in a closed vessel capable of maintaining a relative humidity constant.
(2) A silver halide photographic light-sensitive material described in item (1) above, wherein the closed vessel is maintained at a relative humidity of 50% to 70% at 25 C.

Fig. 1 is a schematic view showing a method of determining a released amount of cyan gas in the present invention.
Referring to Fig. 1, 1 N-NaOH is filled in a washing bottles (I), (III), and (IV), and 1 m² of a light-sensitive material is finely cut and put in a washing bottle (II). The bottles (I) and (II) are stored in a constant temperature bath at 75 C.
Hydrogen cyanide gas released from a sample is captured in the washing bottle (III) and therefore can be identified or quantitatively analysised by a colorimetry analysis method.
The present invention will be described in detail below.
"Hydrogen cyanide" will be also referred to as "cyan gas" or "HCN gas" hereinafter.
On the basis of an assumption that a light-sensitive material, in which a change in photographic properties is large when the material is stored in a closed vessel, releases a gas noxious to the light-sensitive material, the present inventors analyzed gas components released from a light-sensitive material in detail. As a result, a very small amount of cyan gas was detected. In accordance with this analysis result, a very small amount of potassium cyanide and a small amount of a light-sensitive material were put in a closed vessel and heated at 60 C for three days. As a result, the same change in photographic properties, as obtained when a 24-frame patrone film housed in a patrone case was similarly tested, was obtained. The present inventors concluded on the basis of these results that hydrogen cyanide released from a light-sensitive material is accumulated in a closed vessel to undesirably change photographic properties. "Journal of Imaging Science" 32, pp. 28 to 34 (1988) describes that when a film coated with a gold- sensitized silver halide emulsion is dipped in an aqueous solution of potassium cyanide (about 100mg/ℓ), gold in the light-sensitive material is removed to change photographic properties. It is, however, difficult from this reference to predict a change in photographic properties caused by exposing the photographic material to a very small amount of cyan gas released in an order of µg per m² of a light-sensitive material. (If cyan gas is produced in this order, the concentration of cyan gas in a patrone case housing a 24-frame light-sensitive material is in an order of 1 ppm. By way of parenthesis, a lethal dose of cyan gas is said to be 200 to 300 ppm.)
The fact that a very small amount of cyan gas is released from a light-sensitive material, was very surprising, since it is not known to those skilled in the art.
The present invention is achieved by reducing an amount of cyan gas released from 1 m² of a silver halide photographic light-sensitive material, which is sealed in a closed vessel capable of maintaining a humidity constant and having at least one silver halide emulsion layer containing a silver halide emulsion subjected to sensitization by a gold compound and a chalcogenide compound on a support, to be 0.8 µg or less by a test method to be defined below.
WO No. 12847/89 discloses scavenging cyan gas released from a carbon black contained in a shading paper by a heavy metal compound. In the present invention, however, an amount of cyan gas released from a light-sensitive material is reduced. This is the difference between the reference and the present invention. In the manner of present invention, a change in photographic properties of a light-sensitive material stored in a closed vessel can be largely reduced without degrading photographic properties.

1. Method of determining cyan gas amount

(1) Cyan gas collecting apparatus

As shown in Fig. 1, four washing bottles (I) to (IV) are connected by glass tubes each having an inner diameter of 5 mm. The volume of each of the bottles (I), (III), and (IV) is 250 cc. The volume of the bottle (II) is 1 1. (The scrubbing bottles are available from Shibata Kagaku Kikai Kogyo K.K.) In the washing bottles (III) and (IV), the glass tube to be dipped in a solution has a glass bulb with pores (G3) at its distal end in order to increase a cyan gas collection efficiency.
100 cc of 1 N-NaOH are filled in each of the bottles (I), (III), and (IV), and a sample to be measured is put in the bottle (II). An air pump (AP-220 ZN available from IWAKI AIR PUMP) is connected as shown in Fig. 1. An air flow rate is adjusted to be 700 ± 400 cc/min. A variation in air flow rate has no large influence on determination precision of cyan gas. The washing bottles (I) and (II) are set in a constant temperature bath controlled at 75 C. If a room temperature falls within the range of 10°C to 30 C, temperature control of the washing bottles (III) and (IV) need not be performed.
A sample to be measured is maintained at a relative humidity of about 75%, i.e., 75% ± 15%.

(2) Collection of cyan gas produced from light-sensitive material

In the apparatus shown in Fig. 1, 1 m² of a sample was finely cut and put in the bottle (II) and heated at 75 C for two hours while the air pump was operated, thereby collecting cyan gas into the bottles (III) and (IV). In order to increase a determination precision of cyan gas, a non-exposed sample must be used, and collection of the gas must be performed in a dark room.

(3) Determination of cyanide amount

An absorbance at 620 nm is read in accordance with the 38.2 pyridine-pyrazolone absorptiometric method in the item of a 38 cyan compound described in JIS K 0102 Factory Wastes Test Method, and an absorbance obtained by a blank operation is subtracted therefrom, thereby performing determination of the amount of cyanide ions in a collection solution.
The present invention will be described in more detail below.
It was very difficult to predict production or releasing of cyan gas from a substance used in a silver halide photographic light-sensitive material on the basis of knowledge or experiments concerning reactions in normal organic chemistry.
In order to allow general users to enjoy high-quality photographs, it is important to minimize a change in photographic properties upon sealing of a light-sensitive material in a closed vessel at a temperature of 20 C to 25 C over a long time period of 18 months or more. The present inventors have found that, in order to achieve the above object, an amount of cyan gas released from 1 m² of the light-sensitive material must be decreased to be 0.8 jig or less under the test conditions of the present invention.
When the amount of cyan gas released from 1 m² of a silver halide photographic light-sensitive material is reduced to be 0.8 µg or less, preferably, 0.6 _jig or less, more preferably, 0.3 µg or less, and most preferably, a detection limit or less in accordance with the test method as defined above, a change in photographic properties can be reduced when the light-sensitive material is sealed in a closed vessel capable of maintaining a humidity constant.
Finding a source of cyan gas production and removing the cause is a most preferable means in order to suppress releasing of cyan gas from a light-sensitive material without changing its photographic properties.
The present inventors have made various extensive studies and found, that a synthetic polymer, an ultraviolet absorbent containing a cyano group, or a dye containing a cyano group contained in a light-sensitive material can be a source of cyan gas releasing. More specifically, a polymer synthesized by a radical polymerization method can be a cyan gas source. The present inventors have made analysis in more detail and found that a polymer synthesized by using a polymerization initiator containing a cyano group can be a cyan gas source.
JP-A-59-42543 discloses that a polymer coupler synthesized by an azo-based polymerization initiator not containing a cyano group causes only a small amount of fog and a small change in photographic properties of a light-sensitive material at a high temperature and a high humidity. This patent specification, however, does not describe that cyan gas is produced from the polymer coupler, that a change in photographic properties is increased when the light-sensitive material is sealed in a patrone case and stored if a polymerization initiator containing a cyano group is used, and that the polymer coupler has a large influence on a silver halide emulsion sensitized by a gold compound and a chalcogenide compound. That is, the present invention cannot be expected from the above patent specification.
The means for decreasing an amount of cyan gas released from a light-sensitive material will be described in more detail below.
A polymerization initiator of the present invention will be described in detail below.
A polymerization initiator of the present invention is used as an initiator for a generally well-known radical polymerization reaction of an ethylenic unsaturated monomer and includes all initiators capable of generating a radical by, e.g., decomposition caused by heat, light, or radiation or a redox reaction, thereby starting a polymerization reaction of an ethylenic unsaturated monomer.
Examples of such a polymerization initiator are, as described in J. Brandrup and E.H. Immergut, "Polymer Handbook", John Wiley & Sons, 1974, 11-1 to 11-43, page 43 and Takayuki Otsu, "Radical Polymerization (I)", Kagaku Dojin, 1971, pp. 15 to 78, a compound which decomposes with, e.g., heat to generate a radical such as a peroxide (e.g., hydrogen peroxide, persulfate, hydroperoxide, dialkyl peroxide, diacyl peroxide, ester peroxide, and a metal peroxide), an azo compound, monosulfide, and disulfide, and a compound which generates a radical by a redox reaction between an oxidizing agent and a reducing agent. That is, various types of compounds and their combinations can be used.
Of these polymerization initiators, a polymerization initiator not containing a cyano group is most preferable as a polymerization initiator for use in the present invention.
Although preferable examples of the polymerization initiators not containing a cyano group will be listed below, the initiator is not limited to these examples.
A polymerization initiator containing a cyano group is preferably not used at all since it can be a cyan gas source. Note that if no other cyan gas production source is present in a photographic light-sensitive material, the polymerization initiator of this type can be used as needed provided that a total amount of the initiator used in polymerization of a coated polymer is 5 µmol or less per 1 m² of the photographic material.
In addition, the usable total amount of the initiator containing a cyano group can be increased by purifying a produced polymer by, e.g., re-precipitation or column chromatography. Although this amount depends on a degree of purification, it falls within the range of about 5 µmol to about 40 µmol
If another cyan gas production source (a compound containing a cyano group) is present in a photographic light-sensitive material, the usable total amount of the polymerization initiator containing a cyano group is further limited. This amount naturally depends on the type or amount of the other cyano group-containing compound used.
Examples of the above polymerization initiator containing a cyano group will be listed below.
A method of synthesizing a polymer derived from an ethylenic unsaturated monomer for use in the present invention will be described below. Such a polymer can be synthesized by a generally well-known radical polymerization method (described in detail in, e.g., Takayuki Otsu and Masaetsu Kinoshita, "Experiment Method of Polymer Synthesis", Kagaku Dojin, 1972, pp. 124 to 154), and various types of methods such as solution polymerization, suspension polymerization, bulk polymerization, emulsion polymerization, dispersion polymerization, and precipitation polymerization can be performed in accordance with the type (e.g., a solution, a dispersion, a powder, or a grain) or physical properties (e.g., a molecular weight, viscosity, or solubility) of a polymer to be obtained. In particular, solution polymerization and emulsion polymerization can be preferably used.
When a solution polymerization method is to be used, a polymer can be obtained by dissolving an ethylenic unsaturated monomer into a suitable solvent (e.g., water, an organic solvent such as methanol, ethanol, propanol, ethyleneglycol, acetone, methylethylketone, acetonitrile, dioxane, N,N-dimethylformamide, N,N-dimethylacetoamide, ethyl acetate, or tetrahydrofuran or a solvent mixture thereof, or a solvent mixture of such an organic solvent and water) and performing solution polymerization. Alternatively, a monomer or a monomer solution may be dropped into a polymerization vessel. The solution polymerization is performed by using the polymerization initiator described above at a temperature of generally 30°C to about 100°C, and preferably 40 C to about 90 C. Although an amount of the polymerization initiator variously changes in accordance with the type of ethylenic unsaturated monomer, the type of initiator, polymerization conditions (e.g., a temperature and a concentration), and various physical properties (e.g., a molecular weight, viscosity, and solubility) of a produced polymer, it is preferably 0.01 to 5 mol%, and most preferably, 0.03 to 3 mol% with respect to the ethylenic unsaturated monomer.
The type of polymerization initiator may be arbitrarily selected in accordance with, e.g., a polymerization temperature and a polymerization solvent, and two or more types of initiators can be simultaneously used.
When an emulsion polymerization method is to be used, an ethylenic unsaturated monomer is generally emulsion-dispersed in an aqueous medium by using at least one type of an emulsifying agent selected from the group consisting of an anionic surfactant (e.g., TRITON 770 available from Rohm & and House Co.), a cationic surfactant (e. g., cetyltrimethylammonium chloride and stearyltrimethylammonium chloride), a nonionic surfactant (e.g., EMALEX and NP-20 available from Japan Emulsion Co.), gelatin, and polyvinylalcohol, and polymerization is performed in the presence of a polymerization initiator (most preferably a water-soluble initiator) at a temperature of generally about 30°C to about 100°C, and preferably, 40°C to about 90 C.
The type and amount of polymerization initiator to be used in this emulsion polymerization can be similarly determined as in the case of solution polymerization described above.
In the above polymerization methods, a decomposition behavior of an initiator used changes in accordance with, e.g., the type of initiator and a polymerization temperature. When polymerization is completed, however, preferably 80% or more, and most preferably, 95% or more of a polymerization initiator are preferably completely decomposed.
Typical examples of a polymer which can be used in a silver halide photographic light-sensitive material of the present invention and is derived from an ethylenic unsaturated monomer will be described below. The polymer, however, is not limited to these examples.
A polymer coupler for use in the present invention is preferably a polymer, which is derived from a coupler monomer represented by formula (CI) below and having a repeating unit represented by formula (CII), or a copolymer of at least one type of a non-coloring monomer containing at least one ethylene group and not having oxidative coupling ability with an aromatic primary amine developing agent. In this case, two or more types of coupler monomers may be simultaneously polymerized.

wherein R¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a chlorine atom, L¹ represents
(wherein R² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a substituted alkyl group having 1 to 6 carbon atoms), -COO-,
(wherein each of R³ and R⁴ independently represents a hydrogen, hydroxyl, or halogen atom or substituted or nonsubstituted alkyl, alkoxy, acyloxy, or aryloxy),
(wherein R², R³, and R⁴ have the same meanings as described above), L² represents a bonding group for bonding L¹ to Q, i represents 0 or 1, j represents 0 or 1, and Q represents a coupler moiety capable of forming a dye upon coupling with an oxidized aromatic primary amine developing agent.
More specifically, a bonding group represented by L² is represented by
J¹, J², and J³ may be the same or different independently represent, e.g., -CO-, -S0₂-,
(wherein R⁵ represents a hydrogen atom, an alkyl group (carbon atoms = 1 to 6)), a substituted alkyl group (carbon atoms = 1 to 6), -
(wherein R⁵ has the same meaning as defined above),
(R⁵ has the same meaning as defined above and R⁶ represents an alkylen group having 1 to 4 carbon atoms),
(wherein R⁵ and R⁶ has the same meanings as defined above and R⁷ represents a hydrogen atom, an alkyl group (carbon atoms = 1 to 6), or a substituted alkyl group (carbon atoms = 1 to 6)), -0-, -S-,
(wherein R⁵ and R⁷ have the same meanings as defined above),
(wherein R⁵ and R⁷ have the same meanings as defined above), -COO-, -OCO-,
(wherein R⁵ has the same meaning as defined above), and
(wherein R⁵ has the same meaning as defined above).
X¹, X², and X³ may be the same or different and independently represent an alkylene group, a substituted alkylene group, an arylene group, a substituted arylene group, an aralkylene group, or a substituted aralkylene group.
Each of g, r, and s independently represents 0 or 1.
In the above formula (CI), X¹, X², and X³ may be the same or different and independently represent a substituted or nonsubstituted alkylene group, aralkylene group, or phenylene group each having 1 to 10 carbon atoms, and the aralkylene group may be either straight-chain or branched. Examples of the alkylene group are methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and decylmethylene, an example of the aralkylene group is benzylidene, and examples of the substituted and nonsubstituted phenylene group are p-phenylene, m-phenylene, and methylphenylene..
Examples of a substituting group of the alkylene group, the aralkylene group, or the phenylene group are a halogen atom, a nitro group, a cyano group, an alkyl group, a substituted alkyl group, an alkoxy group, a substituted alkoxy group, a group represented by -NHCOR⁸ (wherein R⁸ represents alkyl, substituted alkyl, phenyl, substituted phenyl, aralkyl, or substituted aralkyl), -NHS0₂R^s (R⁸ has the same meaning as defined above), -S0₂R⁸ (wherein R⁸ has the same meaning as defined above), -SOR^s (wherein R⁸ has the same meaning as defined above), -COR^s (wherein R⁸ has the same meaning as defined above), a group represented by
(wherein R⁹ and R¹⁰ may be the same or different and independently represent a hydrogen atom, alkyl, substituted alkyl, phenyl, substituted phenyl, aralkyl, or substituted aralkyl),
(wherein R⁹ and R¹⁰ have the same meanings as defined above), an amino group (which may be substituted by alkyl), a hydroxyl group, and a group which forms a hydroxyl group by hydrolysis. When two or more of these substituting groups are present, they may be the same or different.
Examples of a substituting group of the substituted alkyl group, the substituted alkoxy group, the substituted phenyl group, and the substituted aralkyl group are a hydroxyl group, a nitro group, an alkoxy group having 1 to about 4 carbon atoms, -NHS0₂R⁸ (wherein R⁸ have the same meanings as defined above),
(wherein R⁹ and R¹⁰ have the same meanings as defined above), a group representedgroup represented by
(wherein R⁹ R¹⁰ have the same meaning as defined above), -S0₂R⁸ (wherein R⁸ has the same meaning as defined above), -COR⁸ (wherein R⁸ has the same meaning as defined above), a halogen atom, a cyano group, an amino group (which may be substituted by alkyl).
Q represents a group bonded to a compound represented by formula (CI) or (CII) at a portion of any of R₅₁, to R₅₉, Z¹ to Z³, and Y of formulas (Cp-1) to (Cp-a) below.
R₅₁ to R₅₉, ℓ, m, and p in formulas (Cp-1) to (Cp-9) will be described below.
In the above formulas, R₅₁ represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and each of Rs₂ and R₅₃ independentlyrepresents an aromatic group or a heterocyclic group.
Preferably, an aliphatic group represented by R₅₁ may have 1 to 22 carbon atoms and may be substituted or nonsubstituted and chained or cyclic. Preferable examples of a substituting group of the aliphatic group are an alkoxy group, an aryloxy group, an amino group, an acylamino group, and a halogen atom. These substituting groups may have their substituting groups. More specifically, examples of an effective aliphatic group as R₅₁ are isopropyl, isobutyl, tert-butyl, isoamyl, tert-amyl, 1,1-dimethylbutyl, 1,1-dimethylhexyl, 1,1-diethylhexyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, 2-methoxyisopropyl, 2-phenox- yisopropyl, 2-p-tert-butylphenoxyisopropyl, a-aminoisopropyl, a-(diethylkamino)isopropyl, a-(succinimido)-isopropyl, a-(phthalimido)isopropyl, and a-(benzenesulfonamido)isopropyl.
If R₅₁, R₅₂, or R₅₃ represents an aromatic group (especially a phenyl group), this aromatic group may be substituted. An aromatic group such as a phenyl group may be substituted by, e.g., alkyl having 32 or less carbon atoms, alkenyl, alkoxy, alkoxycarbonyl, alkoxycarbonylamino, aliphatic amido, alkylsulfamoyl, alkylsulfonamido, alkylureido, or alkyl-substituted succinimido. In this case, alkyl may have an aromatic group such as phenylene in its chain. Phenyl may be substituted by, e.g., aryloxy, aryloxycarbonyl, arylcarbamoyl, arylamido, arylsulfamoyl, arylsulfonamido, or arylureido, and a portion of aryl of these substituting groups may be substituted by one or more alkyl groups having 1 to 22 carbon atoms in total.
Phenyl represented by R₅₁, R_s2, or R_sa may be substituted by amino which may be substituted by lower alkyl having 1 to 6 carbon atoms, hydroxyl, carboxyl, sulfo, nitro, cyano, thiocyano, or a halogen atom.
In addition, Rsi, R₅₂, or Rs₃ may represent a substituting group, obtained when phenyl condenses another ring, such as naphthyl, quionlyl, isoquinolyl, chromanyl, coumaranyl, or tetrahydronaphthyl. These substituting groups may have their own substituting groups.
If R₅₁ represents alkoxy, an alkyl portion of alkoxy may be substituted by straight-chain or branched alkyl having 1 to 32, and preferably, 1 to 22 carbon atoms, alkenyl, cyclic alkyl, or cyclic alkenyl, and they may be substituted by, e.g., a halogen atom, aryl, or alkoxy.
If Rsi, Rs₂, or R₅₃ represents a heterocyclic group, this heterocyclic group is bonded to a carbon atom of a carbonyl group of an acyl group or a nitrogen atom of an amido group in a-acylacetoamido via one of carbon atoms forming the heterocyclic ring. Examples of the heterocyclic ring are thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine, and oxazine, and they may have a substituting group on their rings.
In formula (Cp-3), R₅₅ represents a straight-chain or branch-chain alkyl having 1 to 32, and preferably, 1 to 22 carbon atoms (e.g., methyl, isopropyl, tert-butyl, hexyl, or dodecyl), alkenyl (e.g., aryl), cyclic alkyl (e.g., cyclopentyl, cyclohexyl, or nolbonyl), aralkyl (e.g., benzyl or β-phenylethyl), or cyclic alkenyl (e.g., cyclopentenyl or cyclohexenyl), and they may be substituted by a halogen atom, a nitro group, cyano, aryl, alkoxy, aryloxy, carboxyl, alkylthiocarbonyl, arylthiocarbonyl, alkoxycarbonyl, aryloxycarbonyl, sulfo, sulfamoyl, carbamoyl, acylamino, diacylamino, ureido, urethane, thiourethane, sulfonamido, a heterocyclic group, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, dialkylamino, anilino, N-arylanilino, N-alkylanilino, N-acylanilino, hydroxyl, or mercapto.
R₅₅ may also represent aryl (e.g., phenyl or a- or 8-naphthyl). Aryl may have one or more substituting groups such as alkyl, alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl, a halogen atom, a nitro group, cyano, aryl, alkoxy, aryloxy, carboxyl, alkoxycarbonyl, aryloxycarbonyl, sulfo, sulfamoyl, carbamoyl, acylamino, diacylamino, ureido, urethane, sulfonamido, a heterocyclic ring, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, dialkylamino, anilino, N-alkylanilino, N-arylanilino, N-acylanilino, or a hydroxyl group.
In addition, R₅₅ may represent a heterocyclic group (e.g., a 5- or 6-membered heterocyclic ring or condensation heterocyclic group, containing a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom, such as pyridyl, quinolyl, furyl, benzothiazolyl, oxazolyl, imidazolyl, or naphthooxazolyl), a heterocyclic group, aliphatic or aromatic acyl, alkylsulfonyl, arylsulfonyl, alkylcarbamoyl, arylcarbamoyl, alkylthiocarbamoyl, or arylthiocarbamoyl, substituted by the substituting groups enumerated above with respect to the aryl group.
In the above formula, R₅₄. represents straight-chain or branch-chain alkyl having 1 to 32, and preferably, 1 to 22 carbon atoms, alkenyl, cyclic alkyl, aralkyl, a cyclic alkenyl group (which may have the substituting groups enumerated above with respect to R_ss), an aryl group and a heterocyclic group (which may have the substituting groups enumerated above with respect to Rss), alkoxycarbonyl (e.g., methoxycarbonyl, ethoxycarbonyl, or stearyloxycarbonyl), aryloxycarbonyl (e.g., phenoxycarbonyl or naphthoxycarbonyl), aralkyloxycarbonyl (e.g., benzyloxycarbonyl), alkoxy (e.g., methoxy, ethoxy, or heptadecyloxy), aryloxy (e.g., phenoxy or tolyloxy), alkylthio (e.g., ethylthio or dodecylthio), arylthio (e.g., phenylthio or a-naphthylthio), carboxyl, acylamino (e.g., acetylamino or 3-[(2,4-di-tert-amylpheoxy)acetamido]benzamido), diacylamino, N-alkylacylamino (e.g., N-methylpropionamido), N-arylacylamino (e.g., N-phenyl-acetoamido), ureido (e.g., ureido, N-arylureido, or N-alkylureido), urethane, thiourethane, arylamino (e.g., phenylamino, N-methylaniline, diphenylamino, N-acetylanilino, or 2-chloro-5-tetradecaneamideanilino), alkylamino (e.g., n-butylamino, methylamino, or cycloxylamino), cycloamino (e.g., piperidino or pyrrolidino), heterocyclic amino (e.g., 4-pyridylamino or 2-benzooxazolylamino), alkylcarbonyl (e.g., methylcarbonyl), arylcarbonyl (e.g., phenylcarbonyl), sulfonamido (e.g., alkylsulfonamido or arylsulfonamido), carbamoyl (e.g., ethylcarbamoyl, dimethylcarbamoyl, N-methylphenylcarbamoyl, or N-phenylcarbamoyl), sulfamoyl (e.g., N-alkylsulfamoyl, N,N-dialkylsulfamoyl, N-arylsulfamoyl, N-alkyl-N-arylsulfamoyl, or N,N-diarylsulfamoyl), cyano, hydroxyl, or sulfo.
In the above formula, R₅₆ represents a hydrogen atom, a straight-chain or branch-chain aralkyl having 1 to 32, and preferably, 1 to 22 carbon atoms, alkenyl, cyclic alkyl, aralkyl, or cyclic alkenyl, and they may have the substituting groups enumerated above with respect to Rss.
Rss may also represent aryl or a heterocyclic group, and they may have the substituting groups enumerated above with respect to Rss.
In addition, R₅₆ may represent cyano, alkoxy, aryloxy, a halogen atom, carboxyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, sulfo, sulfamoyl, carbamoyl, acylamino, diacylamino, ureido, urethane, sulfonamido, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, dialkylamino, anilino, N-arylanilino, N-alkylanilino, N-acylanilino, or hydroxyl.
Each of R₅₇, Rss, and R₅₉ independently represents a group normally used in a 4-equivalent phenol or a-naphthol coupler. More specifically, examples of R₅₇ are a hydrogen atom, a halogen atom, an alkoxycarbonylamino group, an aliphatic hydrocarbon moiety, an N-arylureido group, an acylamino group, or -0-R₆₂ or -S-R₆₂ (wherein R₆₂ represents an aliphatic hydrocarbon moiety). If two or more R₅₇s are present in one molecule, they may be the same or different. In addition, the aliphatic hydrocarbon moiety may have a substituting group. Furthermore, two R₅₇s may form a nitrogen-containing heterocyclic ring.
If these substituting groups include an aryl group, this aryl group may have the substituting groups enumerated above with respect to Rss.
An example of Rss and R₅₉ is a group selected from an aliphatic hydrocarbon moiety, an aryl group, and a heterocyclic moiety. One of R₅₈ and R₅₉ may be a hydrogen atom, and the above groups may have a substituting group. In addition, R₅₈ and Rss may together form a nitrogen-containing heterocyclic nucleus.
The aliphatic hydrocarbon moiety may be saturated or unsaturated or straight-chain, branched, or cyclic. Preferable examples of the aliphatic hydrocarbon moiety are an alkyl group (e.g., groups of methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, and cyclohexyl), and an alkenyl group (e.g., groups of allyl and octenyl). Examples of the aryl group are a phenyl group and a naphthyl group, and typical examples of the heterocyclic moiety are groups of pyridinyl, quinolyl, thienyl, piperidyl, and imidazolyl. Examples of a substituting group, to which the aliphatic hydrocarbon moiety, the aryl group, and the heterocyclic moiety are introduced, are a halogen atom, nitro, hydroxyl, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl, a heterocyclic ring, alkoxy, aryloxy, arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamido, sulfamoyl, sulfonyl, and morpholino.
ℓ represents an integer of 1 to 4, m represents an integer of 1 to 3, and p represents an integer of 1 to 5.
Of the above coupler moieties, as a yellow coupler moiety, it is preferable that R₅₁ represents t-butyl or substituted or nonsubstituted aryl and R₅₂ represents substituted or nonsubsituted aryl in formula (Cp-1), and that R₅₂ and R₅₃ represent substituted or nonsubstituted aryl in formula (Cp-2).
As a magenta coupler moiety, it is preferable that R₅₄ represents acylamino, ureido, and arylamino and R₅₅ represents substituted aryl in formula (Cp-3), that R₅₄ represents acylamino, ureido, and arylamino and R₅₆ represents a hydrogen atom in formula (Cp-4), and that Rs4. and R₅₆ represent straight-chain or branch-chain alkyl, alkenyl, cyclic alkyl, aralkyl, and cyclic alkenyl in formulas (Cp-5) and (Cp-6).
As a cyan coupler moiety, it is preferable that R₅₇ represents acylamino or ureido at the 2-position, acylamino or alkyl at the 5-position, and hydrogen atom or chlorine atom at the 6-position in formula (Cp-7), and that R₅₇ represents hydrogen atom at the 5-position, acylamino, sulfonamido, and alkoxycarbonyl, R₅₈ represents a hydrogen atom, and R₅₉ represents phenyl, aralkyl, alkenyl, cyclic alkyl, aralkyl, and cyclic alkenyl in formula (Cp-9).
In a polymer coupler used in the present invention, Z₁ to Z₃ and Y in formulas (Cp-1) to (Cp-9) will be described in detail below.
Z₁ represents a hydrogen atom, a halogen atom, sulfo, acyloxy, alkoxy, aryloxy, heterocyclic oxy, alkylthio, arylthio, or heterocyclic thio, and these groups may be substituted by substituting groups such as aryl (e.g., phenyl), nitro, a hydroxyl group, cyano, sulfo, alkoxy (e.g., methoxy), aryloxy (e.g., phenoxy), acyloxy (e.g., acetoxy), acylamino (e.g., acetylamino), sulfonamido (e.g., methanesulfonamido), sulfamoyl (e.g., methylsulfamoyl), a halogen atom (e.g., fluorine, chlorine, and bromine), carboxyl, carbamoyl (e.g., methylcarbamoyl), alkoxycarbonyl (e.g., methoxycarbonyl), and sulfonyl (e.g., methylsulfonyl).
Each of Z₂ and Y independently represents a hydrogen atom or a split-off group bonded to a coupling portion by an oxygen atom, a nitrogen atom, or a sulfur atom. If Z₂ and Y are bonded to a coupling position by an oxygen atom, a nitrogen atom, or a sulfur atom,. this atom is bonded to alkyl, aryl, alkylsulfonyl, arylsulfonyl, alkylcarbonyl, arylcarbonyl, or a heterocyclic group. If the atom is a nitrogen atom, Z₂ and Y also mean a group which contains the nitrogen atom and can form a 5- or 6-membered ring to be an elimination group (e.g., imidazolyl, pyrazolyl, triazolyl, and tetrazolyl).
Alkyl, aryl, and the heterocyclic group described above may have substituting groups. More specifically, examples of the substituting group are alkyl (e.g., methyl and ethyl), alkoxy (e.g., methoxy and ethoxy), aryloxy (e.g., phenyloxy), alkoxycarbonyl (e.g., methoxycarbonyl), acylamino (e.g., acetylamino), carbamoyl, alkylcarbamoyl (e.g., methylcarbamoyl and ethylcarbamoyl), dialkylcarbamoyl (e.g., dimethylcarbamoyl), arylcarbamoyl (e.g., phenylcarbamoyl), alkylsulfonyl (e.g., methylsulfonyl), arylsulfonyl (e.g., phenylsulfonyl), alkylsulfonamido (e.g., methanesulfonamido), arylsulfonamido (e.g., phenylsulfonamido), sulfamoyl, alkylsulfamoyl (e.g., ethylsulfamoyl), dialkylsulfamoyl (e.g., dimethylsulfamoyl), alkylthio (e.g., methylthio), arylthio (e.g., phenylthio), cyano, nitro, and a halogen atom (e.g., fluorine, chlorine, and bromine). If two or more substituting groups are present, they may be the same or different.
Most preferable examples of the substituting group are a halogen atom, alkyl, alkoxy, alkoxycarbonyl, and cyano.
A preferable group of Z₂ is a group bonded to a coupling position by a nitrogen atom or a sulfur atom, and a preferable group of Y is a chlorine atom or a group bonded to a coupling position by an oxygen atom, a nitrogen atom, or a sulfur atom.
Z₃ is a hydrogen atom or represented by formula (R-1), (R-2), (R-3), or (R-4) below.
wherein Rεε represents an aryl group or a heterocyclic group which may be substituted.
wherein each of R64 and R₆₅ independently represents a hydrogen atom, a halogen atom, carboxylic ester, amino, alkyl, alkylthio, alkoxy, alkylsulfonyl, alkylsulfinyl, a carboxylic acid group, a sulfonic acid group, a substituted or nonsubstituted phenyl group, or a heterocyclic ring. These groups may be the same or diferent.
wherein W₁ represents a nonmetal atom required to from a 4-, 5-, or 6-membered ring together with
Preferable examples of formula (R-4) are represented by formulas (R-5) to (R-7) below.

wherein each of R_ss and Rε_z independently represents a hydrogen atom, alkyl, aryl, alkoxy, aryloxy, or hydroxyl, each of Rεε, R₆₉, R₇₀ independently represents a hydrogen atom, alkyl, aryl, aralkyl, or acyl, and W₂ represents an oxygen or sulfur atom.
Although typical examples of a coupler monomer will be listed in Table 6 to be presented later, the monomer is not limited to these examples.
Examples of a non-color-forming ethylenic monomer which is not coupled to an oxidized product of an aromatic primary amine developing reagent are acrylic acid, a-chloroacrylic acid, a-alkylacrylic acid (e.g., acrylic acid and methacrylic acid), an ester or amide derived from these acrylic acids (e.g., acrylamide, methacrylamide, t-butylacrylamide, 2-acrylamide-2-methylpropanesulfonic acid, methylacrylate, methylmethacrylate, ethylacrylate, n-propylacrylate, iso-propylacrylate, n-butylacrylate, t-butylacrylate, n-butylmethacrylate, 2-ethylhexylacrylate, n-hexylacrylate, n-octylacrylate, laurylacrylate, acetoacetoxyethylmethacrylate, glycidylmethacrylate, and methylenebisacrylamide), vinylester (e.g., vinylacetate, vinylpropionate, and vinyllaurate), an aromatic vinyl compound (e.g., styrene and its derivative (e.g., potassium styrenesulfinate and sodium styrenesulfonate), vinyltoluene, divinylbenzene, vinylacetophenone), vinylidenechloride, vinylalkylether (e.g., vinylethylether), maleic ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. Most preferable examples are acrylic ester, methacrylic ester, acrylamide, methacrylamide, and styrene and its derivative. For example, n-butylacrylate and methylacrylate, n-butylacrylate and styrene, methylacrylate and t-butylacrylamide, ethylacrylate and methacrylic acid, and sodium 2-acrylamide-2-methylpropanesulfonate and potassium styrenesulfinate can be used.
A polymer coupler for use in the present invention may be either water soluble or insoluble.
As a polymer coupler of the present invention, a lipophilic polymer coupler or a telomer coupler formed by polymerization of a coupler monomer which is once extracted and then dissolved into an organic solvent may be emulsion-dispersed, or a polymer coupler latex formed by an emulsion polymerization method and a layered-structure polymer coupler latex may be added directly to a gelatin silver halide emulsion. Alternatively, a hydrophilic polymer coupler once extracted and then dissolved in water or a water/water- miscible organic solvent may be added directly to a gelatin silver halide emulsion.
A ratio of a dye-forming portion in the polymer coupler is preferably 5 to 80 wt%, and most preferably, 20 to 70 wt% in consideration of color reproducibility, color forming properties, and stability. In this case, an equimolecular weight (grams of a polymer containing one mol of a coupler monomer) is about 250 to 4,000, but it is not limited to this value.
An addition amount of the polymer coupler latex is 0.005 to 0.5 mol, and preferably, 0.01 to 0.05 mol per mol of silver on the basis of a coupler monomer.
Methods of synthesizing a polymer of a coupler are roughly classified into i) an emulsion polymerization method, ii) a seed polymerization method, and iii) a solution polymerization method, and i) a polymer coupler latex, ii) a layered-structure polymer coupler latex, and iii) a lipophilic polymer coupler, a telomer coupler, and a hydrophilic polymer coupler can be obtained, respectively. Methods of manufacturing these polymers and methods of adding the polymers to an emulsion are described in i) U.S. Patent 4,080,211, ii) JP-A-58-42044, and iii) U.S. Patent 3,451,820, JP-A-62-276548, and JP-A-60-218646.
Compositions of polymer couplers synthesized in accordance with these patents are listed in Table-I to Table-V.
Examples of the coupler monomer used in the present invention are listed in Table-VI.
In the present invention, of the above polymer couplers, preferably a magenta coupler, more preferably, a 2-equivalent magenta coupler, and most preferably, a pyrazole-split-off 5-pyrazolone type two-equivalent magenta polymer coupler are used.
Although the polymer coupler of the present invention may be added to any layer of photographic constituting layers, it is preferably added to a light-sensitive emulsion layer or its adjacent layer. An addition amount of the polymer coupler is preferably 0.01 to 1.0 g, and more preferably, 0.05 to 0.5 g per m2.
A photographic light-sensitive material of the present invention can contain polymer beads (to be referred to as a polymer matting agent hereinafter) as long as image transparency and graininess are not degraded. The polymer matting agent preferably has an average grain size of 0.3 to 5 pm, and two or more types of polymer matting agents having different average grain sizes can be mixed.
Examples of a monomer compound of the polymer matting agent are acrylic ester, methacrylic ester, itaconic diester, crotonic ester, maleic diester, and phthalic diester. Examples of an ester moiety are methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylhexyl, 2-chloroethyl, cyanoethyl, 2-acetoxyethyl, dimethylaminoethyl, benzyl, cyclohexyl, furfuryl, phenyl, 2-hydroxyethyl, 2-ethoxyethyl, glycidyl, and u-methoxypolyethyleneglycol (additional mols = 9).
Examples of a vinylester are vinylacetate, vinylpropionate, vinylbutylate, vinylisobutylate, vinylcaproate, . vinylchloroacetate, vinylmethoxyacetate, vinylphenylacetate, vinyl benzoate, and vinyl salicylate.
Examples of an olefin are dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene.
Examples of styrenes are styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, trifluoromethylstyrene, and vinyl methylester benzoate.
Examples of an acrylamide are acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, α-cyanoethylacrylamide, and N-(2-acetoacetoxydiethyl)acrylamide;

a methacrylamide such as methacrylamide, methylmethacrylamide, ethylmethacrylamide, propyl- methacrylamide, butylmethacrylamide, tert-butylmethacrylamide, cyclohexylmethacrylamide, benzyl- methacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethyl- methacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, _jS-cyanoethyi- methacrylamide, and N-(2-acetoacetoxyethyl)methacrylamide;
an allyl compound such as allyl acetate, allyl caproate, allyl laurate, and allyl benzoate;
a vinylether such as methylvinylether, butylvinylether, hexylvinylether, methoxyethylvinylether, and dimethylaminoethylvinylether;
a vinylketone such as methylvinylketone, phenylvinylketone, and methoxyethylvinylketone;
a vinyl heterocyclic compound such a svinylpyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, and N-vinylpyrrolidone; and
a polyfunctional monomer such as divinylbenzene, methylenebisacrylamide, and ethyleneglycol- dimethacrylate.

Other examples are acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate, e.g., monomethyl itaconate, monoethyl itaconate, and monobutyl itaconate; monoalkyl maleate, e.g., monomethyl maleate, monoethyl maleate, and monobutyl maleate; citraconic acid, styrenesulfonic acid, vinylbenzylsul- fonic acid, vinylsulfonic acid, acryloyloxyalkylsulfonic acid, e.g., acryloyloxymethylsulfonic acid, acryloylox- yethylsulfonic acid, and acryloyloxypropylsulfonic acid;

methacryloyloxyalkylsulfonic acid, e.g., methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, and methacryloyloxypropylsulfonic acid;
acrylamidoalkylsulfonic acid, e.g., 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and 2-acrylamido-2-methylbutanesulfonic acid;
methacrylamidoalkylsulfonic acid, e.g., 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, and 2-methacrylamido-2-methylbutanesulfonic acid;
acryloyloxyalkylphosphate, e.g., acryloyloxyethylphosphate and 3-acryloyloxypropyl-2-phosphate; methacryloyloxyalkylphosphate, e.g., methacryloyloxyethylphosphate and 3-methacryloyloxypropyl-2-phosphate; and sodium 3-aryloxy-2-hydroxypropanesulfonate having two hydrophilic groups. These acids may be a salt of an alkaline metal (e.g., Na and K) or an ammonium ion. In addition, crosslinking monomers described in, e.g., U.S. Patents 3,459,790, 3,438,708, 3,554,987, 4,215,195, and 4,247,673, and JP-A-57-205735 can be used as a monomer compound. Examples of the crosslinking monomer are N-(2-acetoacetoxyethyl)acrylamide and N-(2-(2-acetoacetoxyethoxy)ethyl)acrylamide.

These monomer compounds may be used in the form of grains of a polymer which is singly polymerized or a copolymer which is obtained by polymerizing a plurality of monomers.
Examples of a grain composition are polystyrene, polymethyl(meth)acrylate, polyethylacrylate, poly-(methylmethacrylate/methacrylic acid = 95/5 (mole ratio)), poly(styrene/styrenesulfonic acid = 95/5 (mole ratio)), and poly(methylmethacrylate/ethylene acrylate/methacrylic acid = 50/40/10). A polymer matting agent which is soluble in an alkaline processing solution can be preferably used. Examples of the alkali processing solution-soluble polymer matting agent are methylmethacrylate/methacrylic acid = 60/40 (mole ratio), methylmethacrylate/methacrylic acid = 55/45 (mole ratio), methylmethacrylate/acrylic acid = 60/40 (mole ratio), ethylmethacrylate/methylmethacrylate/methacrylic acid = 30/30/40 (mole ratio), and styrene/methylmethacrylate/methacrylic acid = 40/10/50 (mole ratio).
As the polymer matting agent, a solid of the above polymer may be milled and classified, spherical grains synthesized by a suspension polymerization method may be directly used, or grains may be formed to be spherical by a spray dry method or a dispersion method.
Although an addition amount of such a polymer matting agent depends on, e.g., the type of photographic light-sensitive material or the grain size of polymer matting agent grains, it is preferably 0.02 to 0.4 g/_m2.
A polymer of an ultraviolet absorbent can also be used in the present invention.
Examples of the ultraviolet absorbent usable in the present invention are a benzylidene derivative, a benzophenone derivative, a benzotriazole derivative, and a butadiene derivative. Examples of such absorbents are those described in, e.g., JP-A-47-560, JP-A-58-111942, JP-A-58-178351, JP-A-58-181041, JP-A-58-185677, JP-A-61-118749, JP-A-62-260152, JP-A-63-56651, U.S. Patents 4,178,303, 4,207,253, 4,464,463, 4,464,462, 4,645,735, and 4,551,420, and EP 27,259A and 189,059A.
Of these polymer ultraviolet absorbents, a most preferable example in the present invention is an ultraviolet absorbent not containing a cyano group in an ethylenic unsaturated monomer or a copolymerized ethylenic unsaturated monomer is a copolymer is to be used, having an ultraviolet absorptive group.
Examples of an ethylenic unsaturated monomer having an ultraviolet absorptive group preferably used in the present invention will be presented below, but the monomer is not limited to these examples.
The polymer ultraviolet absorbent used in the present invention may be either a homopolymer or a copolymer of the above ultraviolet absorptive monomers. Examples of a monomer used in copolymerization are acrylic acid, a-alacrylic acid (e.g., an ester derived from an acrylic acids such as methacrylic acid, preferably, lower alkylester and an amide such as acrylamide, methacrylamide, t-butylacrylamide, methylacrylate, methylmethacrylate, ethylacrylate, ethylmethacrylate, n-propylacrylate, n-butylacrylate, 2-ethylhexylacrylate, n-hexylacrylate, octylmethacrylate, laurylmethacrylate, and methylenebisacrylamide), vinylester (e.g., vinylacetate, vinylpropionate, and vinyllaurate), an aromatic vinyl compound (e.g., styrene and its derivative such as vinyltoluene, divinylbenzene, vinylacetophenone, sulfostyrene, and styrenesulfinic acid), itaconic acid, citraconic acid, crotonic acid, vinylidenechloride, vinylalkylether (e.g., vinylethylether), maleate, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- or 4-vinylpyridine.
Of these compounds, acrylic ester, methacrylic ester, and an aromatic vinyl compound are most preferable.
Two or more types of the above comonomers can be simultaneously used.
For example, n-butylacrylate and divinylbenzene, styrene and methylmethacrylate, and methylacrylate and methacrylic acid can be simultaneously used.
A ratio of an ultraviolet absorbent monomer component in an ultraviolet absorptive polymer is preferably 5 to 100 wt%, and most preferably, 50 to 100 wt%.
Preferable examples of the ultraviolet absorptive polymer will be presented below, but the polymer is not limited to these examples.

(PU-1) Copolymer of example compound (MU-1): methylmethacrylate = 7 : 3 (weight ratio)
(PU-2) Homopolymer of example compound (MU-3)
(PU-3) Homopolymer of example compound (MU-5)
(PU-4) Copolymer of example compound (MU-7) : butylmethacrylate = 8 : 2 (weight ratio)
(PU-5) Homopolymer of example compound (MU-7)
(PU-6) Copolymer of example compound (MU-8) : soda 2-acrylamido-2-methylpropanesulfonate = 95 : 5 (weight ratio)
(PU-7) Homopolymer of example compound (MU-11)
(PU-8) Copolymer of example compound (MU-16) : styrene = 7 : 3 (weight ratio)
(PU-9) Copolymer of example compound (MU-17) : methylmethacrylate = 8 : 2 (weight ratio)
(PU-10) Copolymer of example compound (MU-17) : n-butylacrylate = 6 : 4 (weight ratio)
(PU-11) Copolymer of example compound (MU-18) : methylmethacrylate = 5 : 5 (weight ratio)
(PU-12) Copolymer of example compound (MU-18) : methylmethacrylate = 8 : 2 (weight ratio)

The ultraviolet absorptive polymer used in the present invention may be prepared by an emulsion polymerization method as described above or stirring a material, obtained by dissolving lipophilic polymer prepared by polymerization of an ultraviolet absorptive monomer in an organic solvent (e.g., ethyl acetate), together with a surfactant in an aqueous gelatin solution to disperse the material in the form of a latex, and introducing the latex into a photographic light-sensitive material.
Although an amount of the ultraviolet absorbent polymer used in the present invention is particularly not limited, it is preferably 0.01 to 2.0 g/m², and most preferably, 0.05 to 1.0 g/m^2. In addition, these ultraviolet absorbent polymers may be used in a combination of two or more types thereof or in combination with one or more types of other low-molecular ultraviolet absorbent.
In the silver halide photographic light-sensitive material of the present invention, a polymer latex can be used in order to improve or adjust physical properties (e.g., flexibility and dimensional change) of a film.
Such a polymer latex used to improve physical properties of a film preferably has a glass transition temperature lower than room temperature.
Examples of the polymer latex are polyethylacrylate, polybutylacrylate, poly-2-ethylhexylacrylate, ethylacrylate/acrylic acid copolymer (mole ratio = 95/5), and an ethylacrylate/butylacrylate/acrylic acid copolymer (mole ratio = 45/45/10).
The latex for this purpose can be used in any of light-sensitive layers and non-light-sensitive layers in a photographic material or in a plurality of layers. Although an addition amount of the latex changes in accordance with an arrangement of a photographic light-sensitive material, it is preferably 0.05 to 2 g/m², and most preferably, 0.1 to 1 g/m².
The polymer latex is also used when additives are incorporated in a photographic layer. Examples of the additive are a coupler, a UV absorbent, a brightener, a covering power imparting agent, an antioxidizing agent, a pigment, a developing agent, an antistatic agent, an antifoggant, an antitwisting agent, a redox dye- releasing compound, a matting agent, an absorbing dye, a development stopper, an antihalation dye, a filter dye, a sensitizing dye, a plasticizer, a slip agent, and a development inhibitor.
In this case, the glass transition temperature, for example, of the latex is not particularly limited, and various types of latexes can be used in accordance with, e.g., properties of an additive to be incorporated. Methods of incorporating an additive in a polymer latex and examples of the polymer latex and additive are described in the following references.
U.S. Patents 3,047,390, 3,181,949, 3,318,195, 3,359,102, 3,592,645, 3,788,854, and 3,418,127, OLS 2,509,342, U.S. Patents 2,269,159, 2,272,191, and 2,772,163, RD 15,930, OLS 2,541,274, RD 15,913, RD 16,226, OLS 2,541,230, U.S. Patents 3,591,387 and 3,672,892, British Patent 1,403,631, U.S. Patent 4,133,687, RD 16,928, U.S. Patent 3,518,088, British Patent 1,468,858, RD 14,850, U.S. Patents 3,597,197, 3,748,129, 2,731,347, and 4,022,622, RD 17,236, U.S. Patent 4,045,299, RD 14,997, U.S. Patent 3,909,441, British Patent 2,003,486, U.S. Patents 2,304,940, 2,322,027, 2,801,171, 2,269,158, 3,619,195, 4,199,363, and 4,203,716, Belg Pat. 833,510, British Patent 2,016,017, JP-A-53-137131, RD 16,468, British Patents 1,130,581 and 1,363,230, U.S. Patent 3,926,436, British Patent 1,454,054, U.S. Patents 3,745,010 and 3,761,272, and RD 18,815.
In the present invention, a linear polymer derived from an ethylenic unsaturated monomer can be used singly or in the form of a mixture with gelatin as a binder.
A typical example of a synthetic polymer as a binder is represented by the following formula (V-1):
wherein A represents a monomer unit obtained by copolymerizing a coplymerizable ethylenic unsaturated monomer.
Examples of the ethylenic unsaturated monomer in formula (V-I) are styrene, hydroxymethylstyrene, soda vinylbenzenesulfonate, N,N,N-trimethyl-N-vinylbenzylammoniumchloride, a-methylstyrene, 4-vinylpyridine, N-vinylpyrrolidone, a monoethylenic unsaturated ester of aliphatic acid (e.g., vinyl acetate), ethylenic unsaturated monocarboxylic acid or dicarboxylic acid and its salt (e.g., acrylic acid and methacrylic acid), maleic anhydride, an ester of ethylenic unsaturated monocarboxylic acid or dicarboxylic acid (e.g., n-butylacrylate, N,N-diethylaminoethylmethacrylate, and N,N-diethyl-N-methyl-N-methacryloylox- yethylammonium p-toluenesulfonate), and an amide of ethylenic unsaturated monocarboxylic acid or dicarboxylic acid (e.g., acrylamide, soda 2-acrylamido-2-methylpropanesulfonate, and N,N-dimethyl-N'- methacryloylpropanediamineacetatebetaine).
R₁ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom, and Q is a divalent bonding group and represents -0-, -COO-,
or an arylene group having 6 to 10 carbon atoms. R₂ represents -OH, -COOX, -SOεX (wherein X represents a hydrogen atom, an alkali metal, or an alkali earth metal),

(wherein R4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m₂ represents an integer of 1 to 4). R₃ represents -H or -COOX, and X has the same meaning as defined above. Each of x and y represents a mole percentage, in which x represents 0 to 99 and y represents 1 to 100.
m₁ represents 0 or 1.
Typical examples of a linear polymer as a binder represented by formula (V-I) will be presented below.
Effective compounds are the compounds enumerated above and compounds described in JP-A-49-135619, JP-A-51-14022, JP-A-54-1621, U.S. Patents 3,019,104, 3,003,873; 3,043,698, 3,165,412, 3,178,296, 3,271,158, 3,312,553, 3,173,790, and 3,316,097, and British Patents 867,899, 904,863, 861,985, 933,494, 1,010,917, 1,013,905, 976,222, 1,073,238, 1,048,016, 1,069,944, 1,078,335, 1,078,335, 1,076,378, 1,030,001, and 1,053,043.
When a photographic light-sensitive material of the present invention is prepared_' by coating a thickening agent is used in order to adjust the viscosity of a coating solution. An anionic polymer having an interaction with gelatin can be used as the thickening agent. Effective examples of the anionic polymer are compounds described in, e.g., JP-B-41-12835 ("JP-B" means Examined Published Japanese Patent Application), JP-B-57-33777, JP-B-59-7724, JP-A-57-105471, JP-A-51-81123, JP-A-53-39119, JP-A-52-67318, JP-A-55-98746, JP-A-56-5537, JP-A-53-13411, JP-A-53-98745, JP-A-53-18687, U.S. Patents 3,746,547 and 3,767,410, British Patent 1,421,930, and French Patent 21,178,157.
Preferable examples of the thickening agent used in the present invention are compounds represented by the following formulas (V-II) and (V-III): Formula (V-II)
wherein A represents a monomer unit obtained by copolymerizing a copolymerizable ethylenic unsaturated monomer, and two or more types of monomer units may be contained.
Examples of an ethylenic unsaturated monomer represented by A in formula (V-II) are styrene, hydroxymethylstyrene, a-methylstyrene, 4-vinylpyridine, N-vinylpyrrolidone, 1-vinylimidazole, 2-methyl-1- vinylimidazole, a monoethylenic unsaturated ester of aliphatic acid (e.g., vinyl acetate), maleic anhydride, an ester of ethylenic unsaturated monocarboxylic acid or dicarboxylic acid (e.g, n-butylacrylate, N,N-diethylaminoethylmethacrylate, and methacrylate), an ethylenic unsaturated ether (e.g., methylvinylether), an amide of ethylenic unsaturated monocarboxylic acid or dicarboxylic acid (e.g., acrylamide, N-(1,1-dimethyl-3-oxobutyl)acrylamide, N-isopropylacrylamide, {N-(3-acrylamidopropyl-N, N-dimethylammoniolacetatebetaine.
R₁ represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms (e.g., a methyl group, an ethyl group, and a butyl group), and most preferably, a hydrogen atom or a methyl group.
L represents a single bond or a divalent bonding group and may be substituted. L is preferably an alkylene group, an arylene group, or a divalent group formed by combining these groups and one or a plurality of bonds represented by
R² represents a hydrogen atom or an alkyl group or an aralkyl group each having 1 to 10 carbon atoms. Most preferably, L represents
-CONHC(CH₃)₂CH₂-, -COOCH₂CH₂0-, COOCH₂CH₂CCOCH₂CH₂-, -CONHCH₂CH₂0-, -C-ONHCH₂CH₂0COCH₂CH₂-, -COOCH₂CH₂, -CONHCH₂CH₂-, and a single bond.
Q" represents an anionic group, and preferably, a carboxylic group, a sulfo group, or a phosphonic acid group.
n represents 1 or 2 and is defined by the type of Q^n⊖ (e.g., n = 1 when Q^n⊖ represents,e.g, a sulfo group or a carboxyl group).
DMe represents a hydrogen ion, a monovalent metal ion, or an ammonium cation, and preferably, a hydrogen ion, sodium ion, potassium ion, or ammonium ion.
A monomer unit represented by
may be a mixture of two or more types of different monomer units.
Each of x and y represents a mole percentage, in which x represents 0 to 99 and y represents 1 to 100. Preferably, x represents 0 to 75 and y represents 25 to 100.
wherein A, x, and y have the same meanings as defined in formula (V-I), and the examples enumerated above in the item of formula (V-I) are also preferable in formula (V-III). R³ and R⁴ have the same meanings as that of R¹ in formula (I) and may be the same or different. Each of R³ and R⁴ is preferably a hydrogen atom.
X represents a hydrogen atom, a monovalent metal atom, or an ammonium salt, and preferably, a hydrogen atom, a sodium atom, or a potassium atom. Y represents -0- or
(wherein R⁵ represents a hydrogen atom or an alkyl group, an aralkyl group, or an aryl group each having 1 to 10 carbon atoms), and preferably, -0-. Z represents, in addition to those defined above as Rs, a monovalent metal atom or an ammonium salt, and preferably, a hydrogen atom, a sodium atom, or a potassium atom.
Examples of the thickening agent for use in the present invention will be presented below, but the thickening agent is not limited to these examples.
In the present invention, a polymer can be used in, e.g., a undercoating layer, an interlayer, an emulsion layer, a protective layer, a back layer, an antistatic layer, an antihalation layer, and a scavenger layer, for various applications in addition to the applications described above. If a polymer for use in these layers is obtained by radial polymerization of an ethylenic unsaturated monomer, a total amount of an initiator containing a cyano group used in a coated polymer must be adjusted to be 5 µmol or less per m² of a photographic light-sensitive material, as described above.
In addition, in the present invention, a polymer not obtained by radical polymerization of an ethylenic unsaturated monomer can be preferably used.
Examples of such a polymer are a natural substance such as a cellulose derivative, e.g., diacetylcellulose and triacetylcellulose, a saccharide such as dextran, prulane, and gum arabi, a synthetic polymer such as polyester, polyamide, polyurethane, polyurea, and polyether obtained by polycondensation, polyaddition, and ring opening polymerization, and polymers obtained by ion polymerization and coordination polymerization of an ethylenic unsaturated monomer.
Examples of an ultraviolet absorbent used in the present invention are ultraviolet absorbents represented by formulas described in JP-A-53-128333, JP-A-53-134431, JP-A-53-131837, JP-A-53-129633, JP-A-54-18727, and JP-A-53-133033 in which R₂ and R₃ are other than CN, an ultraviolet absorbent represented by a formula described in JP-A-53-97425 in which R_s and R₇ are other than CN, an ultraviolet absorbent represented by a formula described in JP-A-56-27146 in which G is other than CN, an ultraviolet absorbent represented by a formula described in JP-A-54-111826 in which A and B are other than CN, ultraviolet absorbents represented by formulas described in British Patents 2,083,240A, 2,083,239A, and 2,083,241A in which P and Q are other than CN, an ultraviolet absorbent represented by formula (II) described in JP-B-56-21141, benzotriazole-based ultraviolet absorbents described in, e.g., JP-B-48-5496, JP-B-50-25337, JP-B-55-36984, JP-B-49-26139, JP-B-51-6540, JP-B-47-1026, JP-A-61-190537, JP-A-1-306839, JP-A-1-306840, JP-A-1-306841, JP-A-1-306842, JP-A-1-306843, and EP 57-160, benzophenone-based ultraviolet absorbents described in, e.g., JP-B-50-33773, JP-B-56-30538, and U.S. Patents 3,698,907 and 3,215,530 ultraviolet absorbents represented by formulas described in JP-A-58-185677 and JP-A-58-111942 in which R₇ and Rε are other than CN, and an ultraviolet absorbent represented by a formula described in JP-A-58-178351 in which R₃ and R₄ are other than CN.
Examples of the ultraviolet absorbent used in the present invention will be presented below. wherein each of R₁ and R₂ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R₁ and R₂ may be the same or different but are not simultaneously hydrogen atoms. In addition, R₁ and R₂ may form a 5- or 6-membered ring together with N.
Each of X and Y independently represents -COR₃, -COOR₃, -S0₂R₃,
or -COOH. X and Y may be the same or different. Each of R₃ and R4 independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R₄ may be a hydrogen atom. X and Y may be bonded to be integrated. When X and Y are integrated, they represent an atom group required to form a nucleus of 1,3-dioxocyclohexane, varbituric acid, 1,2-diaza-3,5-diox- ocyclopentane, or 2,4-diaza-1-alkoxy-3,5-dioxocyclohexane. n represents 1 or 2. When n is 2, at least one of R_i, R₂, and R₃ may represent an alkylene group or an arylene group to form a dimer.
wherein z represents an atom group required to form an oxazolidine ring, a pyrrolidine ring, or a thiazolidine ring. R₅ represents an alkyl group or an aryl group. Each of X and Y independently represents -COR_s, -COOR₃, -S0₂R₃,
or -COOH. X and Y may be the same or different. R₃ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. X and Y may be bonded to be integrated. When X and Y are integrated, they represent an atom group required to form a nucleus of 1,3-dioxocyclohexane, barbituric acid, 1,2-diaza-3,5-dioxocyclopentane, or 2,4-diaza-1-alkoxy-3,5-dioxocyclohexane. n represents 1 or 2. When n represents 2, one of R₅ and R₃ may represent an alkylene group or an arylene group to form a dimer.
wherein Z¹ represents 0, S, or
R₅ represents an alkyl group or an aryl group, and each of R₆ and R₇ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R₆ and R₇ may be integrated to form a benzene ring or a naphthalene ring. R₈ represents a hydrogen atom or an alkyl group, and R^g represents an alkyl group or an aryl group. R₈ and R₉ may together form a nucleus of 1,3- indandione, barbituric acid, 2-thiobarbituric acid, 1,3-dioxocyclohexane, 2,4-diaza-1-alkoxy-3,5-dioxocyclohexane, 2,4-thiazolidinedione, 2-iminothiazolidine-4-one, hydantoin, 2,4-oxazolidinedione, 2- iminooxazolidine-4-one, or 2-thiooxazolidine-2,4-dione. Each of R₁₀ and R₁₁ independently represents an alkyl group having 1 to 4 carbon atoms.
wherein Z₂ represents an atom group required to. form 5-oxazolone, 5-isooxazolone, 2-thiohydantoin, 2-thiooxazolidine-2,5-dione, rhodanine, thiazolidine-2,4-dione ring. R₁₂ represents an alkoxy group having 1 to 20 carbon atoms, -OCOR₁₇, or a hydrogen atom. R₁₇ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. Each of R₁₃ and R₁₄ independently represents a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, and each of R₁₅ or R₁₆ independently represents an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, or a halogen atom.

wherein R₂₈, R₂₉, R₃₀, R₃₁, and R₃₂ may be the same or different and may be a hydrogen atom or substituted by a substituting group allowed for an aromatic group. R₃₁ and R₃₂ may be ring-closed to form a 5- or 6-membered aromatic ring consisting of carbon atoms. Of these substituting groups, those capable of having substituting groups may be further substituted by allowed substituting groups.
wherein R₁₈ represents hydroxy, an alkoxy group, or an alkyl group. Each of R₁₉ and R₂₀ independently represents a hydrogen atom, hydroxy, an alkoxy group, or an alkyl group. R₁₈ and R₁₉ or R₂₀ and R₁₈ may be at adjacent positions to form a 5- or 6-membered ring. Each of X and Y independently represents -COR₃, -COOR₃, -S0₂R₃,
or -COOH, and X and Y may be the same or different. Each of R₃ and R₄ independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R₄ may be a hydrogen atom. X and Y may be bonded to be integrated. If X and Y are integrated, they represent an atom group required to form a nucleus of 1,3-dioxocyclohexane, barbituric acid, 1,2-diaza-3,5-dioxocyclopentane, or 2,4-diaza-1-alkoxy-3,5-dioxocyclohexane.
Examples of compounds represented by formulas (UVI) to (UVVI) used in the present invention will be presented below, but the present invention is not limited to these examples.
Examples of a dye used in the present invention are compounds described in, e.g., JP-A-1-179041 (except for those in which each of R₁ and R₂ represents a cyano group), JP-A-1-179042 (except for those in which each of X and Y represents a cyano group), JP-A-1-154149 (except for those in which each of X and Y represents a cyano group), DP 2,902,685, JP-A-1-102552, JP-A-64-90442, JP-A-64-40832, JP-A-64-42646, JP-A-63-27838, JP-A-59-154439 (except for those in which each of X and Y represents a cyano group), JP-A-63-64044 (except for those in which each of X and Y represents a cyano group), JP-B-62-41265, EP 29,412 (except for those in which each of A and B represents a cyano group), US 2,089,729, GB 584,609, GB 695,874, US 2,688,541, US 3,544,325,.US 3,563,748, JP-A-54-118247, JP-A-59-154439, JP-B-59-37303, US 2,622,980, US 3,379,533, US 3,540,888, Brit 1,561,272, and JP-A-54-118247.
Formulas of dyes used in the present invention will be described below.

wherein R₁ and R₂ may be the same or different and independently represent a hydrogen atom, an alkyl group or an aryl group. R₁ and R₂ may together form a 5- or 6-membered ring. R₃ represents a halogen atom, alkyl, alkoxy, hydroxy, carboxy, substituted amino, carbamoyl, sulfamoyl, or alkoxycarbonyl. n represents 0, 1, 2, 3, or 4. If a plurality of R₃s are present, these groups may be the same or different. R₁ and R₃ or R₂ and R₃ may be bonded to form a 5- or 6-membered ring. Z represents a group selected from
(wherein R₄ and R₅ may be the same or different and independently represent -COR₆, -SO₂R₆, -CO₂R₆,-CONR₆ •R₇, -SO₂NR₆•R₇, or -SO₂R₆ wherein R₆ and R₇ may be the same or different and independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, and Q represents a hydrogen group for forming a nitrogen-containing 5- or 6-membered heterocyclic ring). L represents a methine group or a nitrogen atom.
wherein R₈ represents an aryl group, and Rg and n have the same meanings as those of R₃ and n in formula (DI), respectively. R_io and R₁₁ have the same meanings as those of R₁ and R₂ in formula (DI), respectively. Rs and R₁₀ or R₉ and R₁₁ may be bonded to form a 5- or 6-membered ring.
Examples of a compound used in the present invention will be presented below, but the present invention is not limited to these examples.
A dye compound used in the present invention can be easily synthesized by a method described in JP-A-63-64044.
In the present invention, a closed vessel means, e.g., a moistureproof bag, a moistureproof plastic case, and a metal case.
Examples of a material of the closed vessel are a metal and a metal foil such as an aluminum plate, a tin plate, and an aluminum foil, glass, a polymer such as polyethylene, polyvinylchloride, polystyrene, polyvinylidene chloride, polypropylene, polycarbonate, and polyamide, and a composite laminate member (called a "laminate material" in packaging technical terms) consisting of various types polymers and materials such as cellophane, paper, and an aluminum foil.
Examples of a sealing method are an adhesive method using various types of adhesives, a thermal fusing method such as heat sealing, and a method using a patrone which is generally used in this field of photography. These sealing methods are described in detail in "Food Packaging Technique Handbook", Japan Packaging Technique Association (ed.), pp. 573 to 609.
In the present invention, a patrone case consisting of a polymer such as polyethylene or polypropylene is preferably used for a roll type photographic light-sensitive material, and a package obtained by heat- sealing, e.g., polyethylene, is preferably used for a sheet type photographic light-sensitive material.
"A humidity in a closed vessel is maintained constant" means that when a humidity difference between the air and the interior of a case is 20%, a humidity change in the case is 10% or less after storage at 250 C for 12 months.
A decrease in humidity in a closed vessel is limited for the reasons described above. An increase in humidity in the closed vessel is not preferred since photographic properties are degraded due to moisture. In the present invention, therefore, the humidity in the closed vessel is preferably set around normal humidity. More specifically, at a temperature of 25 C, a relative humidity in the closed vessel is set to be 50% to 70%, and more preferably, 53% to 68%.
In the present invention, a relative humidity is a value measured at a temperature of 25 C by a conventional method (the relative humidity can be measured by a capacitance type humidity measuring machine such as a humicap humidity sensor available from VAISALA (K.K.)).
A significant effect of the present invention can be obtained when an internal volume of the closed vessel is 0.1 cm3 or less (where x is a surface area (cm²) of a light-sensitive layer of a silver halide photographic light-sensitive material to be incorporated). The effect of the present invention is further enhanced when the internal volume of the closed vessel is 0.07x cm^3. A small size of a film cartridge is preferred because the size of a camera can be reduced. In addition, a small size of the closed vessel is further preferred since portability of a light-sensitive material is improved.
A photographic light-sensitive material containing a silver halide emulsion subjected to chemical sensitization by a gold compound and a chalcogenide compound is particularly easily influenced by cyan gas. A chemically sensitized silver halide emulsion contained in a light-sensitive material of the present invention will be described in detail below.
In a photographic emulsion layer of a photographic light-sensitive material used in the present invention, any silver halide of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride can be used. A preferable silver halide is silver iodobromide containing 30 mol% or less of silver iodide, silver bromide, or silver chlorobromide.
A silver halide grain to be used in the present invention can be selected from a regular crystal not including a twin crystal face and cryotals described in Japan Photographic Society ed., "Silver Salt Photographs, Basis of Photographic Industries", (Corona Co., p. 163) such as a single twined crystal including one twined crystal face, a parallel multiple twinned crystal including two or more parallel twin crystal faces, and a non-parallel multiple twinned crystal including two or more non-parallel twin crystal faces in accordance with its applications. In the case of a regular crystal, a cubic grain consisting of (100) faces, an octahedral grain consisting of (111) faces, and a dodecahedral grain consisting of (110) faces disclosed in JP-B-55-42737 and JP-A-60-222842 can be used. In addition, a grain consisting of (h11), e.g., (211) faces, a grain consisting of (hh1), e.g., (331) faces, a grain consisting of (hk0), e.g., (210) faces, and a grain consisting of (hk1), e.g., (321) faces as reported in "Journal of Imaging Science", Vol. 30, p. 247, 1986 can be selectively used in accordance with an application although a preparation method must be improved. A grain including two or more types of faces, e.g., a tetradecahedral grain consisting of both (100) and (111) faces, a grain consisting of both (100) and (110) faces, and a grain consisting of both (111) and (110) faces can be selectively used in accordance with an application.
The grain of a silver halide may be a fine grain having a grain size of 0.1 microns or less or a large grain having a projected area diameter of 10 microns. An emulsion may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution.
A so-called monodisperse silver halide emulsion having a narrow size distribution, i.e., in which 80% or more (the number or weight of grains) of all grains fall within the range of ± 30% of an average grain size. In order to satisfy target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions having different grain sizes can be coated in a single layer or overlapped in different layers, in emulsion layers having substantially the same color sensitivity. Alternatively, two or more types of polydisperse silver halide emulsions or a combination of monodisperse and polydisperse emulsions can be mixed or overlapped.
The photographic emulsion for use in the present invention can be prepared by using methods described in, for example, P. Glafkides, "Chimie et Physique Photographique", Paul Montel, 1967; Duffin, "Photographic Emulsion Chemistry", Focal Press, 1966; and V.L. Zelikman et al., "Making and Coating Photographic Emulsion", Focal Press, 1964. That is, the photographic emulsion can be prepared by, e.g., an acid method, a neutralization method, and an ammonia method. Also, as a system for reacting a soluble silver salt and a soluble halide, a single mixing method, a double mixing method, or a combination thereof can be used. Also, a so-called back mixing method of forming silver halide grains in the presence of excessive silver ions can be used. As one system of the double mixing method, a so-called controlled double jet method wherein the pAg in the liquid phase generated by the silver halide is kept at a constant value can be used. According to this method, a silver halide emulsion having a regular crystal form and almost uniform grain sizes is obtained.
The silver halide emulsion containing the above-described regular silver halide grains can be obtained by controlling the pAg and pH during grain formation. More specifically, such a method is described in "Photographic Science and Engineering", Vol. 6, 159-165 (1962); "Journal of Photographic Science", Vol. 12, 242-251 (1964); U.S. Patent 3,655,394, and British Patent 1,413,748.
A tabular grain having an aspect ratio of 3 or more can also be used in the present invention. The tabular grain can be easily prepared by methods described in, for example, Cleve, "Photographic Science and Engineering", Vol. 14, pp. 248 to 257, (1970); and U.S. Patents 4,434,226, 4,414,310, 4,433,048, and 4,439,520, and British Patent 2,112,157. When the tabular grain is used, covering power and a color sensitizing efficiency of a sensitizing dye can be advantageously improved as described in detail in U.S. Patent 4,434,226.
The tabular grains are preferably used in the emulsion of the present invention. In particular, tabular grains, in which grains having aspect ratios of 3 to 8 account for 50% or more of a total projected area, are preferable.
A crystal structure may be uniform, may have different halogen compositions inside and outside a crystal, or may be a layered structure. These emulsion grains are disclosed in, e.g., British Patent 1,027,146, U.S. Patents 3,505,068 and 4,444,877, and Japanese Patent Application No. 58-248469.
The silver halide emulsion of the present invention preferably has a distribution or structure of a halogen composition in its grain. A typical example is a core-shell type or double structured grain having different halogen compositions in the interior and surface layer of the grain as disclosed in, e.g., JP-B-43-13162, JP-A-61-215540, JP-A-60-222845, and JP-A-61-75337. In such a grain, the shape of a core portion is sometimes different from that of the entire grain with the shell. More specifically, while the core portion is cubic, the grain with a shell is sometimes cubic or sometimes octahedral. On the contrary, while the core portion is octahedral, the grain with a shell is sometimes cubic or sometimes octahedral. In addition, while the core portion is a clear regular grain, the grain with a shell is sometimes slightly deformed or sometimes does not have any definite shape. Furthermore, not a simple double structure but a triple structure as disclosed in JP-A-60-222844 or a multilayered structure of more layers can be formed, or a thin layer of a silver halide having a different composition can be formed on the surface of a core-shell double structure grain.
In a silver iodobromide grain having the above structure, e.g., in a core-shell type grain, the silver iodide content may be high at a core portion and low at a shell portion or vice versa. Similarly, in a grain having the junction structure, the silver iodide content may be high in a host crystal and relatively low in a junction crystal or vice versa.
In a grain having the above structure, a boundary portion between different halogen compositions may be clear or unclear due to a crystal mixture formed by a composition difference. Alternatively, a continuous structure change may be positively made.
The silver halide emulsion for use in the present invention can be subjected to a treatment for rounding a grain as disclosed in, e.g., EP-0096727B1 and EP-0064412B1 or a treatment of modifying the surface of a grain as disclosed in DE-2306447C2 and JP-A-60-221320.
The silver halide emulsion for use in the present invention is preferably of a surface latent image type.
A silver halide solvent can be effectively used to promote ripening. For example, in a known conventional method, an excessive amount of halide ions are supplied in a reactior vessel in order to promote ripening. Therefore, it is apparent that ripening can be promoted by only supplying a silver halide solution into a reactor vessel. In addition, another ripening agent can be used. In this case, a total amount of these ripening agents can be mixed in a dispersion medium in the reactor vessel before a silver salt and a halide are added therein, or they can be added in the reactor vessel together with one or more halides, a silver salt or a deflocculant. Alternatively, the ripening agents can be added in separate steps together with a halide and a silver salt.
Examples of the ripening agent other than the halide ion are ammonia, an amine compound and a thiocyanate such as an alkali metal thiocyanate, especially sodium or potassium thiocyanate and ammonium thiocyanate.
As a gold compound used in the present invention, especially gold complex salt (described in, e.g., U.S. Patent 2,399,083) can be preferably used.
Most preferable examples of the gold complex salt are potassium chloroaurate, potassium aurithiocyanate, aurictrichloride, sodium aurithiosulfate, and 2-aurosulfobenzothiazolemethochloride.
The content of the gold compound in the silver halide emulsion is preferably 10-⁹ to 10-³ mol, more preferably, 10-⁸ to 10-⁴ mol, and most preferably, 10-⁷ to 10-⁵ mol per mol of a silver halide.
In the present invention, the gold compound can be used together with another heavy metal compound. A method of using a heavy metal compound is described in, e.g., U.S. Patent 2,448,060, 2,566,245, or 2,566,263. The content of the heavy metal compound in the silver halide emulsion is 10-⁹ to 10-³ mol, and most preferably, 10-⁸ to 10-⁴ mol per mol of a silver halide.
A chalcogenide compound and a sensitization method used in the present invention will be described below. Examples of the chalcogenide compound which can be used in the present invention are a sulfur compound, a selenium compound, and a tellurium compound.
In addition to P. Grafkides, "Chimie et Physiquie Photographique (Paul Montel, 1987, 5th ed.), T.H. James, "The Theory of the Photographic Process (Macmillan, 1977, 4th ed.), and H Frieser, "Die Grundlagen der Photographischen Prozess mit Silverhalogeniden (Akademische Verlagsgeselbshaft, 1968), a sulfur sensitization method and a sulfur sensitizer are described in, e.g., U.S. Patents 1,574,944, 1,623,449, 2,278,947, 2,410,689, 2,440,206, 2,449,153, 2,728,668, 3,189,458, 3,501,313, 3,656,955, 4,030,928, 4,054,457, 4,067,740, 4,266,018, and 4,810,626, German Patents 1,422,869, 1,572,260, 971,436, 228,658, and 235,929, British Patents 1,129,356, 997,031, and 1,403,980, EP 61,446 and EP 138,622, JP-A-63-5335, JP-A-63-5336, JP-A-58-80634, JP-A-1-114839, JP-A-1-227140, JP-B-58-30570, JP-B-60-24457, JP-B-62-17216, and Research Disclosure Vol. 176, No. 17643 (December, 1978) and Vol. 187, No. 18716 (November, 1979).
More specifically, examples are compounds containing various types of instable sulfurs, such as a thiosulfate (e.g., sodium thiosulfate and p-toluenethiosulfonate), a thiourea (e.g., arylthiourea, diphenyl- thiourea, triethylthiourea, acetylthiourea, N-ethyl-N'-(4-methylthiazolyl-2)thiourea, carboxymethyltrimethyl- thiourea, and N-aryl-N'-hydroxyethylthiourea), a thioamide (e.g., thioacetoamide), a rhodanine (e.g., rhodanine, N-ethylrhodanine, 5-benzylidene-N-ethylrhodanine, and diethylrhodanine), a disulfide or polysulfide (e.g., dimorpholinodisulfide, 1,2,3,5,6-pentathiacycloheptane, cystine, and lipoic acid), a thiosulfonate (e.g., sodium benzenethiosulfonate), polythionate, element-state sulfur (a-sulfur), a sulfide (e.g., sodium sulfide). Of these compounds, a thiourea, a rhodanine, a thioamide, a disulfide or polysulfide, and a thiosulfonic acid.
A selenium sensitizer and a selenium sensitization method are disclosed in, e.g., U.S. Patents 1,574,944, 1,602,592, 1,623,499, 3,297,446, 3,297,447, 3,320,069, 3,408,196, 3,408,197, 3,442,653, 3,420,670, and 3,591,385, French Patents 2,693,038 and 2,093,209, JP-B-52-34491, JP-B-52-34492, JP-B-53-295, JP-B-57-22090, JP-A-59-180536, JP-A-59-185330, JP-A-59-181337, JP-A-59-187338, JP-A-59-192241, JP-A-60-150046, JP-A-60-151637, and JP-A-61-246738, British Patents 255,846 and 861,984, and H.E. Spencer et al., "Journal of Photographic Science", Vol. 31, pp. 158 to 169 (1983).
The selenium compounds disclosed in the above patents can be used as a selenium sensitizer used in the present invention. In particular, an instable selenium compound which can react with silver nitrate in an aqueous solution to form precipitation of silver selenide can be preferably used. Preferable examples of the selenium compound are described in U.S. Patents 1,574,944, 1,602,592, 1,623,499, and 3,297,446. More specifically, examples are colloidal metal selenium, isoselenocyanates (e.g., arylisoselenocyanate), selenoureas (e.g., selenourea; aliphatic selenourea such as N,N-dimethylselenourea and N,N-diethyl- selenourea; substituted selenourea having an aromatic group such as a phenyl group or a heterocyclic group such as a pyridyl group), selenoketones (e.g., selenoketone and selenoacetophenone), selenoamides (e.g., selenoacetoamide), selenocarboxylic acids and esters (e.g., 2-selenopropionic acid and methyl 3- selenobutylate), selenides (e.g., dimethylselenide, diethylselenide, and triphenylphosphirfeselenide), and selenophosphates (e.g., tri-p-tolylselenophosphate).
A tellurium sensitizer and a tellurium sensitization method are disclosed in, e.g., U.S. Patent 1,623,499, British Patents 1,295,462 and 1,396,696, and Canadian Patent 800,958. Examples of the tellurium sensitizer used in the present invention are colloidal tellurium, a telluro urea (e.g., ethyltellurourea and allyltellurourea), isotellurocyanates (e.g., arylisotellurocyanate), telluroketones (e.g., telluroacetone), a telluride (e.g., potassium telluride, potassium tellurocyanide, and sodium telluropentathionate).
Although an amount of a chalcogenide compound changes in accordance with the type of compound, the type of silver halide grain, and conditions of chemical ripening, it is generally 10-⁹ to 10^-4 mol, and preferably, 10-⁸ to 10-⁵ mol per mol of a silver halide.
The temperature, the pAg, and the pH of chemical sensitization can be arbitrarily selected within the ranges of 30 C to 90 C, 5 to 10, and 4 or more, respectively.
An emulsion preferably used in the present invention is an emulsion subjected to sensitization by a combination of gold and chalcogenide, and most preferably, a gold•sulfur-sensitized emulsion. The gold sulfur sensitization is generally performed after grain formation.
A silver halide grain used in the present invention preferably contains a sulfur-containing silver halide solvent. Although the sulfur-containing silver halide solvent used in the present invention can be added in any process from grain formation to coating of an emulsion, it is most preferably present during chemical sensitization for e center formation. An addition amount of the sulfur-containing silver halide solvent used in the present invention is, preferably, 5.0 x 10^-4 to 5.0 x 10-² mol per mol of silver for a silver halide grain having a grain size of 0.5 µm, 2.5 x 10^-4 to 2.5 x 10-² mol per mol of silver for a silver halide grain having a grain size of 1.0 pm, and 1.25 x 10^-4 to 1.25 x 10^-3 mol per mol of silver for a silver halide grain having a grain size of 2.0 µm.
In the present invention, the sulfur-containing silver halide emulsion means a silver halide solvent which can be coordinated in a silver ion by a sulfur atom.
More specifically, the silver halide solvent can dissolve silver chloride in an amount twice or more the amount of silver chloride which can be dissolved at 60° C, by a silver halide solvent present at a concentration of 0.02 mol in water or a solvent medium mixture of water and an organic solvent mixture (e.g., water/methanol = 1/1).
Most preferable examples are thiocyanate (e.g., potassium rhodanate and ammonium rhodanate), an organic thioether compound (e.g., U.S. Patents 3,574,628, 3,021,215, 3,057,724, 3,038,805, 4,276,374, 4,297,439, and 3,704,130, and JP-A-57-104926), a thione compound (e.g., 4-substituted thiourea, thiocyanate, and an organic thioether compound described in, e.g., JP-A-53-82408, JP-A-55-77737, and U.S. Patent 4,221,863).
More specifically, a compound represented by formula (SIV) is preferable as organic thioether:
wherein m represents 0 or an integer from 1 to 4.
R₁₆ and R₁₇ may be the same or different and independently represent a lower alkyl group (carbon atoms = 1 to 5) or a substituted alkyl group (total carbon atoms = 1 to 30).
Examples of a substituting group are -OH, -COOM, -SO₃M, -NHR₁₉, -NR₁₉R₁₉ (wherein R₁₉ may be the same or different), -OR₁₉, -CONHR₁₉, -COOR₁₉, and a heterocyclic ring.
R₁₉ may be a hydrogen atom, a lower alkyl group, or a substituted alkyl group obtained by being substituted by the above substituting group.
In addition, two or more substituting groups may be substituted, and these substituting groups may be the same or different.
R₁₈ represents an alkylene group (preferably having 1 to 12 carbon atoms).
If m represents 2 or more, m R₁₈S may be the same or different.
One or more groups of -0-, -CONH-, and -S0₂NH- may be present in the middle of an alkylene chain, or the substituting groups described with reference to R₁ and R₁₇, may be substituted therein.
In addition, R₁ and R₁₇ may be bonded to form cyclic thioether.
A compound represented by formula (SV) is preferable as a thione compound:
wherein Z represents
-OR₂₄, or -SR₂₅.
R₂₀, R₂₁, R₂₂, R₂₃, R₂₄, and R₂₅ may be the same or different and independently represent an alkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic moiety. These groups may be substituted (a total number of carbon atoms of each group is preferably 30 or less).
In addition, R₂₀ and R₂₁, R₂₂ and R₂₃, or R₂₀ and R₂₂, R₂₀ and R₂₄, and R₂₀ and R₂₅ may be bonded to form a 5- or 6-membered heterocyclic ring, and a substituting group may be bonded to the heterocyclic ring.
These compounds can be synthesized by methods described in the above-mentioned patent specifications or references, and some of the compounds are commercially available.
Examples of a compound of the sulfur-containing silver halide solvent used in the present invention will be presented below.
When silver halide adsorptive substances are present in addition to a sensitizing dye, upon chemical ' sensitization of an emulsion of the present invention, a developing rate can be preferably increased. These silver halide adsorptive substances other than the sensitizing dye can be added at any timing, e.g., during grain formation, immediately after grain formation, before or during after-ripening.
Although the substances can be added at different timings, they are preferably added before a chemical sensitizing agent (e.g., a gold or sulfur sensitizer) is added or simultaneously with the chemical sensitizer and must be present in at least a process in which chemical sensitization progresses.
As addition conditions of the silver halide adsorptive substances, a temperature may be an arbitrary temperature from 30° C to 80° C and preferably falls within the range of 50° C to 80 C in order to enhance adsorptivity. Although a pH and a pAg may be arbitrarily set, the pH is preferably 6 to 9 and the pAg is preferably 7 to 9, and most preferably, 7.6 to 8.4 upon chemical sensitization.
In the present invention, the silver halide absorptive substance other than the sensitizing dye means a kind of a photographic property stabilizing agent.
That is, many compounds known as an antifoggant or a stabilizer can be exemplified as a silver halide absorptive substance. More specifically, examples are azoles {e.g., benzothiazolium salt, benzoimidazolium salt, imidazoles, benzimidazoles, nitroindazoles, triazoles, benzotriazoles, tetrazoles, and triazines}; a mercapto compounds {e.g., mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptobenzimidazoles, mercaptobenzooxazoles, mercaptothiadiazoles, mercaptooxadiazoles, mercaptotetrazoles, mercaptotriazoles, mercaptopyrimidines, and mercaptotriazines); thioketo compounds such as ox- azolinethione; azaindenes {e.g., triazaindene, tetraazaindene (especially 4-hydroxy-substituted(1,3,3a,7)-tetraazaindenes), and pentazaindenes).
In addition, purines, nucleic acids, and polymer compounds described in, e.g., JP-B-61-36213 and JP-A-59-90844 can be used as an absorptive substance.
Of these compounds, azaindenes, purines, nucleic acids, and mercapto compounds having a carboxyl group or a sulfonic acid group can be most preferably used in the present invention. An addition amount of these compounds is 0.05 to 5.0 millimol, and preferably, 0.1 to 3.0 millimol per mol of a silver halide.
Examples of a compound which can be effectively used in the present invention will be described below.
The above various additives can be used in the light-sensitive material of the present invention. In addition to the above additives, however, various additives can be used in accordance with applications.
These additives are described in Research Disclosure, Item 17643 (Dec. 1978) and Item 18716 (Nov. 1979) and they are summarized in the following table.
In this invention, various color couplers can be used in the light-sensitive material. Specific examples of these couplers are described in above-described Research Disclosure, No. 17643, VII-C to VII-G as patent references.
Preferred examples of a yellow coupler are described in, e.g., U.S. Patents 3,933,501, 4,022,620, 4,326,024, and 4,401,752, JP-B-58-10739, and British Patents 1,425,020 and 1,476,760.
Examples of a magenta coupler are preferably 5-pyrazolone and pyrazoloazole compounds, and more preferably, compounds described in, e.g., U.S. Patents 4,310,619 and 4,351,897, EP 73,636, U.S. Patents 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, and U.S. Patents 4,500,630 and 4,540,654.
Examples of a cyan coupler are phenol and naphthol couplers, and preferably, those described in, e.g., U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011, and 4,327,173, West German Patent Application (OLS) No. 3,329,729, EP 121,365A, U.S. Patents 3,446,622, 4,333,999, 4,451,559, and 4,427,767, and EP 161,626A.
Preferable examples of a colored coupler for correcting additional, undesirable absorption of a colored dye are those described in Research Disclosure No. 17643, VII-G, U.S. Patent 4,163,670, JP-B-57-39413, U.S. Patents 4,004,929 and 4,138,258, and British Patent 1,146,368.
Preferable examples of a coupler capable of forming colored dyes having proper diffusibility are those' described in U.S. Patent 4,366,237, British Patent 2,125,570, EP 96,570, and West German Patent Application (OLS) No. 3,234,533.
Typical examples of a polymerized dye-forming coupler are described in U.S. Patents 3,451,820, 4,080,211, and 4,367,282, and British Patent 2,102,173.
Couplers releasing a photographically useful residue upon coupling are preferably used in the present invention. Preferable examples of a DIR coupler releasing a development inhibitor are described in the patents cited in the above-described Research Disclosure No. 17643, VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, and U.S. Patent 4,248,962.
Preferable examples of a coupler imagewise releasing a nucleating agent or a development accelerator upon development are those described in British Patent 2,097,140, 2,131,188, and JP-A-157638 and JP-A-59-170840.
Examples of a coupler which can be used in the light-sensitive material of the present invention are competing couplers described in, e.g., U.S. Patent 4,130,427; poly-equivalent couplers described in, e.g., U.S. Patents 4,283,472, 4,338,393, and 4,310,618; DIR redox compound or DIR coupler releasing couplers, or DIR coupler releasing couplers or redox described in, e.g., JP-A-60-185950 and JP-A-62-24252; couplers releasing a dye which turns to a colored form after being split off described in EP 173,302A; bleaching accelerator releasing couplers described in, e.g., RD. Nos. 11449 and 24241 and JP-A-61-201247; and a legand releasing coupler described in, e.g., U.S. Patent 4,553,477.
The couplers for use in this invention can be introduced in the light-sensitive material by various known dispersion methods.
Examples of a high-boiling solvent used in an oil-in-water dispersion method are described in, e.g., U.S. Patent 2,322,027.
Examples of a high-boiling organic solvent to be used in the oil-in-water dispersion method and having a boiling point of 175° C or more at normal pressure are phthalic esters (e.g., dibutylphthalate, dicyclohexyl- phthalate, and di-2-ethylhexylphthalate), phosphates or phosphonates (e.g., triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate, tricyclohexylphosphate, and tri-2-ethylhexylphosphate), benzoates (e.g., 2-ethylhexylbenzoate, dodecylbenzoate, and 2-ehtylhexyl-p-hydrexybenzodate), amides (e.g., N, N-diethyldodecanemide, N,N-diethyl lauribamide, N-tetradecylpyrolidove), alcohls and phenols (e.g., isostearly alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylates (e.g., bis(2-ethylhexyl)sebacate, dioc- tylazelate, glyceroltributylate, isostearyllactate, and trioctylcitrate), an aniline derivative (e.g., N,N-dibutyl-2-butoxy-5-tert-octylaniline), and a hydrocarbon (e.g., paraffin, dodecylbenzene, diisopropylnaphthalene). An organic solvent having a boiling point of about 30 C or more, and preferably, 50 C to about 160` C can be used as a co-solvent. Typical examples of the co-solvent are ethyl acetate, butyl acetate, ethyl propionate, methylethylketone, cyclohexane, 2-ethoxyethylacetate, and dimethylformamied.
Steps and effects of a latex dispersion method and examples of an loadable latex are described in, e.g., U.S. Patent 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.
The present invention can be applied to various color light-sensitive materials. Examples of the material are a color negative film for a general purpose or a movie, a color reversal film for a slide or a television, color paper, a color positive film, and color reversal paper.
When the present invention is used as a color photographic material for photographing, the present invention can be applied to light-sensitive materials having various structures and to light-sensitive materials having combinations of layer structures and special color materials.
Typical examples are: light-sensitive materials in which a special coupling speed of a color coupler or diffusibility is combined with a speacial layer structure, as disclosed in, e.g., JP-B-47-49031, JP-B-49-3843, JP-B-50-21248, JP-A-59-38147, JP-A-59-60437, JP-A-60-227256, JP-A-61-4043, JP-A-61-43743, and JP-A-61-42657; light-sensitive materials in which a single color-sensitive layer is divided into two or more layers, as disclosed in JP-B-49-15495 and U.S. Patent 3,843,469; and light-sensitive materials in which an arrangement of high- and low-sensitivity layers or layers having different color sensitivities is defined, as disclosed in JP-B-53-37017, JP-B-53-37018, JP-A-51-49027, JP-A-52-143016, JP-A-53-97424, JP-A-53-97831, JP-A-62-200350, and JP-A-59-177551.
Examples of a support suitable for use in this invention are described in the above-mentioned RD. No. 17643, page 28 and ibid., No. 18716, page 647, right column to page 648, left column.
The color photographic light-sensitive materials of this invention can be developed by the conventional methods as described in, e.g., the above-described Research Disclosure, No. 17643, pages 28 to 29 and ibid., No. 18716, page 651, left to right columns.
A color developer used in developing of the light-sensitive material of the present invention is an aqueous alkaline solution mainly containing, as a main compornent, preferably, an aromatic primary amine- based color developing agent. As the color developing agent, although an aminophenol-based compound is effective, a p-phenylenediamine-based compound is preferably used. Typical examples of the p-phenylenediamine-based compound are 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-#-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-_¡3-methoxyethylaniline, and sulfates, hydrochlorides, and p-toluenesulfonates thereof. These compounds can be used in a combination of two or more thereof in accordance with applications.
In general, the color developer contains a pH buffering agent such as a carbonate, a borate or a phosphate of an alkali metal, and a development restrainer or antifoggant such as a bromide, an iodide, a benzimidazole, a benzothiazole or a mercapto compound. If necessary, the color developer may also contain a preservative such as hydroxylamine, diethylhydroxylamine, a hydrazine sulfite, a phenylsemicar- bazide, triethanolamine, a catechol sulfonic acid or a triethylenediamine(1,4-diazabicyclo[2,2,2]octane); an organic solvent such as ethyleneglycol or diethyleneglycol; a development accelerator such as benzylalcohol, polyethyleneglycol, a quaternary ammonium salt or an amine; a dye forming coupler; a competing coupler; a fogging agent such as sodium boron hydride; an auxiliary developing agent such as 1-phenyl-3-pyrazolidone; a viscosity imparting agent; and a chelating agent such as an aminopolycarboxylic acid, an aminopolyphosphonic acid, and alkylphosphonic acid or a phosphonocarboxylic acid. Examples of the chelating agent are ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid and ethylenediamine-di(o-hydroxyphenylacetic acid), and salts thereof.
In order to perform reversal development, black-and-white development is performed and then color development is performed. As a black-and-white developer, well-known black-and-white developing agents, e.g., dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, and an aminophenol such as N-methyl-p-aminophenol can be used singly or in a combination of two or more thereof.
The pH of the color and black-and-white developers is generally 9 to 12. Although a replenishment amount of the developer depends on a color photographic light-sensitive material to be processed, it is generally 3 liters or less per m² of the light-sensitive material. The replenishment amount can be decreased to be 500 m or less by decreasing a bromide ion concentration in a replenishing solution. In order to decrease the replenishment amount, a contact area of a processing tank with air is preferably decreased to prevent evaporation and oxidation of the solution upon contact with air. The replenishment amount can be decreased by using a means capable of suppressing an accumulation amount of bromide ions in the developer.
A color development time is normally set between 2 to 5 minutes. The processing time, however, can be shortened by setting a high temperature and a high pH and using the color developing agent at a high concentration.
The photographic emulsion layer is generally subjected to bleaching after color development. The bleaching may be performed either simultaneously with fixing (bleach-fixing) or independently thereof. In addition, in order to increase a processing speed, bleach-fixing may be performed after bleaching. Also, processing may be performed in a bleach-fixing bath having two continuous tanks, fixing may be performed before bleach-fixing, or bleaching may be performed after bleach-fixing, in accordance with applications. Examples of the bleaching agent are a compound of a multivalent metal such as iron (III), cobalt (III), chromium (VI) and copper (II); a peroxide; a quinone; and a nitro compound. Typical examples of the bleaching agent are a ferricyanide; a dichromate; an organic complex salt of iron (III) or cobalt (III), e.g., a complex salt of an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and 1,3-diaminopropanetetraacetic acid, and glycoletherdiaminetetraacetic acid, or a complex salt of citric acid, tartaric acid or malic acid; a persulfate; a bromate; a permanganate; and a nitrobenzene. Of these compounds, an iron (III) complex salt of aminopolycarboxylic acid such as an iron (III) complex salt of ethylenediaminetetraacetic acid, and a persulfate are preferred because they can increase a processing speed and prevent an environmental contamination. The iron (III) complex salt of aminopolycarboxylic acid is effective in both the bleaching and bleach-fixing solutions. The pH of the bleaching or bleach-fixing solution using the iron (III) complex salt of aminopolycarboxylic acid is normally 5.5 to 8. In order to increase the processing speed, however, processing can be performed at a lower pH.
A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre- bath, if necessary. Effective examples of the bleaching accelerator are described in, e.g., U.S. Patent 3,893,858. A compound described in U.S. Patent 4,552,834 is also preferable. These bleaching accelerators may be added in the light-sensitive material. These bleaching accelerators are effective especially in bleach-fixing of a photographic color light-sensitive material for photographing.
Examples of the fixing agent are a thiosulfate, a thiocyanate, a thioether-based compound, a thiourea and a large amount of an iodide. Of these compounds, a thiosulfate, especially, ammonium thiosulfate can be used in a widest range of applications. As a preservative of the bleach-fixing solution, a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferred.
The photographic light-sensitive material of the present invention is normally subjected to washing and/or stabilizing steps after desilvering. An amount of water used in the washing step can be arbitrarily determined over a broad range in accordance with the properties (e.g., a property determined by use of a coupler) of the light-sensitive material, the application of the material, the temperature of the water, the number of water tanks (the number of stages), a replenishing scheme representing a counter or forward current, and other conditions. The relationship between the amount of water and the number of water tanks in a multi-stage counter-current scheme can be obtained by a method described in "Journal of the Society of Motion Picture and Television Engineers", Vol. 64, pp. 248 - 253 (May, 1955).
According to the above-described multi-stage counter-current scheme, the amount of water used for washing can be greatly decreased. Since washing water stays in the tanks for a long period of time, however, bacteria multiply and floating substances may be undesirably attached to the light-sensitive material In order to solve this problem, in the process of the color photographic light-sensitive material of the present invention, a method of decreasing calcium and magnesium ions can be effectively utilized, as described in JP-A-61-131632. In addition, a germicide such as an isothiazolone compounds and cyaben- dazoles described in JP-A-57-8542, a chlorine-based germicide such as chlorinated sodium isocyanurate, and germicides such as benzotriazole described in Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents", Eiseigijutsukai ed., "Sterilization, Antibacterial, and Antifungal Techniques for Microorganisms", and Nippon Bokin Bokabi Gakkai ed., "Dictionary of Antibacterial and Antifungal Agents".
The pH of the water for washing the photographic light-sensitive material of the present invention is 4 to 9, and preferably 5 to 8. The water temperature and the washing time can vary in accordance with the properties and applications of the light-sensitive material. Normally, the washing time is 20 seconds to 10 minutes at a temperature of 15° C to 45 C, and preferably, 30 seconds to 5 minutes at 25° C to 40 C. The light-sensitive material of the present invention can be processed directly by a stabilizing agent in place of washing. All known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be used in such stabilizing processing.
Stabilizing is sometimes performed subsequently to washing. An example is a stabilizing bath containing formalin and a surfactant to be used as a final bath of the photographic color light-sensitive material. Various chelating agents or antifungal agents can be added in the stabilizing bath.
An overflow solution produced upon washing and/or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.
The silver halide color light-sensitive material of the present invention may contain a color developing agent in order to simplify processing and increase a processing speed.
The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical examples of the compound are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.
Each processing solution in the present invention is used at a temperature of 10° C to 50 C. Although a normal processing temperature is 33 C to 38 C, processing may be accelerated at a high temperature to shorten a processing time, or image quality or stability of a processing solution may be improved at a lower temperature. In order to save silver for the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or U.S. Patent 3,674,499 may be performed.
The silver halide light-sensitive material of the present invention can also be applied to thermal development light-sensitive materials described in, e.g., U.S. Patent 4,500,626, JP-A-60-133449, JP-A-59-218443, JP-A-61-238056, and EP 210,660A2.
The light-sensitive material of the present invention is characterized in that an amount of released hydrogen cyanide is a small, (gold/silver) weight ratio is small, and photographic properties are not much degraded during storage. Therefore, photographic properities Brownie film or a 110 film, in which the light-sensitive material of the present invention and a light screen described in, e.g., WO No. 12847/89, or U.S. Patent 3,900,323 or 4,211,837 are conbined, are not much degraded during storage. In these points those photographic material is preferable.
The present invention will be described in more detail below by way of its examples.

EXAMPLES

Comparative Example

(Preparation of emulsion)

20 g of inert gelatin, 2.2 g of potassium bromide, and 2.05 g of potassium iodide were dissolved in 800 mℓ of distilled water to prepare an aqueous solution. 150 cc of an aqueous solution containing 5.0 g of silver nitrate were added to the above aqueous solution at one time under stirring at 45 C, and an excessive amount of potassium bromide was added thereto. Thereafter, physical ripening was performed for 20 minutes. In addition, 0.2 mol/k, 0.67 mol/t and 2 mol/ℓ of silver nitrate and potassium halide aqueous solutions (in which 42 mol% of potassium iodide were mixed with respect to 58 mol% of potassium bromide) were added at flow rates of 10 cc/min in accordance with a method described in U.S. Patent 4,242,445, thereby growing of silver iodobromide grains having a silver iodide content of 42 mol%. The obtained grains were washed with water for desalting, thereby preparing an emulsion 1. A finished amount of the emulsion 1 was 900 g, and its grain size was 0.54 µm.
3,800 cc of distilled water and 135 cc of an aqueous 10% solution of potassium bromide were added to the total amount (900 g) of the emulsion 1, and the resultant mixture was heated up to 70 C and stirred. 1,350 cc of an aqueous solution containing 148.5 g of silver nitrate and 1,440 cc of an aqueous solution containing 112.5 g of potassium bromide were simultaneously added over 30 minites, and 3,600 cc of an aqueous solution containing 450 g of silver nitrate and 3,870 cc of an aqueous solution containing 337.5 g of potassium bromide were simultaneously added over 60 minutes. Thereafter, desalting was performed to prepare an unsensitized silver iodobromide emulsion 2 having a silver iodide content of 10 mol% and a grain size of 0.87 µm. The emulsion 2 comprised twined crystals having an aspect ratio of 2.3, and its (111) face ratio was 85%.
Hypo in an amount of 25 ppm per Ag and HAuCℓ₄ in an amount of 10 ppm of Au per Ag were added to the prepared emulsion 2, and the resultant emulsion was stirred at 60° C for 70 minutes, thereby preparing chemically sensitized emulsion A.
Subsequently, 15 ppm of hypo were added to the emulsion 2 to similarly perform chemical sensitization at 60 C for 70 minutes, thereby preparing an emulsion B.
These silver halide emulsions were coated on an undercoated triacetylcellulose film support so as to have the following compositions, thereby forming a sample 101.
A sample 102 was formed following the same procedures as for the sample 101 except that the emulsion A of the layer 1 was replaced by the emulsion B. In addition, a sample 103 was formed following the same procedures as for the sample 101 except that an aqueous HAuCℓ₄ solution in an amount of 50 ppm of Au per Ag were added, to the layer 1 of sample 101.
These three samples were formed into strips having a width of 3.5 cm and a length of 20 cm and put in a metal closed vessel having volume of 6000 cm^3. In addition, 70%-moisture-controlled glycerin and a small amount of an acidic aqueous solution containing 6 µg of KCN were added to the closed'vessel, and the vessel was heated at 60 C for three days. As a control, a sample was formed following the same procedures as described above except that no KCN was added, and a sample stored at room temperature was also prepared. These samples were subjected to sensitmetry exposure and color development in accordance with a method described below. The developed film strips were subjected to yellow image sensitmetry at a density of status M. The obtained results are summarized in Table 1.
Compositions of the processing solutions will be described below.
As is apparent from Table 1, although the gold·sulfur-sensitized sample 101 had higher sensitivity than that of the sample subjected to only sulfur sensitization, an increase in fog and a reduction in sensitivity caused by HCN gas were extremely large.
Since fog was significantly increased in room-temperature storage properties test of the sample 103 which was coated after gold was after-added, no characteristic value could be calculated.

EXAMPLE 1

The emulsion A used in the above comparative example was coated on an undercoated triacetylcellulose support so as to have the following compositions, thereby forming a sample 201.

Layer 1: Blue-sensitive emulsion layer

Layer 2: Protective layer

A sample 202 was formed following the same procedures as for the sample 201 except that the emulsion A was replaced by an equal amount of the emulsion B.
Subsequently, a sample 203 was formed following the same procedures as for the sample 201 except that M-1 added to the layer 2 was changed to an equal amount of M-2, and a sample 204 was formed following the same procedures as for the sample 202 except that M-1 of the layer 2 was changed to M-2. The obtained samples 201 to 204 were cut into strips having a width of 3.5 cm and a length of 117 cm and sufficiently moisture-conditioned at a temperature of 25 C and a relative humidity of 65%. Thereafter, each strip was sealed in a closed vessel (patrone case) having a volume of about 30 cm³ and heated at 60° C for three days. These strips and strips of the samples 201 to 204 stored at room temperature were subjected to sensitmetry exposure and the color development described above, and the developed films were subjected to sensitmetry. The obtained results are summarized in Table 2 in which sensitivity is represented by a logarithm of a reciprocal of an exposure amount at a point for giving a density of fog density + 0.15.
In addition, entirely independently from the above steps, an area of 1 m² of each of the samples 201 to 204 was finely cut in a dark room, and released HCN gas was analyzed by the pyridine-pyrazolone absorptiometric method described in this patent specification. The obtained results are also summarized in Table 2.
As is apparent from Table 2, a resistance against a forced deterioration test of the sample 203 of the present invention, in which the polymerization initiator of the polymer matting agent in the layer 2 was changed from X-3 to 1-1 to eliminate releasing of HCN gas, was significantly improved as compared with those of the samples 201 and 202 containing the matting agent synthesized by the polymerization initiator (X-3) and releasing HCN gas. A correlation between the samples 201 and 202 matches well with the deterioration test by HCN shown in Table 1 of the comparative example.

EXAMPLE 2

Layers having the following compositions were simultaneously coated on an undercoated triacetylcellulose film support, thereby forming a sample 301 as a multilayered color light-sensitive material.
In each emulsion used in this examples, HAuCℓ₄ as a gold compound was used in an amount of 10-⁶ to 10-⁵ mol per mol of a silver halide and Na₂S₂0₃ as a chalcogenide compound was used in an amount of 10-⁶ to 10-⁵ mol per mol of a silver halide, upon chemical sensitization performed, after grain formation and desalting. Although amounts of the compounds were changed in accordance with the grain size of an emulsion or the characteristics of a grain, the compounds were used in amounts falling within the above ranges so that most preferable properties were obtained. Note that neither gold nor chalcogenide was used in a fine silver iodobromide emulsion in a layer 13.

(Compositions of light-sensitive layers)

Coating amounts of a silver halide and a colloidal silver are represented in units of g/m² of silver, those of a coupler additive and gelatin are represented in units of g/m², and that of a sensitizing dye is represented by the number of mols per mol of a silver halide in the same layer.

Layer 1: Antihalation layer

Layer 2: Interlayer

Layer 3: Low-sensitivity red-sensitive emulsion layer

Silver iodobromide emulsion (Agl = 2 mol%, internally high Agl type, sphere-equivalent diameter = 0.3 µm, variation coefficient of sphere-equivalent diameter = 29%, grain mixture of regular and twinned crystals, diameter/thickness ratio = 2.5)

Layer 4: Medium-sensitivity red-sensitive emulsion layer

Silver iodobromide emulsion (Agl = 4 mol%, internally high Agl type, sphere-equivalent diameter = 0.55 _um, variation coefficient of sphere-equivalent diameter = 20%, grain mixture of regular and twinned crystals, diameter/thickness ratio = 1)

Layer 5: High-sensitivity red-sensitive emulsion layer

Silver iodobromide emulsion (Agl = 10 mol%, internally high Agl type, sphere-equivalent diameter = 0.7 pm, variation coefficient of sphere-equivalent diameter = 30%, grain mixture of regular and twinned crystals, diameter/thickness ratio = 2)

Layer 6: Interlayer

Layer 7: Low-sensitivity green-sensitive emulsion layer

Silver iodobromide emulsion (Agl = 2 mol%, internally high Agl type, sphere-equivalent diameter = 0.3 µm, variation coefficient of sphere-equivalent diameter = 28%, grain mixture of regular and twinned crystals, diameter/thickness ratio = 2.5)

Layer 8: Medium-sensitivity green-sensitive emulsion layer

Silver iodobromide emulsion (Agl = 4 mol%, internally high Agl type, sphere-equivalent diameter = 0.55 µm, variation coefficient of sphere-equivalent diameter = 20%, grain mixture of regular and twinned crystals, diameter/thickness ratio = 4)

Layer 9: High-sensitivity green-sensitive emulsion layer

Silver iodobromide emulsion (Agl = 10 mol%, internally high Agl type, sphere-equivalent diameter = 0.7 µm, variation coefficient of sphere-equivalent diameter = 30%, grain mixture of regular and twinned crystals, diameter/thickness ratio = 2.0)

Layer 10: Yellow filter layer

Layer 11: Low-sensitivity blue-sensitive emulsion layer

Silver iodobromide emulsion (Agl = 4 mol%, internally high Agl type, sphere-equivalent diameter = 0.5 µm, variation coefficient of sphere-equivalent diameter = 15%, octahedral grain)

Layer 12: High-sensitivity blue-sensitive emulsion layer

Silver iodobromide emulsion (Agl = 10 mol%, internally high Agl type, sphere-equivalent diameter = 1.3 µm, variation coefficient of sphere-equivalent diameter = 25%, grain mixture of regular and twinned crystals, diameter/thickness ratio = 4.5)

Layer 13: 1 st protective layer

Fine grain silver iodobromide (average grain size = 0.07 µm, Agl = 1 mol%)

Layer 14: 2nd protective layer

In addition to the above additives, in order to improve storage stability, processability, a resistance to pressure, a mildew.bacteria resistance, antistatic properties, and coating properties, Cpd-3, Cpd-5, Cpd-6, Cpd-7, Cpd-8, P-1, P-2, W-1, W-2, and W-3 to be presented below were added.
ExM-9 in the layers 7 and 8 of the sample 301 was replaced with an equal amount of ExM-16 to prepare a sample 302.
UV-2 and UV-3 were used instead of UV-5 used in the layer 13 of the sample 302, and ultraviolet absorption characteristics in a dry film were controlled by adjusting an amount, thereby forming a sample 303. A sample 304 was formed following the same procedures as for the sample 303 except that the polymer matting agent M-1 (polymerization initiator X-3) in the layer 14 of the sample 303 was replaced by an equal amount of M-2 (polymerization initiator 1-1).
Each sample was cut into a strip having a width of 3.5 cm and a length of 117 cm and moisture-conditioned at a temperature of 25°C and a relative humidity of 60%. This moisture-conditioned strip was curled into a patrone and perfectly sealed in a patrone case. Thereafter, each sample was forcedly deteriorated at a temperature of 60 C for three days. These samples together with samples stored at room temperature were subjected to sensitmetry exposure and color development.
Independently from the above forced deterioration test, each of the samples 301 to 304 was similarly sealed in a patrone case and left to stand at a constant temperature of 25 C for 18 months. These samples together with samples stored in a freezer (-16 C) were exposed and developed.
Cyan, magenta, and yellow image densities of the developed samples were measured on the basis of status M density, thereby calculating a fog value, sensitivity, and gradation.
The sensitivity is represented by a logarithm of a reciprocal of a exposure amount for giving a density of fog density + 0.15 for each color image.
A point of exposure amount which was 100 times as greater as a exposure amount of photographic speed of each image was calculated on a curve, and the gradation was represented by an inclination angle (tangent) obtained when the two points were connected by a straight line. An amount of HCN gas released from an area of 1 m² of each sample was obtained by a pyridine-pyrazolone absorptiometric method. The amount of HCN gas was determined in a dark room heated at 75⁰ C for two hours.
The results of forced deterioration test and HCN gas released amount are summarized in Table 3a, and the results of storage at 25° C for 18 months are summarized in Table 3b.
As is apparent from the results shown in Table 3a, an increase in fog, a reduction in sensitivity, and a gradation change (soft tone) were very small in each of the samples 303 and 304 in which the polymer coupler in the layers 7 and 8, the UV absorbent in the layer 13, and the polymer matting agent in the layer 14 do not produce HCN gas. That is, the improving effect of the present invention is clearly found. In particular, since a gradation change in the blue-sensitive layer is surprisingly small to cause no color unbalance in an actual print, the effect of the present invention is very preferable.
As is apparent from Table 3b, even when the samples were stored at room temperature for a long time period, exactly the same improving effect as that obtained by the forced test is obtained. This is a very preferable result since a change in properties of the materials is very small when they are stored as products in general markets.
In a process from the sample 301 to the sample 304, improvements in the polymer couplers in the layers 7 and 8, the UV absorbent in the layer 13, and the polymer matting agent in the layer 14, reduce the amount of produced HCN gas stepwise, thereby reducing the deterioration in photographic properties accordingly.

EXAMPLE 3

Each of the samples 301 and 304 formed in Example 2 was cut into eight strips having a width of 3.5 cm and a length of 117 cm and curled into general patrones.
One strip of each of the samples 301 and 304 was moisture-controled at temperature of 25 C, and relative humidity of 40%. Similarly, the strips were moisture-conditioned at a temperature of 25° C and relative humidities of 45%, 50%, 55%, 60%, 65%, 70%, and 75% and perfectly sealed in patrone cases at the respective humidities, thereby performing a forced deterioration test at 50° C for 14 days.
Following the same procedures as in Example 2, these samples together with the samples 301 and 304 stored at room temperature were subjected to sensitmetry. Differences between the forcedly deteriorated sample and the sample stored at room temperature are represented as △fog Asensitivity, and △gradation for each humidity and summarized in Table 4.
As is apparent from the results shown in Table 4, when the film samples were sealed in closed vessels with a small space while humidity was variously changed, deterioration in properties throughout the humidity range of the sample 304 of the present invention was smaller than those of the comparative sample 301 in which production of HCN gas was found. In particular, since the sample of the present invention did not release HCN gas at a comparatively high humidity of 50% to 70%, the improving effect of the present invention was very good. When the humidity in the patrone case was set to be 45%-or less, no large difference was found between the two samples. In other words, deterioration caused by HCN_- gas is reduced at a low humidity. However, a static failure may be caused by the low humidity in a light-sensitive material manufacturing process, and the material gradually absorbs moisture in the air during storage of a long time period (in, e.g., shops) to increase the humidity in a patrone case to lead to degradation in storage stability. Therefore, it is not preferable to set the humidity to be less than 50%. The humidity of 70% or more is also not preferable since deterioration caused by the humidity is large.

EXAMPLE 4

Each of the samples 301 and 304 formed in Example 2 was cut into three strips having a width of 3.5 cm and lengths of 73 cm (corresponding to a 12-frame film), 117 cm (corresponding to a 24-frame film), and 328 cm (corresponding to a 72-frame film), and sufficiently moisture-conditioned at a temperature of 25° C and a relative humidity of 60%. The moisture-conditioned samples were directly, perfectly sealed in patrone cases in the same place (dark room). These samples were left to stand in a constant temperature tank at a temperature of 60 C for three days and then extracted. These samples together with the samples 301 and 304 stored at room temperature were exposed and developed to perform sensitmetry. Characteristic values are calculated following the same procedures as in Examples 2 and 3 and summarized as a difference with respect to the sample stored at room temperature in Table 5.
As is apparent from Table 5, in the sample 301 as a comparative example, deterioration in photographic properties was increased when the sample length was increased because an amount of released HCN gas was increased accordingly. In the sample 304 of the present invention, however, no such tendency was found. This result indicates that, according to the present invention, the size of a film patrone, a cartridge, or a patrone case can be decreased as the size of a camera is decreased without degrading storage stability.

EXAMPLE 5

Layers having the following compositions were coated on an undercoated triacetylcellulose film-support, thereby forming a sample 401 as a multilayered color light-sensitive material.
In each emulsion used in this example 5, HAuC14 as a gold compound was used in an amount of 10-⁶ to 10-⁵ mol per mol of a silver halide and Na₂S₂0₃ as a chalcogenide compound was used in an amount of 10^-6 to 10-⁵ mol per mol of a silver halide, upon chemical sensitization, after grain formation and desalting. Although the amounts of the compounds were changed in accordance with the grain size of an emulsion or the characteristics of a grain, the compounds are used in amounts falling within the above ranges so that most preferable properties were obtained. Note that neither gold nor chalcogenide was used in a fine grain silver iodobromide emulsion in a layer 15.

(Compositions of light-sensitive layers)

Coating amounts of a silver halide and a colloidal silver are represented in units of g/m² of silver, those of a coupler, an additive, and gelatin are represented in units of g/m² and that of a sensitizing dye is represented by the number of mols per mol of a silver halide in the same layer.

Layer 1: Antihalation layer

Black colloidal silver

Layer 2: Interlayer

Fine grain silver iodobromide (Agl = 1.0 mol%, sphere-equivalent diameter = 0.07 µm)

Layer 3: 1st red-sensitive emulsion layer

Silver iodobromide emulsion (Agl = 5.0 mol%, surface high Agl type, sphere-equivalent diameter = 0.9 µm, variation coefficient of sphere-equivalent diameter = 21 %, tabular grain, diameter/thickness ratio = 7.5)
Silver iodobromide emulsion (Agl = 4.0 mol%, internally high Agl type, sphere-equivalent diameter = 0.4 µm, variation coefficient of sphere-equivalent diameter = 18%, tetradecahedral grain)

Layer 4: 2nd red-sensitive emulsion layer

Silver iodobromide emulsion (Agl = 8.5 mol%, internally high Agl type, sphere-equivalent diameter = 1.0 µm, variation coefficient of sphere-equivalent diameter = 25%, tabular grain, thickness/diameter ratio = 3.0)

Layer 5: 3rd red-sensitive emulsion layer

Silver iodobromide emulsion (Agl = 11.3 mol%, internally high Agl type, sphere-equivalent diameter = 1.4 gm, variation coefficient of sphere-equivalent diameter = 28%, tabular grain, diameter/thickness ratio = 6.0)

Layer 6: Interlayer

Layer 7: 1st green-sensitive emulsion layer

Silver iodobromide emulsion (Agl = 5.0 mol%, surface high Agl type, sphere-equivalent diameter = 0.9 µm, variation coefficient of sphere-equivalent diameter = 21%, tabular grain, thickness/diameter ratio = 7.0)
Silver iodobromide emulsion (Agl = 4.0 mol%, internally high Agl type, sphere-equivalent diameter = 0.4 µm, variation coefficient of sphere-equivalent diameter = 18%, tetradecahedral grain)

Layer 8: 2nd green-sensitive emulsion layer

Silver iodobromide emulsion (Agl = 8.5 mol%, internally high iodide type, sphere-equivalent diameter = 1.0 µm, variation coefficient of sphere-equivalent diameter = 25%, tabular grain, diameter/thickness ratio = 3.0)

Layer 9: Interlayer

Layer 10: 3rd green-sensitive emulsion layer

Silver iodobromide emulsion (Agl = 11.3 mol%, internally high Agl type, sphere-equivalent diameter = 1.4 µm, variation coefficient of sphere-equivalent diameter = 28%, tabular grain, diameter/thickness ratio = 6.0)

Layer 11: Yellow filter layer

Layer 12: Interlayer

Layer 13: 1 st blue-sensitive layer

Silver iodobromide emulsion (Agl = 2 mol%, homogeneous iodide type, sphere-equivalent diameter = 0.55 µm, variation coefficient of sphere-equivalent diameter = 25%, tabular grain, diameter/thickness ratio = 7.0)

Layer 14: 2nd blue-sensitive emulsion layer

Silver iodobromide emulsion (Agl = 19.0 mol%, internally high Agl type, sphere-equivalent diameter = 1.0 µm, variation coefficient of sphere-equivalent diameter = 16%, octahedral grain)

Layer 15: Interlayer

Fine grain silver iodobromide (Agl = 2 mol%, homogeneous iodide type, sphere-equivalent diameter = 0.13 gm)

Layer 16: 3rd blue-sensitive emulsion layer

Silver iodobromide emulsion (Agl = 14.0 mol%, internally high Agl type, sphere-equivalent diameter = 1.7 µm, variation coefficient of sphere-equivalent diameter = 28%, tabular grain, diameter/thickness ratio = 5.0)

Layer 17: 1 st protective layer

Layer 18: 2nd protective layer

Fine grain silver chloride (sphere-equivalent
In addition to the above additives, B-1 (0.20 g/m² in total), 1,2-benzisothiazoline-3-one (about 200 ppm on the average with respect to gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm on the average with respect to gelatin), and 2-phenoxyethanol (about 10,000 ppm on the average with respect to gelatin) were added to the layers.
Samples 402 and 403 were prepared by using Cpd-16 and Cpd-17, respectively, instead of the dye Cpd-11 added to the layer 1 of the sample 401. In addition, samples 404 to 406 were formed by using Cpd-18, Cpd-19, and Cpd-20, respectively, instead of Cpd-11 of the sample 401. Following the same procedures as in Example 2, each sample was cut into a strip having a width of 3.5 cm and a length of 117 cm and moisture-conditioned at a temperature of 25° C and a relative humidity of 60%. The moisture-conditioned sample was curled into a patrone and perfectly sealed in a patrone case.
A strip having a width of 3.5 cm and a length of 20 cm of each of the samples 401 to 406 and six samples sealed into patrone cases as described above, were left to stand in an air constant temperature/constant humidity bath having a volume of about 0.45 m³ at a temperature of 50 C and a relative humidity of 60% for three days. Thereafter, these samples together with the samples 401 to 406 stored at room temperature were subjected to sensitmetry exposure and color development, and density measurement was performed. The results are summarized in Table 6. The value of each of △fog, Asensitivity, and Agradation is obtained subtracting a characteristic value of the sample stored at room temperature. Note that a relative humidity in the patrone case during being left to stand at 50° C for three days and a relative humidity in the air constant temperature/constant humidity bath at 50 C, were measured. As a result, the relative humidity in the patrone case was 63% to 65%, and that in the constant temperature/constant humidity bath was 60%.
Following exactly the same procedures as in Example 2, amounts of HCN gas released from the samples 401 to 406 were determined. The results are summarized in Table 7.
As is apparent from Tables 6 and 7, since no HCN gas was released in the samples 404 to 406 using the dyes Cpd-18 to Cpd-20 of the present invention and sealed in a patrone case, a degree of deterioration in photographic properties, i.e., changes in fog, sensitivity, and gradation were smaller than those of the samples 401 to 403 as comparative examples. That is, very preferable results were obtained by the present invention. In addition, when the strips were subjected to the deterioration test in the constant temperature/constant humidity bath having a large volume, amounts of HCN gas released from the samples 401 to 403 were very small and the gas was diluted by air. Therefore, no adverse affect on the light-sensitive material was found.
Formulas or names of the compounds used in the present examples will be presented below.

Claims

1. A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer containing a silver halide emulsion subjected to chemical sensitization by a gold compound and a chalcogenide compound on a support,
wherein an amount of hydrogen cyanide released from 1 m² of said light-sensitive .material in a wet atmosphere at 75° C for 2 hours is 0.8 µg or less, and said light-sensitive material is sealed in a closed vessel capable of maintaining a relative humidity constant.

2. The silver halide photographic light-sensitive material according to claim 1, characterized in that said closed vessel is maintained at a relative humidity of 50% to 70% at 25° C.

3. The silver halide photographic light-sensitive material according to claim 1, characterized in that the amount of hydrogen cyanide released from 1 m² of the light-sensitive material is 0.6 µg or less.

4. The silver halide photographic light-sensitive material according to claim 1, characterized in that the amount of hydrogen cyanide released from 1 m² of the light-sensitive material is 0.3 µg or less.

5. The silver halide photographic light-sensitive material according to claim 2, characterized in that the closed vessel is maintained at a relative humidity of 53% to 68%.

6. The silver halide photographic light-sensitive material according to claim 1, characterized in that the internal volume of the closed vessel is 0.07 x cm³ or less (x represents a surface area (cm²) of light-sensitive layer of the silver halide photographic light-sensitive material).

7. The silver halide photographic light-sensitive material according to claim 2, characterized in that the internal volume of the closed vessel is 0.07 x cm³ or less (x represents a surface area (cm²) of light-sensitive layer of the silver halide photographic light-sensitive material).

8. The silver halide photographic light-sensitive material according to claim 1, characterized in that the light-sensitive material contains a polymer material obtained by polymerization using a polymerization initiator which does not have cyano group.

9. The silver halide photographic light-sensitive material according to claim 8, characterized in that the polymer material is a polymer coupler.

10. The silver halide photographic light-sensitive according to claim 8, characterized in that the polymer material is a polymer matting agent.

11. The silver halide photographic light-sensitive according to claim 8, characterized in that the polymer material is a polymer ultraviolet absorbent.

12. The silver halide photographic light-sensitive material according to claim 1, characterized in that the light-sensitive material comprises at least one ultra-violet absorbent represented by formula (UVI), (UVII), (UVIII), (UVIV), (UVV) or (UVVI):

wherein R, and R₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group R₁ and R₂ are not simultaneously hydrogen atoms, and R, and R₂ may form a 5- or 6-membered ring together with N;

X and Y each represent -COR₃, -COORs, -S0₂R₃,

or -COOH, R₃ and R₄ each represent an alkyl group or an aryl group, and R₄ may be a hydrogen atom. X and Y may be bonded to be integrated;

n represents 1 or 2, and when When n is 2, at least one of Ri, R₂, and R₂ may represent an alkylene group or an arylene group to form a dimer;

wherein z represents an atom group required to form an oxazolidine ring, a pyrrolidine ring, or a thiazolidine ring;

R₅ represents an alkyl group or an aryl group;

X and Y each represent -COR₃, -COOR₃, -SO₂R₃,

or -COOH, R₃ represents an alkyl group, or an aryl group, and X and Y may be bonded to be integrated;

n represents 1 or 2, and when When n represents 2, one of R₅ and R₃ may represent an alkylene group or an arylene group to form a dimer;

wherein Z₁ represents 0, S, or

R₅ represents an alkyl group or an aryl group;

R₆ and R₇ each represent a hydrogen atom, an alkyl group, or an aryl group and R₆ and R₇ may be integrated to form a benzene ring or a naphthalene ring;

R₈ represents a hydrogen atom or an alkyl group; and

R₉ represents an alkyl group or an aryl group, and

R₉ and R₉ may together form a nucleus;

wherein Z₂ represents an atom group required to form 5-oxazolone, 5-isooxazolone, 2-thiohydantoin, 2-thiooxazolidine-2,5-dione, rhodanine, thiazolidine-2,4-dione ring;

R₁₂ represents an alkoxy group, -OCOR₁₇, or a hydrogen atom, R₁₇ represents an alkyl group or an aryl group;

R₁ and R₁₄ each represent a hydrogen atom or an alkoxy group; and

each of R₁₅ or R₁₆ each represent an alkyl group, or an alkoxy group, or a halogen atom;

wherein R₂₈, R₂₉, R₃₀, R₃₁, and R₃₂ may be the same or different and may be a hydrogen atom or a substituting group allowed for an aromatic group;

wherein R₁₈ represents hydroxy, an alkoxy group, or an alkyl group;

R₁₉ and R₂₀ each represent a hydrogen atom, hydroxy, an alkoxy group, or an alkyl group, and R₁₈ and R₁₉ or R₂₀ and R₁₈ may be at adjacent positions to form a 5- or 6-membered ring; and

X and Y each represent -COR₃, -COOR₃, -SO₂R₃,

or -COOH, R₃ and R₄ each represent an alkyl group or an aryl group and R₄ may be a hydrogen atom, and X and Y may be bonded to be integrated.

13. The silver halide photographic light-sensitive material according to claim 1, characterized in that the light-sensitive material comprises at least one dye represented by formula (DI) or (DII):

wherein R₁ and R₂ each represent a hydrogen atom, an alkyl group or an aryl group, and R₁ and R₂ may together form a 5- or 6-membered ring;

R₃ represents a halogen atom, alkyl, alkoxy, hydroxy, carboxy, substituted amino, carbamoyl, sulfamoyl, or alkoxycarbonyl;

n represents 0, 1, 2, 3, or 4, a plurality of R₃s may be the same or different, and R₁ and R₃ or R₂ and R ₃ may be bonded to form a 5- or 6-membered ring;

Z represents a group selected from

or

wherein R₄ and R₅ each represent -COR₆, -SO₂R₆, -CO₂R₆,-CONR₆·R_Ø, -SO₂NR₆·R₇, or -SO₂R₆ wherein R₆ and R₇ each represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, and Q represents a hydrogen group for forming a nitrogen-containing 5- or 6-membered heterocyclic ring);

L represents a methine group or a nitrogen atom;

wherein R₈ represents an aryl group, and R₉ and n have the same meanings as those of R₃ and n in formula (DI), respectively, R₁₀ and R₁₁ have the same meanings as those of R₁ and R₂ in formula (DI), respectively, and R₉ and R₁₀ or Rg and R₁₁ may be bonded to form a 5- or 6-membered ring.

14. The silver halide photographic light-sensitive material according to claim 2, characterized in that the amount of hydrogen cyanide released from 1 m² of the light-sensitive material is 0.6 µg or less.

15. The silver halide photographic light-sensitive material according to claim 2, characterized in that the amount of hydrogen cyanide released from 1 m² of the light-sensitive material is 0.3 µg or less.